Glassy, Amorphous and Nano-Crystalline Materials

Glassy, Amorphous
and Nano-Crystalline Materials

Hot Topics in Thermal Analysis and Calorimetry
VOLUME 8
Series Editor
Judit Simon, Budapest University of Technology and Economics, Hungary
For other titles published in this series, go to

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Jaroslav Šesták l Jiřı́ J. Mareš l Pavel Hubı́k
Editors
Glassy, Amorphous
and Nano-Crystalline
Materials
Thermal Physics, Analysis, Structure
and Properties
Editors
Jaroslav Šesták Jiřı́ J. Mareš
New Technologies – Institute of Physics, v.v.i.
Research Centre in the Westbohemian Academy of Sciences
Region of the Czech Republic
University of West Bohemia Cukrovarnická 10
Univerzitnı́ 8 16200 Prague 6
30614 Plzeň Czech Republic
Czech Republic [email protected]
[email protected]
Pavel Hubı́k
Institute of Physics, v.v.i.
Academy of Sciences
of the Czech Republic
Cukrovarnická 10
16200 Prague 6
Czech Republic
[email protected]
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Preface
Early Research into Amorphous Semiconductors
Numerous aspects of physics and chemistry of non-crystalline solids and glassy

state which are discussed in the present book can only hardly be prefaced without
rude simplification. Therefore, let us make instead a short excursion to the prehis-
tory of research into amorphous semiconductors, the topic on which the common
epistemological features of the other subjects treated in this book may be demon-
strated.
It is a matter of fact that in everyday life we encounter more frequently non-
crystalline than crystalline solids. We can even with some exaggeration say that in
the Nature the perfect crystals are as rare as diamonds. In spite of that, the existence
of the class of non-crystalline materials has been recognized only recently. One of
the reasons for such a state of the art is probably the fact that the positivistic
continuous model of matter dominated till the end of the nineteenth century and
that the fundamental conjectures of atomism were too closely bound up with the
idea of the regular ordering of atoms; early atomic theories accounting for the
regular shape of snow flakes [1] and for the anisotropy of optical properties of
transparent crystals [2], namely, exploited the idea that such a regularity is due to
the closest filling of the space by identical hard polyhedrons or spheres, atoms.
Denying atomic order in solids would thus undermine the strongest intuitive
argument in favour of atomism, namely, that just the satisfaction of geometrical
constrains between neighbouring atoms and their close packing accounts for actu-
ally observed regular shape of crystals. Interestingly enough, in the scientific
disputations about the structure of matter, the existence of glass, for a long time
known amorphous, i.e. “shapeless” material par excellence, was tacitly ignored.
The serious attempts to treat the atomic structure of amorphous or glassy state
are thus relatively recent, belonging to the first half of the twentieth century. The
glass was at that time considered to be nothing but undercooled liquid i.e. a solid
having essentially the atomic structure of original melt. Such a picture was an
immediate consequence of phenomenological principle of continuity between
v
vi Preface
liquid and solid state proposed by Frenkel [3], which was, among others, partially
confirmed by means of X-ray analysis. Accordingly, namely, some characteristic
structural patterns observed in the solid phase are, as a rule, observed in the liquid
melt as well. From the broadening of X-ray diffraction patterns it was even possible
to conclude that the glass comprises nanocrystals of typical size ~2 nm. (Today
such a material would be classified rather as a nanocrystalline aggregate than glass.)
Nevertheless, the phenomenological model provided neither the algorithm for the
reconstruction of atomic lattice of glass nor the basis for the derivation of its
physical properties from the structural ones. The first realistic model of glass lattice
due to Zachariasen [4] was thus rather a result of physical reasoning than of a purely
descriptive phenomenology. Crucial for the establishment of the model was the
observation (from today’s point of view not very exact!) that the mechanical
properties of a glass, e.g. elastic bulk modulus or hardness, and of a corresponding
crystal are similar. Consequently, the underlying building blocks have to have
similar structural energies and must be matched together without further expense
of energy. In order to satisfy these conditions it was suggested to identify the
“underlying building blocks” with the nearest neighbourhood of each atom, the
arrangement of which was only slightly changed with respect to that in a crystal.
Cumulating small deviations of bond lengths (~1%) and tiny variations of bond
angles (~1 ) made it possible to match building blocks together and to construct a
random amorphous lattice without appreciable increase of structural energy. It can
be shown that such a random lattice being locally almost identical with the periodic
lattice of the corresponding crystal should reveal up to the second or the third
coordination sphere practically the same radial distribution of atoms. For the
following coordination spheres, however, huge differences are expected. The
overall structural properties of amorphous solid may then be characterized quite
simply by saying that the short-range order of atoms is preserved while the long-
range order is absent. Evidently, this is quite a new concept of disorder, differing
essentially from that encountered e.g. in gases. Being once established, the model of
locally ordered homogeneous random network based on the absence of long-range
order started to play more and more important role in modern solid state physics and
chemistry.
By admitting new structural model, the problem of amorphous state was by no
means definitely solved but just on the contrary. The researchers had to struggle
with qualitatively new difficulties which appeared by computing the mechanical,
optical and electronic properties of amorphous solids. As the semiconductors are
materials which are known to be most sensitive to the changes of structural and
chemical disorder, they may serve as a good example illustrating the fascinating
development of solid state physics which followed. The quantum band model of
solids as established in the 1930s was tailor-made for crystals having perfectly
periodic lattice disturbed by only a small number of imperfections. Accordingly to
Wilson’s classification [5], the semiconductors were materials characterized by a
“not very large” energy gap (~1 eV) in their electronic band structure. The very
existence of the electronic band structure of solids was at that time treated as a
direct consequence of periodicity of crystal lattice. Such an opinion was basically
Preface vii
due to the establishment of famous Bloch’s theorem [6] which enabled one to solve
electronic structure of periodically arranged atoms even analytically (see e.g.
Kronig-Penney model [7]). According to Bloch’s theorem, namely, the interaction
of an electron with the periodic crystal lattice may be replaced by its movement in a
certain periodic potential. The solution of Schrödinger equation in such a periodic
field has a special form of harmonic wave with periodically modulated amplitude.
In amorphous solids such a marvelous mathematical simplicity due to the perfect
translational symmetry and long range order of crystals was lost forever and
researchers have to learn how to do without Bloch’s theorem. Moreover, the
situation was further complicated by quite an astonishing experimental observation
of Kolomiets [8] that chalcogenide glasses behave like intrinsic semiconductors
which are essentially non-sensitive to the doping. Unexpectedly enough, theorists
had to account for the surviving of the band model in the absence of lattice
periodicity and for experimentalists quite a new field of research was opened,
amorphous semiconductors. It should be stressed here that just these two circum-
stances had enormous impact on the further development of semiconductor science
and technology.
The real boom of research into amorphous semiconductors was initialized by
works of Ovshinski who reported about switching between a highly resistive and
conductive state effected by an electric field and memory effects in chalcogenide
glasses [9]. Immediately afterwards a plenty of new effects such as photodoping,
reversible photostructural changes and optical memory effect having a huge appli-
cation potential for imaging and electrophotography (e.g. Xerox process) were
discovered. Hand in hand with the promise of further applications steeply increased
interest not only in chalcogenide glasses but also in other types of amorphous
semiconductors (e.g. tetrahedrally bounded semiconductors) and in non-crystalline
materials in general. Quite naturally there appeared a demand for a new scientific
journal (Journal of Non-Crystalline Solids, 1st issue 1969) covering all these hot
topics.
What were actually the main achievements in amorphous semiconductors during
the decade from1965 to 1975? First of all it was recognized that the band gap does
exists also in amorphous semiconductors in spite of the absence of atomic long-
range order. The band gap is, however, not empty but it contains an appreciable
amount of localized states and its edges are no more sharp [10]. The position of the
band gap edges and actual width of the band gap thus depends on the method of
measurement. Transport band edges coincide with so called mobility edges where
the mobility of carriers dramatically changes while the optical band gap (Tauc’s
optical gap [11, 12]) is determined by means of extrapolation of absorption curve.
The localized states within the gap are, moreover, no passive entity. As a rule, at
room and lower temperatures, they enable a special type of carrier transport via
localized states, the so called hopping [13]. A new light on the character of
localized states within the gap shed the path-breaking discovery of possibility of
effective doping of amorphous silicon prepared by glow-discharge technique [14].
Passivation of localized gap states by hydrogen or other chemicals opened a new
way to the tailoring of these materials. Besides the purely technological progress,
viii Preface
the research into amorphous semiconductors stimulated development of qualita-

tively new methods of computing electronic structure of disordered solids and
brought about changes in understanding to apparently closed topics [15].
We can thus claim that the research into amorphous semiconductors completely
changed, within practically 1 decade, the gist of solid state physics as a whole. The
concept of disorder became a corner stone of a lot of theories; the era of order was
shared by the era where the concept of disorder dominated. And finally, in episte-
mological context provided the discovery of various aspects of disorder a valuable
key to our understanding of a lot of natural systems and phenomena belonging not
only to the scope of solid state physics and chemistry but also to biology, astro-
physics and even to sociology.
May 2010 Jiřı́ J. Mareš

Institute of Physics ASCR, v.v.i.
Prague, Czech Republic
Jan Tauc
Brown University
Providence, Rhode Island, USA
1. Kepler J (1987) Strena seu de Nive Sexangula. G. Tambach, Fracofurti ad Moenum (1611),
German transl.: Vom Sechseckigen Schnee. Ostwald’s Klassiker vol 273, Geest and Portig,
Leipzig
2. Huyghens C (1903) Traité de la Lumiére. Pierre van der Aa, Leide (1690), German transl.:
Abhandlung über das Licht. W. Engelmann, Leipzig
3. Frenkel YaI (1945) Kinetitsheskaya teoria zhidkostei. Izd. AN SSSR, Moscow; English
transl.: Kinetic theory of liquids. Clarendon, Oxford (1946)
4. Zachariasen WH (1932) The atomic arrangement in glass. J Am Chem Soc 54:3841–3851
5. Wilson AH (1931) The theory of electronic semi-conductors. Proc R Soc London A 133:458–
491; Proc R Soc London A 134:277–287
6. Bloch F (1929) Über die Quantenmechanik der Elektronen in Kristallgittern. Z Phys 52:555–
600
7. Kronig R de L, Penney WG (1931) Quantum mechanics of electrons in crystal lattices. Proc R
Soc London A 130:499–513
8. Kolomiets BT (1964) Vitreous semiconductors (I), (II). Phys Stat Sol 7:359–372, 713–731;
Original report in: Proc IC on Semicon Phys Prague’60, Czechoslovak Acad Sci (1961), p 884
9. Ovshinski SR (1968) Reversible electrical switching phenomena in disordered structures.
Phys Rev Lett 21:1450–1453
10. Cohen MH, Fritzsche H, Ovshinsky SR (1969) Simple band model for amorphous semicon-
ducting alloys. Phys Rev Lett 20:1065–1068
11. Tauc J, Grigorovici R, Vancu A (1966) Optical properties and electronic structure of amor-
phous germanium. Phys Stat Sol 15:627–637
12. Tauc J (ed) (1974) Amorphous and liquid semiconductors. Plenum, London
Preface ix
13. Mott NF, Davies EA (1971) Electronic processes in non-crystalline materials. Clarendon,
Oxford
14. Spear WE, LeComber PG (1975) Substitutional doping of amorphous silicon. Solid State
Commun 17:1193–1196
15. Shklovskii BI, Efros AL (1979) Elektronnye svoistva legirovanykh poluprovodnikov (Elec-
tronic Properties of Doped Semiconductors). Nauka, Moscow
About the Editors
Prof. Jaroslav Šesták, MEng., Ph.D., DSc.

Senior Scientist of the Institute of Physics, Academy of Sciences
of the Czech Republic and New Technologies Research Centre,
University of West Bohemia – specialised in thermodynamics
(kinetics) and material science (particularly applied to inorganic
glasses), 287 papers in impact journals, over 2,500 SCI citation
responses, 15 books and book chapters, received degree of Doc-
tor Honoris Causa of the University of Pardubice (January 2010).
Dr. Jiřı́ J. Mareš, Ph.D.

Deputy Director of the Institute of Physics, Academy of Sciences
of CR – specialised in condensed matter physics, deals with quan-
tum properties of disordered systems and with fundamental pro-
blems of thermal physics and electrostatics, 123 papers in impact
journals, over 230 citation responses, 3 books and book chapters.
Dr. Pavel Hubı́k, Ph.D.

Senior Scientist of the Institute of Physics, Academy of Sciences
of CR – deals with defects in semiconductors and with electron
and thermal properties of solid state, 51 papers in impact journals,
over 110 citation responses, 2 books and book chapters.
xi
Acknowledgments
Prepared under the support of the following projects:

Institutional Research Plan No AV0Z10100521 of the Institute of Physics, v.v.i.,
Academy of Sciences of the Czech Republic
Grant Agency of the Academy of Sciences of the Czech Republic Project No
IAA100100712
Czech Science Foundation Projects No P204/10/0212 and No P204/11/0964
Czech Industrial Grants (MPO) No 2A-1TP1/037 in the program 2A – Sustainable
welfare and Nos FR-TI 1/335, FR-TI 1/369 and FR-TI 1/278 in the program TIP
Ministry of Education, Youth and Sport (MŠMT) Project No 1M06031
xiii
Contents
1 Introduction: Some Essential Attributes of Glassiness

Regarding the Nature of Non-crystalline Solids . . . . . . . . . . . . . . . . . . . . . . . . . 1
Hiroshi Suga
2 Heat Capacity and Entropy Functions in Strong and

Fragile Glass-Formers, Relative to Those of Disordering
Crystalline Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
C. Austen Angell
3 Vibration Forms in the Vicinity of Glass Transition,

Structural Changes and the Creation of Voids When
Assuming the Role of Polarizability. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
Jaroslav Šesták, Bořivoj Hlaváček, Pavel Hubı́k, and Jiřı́ J. Mareš
4 Some Aspects of Vitrification, Amorphisation and

Disordering and the Generated Extent of Nano-Crystallinity . . . . . . . . . 59
Jaroslav Šesták, Carlos A. Queiroz, Jiřı́ J. Mareš,
and Miroslav Holeček
5 Basic Role of Thermal Analysis in Polymer Physics. . . . . . . . . . . . . . . . . . . . 77

Adam L. Danch
6 Phases of Amorphous, Crystalline, and Intermediate

Order in Microphase and Nanophase Systems. . . . . . . . . . . . . . . . . . . . . . . . . . 93
Bernhard Wunderlich
7 Thermal Portrayal of Phase Separation in

Polymers Producing Nanophase Separated Materials. . . . . . . . . . . . . . . . . 115
Ivan Krakovský and Yuko Ikeda
xv
xvi Contents
8 Solid Forms of Pharmaceutical Molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129

Bohumil Kratochvı́l
9 Chalcogenide Glasses Selected as a Model System

for Studying Thermal Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
Zdeněk Černošek, Eva Černošková, and Jana Holubová
10 Viscosity Measurements Applied to Chalcogenide

Glass-Forming Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
Petr Koštál, Jana Shánělová, and Jiřı́ Málek
11 Thermal Properties and Related Structural Study

of Oxide Glasses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
Marek Liška and Mária Chromčı́ková
12 Oxide Glass Structure, Non-bridging Oxygen and Feasible

Magnetic Properties due to the Addition of Fe/Mn Oxides . . . . . . . . . . . 199
Jaroslav Šesták, Marek Liška, and Pavel Hubı́k
13 New Approach to Viscosity of Glasses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217

Isak Avramov
14 Transport Constitutive Relations, Quantum Diffusion

and Periodic Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
Jiřı́ J. Mareš, Jaroslav Šesták, and Pavel Hubı́k
15 In-Situ Investigation of the Fast Lattice Recovery during

Electropulse Treatment of Heavily Cold Drawn
Nanocrystalline Ni-Ti Wires . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
Petr Šittner, Jan Pilch, Benoit Malard, Remi Delville,
and Caroline Curfs
16 Emanation Thermal Analysis as a Method for Diffusion

Structural Diagnostics of Zircon and Brannerite Minerals . . . . . . . . . . . 261
Vladimı́r Balek, Iraida M. Bountseva, and Igor von Beckman
17 Scanning Transitiometry and Its Application in Petroleum

Industry and in Polymer and Food Science . . . . . . . . . . . . . . . . . . . . . . . . . . . . 271
Jean-Pierre E. Grolier
18 Constrained States Occurring in Plants Cryo-Processing

and the Role of Biological Glasses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
Jiřı́ Zámečnı́k and Jaroslav Šesták
Contents xvii
19 Thermophysical Properties of Natural Glasses

at the Extremes of the Thermal History Profile . . . . . . . . . . . . . . . . . . . . . . . 311
Paul Thomas, Jaroslav Šesták, Klaus Heide,
Ekkehard Füglein, and Peter Šimon
20 Hotness Manifold, Phenomenological Temperature

and Other Related Concepts of Thermal Physics. . . . . . . . . . . . . . . . . . . . . . 327
Jiřı́ J. Mareš
21 Historical Roots and Development of Thermal

Analysis and Calorimetry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 347
Jaroslav Šesták, Pavel Hubı́k, and Jiřı́ J. Mareš
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 371
Chapter 1
Introduction: Some Essential Attributes
of Glassiness Regarding the Nature
of Non-crystalline Solids
Hiroshi Suga
1.1 Character of the Amorphous Solids
Glass products have long been used from ancient times not only in our daily life but
also in some laboratory experiments such as the U tube for the measurement of
volume of a gas as a function of pressure. Liquefaction of the last “permanent gas
helium” was done successfully with an apparatus entirely made of glass. Formerly
the glasses have been produced by cooling the melts of silicate minerals without
crystallization until they becomes hard and brittle solids. Later the glasses were
found to exhibit hallo diffraction patterns similar to those of the liquids. Some
important concepts are involved in this description. The first is the method of
preparation. The melt-cooling was used in some of the modern definitions of
glasses. The second is the starting materials of inorganic origin. Organic substances
such as glycerol and synthetic polymers were found to behave similarly. Thus the
term glasses can be extended to a wide range of substances that easily undercool to
form amorphous solids. The third is the metastability of the undercooled liquids and
glasses compared to the corresponding crystalline solids. If the cooling rate is
adequately slow to induce nucleation, the melt becomes crystalline solid possessing
regular lattice with lower Gibbs energy. Thus the formation of glass is a problem of
bypassing or avoiding the crystallization. Although the main subjects of this book
are the structures and properties of ordinary network glasses of inorganic origin, it
will be instructive to start with the description of the general features of glassiness
exhibited by various kinds of condensed matters in which the constituents are held
together by interaction forces, such as the van der Waals, hydrogen bonding, ionic
or covalent bonds.
In spite of the long history of practical usage of the ordinary glasses, the scientific
research of the glassy state began in the twentieth century. It is surprising to realize
H. Suga (*)
Osaka University, Toyonaka, Osaka 560-0043, Japan
e-mail: [email protected]
J. Šesták et al. (eds.), Glassy, Amorphous and Nano-Crystalline Materials, 1

Hot Topics in Thermal Analysis and Calorimetry 8, DOI 10.1007/978-90-481-2882-2_1,
2 H. Suga
that the first measurement of glass transition is more recent event than the discovery
of the radioactivity. Pioneering work of the calorimetric measurement by Gibson
and Giauque [1] has shown that glycerol glass exhibited a sudden increase in the heat
capacity Cp over a narrow temperature region, and possessed a residual entropy S0 at
0 K. The temperature region is called the glass transition temperature Tg, and is an
important keyword for the glass science and technology. Other thermodynamic
quantities such as the volume V and thermal expansivity a also undergo some
changes at Tg. This experiment gave the first paramount example of the solid that
deviated from the third law of thermodynamics. In Simon’s word [2], the law is
expressed as “The contribution to the entropy of a system by each aspect which is in
internal equilibrium tends to zero at 0 K.” The realization of the internal equilibrium
in some systems becomes quite serious for a human being with a short life span. In
this way, the glasses are the frozen-in non-equilibrium states with respect to some
degrees of freedom in a metastable phase of the system. In modern terminology, the
glasses or glassy states are designated as non-ergodic. Thus any liquid that satisfies
the ergodicity hypothesis in statistical mechanics becomes out of equilibrium with
some aspects of the system during a continuous cooling. The breaking of the
ergodicity occurs at a small temperature interval Tg, which depends naturally on
the experimental time-scale. In this way, the glass transition temperature, the
residual entropy, the metastability, and the crystallization are the important key-
words for the thermodynamic characterizations of the glassy systems.
Over the past 50 years, many amorphous solids have been prepared by various
methods other than the traditional liquid-cooling. Amorphous semiconductor used
for the solar cells is one example. Much of the intense research interest in amorphous
solids is driven by the technological importance of these solids. Intellectual fascina-
tion with the amorphous solids arises from the basic understanding of the state of
aggregation of the constituent entities in the solids. These amorphous solids combine
liquid-like disordered structure and crystal-like rigidity, and display unique features
that are generally absent in their counterparts in the crystalline solids. The exotic
formation of amorphous solids can be done by either physical or chemical methods.
Some methods do not pass at all their liquid state during the formation of amorphous
solids. Glasses are just one example of the amorphous solids formed from the
liquid states. What is the relation between glasses and amorphous solids? The
question was raised by Secrist and Mackenzie [3]. The two terms had been used
for some times without any clear distinction.
Molecular assembly is traditionally divided into four states of aggregation of the
constituent molecules. The division of assembly into gas, liquid, and solid is based
on the mechanical properties of the assembly, such as density and fluidity. Further
division of the solid into crystalline and non-crystalline solids is obviously based on
the structural point of view. The division of metastable liquids below their melting
points into glassy and undercooled liquids is based on the non-equilibrium and the
equilibrium nature of both states based on the thermodynamic reasoning. Thus
criteria of the classification are multifarious in nature. The glasses are just one
example of the amorphous solids with frozen-in disordered structure of liquids,
but the reverse is not true necessarily without some experimental verification.
1 Introduction: Some Essential Attributes of Glassiness 3
One method to answer this question is to detect in amorphous solids possible

existence of either the glass transition or the residual entropy that have been
observed to occur concomitantly in many glass-forming liquids. This problem is
discussed first in the following section.
It is worthy to note here another metastable nature of the polymeric materials.
Most of the synthetic polymers consist of the crystalline and amorphous parts. The
ratio of both parts can be changed arbitrarily by keeping them at particular temper-
ature range. This nature produces a wide variety of properties in one and the same
polymer, and enhances the usefulness in the applications of the polymeric materi-
als. According to the phase rule, however, only a single phase should appear
generally in any single-component system at a particular T and p other than the
melting line. The coexistence of two parts will be a consequence of a distribution of
masses in the constituent molecules of the system. Any synthetic polymers, even
composed of one kind of pure monomer, cannot be regarded as the “single-
component system,” for which the phase rule holds rigorously. One intriguing
exception would be atactic polymers in which a trace of crystalline part cannot
be observed to exist. It is not easy to imagine any conformation of the molecules in
the atactic polymer that guarantees the translational invariance in the spatial
arrangement of molecules placed on any regular lattice points. Strictly speaking,
there exists no single-component system in pure substances if we take into consid-
eration the existence of isotopes. The effect of isotope on the phase behaviour
appears, however, only at very low temperatures. In fact, liquid helium, being a
mixture of He3 and He4, exhibits a phase separation at a cryogenic temperature that
depends on the composition. The phase separation is a kind of ordering process that
reduces the entropy of the system. Most of the substances are believed to be in
frozen-in disordered states with respect to their isotopic species.
1.2 Preparation and Characterizations of Amorphous Solids
A wide variety of amorphous solids can be prepared by physical and chemical

methods. The former is (1) rapid cooling of liquid; (2) deposition of vapour onto a
cold substrate; (3) mechanical milling of crystal; (4) particle bombardment onto
crystal; (5) compression or depression of crystal, and so on. While the latter is
(6) gelation; (7) precipitation by chemical reaction; (8) dehydration of hydrate
crystal, and so on. In the former processes, the composition of substance does not
change during the formation of amorphous solids [4]. The liquid-cooling (1) is the
most familiar one. A hyper-quenching method, with a cooling rate of nearly 106 K
s1, was developed and applied to water or metallic liquids that had strong crystalli-
zation tendency. The other physical methods do not pass in principle their liquid
state. Vapour deposition is one of the powerful methods in forming amorphous
solids. The kinetic energies of vapour molecules are extracted efficiently during the
condensation on to a substrate kept at a temperature far below the hypothetical Tg, so
as to arrest the deposited molecules in a frozen disordered state. Crystals are used in
4 H. Suga
the remaining physical methods. High energy in the form of compression, shear
stress, or radiation is supplied to the crystal to destroy the neatly ordered arrange-
ments of the constituents. Amorphization of ice, SiO2 and others were done by this
way. Mechanical milling was another energizing method and applied first to a
metallic mixture forming an amorphous alloy. These non-equilibrium processes
can be done without passing their liquids. Amorphization by any low-temperature
routs is useful particularly for substances that are unstable at high temperatures.
Thermal decomposition can be observed in some of the molecular crystals. The
various methods for production of the amorphous solids are depicted schematically
in Fig. 1.1.
Mechanical alloying is a non-equilibrium amorphization process and has been used
in the development of new metallic systems. This can be done by milling of a mixture
composed of two or more metals at room temperature. In contrast to the metallic
systems, milling of molecular crystals produces amorphous solids even in a single
system. For example, salicin, deoxycholic acid, trehalose, tri-O-methyl-b-cyclodextrin,
etc. have been amorphized easily even in single system. Supply of mechanical energy
to a crystalline substance beyond a critical level induces lattice instability of the crystal
and freezes it in an energized state that has lost the original periodicity. Obviously the
process must be carried out at temperatures below the “crystallization-dangerous”
region of the resulting amorphous solids. Nature of the formed amorphous solid
depends on the milling conditions. Both the Tg-value and the enthalpy of crystallization
of the obtained solid are found to increase asymptotically with the milling time.
For some binary molecular crystals, milling of a mixture results in the molecular
alloys with a single Tg varying with the composition. This indicates that the
component molecules mix uniformly in a molecular level to exhibit a single
relaxation process over the whole composition range. Formation of solid solutions
in the crystalline state is highly limited by many factors such as the shared crystal
Vapor Liquid
Condensation Quenching
CHEMICAL
(Glass)
METHODS
Amorphous Solid
Gelation
Dehydration
Precipitation
Grinding
Pressurization
Bombardment of particles
Crystal
Fig. 1.1 Various methods of preparation of amorphous solids

symmetry, the similar sizes of the unit cells, the similar molecular shapes, and so
on. Alloying of otherwise immiscible substances in the solid state is possible only
under non-equilibrium condition.
The chemical methods accompany necessarily some changes in chemical poten-
tials of the system. In method (6), the sample in a sol is brought into a gel state and
then removal of extra components forms corresponding amorphous solid. Some
oxides were amorphized by this way in the form of fibres or lumps. The method (7)
utilizes the fact that some chemical reactions in solution produce amorphous
precipitates. Students in the course of analytical chemistry experience fine precipi-
tates in the exercise when H2S gas is passed into an aqueous solution including As3+
or Sb3+ ions. The yellow precipitates are fine particles and are known to be
amorphous from powder X-ray diffraction experiment. Some hydroxides are also
amorphous when they are precipitated in solutions. While, water molecules are
important ingredients in hydrate crystals. If the molecules are extracted by rapid
evacuation, the resulting anhydride cannot keep anymore the crystalline lattice in
some hydrate crystals. Magnesium acetate tetrahydrate, Mg(CH3COOH)2·4H2O,
belongs to this category. By evacuation, the hydrate crystal changes into amorphous
anhydride. In this way, there exist many methods for the formation of amorphous
solids other than the traditional liquid cooling.
The chemical precipitates As2S3(am) was examined by thermal analysis, and
found to exhibit a glass transition Tg at about 477 K. The temperature was
essentially the same as that of As2S3(am) prepared by the liquid-cooling of orpi-
ment, being crystalline mineral As2S3(cr) occurring in nature. While, Sb2S3(am)
can be prepared either by the chemical precipitation or by vapour deposition. Both
the samples showed Tg at essentially the same temperature of 489 K. These results
[5, 6] are summarized in Table 1.1.
The Cp values of the amorphous tri-O-methyl-b-cyclodextrin were essentially
the same at temperatures below and above Tg for both samples prepared by the
mechanical milling and the liquid-quenching. Thus it turned out that the terms
amorphous solids and glasses are synonymous. Obviously the extent of frozen-in
disorder of any amorphous solids depends on the condition by which the amorphous
solids were formed. In the vapour deposition experiments, it was revealed that the
lower the substrate temperature, the larger the amount of residual entropy S0. This
indicates that the faster removing of the kinetic energy of vapour molecules results
in larger extent of frozen-in disorder in the solid. The extent of frozen-in disorder in
amorphous solid can be described also by the concept of fictive temperature Tfic,
that was introduced by Tool as an extra variable necessary for the description of
glass and was defined as the temperature at which a glass with a given enthalpy
would be at equilibrium if it followed the iso-structural change as the temperature
was changed [7]. The thermal motions in high-temperature liquids permit rapid and
effective exploration of alternative molecular packing. But such structural change
becomes increasingly sluggish as the temperature is lowered, and it largely ceases if
further cooling passes through Tg. If a liquid is cooled at a constant rate, the
equilibrium enthalpy deviates from the equilibrium curve at a particular tempera-
ture Tfic. The value becomes lower as the cooling rate is lowered. The value Tfic will
6 H. Suga
Table 1.1 Glass transition temperature Tg of various amorphous solids

Substance Tg/K Method Substance Tg/K Method
Propane 46 VC Methanol 103 VC
(Propane)x(propene)1x 46 ~ 55 VC Vinyl acetate 123 LQ
Propene 55 VC Isopropylbenzene 126 LQ
55 LQ H2O 135 VC
(Propene)x(1-butene) 1x 55 ~ 60 VC Ethylene glycol 153 LQ
1-Butene 60 VC 1,3-Propanediol 166 LQ
60 LQ m-Cresol 200 LQ
(Propene)x(1-pentene)1x 55 ~ 72 VC Resorcinol 250 LQ
(Butane)x(1-butene)1x 60 ~ 62 VC Salicin 333 MM
(1-Butene)x(1-pentene)1x 60 ~ 72 VC Sucrose 342 MM
1-Pentene 72 VC Tri-O-methyl- 352 LQ
b-cyclodextrin
(TMCD)
CCl4 60 VC 352 MM
Isopentane 65 LQ Phenolphthalene 362 MM
CHCl3 79 VC TMCD + benzoic acid 337 LQ
3-Methylpentane (0.1 MPa) 77 LQ 337 MM
(108 MPa) 85 LQ Brucine 359 MM
(198 MPa) 92 LQ Deoxycholic acid (DCA) 363 MM
Ethanol 90 LQ Trehalose 384 MM
Cyclohexene 92 LQ Magnesium acetate 469 DH
Dichloromethane 93 LQ As2S3 477 CR
1-Propanol (0.1 MPa) 97 LQ 477 LQ
(108 MPa) 104 LQ Sb2S3 489 VC
(198 MPa) 109 LQ Polytetrahydrofuran 185 LQ
Butyronitrile 97 VC Polyoxacyclobutane 193 LQ
97 LQ Polyoctamethyleneoxide 255 LQ
LQ Liquid quenching, VC Vapour condensation, CR Chemical reaction, MM Mechanical milling
of crystal, DH Dehydration of hydrate crystal
change with time in the glassy state, depending on the annealing conditions at
temperatures below the initial Tfic. Thus the determination of Tfic of a sample at the
measurement stage requires the determinations of enthalpy of the actual glass and
of the equilibrium liquid. In this way, calorimetric measurements give the quantita-
tive data of Cp, Tg, S0 and Tfic at the same time. Figure 1.2 shows (a) the heat
capacity and (b) the entropy of isopropylbenzene [5] plotted against temperature.
The figure shows common features of the amorphous solids prepared by the rapid-
cooling of liquid. The heat capacity of a liquid is generally larger than its crystal,
primarily because the configurational degrees of freedom are excited in the liquid
but not in the crystal. In addition to the primary or a glass transition Tg,a, a
secondary or b glass transition Tg,b can be found by the measurement. The heat
capacity jump associated with the b transition is so small that very careful and
Fig. 1.2 Heat capacity and en-

tropy of isopropylbenzene
precise measurements are required for the detection. The quantity TK is designated
as the Kauzmann temperature and is described later.
Many physical properties, say the enthalpy, of glass tend to relax toward the
equilibrium values of the liquid at a constant temperature with a characteristic time.
The relaxation process for the configurational enthalpy is well described by the
Kohlrausch-Williams-Watts’ (KWW) equation [7],
DHc ðtÞ ¼ DHc ð0Þ exp½ðt=tÞb ; (1.1)
where Hc is the part of enthalpy related to the structure or configuration of the

liquid, t is the average relaxation time, b (0 ≦ b ≦ 1) is the non-exponential
parameter, DHc(t) and DHc(0) are the configurational enthalpy to be relaxed at
the time t ¼ t and t ¼ 0, respectively. The non-exponential relaxation is one of the
characteristic phenomena observed in many glasses. The smaller is the b value, the
larger is the distribution of relaxation times. The remaining part of the enthalpy,
called the vibrational enthalpy Hvib, responds always quickly to the temperature
variation. Since the total enthalpy of a sample, Htotal ¼ Hvib + Hc, can be kept
constant under the adiabatic condition, it follows
dDHc ðtÞ=dt ¼ ½dHvib ðtÞ=dT ½dT=dt ¼ Cvib ½dT=dt: (1.2)
Obviously the temperature T means the vibrational temperature. The structural

relaxation is, therefore, a process by which T and Tfic equalize. This is essentially
8 H. Suga
a problem of heat conduction between two thermal reservoirs with T and Tfic,
respectively. Thus the enthalpy relaxation causes a spontaneous temperature
change of sample under an adiabatic condition. The following equation is derived
for the sample temperature in an adiabatic calorimeter as a function of time [8].
TðtÞ ¼ a þ bt þ c exp½ðt=tÞb : (1.3)
The second term bt is the temperature change arising from residual heat leakage,
and is of the order of several mK h1 in most of the experimental temperature
range. Analysis of the T ~ t curve of the calorimeter enables us to deter-
mine experimentally the kinetic parameters governing the structural relaxation
through the enthalpy. It should be reminded that a constant temperature of a sample
with time is a prerequisite for the thermal equilibrium (the zeroth law of thermody-
namics). Any spontaneous temperature change with time under an adiabatic condi-
tion indicates that the sample is in a non-equilibrium state and is relaxing toward the
equilibrium state. The time domain covered by this method is 0.1 ks ~ 1 Ms and can
be extended by patience of experimentalist. The Tg value determined by the
calorimetry corresponds to the temperature at which becomes t 103 s or 1 ks,
being the time necessary for a single heat-capacity determination. It is interesting
to note that for 1-pentene prepared by vapour-deposition, Tfic ¼ 85 K and b ¼ 0.45,
is quite different from those for the liquid-cooled sample, Tfic ¼ 72 K and b ¼ 0.92.
This indicates the effectiveness of the formation of glass with high extent of
disorder along with wider distribution of the relaxation times by the vapour-
condensation process compared to an ordinary cooling process. In this way, the
adiabatic calorimeter does work as an ultra-low frequency spectrometer in addition
to the conventional tool.
The viscosity of liquid is one measure of the structural relaxation time for the
undercooled fluid, and is an important quantity from a practical point of view. The
viscosity can be measured routinely and it becomes a convenient kinetic parame-
ter for the glass relaxation. Over a small temperature interval, the viscosity changes
by several orders of magnitude from typically 101 Pa s in the liquid state to about
1012 Pa s in the glassy state. Since a value of in the order of 1012 Pa s is associated
with the solid state, one can define Tg newly as the temperature at which the
viscosity reaches this particular value as the temperature is lowered. According to
the Maxwell theory of viscoelasticity, the viscosity can be related to the relaxation
time t through the following equation [9].
t ¼ G1
1 ; (1.4)
where G1 is the instantaneous shear modulus. Numerical evaluation of this equa-

tion shows that the new definition, (Tg) ¼ 1012 Pa s, corresponds to the relaxation
time of several hundred seconds at Tg, being again the time scale for a single heat-
capacity determination. For some network-forming glasses, such as ordinary sili-
cate glasses, the viscosity changes with temperature T in the Arrhenius fashion,
¼ 0 exp [A/T]. Many molecular liquids, on the other hand, show pronounced
deviation from the Arrhenius behaviour and can generally be better described by the
Vogel-Tammann-Fulcher (VTF) equation.
¼ 0 exp ½A=ðT T0 Þ; (1.5)
where 0, A, and T0 are the constants depending on the nature of the liquid. In this
way the viscosity , hence the relaxation time t tends to diverge towards the
temperature T0.
Experiments of the enthalpy relaxation at a temperature below Tg showed that
the relaxation rate depended not only the amount of DHc but also the initial sign of
departure. The rate depends on whether the relaxation is structure-breaking or
structure-forming process. The data for t plotted against 1/T exhibit generally
non-Arrhenius behaviour, and the relaxation time diverges towards a temperature
T0 as the temperature is lowered, as already mentioned in the case of viscosity.
Experimental data showed that this temperature is quite near to the Kauzmann
temperature TK, at which the extrapolated entropy of liquid crosses that of crystal
[9]. Since any liquid that possesses entropy less than that of crystal is hard to
imagine, the extrapolated entropy of the liquid should bend at TK, and follows that
of the crystal in the temperature range below TK. The seemingly second-order
transition that the actual liquid exhibits at Tg is considered to be a kinetic manifes-
tation of the underlying equilibrium phase transition arising from the variation
of the entropy at the Kauzmann temperature TK. There exists other scenario that
avoids the entropy crisis at TK. Experimental verification of the validity of any
models that should occur at TK in an equilibrium liquid is not possible owing to our
short life span.
The deviation from the Arrhenius behaviour of t is correlated phenomenologi-
cally with a fragility parameter m as follows [10].

m ¼ d log t=d Tg =T jT ¼Tg (1.6)
For the Arrhenius behaviour, for which m is assigned to be 17, the liquid is designated
as strong liquid. The structure does not change much with temperature and the heat
capacity jump DCp at Tg is rather small. The larger the m value is, the structure
becomes fragile with change in temperature. These are designated as fragile liquids,
and exhibit rather large jump DCp at Tg.
Adam and Gibbs [11] proposed a model for explaining the non-Arrhenius
behaviour of the relaxation time. They expressed the relaxation time t by the
following equation.
t ¼ Aexp½z Dm=kT ¼ Aexp½NA Dmsc =kTScðTÞ: (1.7)
Here Sc(T) is the macroscopic configurational entropy of liquid, Dm the chemical

potential per molecule hindering the cooperative rearrangement of a group of mole-
cules, z* the number of molecules constituting the group (or cluster), sc* the
10 H. Suga
configurational entropy of the smallest group that can undergo the rearrangement, and
NA is Avogadro constant. The configurational entropy is determined by subtracting the
vibrational entropy from the experimentally determined entropy. The vibrational heat
capacity of the glass expressed in terms of a combination of the Debye and the Einstein
heat-capacity functions should be determined first by the least-square’s fitting of the
experimental data in the low-temperature range. The value Sc(T) becomes zero at TK
for the ideally equilibrated liquid, and this situation results in the divergence of t
towards TK as the temperature is lowered.. The non-Arrhenius behaviour can be
considered to be due to the fact that t is a function of T as well as of Sc. Likely the
number z* will not be constant but change with temperature. This entropy theory is
supported by experiment [12], showing good correlation between TSc(T) and log t for
some glasses prepared under different conditions. In spite of the large differences in Tg
among the samples, the glass transition takes place at essentially the same TSc value.
The number of molecules z* in a cooperatively rearranging unit, or a cluster, can
be estimated by considering the following relation that can be derived from
Eq. (1.7).
z ðT1 Þ=z ðT2 Þ ¼ ScðT2 Þ=ScðT1 Þ (1.8)
If the value z* be assumed to be 1 for the liquid at high temperatures where the
unimolecular process is dominant, the equation makes possible to estimate the
number of molecules z* in the undercooled and glassy states. This has been
done for some systems [13].
1.3 Glass Transitions in Crystals: Glassy Crystals
Most of the molecular crystals fuse directly into isotropic liquids. Some crystals fuse
in two steps, either through the liquid crystal phases or the orientationally disordered
crystal phases. These mesophases have the entropy values close to those of the
isotropic liquids, indicating a great deal of disorder in these mesophases. Most of the
orientationally disordered crystals have face-centred cubic (fcc) or body-centred
cubic (bcc) lattice with molecules possessing a great deal of orientational disorder. If
such a phase is cooled rapidly by avoiding the transformation into an ordered crystal,
the undercooled disordered phase undergoes freezing-in process at a temperature at
which the relevant relaxation time t crosses the experimental time, as in the case of
ordinary glasses. Particularly the glassy states of crystals designated as “glassy
crystals” are interesting. This is because glasses and crystals are two extremes in
our concept of structural regularity in solids, and the seemingly contradicting
concepts must be combined in this new state of aggregation of molecules [5].
Analogy between the dielectric and enthalpy relaxations will be helpful in under-
standing the concept of frozen-in disordered crystals. Dipolar liquids generally show
the dielectric relaxation in the equilibrium or undercooled liquid phases depending
on the frequency f of an external electric field. The dielectric permittivity drops at a
temperature at which the dielectric relaxation time td becomes (2pf)1, indicating a

freezing-in of the orientation polarization. The actual Tg value of the liquid corre-
sponds to the temperature at which the value td becomes ~1 ks. The same thing can
happen in some orientationally disordered crystals in which the centres-of-mass of the
molecules form three-dimensional lattice but their orientations are random among
several equi-energetical directions, say eight [111] directions of their fcc or bcc
lattices. These crystals exhibit, therefore, the dielectric relaxation likely if the crystal
is composed of polar molecules. The reorientational motion is dynamic at high
temperatures but becomes quiet as the temperature is lowered until the motion
becomes dormant. The heat capacity drops suddenly more or less in a narrow
temperature range just in a way similar to the liquids. In spite of the paradoxical
nature of the concepts involved in the nomenclature “glassy crystals,” time is now
giving it proof as an intriguing new state of aggregation of molecules.
Cyclohexanol forms an fcc lattice below Tfus. The high crystallographic symme-
try arises entirely from a great deal of orientational disorder of the molecule that has
only mirror symmetry. When the fcc phase is cooled by avoiding the transformation
into an ordered low-temperature phase, the undercooled orientationally-disordered
phase exhibits Tg at about 150 K and has a definite amount of residual entropy. The
behaviour of enthalpy relaxation is unable to discriminate in all aspects from those
of ordinary glasses only except for the existence of a long-range positional order in
cyclohexanol crystal. The heat-capacity tail below Tg is noticeable. The long Cp tail
below Tg causes the Sc to decrease over a wide range of temperature. This phenom-
enon has been observed more or less in many glassy liquids and the effect on the
residual entropy of cyclohexanol crystal was discussed in details [14]. The heat
capacity along with the entropy of cyclohexanol crystal is shown in Fig. 1.3.
In the case of ethanol, two kinds of glass transitions were observed for its liquid
and the orientational disordered phases, respectively. Some textbooks described
that ethanol was a good glass-forming liquid based on the observation of Tg. The
old observation of Tg by calorimetric measurements turned out to be for its
orientational disordered phase and not for the liquid. Glassy liquid of ethanol
can be realized only by a rapid cooling of the liquid with a rate faster than 50 K
min1. The glass transition for the liquid takes place at essentially the same
temperature of 97 K. Two glass transitions can occur for different phases of one
and the same substance of C2H5OH. This observation strongly suggests that the
kinetic feature of the molecular reorientation in condensed phases is primarily
responsible for the freezing process and that the reorientational motion governs
the translation-rotation-coupled rearrangement of molecules in the liquid. Fig-
ure 1.4 shows the heat capacity and entropy of ethanol around their glass transi-
tions, respectively [5].
Table 1.2 lists some examples of the glassy crystals along with their Tg
values. Likely, glassy state of undercooled liquid crystal can be realized by avoiding
the transformation of the liquid crystalline phase into an ordered crystal [5].
In a liquid crystalline phase, molecules of an elongated shape have almost
parallel orientational order, but positional disorder. Another name “anisotropic
liquids” given to the liquid crystals comes from this fact. The next substance
12 H. Suga
cyclohexanol
200
Cp/JK–1 mol–1
100
Ttrs Tfus
Tg
0
0 100 200 300
T/K
200
S/JK–1 mol–1
100
Ttrs Tfus
Tg
0
0 100 200 300
T/K
Fig. 1.3 Heat capacity and entropy of cyclohexanol
N-p-n-hexyloxy-benzylidene-p0 -n-butylaniline, C6H13O C6H4 CH ¼ N C6H4

C4H9 provides one example of the liquid crystals. This substance shows the
following phase sequence: Crystal – Smectic G – Smectic B – Smectic A – Nematic
– Isotropic liquid (IL). The highly disordered nature of the Smectic G phase is
quantified by the large entropy change DtrsS (Cr SG) amounting 75.98 J K1 mol1
that exceeds far the sum of the remaining entropies of transition: 2.53 (SG SB) + 10.14
(SB SA) + 9.37 (SA – N) + 5.37 (N – IL). The smectic G phase possessing a great deal
of disorder readily undercools and exhibits two-step glass transitions at temperatures
around 200 K. The nature of double glass transitions is not clear at the moment, but one
of them will be associated with the freezing of molecular modes characteristic of
layered structure, either the undulation mode of a layer or anisotropic translational
diffusions parallel and perpendicular to a smectic layer.
It turned out that the glass transitions were not characteristic property of liquids
but of wide occurrence in a variety of substances irrespective of their translational
invariance with respect to their centres-of-mass. The glassy crystals can be a model
Fig. 1.4 Heat capacity and

en-tropy of ethanol
Table 1.2 Glass transition temperature Tg of various glassy crystals

Metastable phase Tg/K Stable phase Tg/K
Thiophene 37 Thiophene 42
2,3-Dimethylbutane 76 Buckminsterfullerene C60 87
Isocyanocyclohexanol 55 b-Cyclodextrin·11H2O 150
130 Ethylene oxide·6.86H2O 85
160 Tetrahydrofuran·17H2O 85
CFCl2–CFCl2 60 Acetone·17H2O 90
90 CO 18
130 RbCN 30
Ethanol 90 CsNO2 42
Cyclohexene I 92 Tl NO2 60
II 93 SnCl2·2H2O 150
Cycloheptane I 100 SnCl2·2D2O 155
II 100 H2O (hexagonal) 105
III 93 H2O (cubic) 140
Cycloheptatriene 106 D2O (hexagonal) 115
Cycloheptanol 135 Pinacol·6H2O 155
Cyclohexanol 150 H3BO3 290
Cs0.7Tl0.3NO2 48 D3BO3 298
C2Cl6 in thiourea adduct 59 Lysozymea ca 150
Myoglobina ca 170
a
Tg value of the protein crystal depends strongly on the water content
14 H. Suga
substance for elucidating the complex nature of disordered solids, as the degrees of
freedom associated with the freezing in the glassy crystals are almost pure orienta-
tional ones, weakly coupled with lattice vibrations [5, 14]. The situation will greatly
simplify the character of frozen disorder.
The frozen-in disordered state is not limited to the metastable undercooled phase
of crystal. Another category of glassy crystals can be found in the stable crystals,
such as CO and H2O crystals. Both of the substances provide good examples of
crystals that do not obey the third law of thermodynamics. Structural and dynamic
studies of CO crystals disclose the presence of a head-to-tail motion of the weakly
polar molecules. The motion is active at high temperatures but cannot overcome a
potential barrier hindering the motion at low temperatures before the crystal reaches
a hypothetical ordering temperature. On the other hand, the name “crystal” derives
from the Greek “krustallos” which meant ice. Ice has long been considered as a
typical crystalline substance surrounding us. Thus the deviation of ice from the
third law of thermodynamics embarrassed many scientists since 1936 when the
residual entropy of ice was found experimentally. Each water molecule in ice Ih has
six equi-energetical orientations in the hydrogen-bonded network, but their reor-
ientational motions must be done in a highly cooperative way under the constraints
of the “ice rules.” The relaxation time for the cooperative motion becomes longer
and longer as the temperature is lowered until the disorder becomes immobilized
below a certain temperature. Whether the disorder should be described as static or
dynamic depends inter alia on the height of the potential barrier, along with the
temperature and the time-scale of the observation. The half-hydrogen model pro-
posed by Pauling cannot be an equilibrium structure of ice crystal at 0 K, but
absence of any anomalous heat capacity ascribable to an ordering transition has
puzzled many scientists for a long time [15].
In fact, a glass transition was found to occur at about 15 K for CO and 105 K for
ice Ih. Thus the freezing process is believed to occur during cooling before a
hypothetical ordering temperature is reached for each crystal [5, 14]. The dielectric
and enthalpy relaxation times of ice, td and tH, turned out to lie on the same straight
line in an Arrhenius plot. Extrapolation of these data to 60 K, a hypothetical ordering
temperature of ice Ih proposed by Pitzer and Polissar [15], gave a value of 1013 s for
t. It must be this geological time that hindered the crystal from realizing an ordered
phase of ice Ih in our laboratory time. Onsager [16] has suggested using some impure
ice samples for inducing the expected ordered phase. The impurity might hopefully
relax the severe constraints “ice rules” imposed to the cooperative motion of water
molecules in the lattice and enhance the orientational mobility.
A minute amount of KOH doped into the ice lattice was found to accelerate
dramatically the reorientational motion of water dipoles [17]. The hydroxide ion
OH– creates necessarily a hydrogen bond without proton in the neighbourhood, and
the creation of this L (leer in German) defect in the network will surely relax the
severe constraints for the cooperative water motion. Thus, an ice sample doped with
KOH in the mole fraction of 2 105 and kept at 65 K for 2 days induced a first-
order phase transition at 72 K. The transition removed a substantial fraction of the
residual entropy and changed the lattice symmetry from P63/mmc of Ih to Cmc21 of
the low temperature phase. The proton-ordered phase was designated as ice XI.
Examination of the experimental data showed that the relaxation time of the doped
ice was shortened by a factor of 108 at 90 K. This is the reason why the suggested
ordering transition has escaped notice since 1936 when the residual entropy was
first observed, and now appeared by the catalytic action of the minute amount of
dopant that relaxed greatly the serious constraints imposed to the rearrangements of
the water molecules in ice Ih. The Kauzmann paradox does not occur in ice crystal
because Ih is the most stable modification of ice under atmospheric pressure. This
experiment shows the wide validity of the third law of thermodynamics in one hand,
and reveals a facet of a possible ordering process for the otherwise frozen-in
disordered systems in other hand.
Essentially the same things were observed for the clathrate hydrates of the type II
structure. The host lattice composed of water molecules forms two kinds of cages that
accommodate some guest molecules of suitable size and shape. Two kinds of molec-
ular disorder exist in the crystal; the first is the orientational disorder of the host water
molecules similar to that of ice, and the second is the reorientational motion of the
guest molecules inside the cages. This can be clearly indicated by the observation of
two kinds of the dielectric relaxations, if the guest is dipolar molecule. The one that
appears at higher temperature is for the water dipole, and the other occurring at
cryogenic temperature is for the guest dipole. The latter exhibits a great deal of
orientational disorder inside the cavity with almost spherical symmetry. The calori-
metric measurement of the clathrate hydrate enclathrating tetrahydrofuran showed a
tiny heat capacity anomaly with relaxational nature that is similar to the ice crystal.
When the crystals are doped with a minute amount of KOH, a first-order phase
transition appeared at 61.9 K. The transition temperature depended on the nature of
the guest molecules: 46.6 K for acetone hydrate, and 34.5 K for trimethylene oxide
hydrate. Dielectric measurements showed that both of the host and guest molecules in
the tetrahydrofuran hydrate were ordered at temperatures below Ttrs. Most probably,
the ordering of the host water dipoles produced a strong electric field that forced the
guest molecules to align along a preferred orientation.
Our experiments are always governed by the Deborah number D [18], which is
defined as the ratio of the relaxation time t and observation time t; D ¼ t/t. As far as
D « 1, we can observe the whole shape of heat capacity anomaly associated with the
possible ordering transition that is determined by the intermolecular interaction and
cooperative nature of the interaction. For a system D » 1, we will miss a part or full of
the relevant thermodynamic quantity owing to our limited experimental time. The
relaxation time is determined by the disordered structure and barrier height hinder-
ing the rearrangement of the structure. A particular impurity doped into the system
will modify the cooperative nature of the rearrangement and shorten the relaxation
time as a whole. Only this process makes possible to observe a transition that has
been concealed for a kinetic reason. Modification of chemical potential of a system
by a particular impurity can hopefully result in a drastic change of dynamical
situation in the system. We may call this new field “doping chemistry.”
A particular kind of dopants acted on frozen-in disordered system as catalyst for
releasing the immobilized state and recovering the equilibrium state in our
16 H. Suga
observation time. In relation to this fact, one might raise an inquiry “What kind of
physical or chemical impurity will release the frozen-in state of the liquid?” If a
particular dopant were discovered luckily for this purpose, we will be blessed to
observe in reality what will happen at the Kauzmann temperature of a liquid? As a
matter of fact, it is not easy for us to imagine some disordered solids without any
configurational entropy, designated as an “ideal glass.”
1.4 Other Aspects of Glassy Solids
In spite of its simple molecular structure, a wide variety of states of aggregation of

water molecules have been observed hitherto. At least 13 forms of ice designated as
Ih, Ic, II, III, IV, ···, XI, as well as vapour-deposited amorphous ice have been found to
exist under atmospheric and high pressures as of 1982. Amorphous ice is, galactically
speaking, a very abundant material in space. The Comet’ tail is strongly connected to
the formation of amorphous ice. The idea that there is an amorphous solid form of
water was first put forward in 1935 when water vapour was deposited onto a cold
substrate [15]. A calorimetric measurement showed that the amorphous ice exhibited a
glass transition at 135 K [19] and had a strong crystallization tendency. The crystalli-
zation starts to occur progressively at temperatures even below Tg, so that the heat
capacity jump is masked to some extent by an exothermic effect arising from the
crystallization. Hyper-quenching of the liquid water can also produce the amorphous
ice and its Tg value was determined to be 136 K by a DSC measurement [20]. These
values are consistent with that obtained by extrapolation of unambiguous Tg data from
glass-forming binary solutions up to pure water. On the other hand, Angell has
proposed that the Tg of amorphous ice must be higher than 150 K [21]. The discussion
is mainly based on the fact that if the heat capacity of the undercooled liquid follows
the extrapolated line of the equilibrium water, the entropy of the amorphous ice
becomes smaller than that of hexagonal ice below about 150 K. Heated discussions
about this problem are still continued.
Pressurization of Ih at low temperatures above 1.3 GPa turned out to be a new way
for preparation of high-density amorphous (HDA) ice [22]. The HDA ice transforms
to a low-density amorphous (LDA) ice by warming the HDA ice under atmospheric
pressure. Both the amorphous ices change each other by an apparent first-order
transition. The phenomenon designated as “polyamorphism” has opened a new
realm in amorphous solids. Particularly interesting is the properties of LDA ice. It is
becoming increasingly clear that the LDA ice is of extraordinary character among
amorphous solids. What is unexpected is that the thermal conductivity increases
sharply when the HDA ice transforms to LDA ice. Usually the denser forms of
substances are the better thermal conductors. Even more unexpected is that the
thermal conductivity of the LDA ice increases with decreasing temperature, the
opposite behaviour to that of the HDA ice and of all other amorphous solids.
The LDA behaviour is like that of crystals in which the scattering of phonons by
other phonons decreases with decreasing temperature. This anomalous behaviour

implies the existence of a special kind of order in the LDA ice [23]. This conclusion
is consistent with the observation that LDA ice does not show boson peaks that are
widely observed in glass-forming liquids. An X-ray scattering experiment showed that
the dispersion relation of LDA ice for vibrational modes is similar to that of cubic ice
Ic, the metastable form of ice at atmospheric pressure. It seems likely that in LDA ice
we are closely approaching an ideal glassy state [24]. It is an embarrassment, however,
that it is not certain that a characteristic Tg can be assigned to this almost ideal glass.
Recent discovery of very high-density amorphous (VHDA) ice makes the situation
more complex [25]. Further works with novel idea is highly encouraged for an
improved understanding of this intriguing and important substance.
Another interest is concerning with cryo-preservation of biological substances:
cryogenic storage by amorphization of the water solution system within the biologi-
cally active cell. When the biological cell is kept at low temperature without formation
of ice, the biological activity is preserved, independently of the storage period. The
solution system is in a glassy state at low temperatures, with all the molecules and ions
being in a frozen state. For successful vitrification, diverse treatments of the cell or
issues are required to protect from ice formation. The optimum conditions for the
successful preservation depend on the particular cells/tissues and added glass-forming
substances.
It is interesting to describe here some analogies between proteins and glasses.
Proteins are known to have a free-energy landscape possessing a large number of
energy valleys, separated by potential barriers. This arises from the conformational
degrees of freedom of the polypeptide chains. The energy valleys are called the
conformational substates and correspond to slightly different higher-order struc-
tures in a protein molecule. At physiological temperatures, protein molecule fluc-
tuates among many substates, as if they were liquid. This fluctuation is believed to
play an important role in the biological activity such as the enzyme-substrate
reactions. With lowering temperature, they are expected to freeze in a substate. In
fact, protein crystals undergo the glass transition at low temperatures, depending
strongly on the amount of water in the crystal. Water molecules are important
ingredient of the protein crystal [26]. Lowering of the water content in the crystal
causes a decrease in the mobility of the component molecules, resulting in an
increase of Tg. Below a certain amount of water, the glass transition takes place
at temperatures above 300 K. This means that conformational and orientational
degrees of freedom of both molecules are in a frozen-in disordered state at our
physiological temperatures. Any biological function cannot be expected to appear
in such a frozen-in non-equilibrium state.
Figure 1.5 summarizes all the observed states of aggregation of molecules in the
equilibrium and non-equilibrium states of molecular assembly, as revealed by
calorimetric measurements. It can be concluded that the glass transitions observed
exclusively in liquids so far are just one example of “transitions” that must be of
wide occurrence in solids in relation to the freezing of some degrees of freedom,
irrespectively of the translational invariance in the system. Molecular assembly can
produce various states of aggregation that are much richer than our anticipation.
18 H. Suga
Fig. 1.5 Various states of aggregation of molecules in equilibrium and nonequilibrium states
The subdivision of the glassy states will deepen our basic understanding of the
substance and require a renewal of the concept of the glass transition. Freezing
processes in seemingly dissimilar substances could be analyzed on the same ther-
modynamic basis, indicating the universality of the underlying thermodynamic
principles. A new realm of amorphous solid-state science with many unsolved
problems is confronting us and must be challenged.
Acknowledgements The author would like to express his sincere thanks to the late Professor
I. Nitta and Professor Emeritus S. Seki for the continued encouragements throughout the present
works. Thanks are extended to many collaborators for their hard works and useful discussions.
References
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Chapter 2
Heat Capacity and Entropy Functions
in Strong and Fragile Glass-Formers, Relative
to Those of Disordering Crystalline Materials
C. Austen Angell
2.1 Introduction
The glassy state problem is often separated into two major components [1, 2]. One
of these concerns the reasons that glasses form in the first place, and deals with the
circumstance that glasses are usually metastable with respect to crystals so that
crystallization must be avoided. The second deals with the question of how liquids
behave when crystals do not form, and it is with this component that we are
concerned in this chapter. Here the central phenomenon with which we must
deal, in seeking to understand vitrification, is the heat capacity function and the
change in that function that accompanies the freezing in of the disordered state.
This phenomenon is illustrated in Fig. 2.1 for a typical molecular liquid, 2-pentene
vitrified by both liquid cooling and by vapor deposition [3].
The fairly abrupt change in heat capacity that is observed as the system falls out
of equilibrium (essentially because the systems’ molecular motions have become
too sluggish to follow the cooling) irrespective of whether the substance under
study is a liquid, a plastic crystal, or a disordered superlattice. It is the phenomenon
that many would consider to be the most characteristic feature of glassformers and
vitrification . . . and yet, for the archetypal glassformer SiO2 in its purest anhydrous
state, and for glassy water –the most abundant form of water in the universe – this
change in heat capacity on structural arrest during cooling is barely detectable [4]. It
is not surprising that the vitrification of liquids is found to be the source of much
confusion.
It is clear to any reader of the recent literature on glassforming liquids (now
“glassformers”) that investigators in the field have given most of their attention to
the spectacular manner in which the majority of glassformers change their viscosity
C.A. Angell (*)

Department of Chemistry and Biochemistry, Arizona State University,
Tempe, AZ 85287-1604, USA

22 C.A. Angell
200
Glasses prepared by
both liquid and vapor
deposition routes
150
VQ sample
Cs / J K–1 mol–1
LQ sample
100 ΔCp
CR sample
50 some “secondary”
Tg J-G excitation
vibrational
0
0 50 100 150
T/K
Fig. 2.1 Heat capacity of 1-pentene prepared by both liquid cooling and by vapor deposition. The
excess heat capacity is indicated by double arrows and is seen to increase markedly with
decreasing temperature (From Takeda et al. Ref. [3], by permission)
(or relaxation times) on approach to the glass transition. In the most interesting
cases now known as “fragile” liquids [5, 6], the temperature dependence of
viscosity departs dramatically from the Arrhenius equation typical of most rate
processes in condensed matter, accelerating as the glass transition is approached to
such an extent that a temperature change of 3 K can induce an order of magnitude
change in viscosity. The behavior is not as dramatic as the power law divergences
observed in critical phenomena, but in some cases this behavior is approached.
Indeed, as we will discuss further below, this is probably not an accident.
Most theories for the viscosity (or, more generally, for the relaxation time) connect
viscosity temperature dependence to the temperature dependence of one or other
thermodynamic property. In the 1959 free volume model of Cohen and Turnbull
[7], the thermodynamic property was the unoccupied volume (integral of an expan-
sivity component), in Adam-Gibbs theory [8] it was the configurational part of the
entropy (integral of a heat capacity component), while the more recent “shoving
model” of Dyre and colleagues [9] use the temperature dependence of a modulus,
the “infinite frequency” shear modulus, to explain the super-Arrhenius behavior. So a
proper appreciation of the thermodynamic properties of the glassformer would seem
to be a prerequisite of a detailed understanding of the transport behavior.
Here we will consider the highly variable forms that the heat capacities of glass-
forming liquids can take, and will then show that,Rin spite of this great variation, the
integrals of the heat capacities, the entropies, S ¼ CpdT – and particularly its excess
over the entropy due to vibrations – fall into a pattern that mimics the well-known
pattern made by the viscosities of glassformers when plotted in Tg-scaled Arrhenius
2 Heat Capacity and Entropy Functions 23
form (the “strong/fragile” liquid pattern). While the origin of the “strong/fragile”
pattern for viscosities (and relaxation times) remains more or less mysterious, the
pattern for the entropies can be simply reproduced using a two-parameter model of
configurational excitations [10], as will be demonstrated. Finally, we will interpret the
“strong liquid” extreme of this pattern in a provocative way by showing the similarity
that the heat capacity function for these liquids bears to a well-known heat capacity
form for disordering excitations in solids, the lambda transition.
The entropy variations can be accounted for quite pleasingly with the help of a
simple two-state excitations model [11], provided that apparently pathological
systems like water and silicon, which are extremely poor glassformers by liquid
routes, and the liquids classified as “strong” on the basis of their viscosity data, are
excluded. Even the latter follow the expectations of two-state excitations when only
very high temperature data, obtained by computer simulation, are considered [12].
This encourages consideration of the possibility that the much more challenging
pattern offered by the heat capacities themselves might have a systematic explana-
tion. As an aid to understanding this problem we include consideration of the
relatively well-understood cases of disordering solids, the order–disorder transi-
tions or lambda transitions.
Before launching into a review of the heat capacity functions, their integrals and
their patterns of behavior, let us give some brief consideration to non-glassy
systems in which structural arrest of ordering processes is commonly observed.
Since the archetypal glassformer, silica, has barely any thermal signature of the
glass transition, we cannot make a large jump in heat capacity on structural arrest a
criterion for inclusion in the discussion. Thus we start with the simplest and most
familiar case, the freezing in of a defect population during the cooling of a simple
crystal, for instance potassium iodide.
We do not know of any heat capacity studies of this trapping of the configu-
rational state of the system, but its generic relation to the glass transition phenome-
nology can be judged from a comparison of a quantity which, like the viscosity of
silica, is exponentially sensitive to the freezing of the excitation population. This is
the ionic conductivity, which is shown in Arrhenius form in Fig. 2.2, in the form
preferred by many in the ionics field because it is suggested by theoretical treat-
ments, viz., log (sT) vs 1/T where s is the specific conductivity. Comparison is
made with the variation of the diffusivities of different elemental components of
various metallic glassformers through their Tgs [13].
Notwithstanding the similarity of Fig. 2.2a, b, the metallic glassformers of Figure
2b have quite marked heat capacity jumps at their Tgs. At higher temperatures it
becomes clear, also, that their diffusivities follow a super-Arrhenius path in tempera-
ture, though in the temperature domain immediately above Tg they are usually
following the Arrhenius law with higher activation energies than below Tg.
Passing to systems that begin to resemble glassformers a little more closely, we
show the relaxation times for some ionic crystal rotator phases, in which the rotation of
a structural element causes little distortion of the crystal lattice. A series of these were
studied by Fujimori and Oguni [14], and their relaxation time behavior is shown in
Fig. 2.3a. In this case the thermal consequences of the structural arrest at the “glass
24 C.A. Angell
– 2.0
IONIC CONDUCTIVITY
2
IN KI CRYSTAL,
1 In the domain of defect
concentration freeze-in
This figure will be printed in b/w

Ig (σT ) (Ω –1cm–1 deg K)
– 4.0
“Tg” !!!
But at 10–9 Scm–1,

not the usual 10–15,
– 6.0 because defect
equilibration is so
2 1 slow, depending on
diffusion in from
the crystal surface
– 8.0
1.2 1.6 2.0 ×10–3
1 / T (T in °K)
10–16 B in V4
10–17 Ni in INN
Fe in V4
10–18
Diffusivity (m2s–1)
Fe in V1
10–19 Al in V4
10–20
10–21
10–22
10–23
10–24
1.4 1.5 1.6 1.7 1.8 1.9 2.0
3
10 K / T
Fig. 2.2 (a) Temperature dependence of ionic conductivity in single crystal of potassium iodide in
the temperature range where the defect population freezes in for this crystal dimension. (b)
Temperature dependence of metallic diffusivity of atomic components through Tg in different
metallic glasses (From Faupel et al. Ref. [13], by permission)
T/K
300 200 100 50
10
0
log (t / s)
–10
–20
0 5 10 15 20
T –1 / vvRK–1
150
70
Cs , m / ( J. K–1. mol–1)
140
100
60
100 120 Tfus
50
Tg
Ttrs
0
0 100 200 300
T/K
Fig. 2.3 (a) Arrhenius plots of the dielectric (higher T points) and calorimetric relaxation times
(lower T points) for several rotator phases (in order from left) H3BO3, D3BO3 (identical curve with
H3BO3 one), SnC122H20, SnC122D20, C4H3BrS, Cm, TINO2 (From Fujimori and Oguni Ref.
[14]). (b) The weak jump in heat capacity that accompanies the glass transition in C4H3BrS,
typical of the systems with the relaxation time behavior seen in Fig. 2.3a (From Fujimori and
Oguni Ref. [15], by permission)
temperature” (which was characterized by a relaxation time of 1,000 s in this case)

were determined, and the results are shown in Fig. 2.3b for one case, bromothiophene
[15]. Clearly the glass transition is a very weak phenomenon in this case (and others
26 C.A. Angell
like it [16]), and accordingly the relaxation times are in good accord with the
Arrhenius law.
Other cases of disordering processes with relaxation time behavior that follows
the Arrhenius law, also have very weak thermal signatures of structural arrest, but
an overall more interesting heat capacity behavior. One of the more relevant is the
large quasi-spherical molecule, C60, the packing of which has a dipolar excitation
and so can be studied by dielectric relaxation. The relaxation process also follows
the Arrhenius law, as might be expected from the tiny change of heat capacity at its
“glass transition”. The heat capacity in this case is shown in Fig. 2.4.
a
600
C60
C p (J mol–1 K–1)
400
200
0
0 100 200 300
T (K)
b 100
C60
90
C p (J mol–1 K–1)
80
70
60
70 80 90 100
T (K)
Fig. 2.4 (a) Heat capacity of C60 between 0 and 300 K showing order–disorder transition at
260 K (b) Blowup of the small anomaly near 90 K showing a DCp of 6 J/mol K (From Ref. [4]
with permission of AAAS)
The effect of rotational disorder freezing at t ¼ 1,000 s, is again extremely weak,

but nevertheless has been precisely determined by the adiabatic calorimetry of the
Osaka laboratory [17], and its relaxation time could be determined, and shown in
accord with the dielectric data [17]. The interesting point here is that the heat
capacity function proceeds to a sharp peak at a temperature almost three times Tg.
There are many other sharply peaked disordering transitions that have almost no
disorder left when they finally undergo a configurational arrest. A good example to
compare with the rotational disordering of the substances in Fig. 2.2 is that of
NaNO3 which again has the classical lambda form but no low temperature arrest
that can be observed with standard calorimetry. On the other hand, in the case of
TlNO2 for which relaxation time data are seen in Fig. 2.3a, the arrest can be
detected and has been described by Moriya et al. [18]. In this case there is no
melting phenomenon as in Fig. 2.3b until much higher temperature, and the heat
capacity function can be seen to develop into a lambda peak like that of C60.
These systems are clearly characterized by energy landscapes that are rather
different in character from those discussed in the literature of glassforming sub
stances [19]. While high states of configurational excitation can obviously be
obtained, the states excited are apparently not characterized by energy minima
that are separated from neighboring minima by significant energy barriers, by
means of which the system can be trapped when the temperature is lowered. Such
states are more closely related to anharmonic excitations than to true microstates in
the sense that they are usually discussed. Later we will consider the case of a
lambda transition in a metallic alloy superlattice that is rather different in character
and will be quite useful to our broadened discussion.
Finally there are the intermediate cases where the disordering elements are
arranged, center-of-mass-wise, on a crystal lattice like the above cases but can
undergo a rotational disordering excitations that have larger volume requirements
than the above and are accompanied by much larger heat capacity steps, when the
disorder becomes frozen, than the ones discussed above. There seems to be a
continuous series here in which the increasing heat capacity jump is accompanied
by an increasing departure from Arrhenius behavior of the relaxation. A collection of
data taken from the extensive study Brand et al. [20] – to which cases have been
added at either extreme by us [21], is shown in Fig. 2.5. This pattern is very similar to
that known for the glassforming liquids, but is richer in “strong” glassformer cases.
Understanding the manner in which systems make the transition from the lambda
type to the typical glassformer type is one of the major statistical thermodynamic
problems in this field.
2.2 Glassforming Liquids, Strong and Fragile
With this background we now show the contrasting behavior of different members of
the conventional type of glassformer, viz., liquids that slow down with decreasing
temperature until they vitrify at Tg, as in Fig. 2.1. To make the immediate contrast with
28 C.A. Angell
Fig. 2.5 Plastic crystal properties. Left: Tg-scaled Arrhenius plot for the relaxation times (mostly
dielectric); right: Tg-scaled temperature dependence of the heat capacity, relative to that of the
glassy state at Tg. (From Ref. [21] by permission) note the correlation of DCp with the position in
the scaled Arrhenius plot
5.0 Cp (Sosman, exp., 1927)

Cp (Richet, exp., 1982)
Cv (Horbach, simulation) Ceq
v
4.0
Cv,Cp [kB / particle]
3.0 Cvib
40.0
Cv (J / K.mole
35.0 BeF2
2.0
30.0
25.0 classical
1.0
20.0
0.0 1.0 2.0 3.0 4.0 5.0 6.0
T / 1000 (K)
0.0
0 1000 2000 3000 4000 5000
T [K]
Fig. 2.6 Heat capacity of SiO2 from experiment (points below 2,000 K) and simulation (points
above 2,500 K). The latter are conducted at constant volume which will depress the value below its
constant pressure value. A point at 6,100 k that establishes a peak in Cp (Like that seen in the inset
for BeF2) was omitted from this figure in ref. [23]. A peak value for SiO2 was also evident in earlier
studies, by Soules. Inset: heat capacity of BeF2 by experiment (low T points) and simulation (From
Ref. [4] by permission)
Fig. 2.1 we show in Fig. 2.6, the available data, experimental [22] and computer
simulation [23], for the classical case, SiO2. Because of its high glass temperature, the
experimental data are limited in range, but they are well supplemented by the
computer simulation data on the BKS model of silica [24] that reproduces many silica
properties faithfully [25]. The striking difference from the case of the molecular liquid
of Fig. 2.1 is reinforced by the data on the weak field analog of SiO2, BeF2, for which
data far above the glass temperature, to 2Tg, are available [26]. The small jump in Cp
for laboratory SiO2 that was reported in the studies of Ref. [22] almost certainly owes
its strength to the presence of some residual OH in the structure, as high temperature
DSC studies of truly dry SiO2 [27] detect essentially no “jump” signal at Tg, despite
their superior sensitivity over the drop calorimetry method [22]. This is the implication
of the simulation data of Fig. 2.6, when extrapolated back to 1473 K where the
viscosity reaches 1012 Pa.s, commonly associated with Tg in inorganic glasses. The
striking aspect of Fig. 2.6 is not so much the small value of the excess Cp of liquid over
crystal at Tg, but the fact that the excess (often called “configurational”) component of
the heat capacity rises with increasing temperature, and then peaks at a temperature far
above both Tg and Tm. More extensive, but so far unpublished, simulations on BeF2
(P. H. Poole, private communication) confirm the peak value seen in Fig. 2.6 (insert)
[28], and also verify the link-up with the experimental values. Strong liquids appar-
ently behave more like the crystalline materials that exhibit lambda transitions, than
they behave like the normal fragile liquids.
We will come back to this similarity a little later but first, for the purposes of this
chapter, we need to examine the other extreme in a little more detail. Note in
Fig. 2.1 how the difference between liquid and crystal heat capacities is increasing
as the temperature decreases. It has been noted by a number of workers [29, 30] that
this excess Cp can be well described by a hyperbolic function of temperature,
DCp ¼ k/T. Indeed, it is this form of temperature dependence that allows the
transformation of the Adam-Gibbs equation for the relaxation time, into the famil-
iar Vogel–Fulcher–Tammann equation [31]. Modeling this form of excess heat
capacity has proven rather difficult. The fact that it shows no maximum eliminates
the possibility of accounting for the excess with any simple two-state model, as
adequately demonstrated on many occasions but particularly by Moynihan and the
author [10]. One recent and provocative attempt that does account quantitatively for
both the excess heat capacity and the excess entropy with the same parameter set, is
that of Matyushov and the author [32] whose “Gaussian excitations” model fitting
of the data is shown in Fig. 2.7. What is provocative is that the equations that fit the
data so well insist that, at a temperature some 10–20% below Tg, the system in
equilibrium would undergo a first order transition to a low entropy state, thereby
resolving the Kauzmann paradox in an unconventional way.
Before looking further into this matter, we will look at the excess entropy
functions seen in Fig. 2.7, in a different way, so as to compare them with the
corresponding liquid relaxation time behavior. We plot them in such a way that they
have a common value, unity, at the glass transition temperature. This requires a
scaling by the value each liquid possesses at Tg.
30 C.A. Angell
a 8
glycerol
6
MTHF
Scx
4
toluene
PC
2
salol OTP
0
100 200 300
T/K
b
16 salol
OTP
12
MTHF
toluene PC
Cpcx
glycerol
8
0
100 200 300
T/K
Fig. 2.7 The excess entropy (part (a) and excess heat capacity part (b) of a series of fragile liquids
(m > 85). The thick lines are the experimental data and the thin lines are the theoretical best fits
continued to lower temperatures to show the predicted first order phase transitions. Only the
intermediate liquid, glycerol, the excess heat capacity of which changes little with temperature,
offers different behavior. The hyperbolic relation predicts extreme behavior will emerge as liquids
of increasingly low cohesion are studied from Ref. [32] by permission
The value of the excess entropy relative to its value at Tg, is presented as a
function of inverse absolute temperature scaled by Tg itself, in order that the plot of
excess entropies can have the same relation to temperature as does the viscosity in
the so-called fragility plot (sometimes given the author’s name). This plot, an
example of which appears in Fig. 2.5 for plastic crystals, is now used to compare
different rates of excitation of the disorder in liquids. Figure 2.8 shows that, as
T rises above Tg, some liquids approach the tops of their energy landscapes more
rapidly than others. At the top of the landscape, ToL, the entropy per rearrrangeable
unit kBlnW reaches kB, because all of the eN microstates are accessible and
accordingly lnW ¼ 1. Thus this plot displays the “thermodynamic fragilities”, of
the liquids in a way that the jump in heat capacity does not. And the thermodynamic
Fig. 2.8 Thermodynamic

fragility plot showing the
relative rates of excitations of
the excess entropy. The case
of water is anomalous and
implies a lambda like peak in
the heat capacity to
rationalize the high and low
temperature branches of the
relative entropy behavior.
Reproduced from Angell,
C. A. Chem. Rev. 102,2627
(2002) by permission
fragilities correlate with the kinetic fragilities [33] in a manner that the jump in heat
capacity does not [34]. The scaling by the excess entropy at Tg makes the display
independent of the choice of number of “beads” [32, 35–37] per mole of liquid, but
does not safeguard against anomalous entropies of fusion due to anomalously high
entropies in the crystalline state, and the latter will invalidate the assumption that
the crystalline state entropy represents the vibrational entropy of the liquid at its
melting point. Thus the position of SiO2 in this plot is anomalous, unless the excess
entropy is assessed by thermodynamic integration from the ideal gas state, and
subtraction of a harmonic entropy, as was done in Ref. [38].
There is one liquid in this plot that behaves in a highly anomalous manner. That
liquid is water, about which much is known but much also remains mysterious.
Water, which can be vitrified by a number of alternative routes, is known to have
an extremely weak glass transition, but it also has, according to two independent
assessments [39, 40] a very small entropy at its Tg. Thus at the extreme of high
temperature its relative entropy is expected to be large. At the same time, its
extremely weak calorimetric glass transition, comparable to that seen in Fig. 2.3
for dipole disordering in C60, means that the rate of excitation of entropy imme-
diately above Tg is very small. Thus, it appears like the strongest liquid near Tg,
but higher in temperature, in the moderately supercooled liquid region where its
entropy relative to ice is well known, its excess entropy is very high. Accordingly,
in the intermediate range where direct observations cannot be made because of the
instability of the liquid against crystallization (hence the description “no-man’s
land”), the excess entropy must undergo a very rapid change. This entropy would
be associated with a hidden lambda transition, or to a hidden first order transition
like that seen in supercooled silicon in the Stillinger–Weber model [41], and more
32 C.A. Angell
LiCl 1:75 TLL

MgCl2 1:20
Tg
AlCl3 1:30
H2O vapor deposit
100
no-man’s land
Water
Cp (J mol–1 K–1)
80
N2H4.2H2O
60
40
H2O (LDA)
Ice FS ΔS = 4.3 J/mK)
20
140 180 220 240 260 300
T (K)
Fig. 2.9 Heat capacity of water in normal, supercooled liquid and glassy states, showing two
possible interpolations to preserve a continuity that must exist in view of the vitrifiability of liquids
water under sufficiently high cooling rates (From Ref. [4] by permission of AAAS)
recently in ab initio simulations. These two options are shown in Fig. 2.9 and
are seen to make a very plausible rationalization of the observations made in
the two accessible regions (near the melting point on the one hand and near Tg on
the other).
Figure 2.8 contains only experimental data except for the case of water where
there a data gap between high a low T (discussed below). The presence of peaks in
the high temperature heat capacity of BeF2, and to a lesser extent SiO2 from
simulation studies (Fig. 2.6), suggests that these (and perhaps other strong liquids
as well), might show water-like behavior at higher temperatures when the extended
measurements (particularly at higher pressures) become available.
Water and its anomalies are often discussed in terms of the presence of a second
critical point that occurs just beyond the range of observability [42–45]. Opinions
differ on whether it lies at positive or negative pressures [4], with some suggesting
it might even be subsumed into the liquid–gas spinodal as suggested by the stability
limit conjecture of Speedy [46] (in updated form to include a second spinodal for
the low density liquid). Such a “critical point-free” scenario [4] is after all, the form
that is suggested by all the empirical equations of state for water [47], though these
seem to be generally discounted by workers in the field. On the other hand, if the
second critical point not only exists but also were, serendipitously, to fall at ambient
pressure, then the heat capacity curve for ambient pressure water would (in absence
of crystallization) have exactly the lambda form, since a critical point transition is
one example of this very general cooperative transition. This is indicated as the
upper (dash-dotted) curve in Fig. 2.9. The lower dashed curve corresponds to
the case of a weak first order transition that would occur at ambient pressure
if the critical point lies at negative pressure or is subsumed into the liquid–spinodal.
Fig. 2.10 Comparison of the apparent heat capacity responses of CoFe alloy and a silicate glas
after comparable thermal treatments. The darkest curves, in each case, are the standard glass
transitions obtained when heating and cooling rates are the same. The lowermost curves are when
the cooling rates were the most different (very fast in each case, corresponding to quenching in the
most disorder. In each case the most disordered structure is the one trapped in a basin of smallest
depth, but the difference in temperature between the standard Tg and the temperature where the
quenched system stats when the real glass starts to relax, is much greater in the case of real glass.
Notably, glassy water exhibits behavior closer to that of the alloy, where the thermal relaxation
peak for the quenched state, has a sharper peak starting at T closer to Tg (From Ref. [48, 49]
respectively, with the author’s permission)
To complete our development of this increasingly broad picture of the glass

transition under development in this chapter, it is important to add one further, and
very informative, example of the lambda transition. This is the transition that occurs
in the alloy superlattice, Co50Fe50. It is needed in order to make clear that, when the
elementary step of the excitation process in a lambda type order–disorder transition
is one which involves barrier crossing with substantial activation energy, this type
of thermodynamic transition can support an ergodicity-breaking that has all the
rate-dependent phenomena of the usual glass transition.
The heat capacity of this system was studied by Kaya and Sato [48], using
different, increasingly severe, quenching procedures that arrested the ordering
process in different states of excess entropy. The behavior of these were then
evaluated during reheating at a fixed rate for comparison with the behavior observed
when the cooling rate was the same as the standard heating rate (the darkened curve
in Fig. 2.10). In Fig. 2.10 the observations are displayed alongside the more recent
study of Yue and Jensen [49] for a silicate glass subject to a similar procedure
(namely quenching very rapidly from well above Tg followed by reheating at the
standard rate of 20 K/min) that has qualitatively similar consequences (see also
[50]). The darker curve is, in each case, for the condition, cooling rate ¼ subsequent
heating rate. In the case of Fig. 2.10a, the dashed line recalls what we know would
happen if no ergodicity-breaking were to occur, since (unlike the glass transition
equilibrium heat capacity) we know the lambda heat capacity form.
34 C.A. Angell
20
(a) P>Pc, path α Tw
cooling
P=0.250
15 P=0.275
P=0.300
P=0.400
Cp /kB
10
5
T″g
0.2 0.3 0.4

kB T/UA
Fig. 2.11 The constant pressure liquid heat capacity of the attractive Jagla model, for isobars of
pressure close to, and increasingly above, the critical pressure of 0.235, showing the peak in heat
capacity associated with super-critical fluctuations, which diminish with increasing distance from
the critical point. The peak temperatures define the so-called Widom line. note that the cooling
glass transition are always below the peak temperature (From Ref. [51], by permission of the
American Physical Society)
With this background on ergodicity-breaking in a system with a lambda transi-

tion, let us now return to what happens when the conditions in a liquid system with a
critical point are changed so that the critical point is narrowly missed and only the
supercritical fluctuations are encountered. The behavior may be seen in the results
of a recent study by Xu et al. [51] extended by Buldyrev et al. [52], of a model
system that has been parameterized to have a liquid–liquid transition in the stable
liquid domain [53]. This is the ramp model of Jagla [54] with attractive component
of the potential included. The temperature dependence of the isobaric heat capacity
for this system, at a series of pressures increasing in value above the critical
pressure, is shown in Fig. 2.11. The point to be emphasized here is the increasingly
rounded forms as the isobars cross the extension of the coexistence line beyond the
critical point (now becoming known as the Widom line). The strength of the
transition that “gathers-in” the peak of the cooperative transition at Tc is seen to
dissipate to higher temperatures as the isobar departs increasingly from the critical
point. Sufficiently far from Tc the effect of critical point vanishes and one is left
with something reminiscent of the metallic glassformer heat capacity. The similar-
ity of the lowest pressure isobar (the p ¼ 0.240 “scan”) to the heat capacity
behavior of the Co–Fe alloy (Fig. 2.10 left) when heating and cooling rates are
the same, can hardly be missed.
fragile strong / fragile strong / fragile

peak below Tg: peak (or TLL) <Tm but peak above Tm
glassformers: > Tg, so crystallize glassformers:
ΔCp 1-butene, toluene easily: water, Si, Ge BeF2, SiO2
frag
fragile
strong
strong
MD
Tg Tm Tg Tm Tg Tm
(large)
(tiny) (small)
S
abrupt
1st Gradual
order
TK Tg Tm Tg Tm Tg Tm
Fig. 2.12 Changeover in the forms of excess heat capacity, and excess entropy, above the glass
transition on passing from “strong” inorganic network glasses to “fragile” molecular glasses.
Strong network liquids appear like expanded order–disorder transitions (see final section) and
when pure may have tiny glass transitions, while fragile molecular liquids have large DCp glass
transitions and their ordering limits are depressed below Tg. Water, a tetrahedral network based on
hydrogen bonding, lies at the crossover between the two classes of behavior. This can be
interpreted in terms of the increasing Gaussian width in the distribution of excitation energies,
and consequent increasing disorder stabilization of the excitations. This implies that the ordering
in liquids during temperature decrease is an increasingly cooperative de-excitation process when
changing from network to molecular liquid glassformers (From Ref. [2] by permission of Materials
Research Society)
With these examples in mind we can then present the series of heat capacity and
entropy functions that we have recently included in articles that attempt to describe
a broader view of the glass transition phenomenon [2, 55]. The pattern of heat
capacities has been viewed in terms of the effects of increasing cooperativity in the
excitation process as we pass from strong network glasses, at one extreme, through
the intermediate strength network represented by water, to non-network liquids like
the preponderance of glassformers of common experience, ending in the very
fragile liquids in which only the high temperature side of the transition is seen,
because the low temperature side is hidden by the glass transition. Actually, most of
the low temperature side of the transition in these cases, according to theory [32], is
cut off by first order transitions to a de-excited low entropy state. Being, in most
cases, a structure that is closer to that of the crystal form, than the viscous liquid
from which it formed, this low enthalpy phase can often serve as a stepping stone to
the crystalline state (the Ostwald rule of stages, in action). The rapid crystallization
of second liquid phases, when they form above the glass transition, [56, 57] is one
of the factors that has made the study of these phenomena confusing.
36 C.A. Angell
It is striking that the two cases, water and silicon, in which the presence of a
continuous or weak first order transition has been most clearly seen, are two of
the poorest glassformers known [55] (at least when high pressure quenchings are
excluded [58]), this being a consequence of the fact that the transition, with its large
entropy fluctuations generates copious nuclei of the stable crystalline phase which
can only be avoided by hyperquenching, vapor deposition, or pressure-induced
amorphization. Via the pressure path, large samples of both amorphous phases have
now been grown [59].
There are two very important linked implications of Fig. 2.12 to emphasize here.
The first concerns the heat capacity function on the right hand side of the figure (with
its peak only at very high temperatures). This makes us realize that the behavior
observed in the laboratory for strong liquids is the behavior of systems exploring the
low temperature side of an order–disorder transition that has been smeared out as in
Fig. 2.11, by being off-critical to a true lambda transition that in principle could be
experienced at a liquid–liquid critical point at higher pressures. Thus the system
studied in the laboratory is sensing only the approach to a maximum in fluctuations
at the Widom line.
The second is the linked implication that, just as the correlation length for
fluctuations increases as a critical point in a single phase system (e.g. Co50Fe50 of
Fig. 2.10a, or the lambda transition in C60) is approached from below, so must the
correlation length for fluctuations increase with increasing temperature in the range
explored by the laboratory strong liquids. This is of particular interest in the case of
silica where the fluctuations, via their Fourier components, will affect the scattering
of light because the scattering of light is of central concern in the optical fibers used
for information transfer (not to mention the silica glass lasers used in laser fusion
technology). Indeed, the evidence from light scattering studies conducted in rela-
tion to fiber fictive temperature, confirms our expectations [60].
The importance of this is that it is just the opposite temperature dependence of
correlation length to that supposed by glass theorists who, it must be recognized,
have always been concerned with fragile liquids. The theorists, however, have
tended to adopt the increasing correlation length idea as a fundamental interpreta-
tion of viscous slow-down, hence of glass formation, and the fact that the relation
between correlation length and relaxation time is inverted when it comes to the
classical silicate glasses (and other strong liquids, presumably) is a warning that the
universality aspects of the glass transition must be sought elsewhere. For strong
liquids it can now be appreciated that any effect of correlation length on the
dynamics will be in opposition to that of any natural barrier- crossing kinetics
that exist, hence will oppose the slowdown, while for fragile liquids it will enhance
the slowdown. Whether this can be considered as an explanation of the difference
between strong and fragile liquid kinetics is a little difficult to say. We note,
however, that in lambda transitions, the simple Arrhenius form of kinetics is
followed over many orders of magnitude (e.g. TlNO2 [18] in Fig. 2.3a, and C60
[61]) while the magnitude of the fluctuations increases and the correlation length
accordingly starts to diverge.
The presence of first order transitions below Tg, predicted by the analysis of Ref.
[32] would be consistent with the current findings of ultrastable [62], and ultradense
[63], glasses formed by vapor deposition processes on controlled temperature
substrates, when the temperature is controlled at some 10–20% below the standard
Tg. These are reported [64] to convert back to viscous liquids via nucleation and
growth processes – the hallmark of a first order transition. The one micron length
scale reported for the process [64] is reminiscent of the homogeneous nucleation of
ice crystals from aqueous LiCl solutions near Tg [65], now known to be consequent
on the prior polyamorphous transformation of vitreous water [66]. Whether these
new phases are truly amorphous or are some higher order disordered crystal form
transitional to the ground state crystal (hence another example of the Ostwald rule
of stages in action) has yet to be definitively decided. A true first order character
would be expected if the liquid–liquid transition implicit in the behavior of SiO2 at
high pressure becomes modified to occur near ambient pressure for the weaker
network H20 and then passes to negative pressure domain for the more weakly
interacting but more cooperative van der Waals liquids. It will require much more
work to establish whether or not such a simple set of systematic changes across such
a broad swath of liquids, can be supported.
Irrespective of the outcome on the latter question, it should be clear from the
material of this chapter that a rich panoply of thermodynamic behavior accompa-
nies the transition of non-ergodic to ergodic states of condensed matter, in particu-
lar the case of glassy solid to non-viscous liquid, and that much systematic work
remains to be done before the complex patterns of behavior can be fully understood.
Acknowledgments Support of the NSF, DMR (Solid State Chemistry) and Chemistry divisions,
Grant numbers 0454672 and 0404714, is gratefully acknowledged. We have profited from helpful
discussions with Dmitry Matyushov and Ranko Richert. Yuanzheng Yue, Thomas Loerting and
group, Masaharu Oguni Gene Stanley Sergey Buldyrev and group, Srikanth Sastry, Pablo
Debenedetti and Mark Ediger.
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Chapter 3
Vibration Forms in the Vicinity of Glass
Transition, Structural Changes
and the Creation of Voids When Assuming
the Role of Polarizability
Jaroslav Šesták, Bořivoj Hlaváček, Pavel Hubı́k, and Jiřı́ J. Mareš
3.1 Movements Below the Critical Temperature
Under the certain so called critical temperature [1], the liquid phase becomes
factually prearranged and separated into solid-like structures. Certain unoccupied
vacancies existing within the space are called voids (in the obvious meaning of
opening, hollowness or cavity) and are packed with gas-like molecules (so called
“wanderers”). This realism has been known for a long time [2]. Some of the modern
structural theories (such as the so called “mode coupling theory” – MCT, which is
describing the structural phenomena of liquid state at lower temperatures) are also
based on a similar scheme of the local density fluctuation [3]. Such a conjecture of
heterogeneities in liquid phase goes back to the assumption of semi-crystalline
phase published early by Kauzman [4], as well as to the assumptions of coexistence
of gas–liquid semi-structures [5, 6] as related to numerous works of Cohen, Grest
and Turnbull [7–10].
We can extend our vision toward heterogeneity of larger areas, which is often termed
the medium range order (MRO) and adjacent to the existence of nano-solid-like
domains. Below the critical temperature, the liquid structures can be empathized as
a certain, mechanically sub-divided structure formed by blocks (in the conspicuous
meaning of domains, icebergs or clusters) [6, 11] (see Fig. 3.1) and, on the other side,
J. Šesták (*)
New Technologies Research Centre, University of West Bohemia, Univerzitnı́ 8,
CZ-30614 Plzeň, Czech Republic
B. Hlaváček
University of Pardubice, Studentská 573, CZ-53210 Pardubice, Czech Republic
P. Hubı́k and J.J. Mareš
Institute of Physics of the Academy of Sciences ČR, v.v.i., Division of Solid-State
Physics, Cukrovarnická 10, CZ-16200 Praha, Czech Republic

42 J. Šesták et al.
Fig. 3.1 Illustration of a medium range structure. Schematic picture shows a liquid-like (and also
glassy structures) composed of variously bonded blocks displaying the degree of possible cou-
pling. When the separation of macro-molecularly interconnected blocks occurs above the cross-
over temperature, Tcr, it produces rubber elasticity, which is often associated with entanglements.
However, the low molecular compounds [14–16] (Fig. 3.2 at right) never achieve such a rubbery
state. The blocks’ partition can be found by adequate rheological measurements of a shear
viscosity [17–23] at very small gradients. The separation of blocks for low molecular weights
structures is connected with loss of shear module (cf. Fig. 3.3) and with the onset of fluidity (Note
that the entropic elasticity of macromolecules is not incorporated herewith)
as an assortment of individual “semi-evaporated” units, which are subjected to non-

linear anharmonic motions at high amplitudes [5, 6].
For the displacement of block as an entirety, the certain (often maximum)
retardation time, tmax, reveals the state of interconnections inside of the block
structure, characteristic of a given block size and its variability with temperature.
It is assumed that the block size, together with maximum block retardation time
decreases with increasing temperature. The blocks progressively disintegrate as the
critical temperature is gradually approached [12, 13]. On contrary, the blocks bind
themselves to a more rigid structure as the temperature decreases below the
crossover temperature Tcr and further on below the glass transition temperature
Tg. Down from the critical temperature Tc we can contemplate the four subsequent
and most important temperatures, related to the characteristic points, which are
gradually linking liquid and glassy states:
1. Boiling/condensation/liquid temperature, Tb, characteristic for the first-order
transition. At this temperature, vibrating particles are capable to depart away
from their typically nonlinear motion around its vibration focus (further loosing
it at all to become a part of gaseous phase). Gaseous molecules are moving in
both the translation and rotation modes within the whole volume, which are
missing vibrational settings (characterized with energy minima) and vibration
focusing (characteristic for a condensed state).
2. Crossover temperature, Tcr, at this temperature liquid starts to reveal an elastic
response in the shear stress becoming thus viscously-elastic, which is characterized
3 Vibration Forms in the Vicinity of Glass Transition, Structural Changes 43
by a nonzero, internal energy-related shear modulus build on energetic basis

(an entropic elasticity of a rubbery-like network is not accounted for [17–23] but
can be graphically illustrated upon the comparison of Figs. 3.2 and 3.3, in particular
see the area “b” in Fig. 3.2).
3. Glass transition temperature, Tg. The shear modulus at this temperature overcome
the value ~G 108 N/m2 having a tendency to level off with a declining tempera-
ture and further going ahead toward its maximum value of ~109– 1010 N/m2
4. Vogel’s temperature Tv. Below this temperature the Brownian movement
restricts its progress only within isolated regions mostly along the domain’s
interfaces. The spatial adjustment also occurs at certain domains fixation (by, e.
g., chemical bonding) making a three-dimensional web within the sample. In the
macro-scale the sample undertakes the property of a solid phase incapable of the
wholesale creep flow. Note that the time-honored Kauzmann temperature, TK,
may get coincidental with Tv if derived from the entropy plot.
The subsequent succession Tc Tb Tcr Tg Tv can be well recognized and the
following model anticipated, which bears some distinctive characterization of vibra-
tion modes at different temperatures (or at associated temperature regions) – worth of
10
a
9
t >10 s t < 10 s
8
log Er(10) [Nm–2]
6
b
5
X<Xc
4
M 1<M2
X>Xc
3
Tcr
60 80 100 120 140 160 180 200
T [°C]
Fig. 3.2 Left: the course of a shear modulus, G ffi Er/3 for relaxation of an amorphous high-
molecular compound around Tg (according to Tobolsky-Alkonis [22, 23] for typical polystyrene).
Note that in the glass region (area “a”) the temperature Tg is characterized by the shear modulus
G ffi 109– 1010 N/m2, which decreases with increasing temperature and disappears at (or closely
above) the crossover temperature Tcr where the proportionality, Tg ffi 0.8 Tcr, is approximately
applicable. The area “b” represents the rubberlike plateau, which is not taken into account in this
study. The crossover temperature for the polystyrene is localized as Tcr ffi 120 C while Tg ffi 80 C
At right: the scheme of non-linear oscillator, which existence is causing the relaxation module
decline in main transition zone
Tg Tcr T
Fig. 3.3 Course of a shear modulus G for amorphous low-molecular compound around
Tg [14–16]. Note that the glass transition region, Tg, is characterized by the shear modulus
G ffi 109– 1010 [N/m2], which decreases with increasing temperature and disappears at or closely
above the crossover temperature Tcr for which the proportionality Tg ffi 0.8 Tcr is approximately
applicable (match up to Fig. 3.2, which is relevant for high-molecular compounds). Typical allied
facts are the time-dependent hysteresis particularly evident during the sample consequent cooling
23.5
23.0
medium rangelenght l,Å
Fig. 3.4 Mean length of the

glass heterogeneity 22.5
fluctuation as a function of the
glass density (assumed in the
22.0
terms of MRO) estimated on
the basis of sound velocity for
two types of glassy materials 21.5
displayed by the dense and
empty triangles (Adopted 21.0
from Surovcev and Novikov
[29–31], see [12, 13], the
1.80 1.82 1.84 1.86 1.88
dependence compares with
the data in Table 3.1) density, g/cm3
mentioning beforehand of a needful identification. Searching for the size of the holes
we refer to the simplest expression for P–V–T state equation. For example, the van der
Waals equation is suitable to affirm the size of a minimum volume for the associated
van der Waals isothermal curve (and its minimal spinodal points) while setting the
150
Volume (Å3)
100
50
Tg = 168K Tcr = 1.2Tg

TV = 62K
0
0 100 200 300
Temperature (K)
Fig. 3.5 Vertically is given the size of growing voids (in cubic angstroms) for polybutadiene
polymer measured along with increasing temperature (horizontal) starting from the Vogel’s
temperature, over Tg, up to the crossover temperature Tcr (adjusted by means of a positron
annihilation spectroscopy [60–63], see [5])
limits to the upper boundary of possible amplitudes of the oscillators’ vibrations. In the
moment when the limit is prevailed over such a crucial volume occupied by nonlinear
oscillator, the system becomes unstable and can eventually expand toward the volume
of gaseous phase. Below Tb, however, such a process (of maximum volume expan-
sion) can undergo only those particles, which are existing on the liquid surface. The
bottom component on the liquid side of saddle part of the van der Waals curve
(approximately at 0.385 Vc, i.e. just a portion of the critical volume Vc) plays an
important role for the size evaluation of non-linear vibration amplitude. This estimate
is not far away from that, which was given by B. Wunderlich and H. Baur [24, 25] at
the turn of seventies.
Below the Tcr the non-zero shear module has a drastic impact on the void size
and on the extent of maximum diffusion jumps, which are depressed (or even
eliminated) when temperature is dropping off. The presence of inter-block bonding
will raise the shear module to a non-zero level forming thus an elastic network. As
illustrated by Buchenau for the Tg vicinity [26], the changes in average vibration
amplitudes can be determined by experimental measurements of the Debye-Waller
factor. Under Tg the extrapolation of entropy towards negative values is somehow
impossible (worth noting the Kauzmann paradox [4], which was misinterpreted in
that sense documented in vast literature citations). In our view, the stepwise change
of the entropy derivation occurs as a result of compositional and/or structural
changes in liquid state when “semi-evaporated” particles turn out to be associates
to individual non-linear oscillators. From mechanical point of view the matter
above Tg, became composed by the other type of oscillators than those existing
under the glass formation temperature.The notable increase of entropy above Tg is
thus caused by growing number of newly formed non-linear oscillators endowed

with the migrating focuses of their oscillations. Consequently above Tg the liquid is
structurally different as new degrees of freedom are created.
It is assumed that highly non-linear oscillators maintain the individual character
of their motions and herewith are perceived as the simple individual units about a
monomer size [11, 27, 28], cf. Fig. 3.2 right. Alternatively, the blocks are assumed
to possess interconnected microstructure being composed of identical elastically
bonded particles packed to the high compactness level eventually reaching the
density of glassy phase. The mean length of the heterogeneity fluctuation as a
function of the glass density (assumed in the terms of MRO) is experimentally
determined and is best estimated on the basis of sound velocity for two types of
glassy materials as is illustrated by Surovcev and Novikov [12, 13, 29–31] and is
left for a detailed readers perusal.
The existence accidentally distributed, random size molecular clusters in a
viscous liquid has been discussed since the beginning of sixties until present days
[5–10, 29, 32–35]. Inter-clusters regions, which are containing molecules whose
vibrations are strongly anharmonic, are considered herewith to provide a mount
towards non-deterministic vibration movements. The characteristic of such move-
ments of the amplitude switch of non-linear oscillators in liquid state gives rise to
erratic characteristic of Brownian movements as well as to structural irregularities
of glassy state formation.
The blocks, in other hand, are responsible for complex relaxation effects;
because the interconnected linear oscillators are forming their structures interact.
On the other hand, the semi-evaporated particles (acting as non-linear oscillators)
are responsible for an erratic character of displacements due to the Brownian
motion in liquids [36]. The semi-evaporated particles are correspondingly acting
against the external pressure acting on the sample from outside, and exercise a so
called ‘push-aside’ effect upon the individual blocks effective in their vicinity.
Thus created gaps caused by straightforward amplitude jump (cf. Fig. 3.2 right), can
be directed to any direction within amorphous phase. For the non-linear oscillators
of semi-evaporated particles, the minimal change in the initial coordinates in phase
space brings consequential and substantial changes in the motional trajectories of
particles [37–41]. Therefore, particles can perform their oscillations on several
different amplitudes [12, 13] and these motions bring, in the same time, apparent
elements of uncertainty. In most cases it is describable by the non-linear and non-
deterministic theories [42–50] of chaos. For non-liner systems, characterized with
the different initial coordinates, their subsequent positions and momentums cannot
be determined beforehand and the differential changes and variations in initial
conditions bring completely different trajectories in the phase space expression.
The general rule for the non-deterministic chaos theories [37–57] is consequently
reflected into the structure of amorphous soul of glassy state, which durably
depends on the experimental course of action deliberated for cooling. It will surface
its irregular character, which is subject of discussion connected with the uplift of
potential bottom well (and associated particle displacement) and its consecutive
diffusion type displacement represented by the general length parameter l as the
shift in bottom potential well displacement l 6¼ s is much different than as the

particle diameter s from Ref. [58, 59], giving thus more flexibility to correlations of
Parkhurst and Zvanzig type [58, 59], dealing with viscosity and diffusivity.
3.2 Distinguishing Local Heterogeneity Using the Positron

Annihilation Spectroscopy
The volumes of voids were exactly determined and reported in numerous papers on
basis of positron annihilation spectroscopy – PASCA [60–64]. These PASCA
experiments provide the unusually high coefficients of thermal expansion in the
vacancies comprising region where the volumes of voids are exceedingly sensitive
to the temperature changes above the glassy transition as well as to the external
pressure changes in the boiling point area. The coefficient of thermal expansion in
vacancies areas is about ten to a hundred times as high as that in the block-
containing areas. Possible discontinuity in properties for liquid structure turns out
to be apparent locally at expanding spots, which bear a responsibility for a high
coefficient of their thermal expansion. These locally expanding structures appear
particularly above Tg and their number increases with rising temperature and the
sample commences to consists of, at least, two kinds of particles. In the presence of
such mechanically different units above Tg, the matter turn out to be rather
mechanically heterogeneous. As can be seen, PASCA method cannot reach higher
temperatures in structural description (exceeding the crossover temperature Tcr).
Nevertheless, PASCA give good indication how the structure approaching the
critical temperatures Tc can look like. This temperatures areas has been visualized
and described in models presented in previous papers [5, 6, 12, 13] in relation to the
majority of typical equations of state [65–67].
3.3 Three Types of Entropy Contributions in Main

Transition Zone
For the inherent temperatures regions the entropy main contributions can be por-
trayed in three gradual ways [68]. Below the Vogel’s temperature Tv the entropy
S ffi kB ln Wth is solely composed by the vibration energy of particles [52]. In the
region above the Vogel’s temperature, T Tv, but below Tg the entropy value
enlarges by conformation part, i.e., S ffi kB [ln Wth + ln Wconf], which is associated
with the release of particle’s migration freeing thus their originally fixed positions in
the sample space. Finally at T Tg where S ffi kB [lnWth + lnWconf + lnWsemievap],
the overall contribution extends as a result of semi-evaporated non-linear particles at
a higher energy vibration level. The number of excited particles increases with rising
temperature and acutely above Tcr it turns out to form the diffusion process due to
high-amplitude changes.
These types of entropy changes brought together by three distinct contributions
have been experimentally confirmed in recent works of Johari [68]. Thanks to the
reports made on the basis of PASCA experiments, the vacancies areas have a rather
distinct dimension, which is larger than the van der Waals volume, but smaller than
the 0.385-fraction of critical volume Vc of the each particle’s involved. Accordingly,
the estimate of the enthalpy change can be connected with the semi-evaporated state.
As shown by Hirschfelder [2], the total amount of evaporation enthalpy is required to
produce an expansion of cavity to the level twice as high as is the particle diameter
[69]. As the first estimate for the energy (of void creation producing a cavity of
the size of about 0.385 of the fraction of critical volume Vc) a proportionally smaller
part of evaporation enthalpy, DHevap, can be used. Therefore, the assumption of
DHsemievap ffi DHevap/n, where n stays from 2 to 4 (or even higher), is an agreement
with the PASCA experiments as well as with the estimate of viscosity figured out by
Eyring [70, 71] and his co-workers. Remarkable displacements, l – shifts of the
potential well bottoms occur above the Tcr with the onset of diffusion and progress of
the liquid state connected to vanishing shear modulus.
For the heterogeneity size, the polarizability plays an important role because it is
related to the critical volume of the matter which limits dimensions of possible
voids. For example, the molecular polarizability, a, of a monomer can be calculated
by simple adding up the tabulated polarizabilities of individual atoms [72, 73]
ultimately using empirical corrections in the line with Verköczy [6, 73] such as
amolecul ¼ aCn þ aHm þ aC¼C þ aCC where aC ¼ 1 Å3 for bonded carbon in chained
organic molecules and aH ¼ 0.4 Å3 for hydrogen. Special attention must be paid to
double and triple carbon bonds, if isolated, the former increases polarizability by
0.2 Å3 while the latter by 0.4 Å3. Polarizability of nitrogen is about 0.9 Å3 in
molecules of organic compounds and of oxygen about 0.8 Å3 whilst two coupled
free electrons (~NH3) bring a volume enlargement by 0.158 Å3.
3.4 Linear Cooperative Phenomena in the Built-In Blocks
3.4.1 Limiting Values of Block Time Characteristic
For limits of the time dependence, which is solicitous for a fastest time interval of
retardation and/or relaxation, the time interval calculated from the sound velocity,
vsound, is most relevant. For solid blocks, vsound 105 – 106 cm s–1 possess the
minimal length of acoustic waves lmin, which are determined by the mesh size, ro.
The relations 1/nmax ffi tmin and vsound ffi lmin nmax, where lmin ffi 2D ro become
relevant. Substituting from the value estimate (as outlined above) the maximum
frequency, nmax ¼ 1012–1013 s1 in the sample body, the fastest time of material
response in block, tmin nmax1 ¼1012 1013 s can be obtained. On behalf of
Table 3.1 Some characteristic figures of various inhomogeneities domain size calculated base
upon molecular polarizabilities for different levels of chain interconnection
Linear Linear Linear Linear Tempe-
length of a length of a length of a length of a rature of
Approximation domain for domain for domain for domain for glass
Brand name of of monomer ~600 ~300 ~100 ~20 transi-
polymer or type polarizability segments segments segments segments tion, Tg
of the substance (Å3) (nm) (nm) (nm) (nm) (K)
Polystyrene 11.6 1.90 1.52 1.04 0.61 353
Polyisobutylen 7.2 1.62 1.29 0.89 0.52 198
Polybutadiene 6.4 1.55 1.24 0.85 0.5 168
Polyvinylacetate 8.0 1.68 1.34 0.92 0.54 298
Polymethyl- 9.8 1.95 1.56 1.07 0.62 374
metakrylate
SiO2 6.7 1.59 1.27 0.87 0.51 1473
GeO2 7.6 1.65 1.32 0.91 0.53 957
B2O3 4.4 2.05 1.64 1.13 0.66 523
the longest time characteristic of a given material we can take the typical time
connected with the permanent displacement in series of elements inside of the
block space to be bonded together through the elastic force tmax ffi n2 tmin [5].
Using from the subsequent text the most suitable number of interconnections
n ffi 600, we can adapt Table 3.1. A limiting particularity of picking up “n” value
is detailed below.
3.4.2 Estimate on the Number of N-Elements in the Built-In

Blocks and, Accordingly, on Their Size as Related
to the Shear Viscosity Data
Numerous predictions regarding the size of the blocks are reported in literature by
various authors [32, 74–80] based upon different experimental techniques. Focus-
ing our attention in a direction not yet fully familiar for the block size estimate we
can directed our approximations towards rheology searching for yet unfamiliar
parameters. The first one is characterized by the number of linear elements in a
block at which blocks start to be interconnected in shear flow and become open for
mutual interference when producing a non-zero contribution to the response of
elastic shear module. A useful source of data, for the block’s interactions, is the
measurements of shear viscosity when the data are obtained at zero velocity
gradients (already acknowledged for almost 40 years regarding different structures
of polymer melts with various molecular weight values [17–19, 81]). These data
show one common feature: the dependence of shear viscosity on the number of
roughly monomer (acoustical [27]) units in a chain with X sequence. As the first
instance, the X-number is small and remains below a certain limit (X Xc. where
Xc 500–625) where the polymer melt is characterized by constant and gradient-

independent viscosity. In this particular case the module of shear elasticity is zero,
as well as the first normal stress difference remains zero. The macromolecules are
smaller than the critical block size (X Xc) and the blocks, if subjected to shear
flow, do not exhibit any mutual interference. A different level of viscosity, which
rises upon a linear dependence on X, characterizes each polymer at this particular
case. However, at the point when the critical value, Xc, is reached along the
polymer chains, the changes in the rheological properties occurs. The block inter-
connections start to interfere through the overgrown size of macromolecules
(cf. Fig. 3.1). For polymers with X Xc, the melt viscosity in reliance on shear
gradient starts to possess a non-Newtonian character as the gradient grows and the
first normal stress difference starts to become an important flow characteristic. This
effect is usually explained in connection with the chain entanglements, the concept
of which was originally introduced upon sketchy pictures [20, 21, 82] (such as an
evident phenomenon). On the other hand, the nature of couplings [20] was left
undeveloped resuming consequently an alternative in relation to account coopera-
tive motions of molecular areas (also suited for the low molecular structures). The
latter case corresponds more closely to a scheme presented herewith (cf. Fig. 3.1)
being supported by results of Achibat [33, 34] when reporting a relationship
between the domains and the entanglements. This model attributes the property
of inter-blocks bonding either to the entanglements (as the individual blocks start to
be interwoven by polymer network) or to the inflexible bonds of van der Waals type
(or even to the bonds of a chemical nature). The inter-block bonding has a
consequence in the development of non-zero shear module. Although different
polymers have different levels of viscosity (or else chain flexibility), different
molecular weight exhibits different levels of normal stresses. The numerical
value of Xc (for the blocks’ mechanical interference in shear flow) holds a universal
character. Just quoting Ref. [19], it subsists for polystyrene the value Xc ¼ 600, for
poly(vinyl acetate) Xc ¼ 600, for polyisobutylene Xc ¼ 500, for polydimethylsilox-
ane Xc ¼ 625. If the level of critical interconnection is achieved in a linear sequence
for polymers, the blocks become inter-bonded and get exhibiting the shear elasticity
represented by shear modulus or by the first normal stress difference. Such elasticity
created by flexible macromolecules stays entropy related. This type of interconnec-
tion has a “long distance character” relative to the block size and one single
macromolecule can “over-bridge” several blocks, as well. In contrast to the blocks
coupled by flexible macromolecules, the blocks can also be inter-connected by
inflexible chemical bonds. This is the case for the low molecular weight substances
under the crossover temperature. The blocks connected by inflexible bonds cannot
be stretch to higher deformations and have to break up as the temperature is
increased above Tcr. The inter-connection of inflexible blocks reflects such a self-
character toward the internal energy as related to the contribution of shear module
under the Tcr.
The other parameter not yet determined herewith is the crossover temperature
itself. For the measurement purposes, the dependence of shear relaxation
module on temperature in area of main phase transition can provide such a needed
capture information [22, 23] (cf. Fig. 3.2). For clarity reasons of having a
better explanation within the text, some data of Schultz [19] for the main phase
transition can provide such a desirable capture of information; Alkonis [23] and
Tobolsky [22] are exposed for an ideal illustration (cf. Fig. 3.2). The crossover
temperature Tcr is determined on basis of the shear elasticity of relaxation module
related to the internal energy. The value Xc can be determined by sourcing the
zero gradient viscosity curves. At this level of internal connection the blocks start
to interfere in their flow properties. At the temperature Tcr the characteristic
domain size become estimable. For lower temperatures, T Tcr, the part of
force responding to the external deformation has a component related to internal
energy. Taking the approximate size of one oscillator unit in an interconnecting
sequence from the expedient polarizability values [83, 84] and using the inter-
connection number of Xc equal the typical 600, the characteristic size of a domain
of about 6 nm3 is realistically obtained (see
pffiffiffi Tables 3.1 and 3.2). For the linear
dimension of a domain following number 3 6 ¼ 1.81 nm can be situated as a most
typical. This seems to be in good agreement with the published values [32, 74–80]
obtained by different experimental techniques. As the polarizability of molecules
is a simple additive property, the domain size can be easily estimated from the
Table 3.2 Some characteristic accounts for selected compounds

Critical Polarizability
volume (cm3) amolecule (Å3) Critical volume divided
VC by amolecule NAV as Notes: Remarkable
55 amolecule ([Å3] ¼ 1024 related to the deviations from the
Substance NAV cm3) polarizability average value
Ethane 148 4.47 55.1
Propane 200 6.3 52.8
Butane 255 8.2 52.1
Pentane 311 10.0 51.9
Hexane 368 11.9 51.9
Water 45 1.45 51.5
Ethanol 168 5.41 51.7
Propanol 220 6.74 54.4
Acetone 213 6.4 55.0
Methyl- 301 9.93 50.5
propylketon
Propion acid 230 6.9 55.5
Butter acid 290 8.38 57.6
Methylacetate 230 6.9 55.5
HCN 139 89.3 Upper anomalies
Methanol 117 59.0 Upper anomalies
Toluene 316 44.4 Foot anomalies
p-Xylene 378 45.8 Foot anomalies
Benzene 260 41.6 Foot anomalies
Naphthalene 408 38.7 Foot anomalies
polarizability values of individual monomer units and from the Xc values, as

hinted in Table 3.1.
3.5 Polarizability of Molecules Determining

the Critical Volume
Polarizability represents the volume response of electron cloud of atom or molecule

against the effect of a weak external electric field (where the notion “weak” means
the electric field of a much smaller intensity in comparison with the electric
interaction of the atom nucleus with orbiting electrons). For some organic mole-
cules the Table 3.2 provides important information showing that for most com-
pounds the volume allocated to a molecule at a critical temperature is about 50–55
times larger than the volume of its polarizability. Polarizability of a molecule can be
calculated by a simple adding of the contributions of individual atoms [72, 73]
whilst it is important to follow deviations both upwards as (HCN) ! (HCN)3 or
downwards (naphthalene) occurring due to the orientation of aromatic nuclei at the
molecule contacts.
It follows that at the critical volume is the average volume related to a single
molecule described by the value equal to about 50 times of the relevant volume of
electron cloud of each molecule [73]. The table provides beneficial estimate on
critical volumes and basis of polarizability, which has correlation not only to
critical volume but also dielectric constant, density of cohesion energy and so
mutual solubility of liquids and its refraction index [72].Upper deviation shows
possible interconnection of molecules lasting up to the critical temperature
(e.g. (HCN)3). Bottom deviation for aromatic compounds reveals a certain orienta-
tion or better a mutual approach of the “face-to-face” arrangement. It is worth
noting that polarizability is a decisive parameter adjacent to the notion of liquid
state because liquid cannot bears a greater volume than is its critical volume. The
least volume of liquid follows from approximations used in the state equation,
which consequently provides the adjacent volume of resulting glass.
3.6 Alpha Process and Beta Slow Processes
For both the explanatory reasons and the basis of simplicity, we have provided our
illustrations using only examples of translation forms of diffusion displacements.
However, the rotational forms and the orientation forms of diffusion displacements
in the angular coordinates F and C (which signify rotation around the chemical bonds)
possess the equivalent importance. It was Bueche [82] and consequently Eisenberg
[85] as well as Boyer [86, 87], Helflend and Meier [88–91] and Ilavsky [92], who
correctly explained the origin of so-called b slow processes connected with the
orientation and side chains movements. These authors explanations were similar to
those given much later on by Rossler [93–95]; Vogel, Rossler and coworkers [96–100]
related b slow process on Arrhenius a non-Arrhenius thermal relaxations. According
to other authors [82, 101–103], the reorientation motions of molecules are associated
with a secondary beta relaxation taking place in super-cooled liquids. We should
note that besides the slow b process some literature unveil fast b process, which,
however, is not accounted for herewith though having some particularities such as
time tbfast < << tbslow is rather shorter in turn of several orders and involves processes
tbslow tmin. Relaxation time tbslow is much longer due to the limited mechanical
succession of bonding elements.
Another mechanism, which cannot be excluded, is associated with an explana-
tion given by Johari and Goldstein [104–106] who suggested that the b slow
processes are connected with the “islands-of-mobility” persisting even under Tg.
Both approaches seems be acceptable. In our approach, however, the a process is
connected with an infinite number of structural network “inter-connections”, which
directly contribute to the elastic shear modulus under Tcr. As the structural skele-
tally networks of the macro-sample are formed under cooling, two different poly-
mer motion are freeze-in at Tg. Namely we speak about either the rotational
diffusion around chemical bonds at polymer chains and translation motion within
certain macro-scale. It follows that one type of diffusion can become structurally
deficient or better is bypassed and disappears at lower temperatures or can proceed
simultaneously with the a-process. Thus some elements, which participate in b
slow processes, are structurally bypassed and below Tg. are considered as still
mobile, Therefore they cannot contribute in a full extent to the shear modulus
increment within Tg area and adhere them self fully to the elastic network, which
forms the whole sample.
The n-number of elements connected by a process is rather unspecified or better
is only restricted by the sample dimensions. Chaining and interconnecting of the
elements, which compose the a process go imaginary toward infinity under forming
rigid viscous-elastic web of a solid sample. For the b slow process, the limited
interconnection of joined elements, “n” is restricted inside of blocks (cf. Fig. 3.1) by
limited number of particles in linear block’s sequentionality. Thus the basic reciprocal
temperature dependence of b slow processes is often expressed by prime line of
Arrhenius relation [74, 93–95, 98–100] as the temperature declines under Tg temper-
ature. In this region the ability to have controlled motion of blocks through elastic
network is for b-process different than that for a -process. Considering the variable
inter-connection, the number “n” brings an additional point to the perception of
differences of alpha and beta relaxation processes.The relaxation times, t, of compo-
nents with decreasing temperature (for the a-process) increases up to infinity as
a result of enormous growth of elements in the relaxation series (tmax ffi n2 tmin) [5, 6].
The accrual of relaxation time t due to the increment of number of elements “n”
is the main reason for the disposition of shear modulus during cooling below Tcr.
For the a process the number of n-elements can increase up to infinity when an
elastic web inside the sample is accomplished. Below Tcr the cause of relaxation
time increases strengthening the mechanical interconnection of network
connections. On the other hand, the b slow process is different because the
interconnection characterized by “n” is adjusted at a relatively minor value n1 ¼
const., just composed by several units. Only for some exemptions “n” can reach a
higher values and such a fragment have no other choice than to behave Arrhenian.
With an increase of the environs density, which is surrounding mechanically
interconnected friction centres, the whole aggregate behaves adequately friction-
ally. For the b slow process the elements growth terminates with the interference of
blocks’ boundary below Tcr as a consequence of dawdling of n-numeral, which is
exhibited by a standard Arrhenius relation upon decreasing temperature. For this
reason tbslow is not increasing along with the escalating collection but follows mere
Arrhenius growing trend at decreasing temperature.
Acknowledgments The study was supported by the Czech Science Foundation, Project No.
FR-TI 1/335.
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Chapter 4
Some Aspects of Vitrification, Amorphisation
and Disordering and the Generated Extent
of Nano-Crystallinity
Jaroslav Šesták, Carlos A. Queiroz, Jiřı́ J. Mareš, and Miroslav Holeček
4.1 Introduction: Some Particularities of Natural

and Artificial Disordered Materials
Historically, glass is often viewed as a remarkable translucent substance though

usually made from the simplest raw materials upon the effect of firing. Nature,
itself, is the best instance to learn how different temperature changes can provide
various glassy states, altering from very slow rates occurring within geological time
scales (e.g. obsidians – glassy volcanic rocks consisting of natural acidic silicate
glasses) to extremely fast, occurring as a result of fast energetically driven collapse
(e.g., by impact of meteorites, yielding melted droplets then cooled to various
tektites). Mimicking evolution, however, man became responsible for the creation
of further families of a wide variety of glassy and amorphous materials (geopoly-
mers), which have gradually appeared through human creativity, particularly dur-
ing last 100 years. Properly chosen procedure of rapid extraction of heat (often
called quenching) turned up to be a efficient route for successful glass-formation
(vitrification, as a repeatable process) of almost all substances (thus allowing for the
preparation of glasses from different sorts of various inorganic materials, including
metals) in contrast to the traditional chemical approach, seeking just for an appro-
priate composition to vitrify under a customary self-cooling procedure [1, 2].
J. Šesták (*) and M. Holeček

C.A. Queiroz
VICARTE, Faculty of Sciences and Technology, New University of Lisbon,
P-2829-516 Caparica, Portugal
J.J. Mareš
Institute of Physics of the Academy of Sciences ČR, v.v.i., Division of Solid-State
Physics, Cukrovarnická 10, CZ-16200 Praha, Czech Republic

The first natural glasses were formed as the Earth cooled and, therefore, predate
creation of living organisms by about 1.5 billion years. Such primordial glasses
were limited in composition and versatility just as were the first primitive unicellu-
lar organisms. However, some compositions (in an unstable state of glass) survived
unchanged for a enormously long period of time, similarly to certain strains of
bacteria. A still open intellectual terrain ahead is apparent in each of the material
classes associated with real bodies of living organisms, being either promoted
naturally or created synthetically – particularly interesting are glasses when assum-
ing its rather curious but apparent degree of similarity with certain biopolymers
(carrying out genetic information) [3]. Both are in a reinforced (thermodynamically
unstable) state formed due to kinetic reasons, which remain influential until glasses
transform into a stable structure (a melt of the lowest free energy) while biopoly-
mers (occurring in living organisms) stop their role in life by death. Both glasses
and biopolymers adapt to their environment and previous history. There is an
almost limitless range of compositions of glasses and countless numbers of differ-
ent living species, each family having particular molecular building blocks and
severe structural rules, although some compositional restrictions of glasses were
gradually overcome. Although the origin of glass is nevertheless lost in prehistori-
cally obscurity, all imaginable glasses have been increasingly artificially synthe-
sized, making thus the natural and man-made glasses indistinguishable. Another
intriguing parallel can be drawn in their spontaneously apparent emergence of new
phyla or groups of species involving both the disordered state of glasses and highly
ordered situation of biopolymers as well as they are often highly non-equilibrated
status. It may involve our better understanding of possible convergence of glass and
genes assuming known bioactivity of certain inorganic glasses, particularly their
silanol-rich (Si–OH) active surface capable of binding to living tissues owing to
their specific composition, porosity, self-similarity, fractality and thermal pre-
treatments.
Various other silicate glasses were created naturally [4] by accidental melting
due to, e.g., the charge of lightening (‘lechatelierite’). Worth of noting are ‘obsi-
dians’ (glassy volcanic rocks consisting of natural acidic silicate glasses exhibiting
a high melting point) and ‘pumice’ (fumed volcanic glass), which were formed by
terrestrial upshot of volcanism and have attracted the men’s attention since prehis-
toric times (as they were used as cutting tools, amulets or cult objects). Interesting
enough is that the extent of natural glass on earth is in the range of a tenth of a
percent with the ratio of about 4,000 minerals versus few types of natural glasses
while on the moon (and possibly also other planets) it is possible to identify only
~60 minerals where half of them are glasses. The frequency of glass deposits is at
least one order of magnitude higher than that found on the Earth.
The melt-cooling processes, traditionally seen as the solely responsible for the
formation of vitreous states, are not the only methods which generate glassiness.
Other non-crystalline materials are various alumina-silicates (based on the mixture
of meta-kaolin with an alkaline activator, producing thus hardening pastes), which
are frequently termed either as alkaline inorganic polymers, geo-polymers or as
hydro-ceramics; exhibiting, among other interesting properties, amalgamated
4 Some Aspects of Vitrification, Amorphisation and Disordering 61
qualities, intermediate between those peculiar to cements with that characteristic

of glass-ceramics and zeolites.
Herewith we can specifically recognize various manners of disordering a regular
network, which thus ensues disordered states of various cause and portrayal, often in
low-dimensional systems (as thin layers), and including the particularity of quantum
dots or wells, which, however, falls beyond the framework of this brief introduction.
These processes are principally of macroscopic origin, bearing dynamic perspec-
tives, although they can be related with the microscopic structure of matter owing to
adequate theoretical models. Quite generally, one may state that non-crystalline
states can be achieved by certain (seemingly contradictory) methods:
1. By maintaining already existing disorder in the liquid phase when applying fast
heat withdrawal (such as a drastic freeze-in by melt radical undercooling), this
way preventing phase (ordering) transition
2. By vapour (chemical/physical) deposition of substance from their gaseous state
in order to form a disordered thin-film over a solid (cooled) substrate, such as
hydrogenated amorphous silicon, a-Si:H, deposited by plasma-enhanced chemi-
cal vapour deposition, PE-CVD, etc. [1, 5–7], thus avoiding structural ordering
of the deposited phase
3. By implementing disorder on a previously ordered network upon energetically
driven structural disintegrative collapse, e.g., by intensive milling, particle
bombardment, or by pressure induced amorphization
4. By creation of a disordered structure through variously accomplished chemical
reactions including low temperature diagenetic and biotic processes, such as by
sol–gel or trough aqueous amorphization response creating, e.g., natural hyalites
and opals.
Hereafter, we would like to pay attention to the first category of non-crystalline
materials only, which involves the particularity of traditional technology of vitrifi-
cation of silicate melts often upon self-cooling as well as the unconventional
technique of metallic glasses by particularly designed equipment for their quench-
ing [1, 2, 5].
4.2 Some Structural Features of Non-crystallinity

and Nano-crystallinity
The basic reason for the failure of a liquid to crystallize can be attributed to the
problem in the molecular arrangement, not so much in the liquid state (clustering)
but predominantly in the formed crystalline state during the process of ordering,
i.e.; the higher the crystalline symmetry of the phase to appear, the better the
glass-forming ability of its parent melt [5–7]. Furthermore, the probability of
glass-formation increases with the formation of liquid mixtures in which the
Gibbs energy of the non-crystalline arrangement decreases, while that for
corresponding crystalline phase to precipitate remains unchanged. The stronger

the interaction among the mixture components, the deeper the depression of the
freezing point of the solvent; while the viscosity increases, thus diminishing any
possible nucleation. The component interaction, however, should not become too
strong as to generate a new competing crystalline phase which would strolls
toward decreased vitrification.
A noteworthy alternative element crucial for non-crystalline randomness is the
variation of bond angles sometimes assumed to become central in further distin-
guishing special (constrained) states of glassy and amorphous materials. The flexi-
bility of covalent bond is largest for the two-fold coordination of group VI-elements
and is lowest for the tetrahedrally coordinated group IV-elements. For instance, in
the SiO2 glasses the oxygen atoms are bridging the Si-tetrahedral providing the
essential flexibility, which is considered necessary to form a random covalent
network (without exhibiting excess of strain). However, if such a network is formed
without the flexing bridges contribution of the group VI-elements, the structure
becomes amorphous (as in the deposited strain-confined films of, e.g., As2S3), which
can exist in many various forms of non-crystalline configurations (often experimen-
tally irreproducible).
The highly constrained nature of the variously obtained amorphous films sug-
gests that defects might not be randomly distributed but, instead, can be predomi-
nantly located at internal blocks, voids and as strain-relief interfaces between
domains. In contrast to vitrified glasses, the CVD-produced amorphous films can
thus exist in many non-crystalline configurational states, the thermal annealing of
which can lower its strain energy, but, however, cannot transform the over-con-
strained amorphous configuration from one atomic layer to another. A drastic atomic
rearrangement would need to be enforced to accomplish such an ‘unstructured’
reconstruction, which would, instead, materialize overlapping by more pertinent as
well as unprompted crystallization.
However, a possible interference of the so called ‘medium-range order’ or
‘modulated structures’ (often bordering upon nano-crystallinity) becomes particu-
larly common in resolving various non-crystalline materials (pertinent for semi-
conductors), where the concept of homogeneous random network and its associated
defects was most extensively studied. It is closely connected with the fashionable
use of the prefix ‘nano’ (nano-technology, nano-materials) touching the limits
where the ordered and disordered states transpire factually their guaranteed deli-
mitability. The standard observations, based on measurable crystallographic char-
acteristics (XRD diffractograms) can provide data on the amount of crystalline
phases (capable to detect the crystalline phase down to about 2% within the glassy
matrix, certainly under certain crystal-size detectability). If not assuming here the
capability to distinguish a minimum crystallite size (by traditional XRD peak
broadening), nor we account for a specialized diffraction measurement at low
diffraction angles (aiming to calculate the radial distribution function), we can
direct our attention toward the critical amount of crystalline phase in the glassy
sample. This issue is yet befitting the crucial question how to relevantly define
the boundary between yet ‘true glassiness’ and already ‘nano-crystallinity’. There
became known a few proposals, but the generally accepted figure is, for long, the
value of 106 vol.% (less commonly 103%), of crystallites to physically exist
distributed within the glass matrix, as not yet disturbing its experimental non-
crystalline characterization and consequent definition of glassines. The appropri-
ateness of this value is, however, difficult to authorize, persisting its maintenance
on basis of acute convenience and reiterated use [2].
By the same argument, glasses exhibiting the so-called ‘short-range order’ can
be viewed to also encompass intrinsic defects (interconnected islands, voids,
domains interfaces, etc.) defined as a deviation from the lowest energy bonding
arrangement. The extent and size of such structural inhomogeneities are specified
within the so called medium-range-order, which is neighbouring the nano-crystal-
line approach. Throughout freezing of such defected inhomogeneities certain com-
plex processes can subsist, which stages we use to associate with a certain
assortment of temperatures. Experimentally, they are determinable all the way
down from the states of liquid equilibrium through the non-equilibrium under-
cooled liquids, down to the constrained state of glasses (below Tg).
A needed definition of short-range order imposes that each constituent species
(e.g. atoms) fulfils its chemical valence requirement [7] (according to the so-called
8-N rule); however, the stronger heteropolar bonds (e.g. As S) are favoured over
the homopolar bonds (e.g. S S or As As). It is worth noting that the constrained
bond length survives within ~1% equivalency of the bonds existing in the long-
range order on the corresponding crystal. We can distinguish a topological short-
range order, in which the structural defects are subject to relaxation and annihilation
at annealing temperatures close to Tg, which is usually associated with collective
movements of constitutional species related to both the atomic or the whole cluster
hauling. On the other hand, there is commonly a compositional short-range order-
ing, in which chemically similar species (such as Ni, Fe or Co in metallic glasses)
can mutually exchange their atomic positions, often resulting in re-arrangement of
the nearest neighbours, thus ensuing magnetic anisotropy, etc. Finally, there can
happen a diffusional-driven ordering process, connected with mutual survival and
disappearance of various structural defects, often shaped when the samples are
inflicted to great temperature gradients (e.g. quenching), which subsequently yields
various structural adjustments due to relaxation of mechanical stresses and defor-
mations.
4.3 Specificity of Non-crystalline Chalcogenide Materials
Structure modelling has been proven particularly useful in the case of chalcogenide
glasses. However, their representation is difficult (or better too-all-embracing) due
to the great flexibility in the range of the structural units forming their random
network. The general concept of a homogeneously accidental and covalent network
has often been explored and re-examined [6]. Nevertheless, it is difficult to

encompass all differences flanked by various characters of non-and-nano crystalline
chalcogenides, which incongruity is due to the bonding constrains and to the number
of degrees of freedom allowed by their three-dimensional network, arranged
towards the flexibility required accommodating the given random mismatch [7, 8].
For a binary AxBx1 exhibiting only a short range order, the average coordination
number is m ¼ x Ncn(A) + (1 x) Ncn(B) where the number of constrains (Nco) per
atom (A and B) is given by Nco(m) ¼ m/2 + m(m 1)/2 ffi m2/2. When equating the
number of constrains to the ideal three spatial degrees of freedom, Phillipspffiffiffi [8]
showed that a most favourable average coordination is mc ¼ 6¼ 2.45
corresponding to an optimal connectivity. As a consequence, the glass-forming
tendency occurs greatest when the short-range order imposed by bond stretching
and bending forces is just sufficient to exhaust the local degrees of freedom. The
internal strain increases with m while the entropy follows the opposite trend because
the non-crystalline state becomes insufficiently interconnected (‘cross-linked’).
Therefore, the conventional state of chalcogenide glasses is typically restricted to
lie in the region ~3.3 > m > 2; while with m > 3.3 becomes over-constrained amor-
phous; yet higher, with m > 4.3, associates with unusual non-crystalline metals. On
the other hand, those having the lower connectivity (m < 2) are assumed to be under-
cross-linked amorphous materials, such as thin films of inert gases or halides. As any
other possible criteria, this one suffers from uncertainty around the borderlines (m
ffi 2 or m ffi 3.3), since the long-range interactions, ionicity, size effects, etc., have
been neglected, as well as its applicability to the class of quenched tetrahedral
glasses (e.g., AIIB2V like CdAs2 and their derivatives with admixtures of Ge, P, etc.).
Even glasses with the average coordination m ¼ mc contain a considerable strain,
which magnitude can be accessed from the difference in heats of solution, such as,
that for vitreous silica (m ¼ 2.67) 2.16 kcal/mol, while for crystalline a-christobalite
one obtains 1.52 kcal/mol. The flexibility of covalent bond is largest for the two-
fold coordination groups of VI-elements and is lowest for the tetrahedrally coordi-
nated groups of IV-elements. For instance, in the SiO2 glasses the oxygen atoms are
bridging the Si-tetrahedral providing the essential flexibility, which is considered
necessary to form a random covalent network. However, if such a covalent random
network is formed without the flexing bridges the structure tends to become
amorphous (as the deposited strain-confined films of, e.g., As2S3), which can
exist in many various forms of non-crystalline configurations (often experimentally
irreproducible). Structural ordering associated with a medium-range order (i.e.,
sizable nano-crystalline heterogeneity) is known to exist in many deposited-like
structures, such as hydrogen-rich interconnecting tissue of a thin film deposited by
glow-charge over a-Si:H alloys [9], or domains of ~600 Å found at evaporated thick
films of As2Se3, or smaller domains existing at most amorphous structures based on
As2S3 or GaSe2. It is known that such chalcogenide melts variously thermally
annealed exhibit already various stages of melt structural ordering (clusters,
nano-crystalline regions, etc.).
4.4 Pressure and Temperature-Induced Amorphization
Worth special noting is the transformation of a crystalline-to-amorphous phase,

which can be achieved without going through the conventional steps of bulk-liquid
melting-and-quenching. Such methods are envisaging the micro-processes
involved, where, e.g., powdered particles could melt in their neighbourhood thanks
to high temperatures locally achieved due to the plastic deformation. Such pro-
cesses are hauling a lot of energy and, moreover, may include many other processes
of interstitial incorporation and segregation into non-stoichiometric sites, defective
links, etc. Such a process of amorphization can result from chemical, irradiative,
thermal or pressure-induced disruption of the crystalline order, when the free
energy of the crystal obviously exceeds that of an allied amorphous phase
[10–12]. Compressive amorphization was first discovered already 25 years ago
when ice-crystals were observed to amorphize at 77 K and 1 GPa [10, 13]. There are
numerous examples of amorphization of originally genuine well-crystallized mate-
rials, which is inducible by a variety of processes, ranging from bombardment with
high energy particles, spray- and freeze-drying, dehydration of hydrates (common
in pharmaceuticals [14]), to continuous grinding and milling (grains miniaturization
below perceptible nano-crystallinity), cold-rolling (common with metals’ tryout
[12, 15–17]), and experimentally recognized and thus applicable to an inquisitive
assortment of materials [e.g. 18].
Rather different routes to non-crystallinity can be best monitored in the ring
statistics of silica, which gets recovered after amorphization. These cases involve
the breaking and reforming of bonds and its reconstruction. Usually, pressure
induced amorphization signifies the existence of a metastable amorphous phase
with a lower free energy compared to the parent crystal and that transformation into
a more stable high-pressure crystalline phase is kinetically hindered [18, 19]. This
metastable amorphous phase may correspond to high-pressure thermodynamic
melting of the parent crystal phase at a significantly low temperature, where the
Clapeyron slope for the melting transition (dP/dT) is negative. For instance, the
metastable extension of the melting curve of SiO2 to higher pressures [19] yields
reasonable estimates of the amorphization pressure of quartz, which occurs around
30 GPa at ambient temperature [6]. Some correlations indicate that the denser the
starting ambient for the crystalline phase, the higher the mechanical work needed to
complete the route to obtain a denser glass.
Worth of attention is the functional model by Ponyatovsky and Barkolov [20],
where crystalline instability under thermobaric stress (shown by perturbation of
P and/or T) is attributed to the coexistence of a low-density amorphous phase
(¼ LDA) and a high-density amorphous phase (¼ HDA). The LDA and the HAD
phases represent polymorphs with the same composition as the crystal but different
density. Thermobaric amorphization was experimentally studied in zeolites [11, 21,
22], which readily convert to amorphous alumina-silicates under heating and/or at
modest pressures. In the case of a zeolite collapse, order–disorder transitions are
found dependent on the rate at which the thermobaric stress is applied [11].
Whether amorphization is thermally induced isobarically or pressure-induced
isothermally, the low-density crystalline structure should convert to a final high-
density HDA phase via a low density LDA phase. The zeolite–LDA transition
is expected to be of the displacive type, while the LDA-HDA transition is recon-
structive.
Another fascinating finding is the noticeable fact that the temperature of isobaric
amorphization, TA, shows a significant depression as the heating rate is reduced.
This type of kinetic behaviour seems reminiscent of the comparable trend followed
by the glass transition temperature, Tg, on varying the cooling rate. The relatively
large scale of the changes in TA, is though to suggest that this effect might be
controlled by the viscosity of a very strong liquid. The idea of a perfect glass, with
zero configurational entropy, Sc, was first discussed by Kauzmann [24], in the
context of melt-quenching, and coincides in Adam–Gibbs theory [25] and with the
discontinuity at the Vogel temperature (Tv) in the Vogel–Fulcher–Tammann–Hesse
(VFTH) three-parameter viscosity relation:

B
ðTÞ ¼ exp (4.1)
T Tv
where Tv > 0 K, B and o (pre-exponential factor) are fitting parameters, being

Tv usually determined from adjusted experimental viscosity data reported for
T > Tg > T v .
An interesting outcome of the comparisons between the dynamics of zeolite
collapse, and that of structural relaxation in conventional melts, is that below Tg,
i.e., for very slow heating or for low pressure-increase rates, respectively for
the isobaric and for the isothermal amorphization processes, zeolites are expected
to collapse more rapidly than the final HDA phase can respond. In either case,
highly ordered glasses with very low configurational entropy, Sc, might be obtained
if the LDA phase could be isolated [11]. Indeed, Angell and co-workers [23] have
speculated that the ideal glass state might be better approached via such a
phase transition involving a kind of ‘superstrong’ liquid. If the LDA phase is
chemically ordered, then the network will comprise only even membered rings,
and this compares with the chemically disordered HDA phase where odd membered
rings are required topologically to accommodate bonding contacts (as Al Al
or Si Si). Zeolites and glasses amorphized from them show a clear relationship
between the size of secondary building units and features in the Boson peak, i.e., the
Boson peak, accessed in the low-frequency range of vibrational spectroscopy,
is hugely enhanced in low-density networks [22]. If amorphization can ever bestow
a practical route to the state of an “ideal” glass accomplished directly from the
crystalline state, rather than via freeze-in from the liquid state, then the idea of
Kauzmann glass [24, 25] might be better realized, though the specificity of such an
ideal glassy state as recently have been argued [26].
4.5 Vitrification Versus Crystallization: Reduced Tg

and the Hrubý Parameter
For a quenched glass, the energy radial distribution function (often investigated by
X-ray diffraction) depends on a general configurational coordination, showing a
minimum, which bottom lies higher than that of the minimum of a corresponding
crystalline state because of the inherent strain energies. The barrier between the two
main minima represents the kinetic hindrance preventing crystallization of the glass
below Tg, which surmounting is only possible by a substantial atomic rearrangement.
The amorphous deposited solids, in contrast, can exist in many near-crystalline
configurationally coordinations exhibiting thus multiple (but smaller) energy distribu-
tion of minima. Over-constrained state can be lowered by suitable thermal treatment
(e.g. common annealing, which supports compacting the structure thus lowering and
even overlapping the minima). In some cases, the mere temperature increase may
yield a catalyst-like pseudo-crystallization to occur yet below Tg [1, 27, 28, 31].
Šesták [28] revealed that quenched glasses disclose upon heating a regular glass
transformation, Tg, which is a noticeable step-wise deviation from the base line
measured by, e.g., differential thermal analysis (DTA). Upon further temperature
increase Tg is followed by crystallization as a base-line reversal deviation peak
(Fig. 4.1). On contrary, in amorphous materials the Tg effect is often overlapped by
a too early crystallization, the last being shown by non-matching onset and outset of
the DTA peak base lines. Worth repeating is that rapidly quenched metallic glasses
does not habitually expose distinguishable thermal changes, which can be notice-
ably associable with the entire glass transition.
Well before the development of any generalized nucleation theory for condensed
systems, Tammann [29, 30] already called earlier attention to a tendency revealing
that the higher the melt viscosity at the melting temperature (Tm), the lower its
crystallizability. Qualitatively, this tendency can be explained by an increased
inhibition of motion or molecular rearrangement of the basic units of any melt
with increasing viscosity. The quality of the glassy state is possible to quantify by
examining the reduced quantities [5] such as typically glass transition temperature
(Tgr) given by the ratio Tg/Tm; a lower ratio reveals a higher difference of Tg and Tm
thus showing a greater stability of the glassy state. Referring to a large set of
available experimental data obtained for nucleation of several silicate glasses,
Zanotto [32–34] concluded that glasses having Tgr higher than ~0.58–0.60 display
only surface (mostly heterogeneous) crystallization, while glasses showing volume
(homogeneous) nucleation have Tgr < 0.58 0.60. The reduced glass transition
temperature was examined in more details by Sakka and Mackenzie [36], and for
metallic glasses by Davis [37]. Determination of theoretical values of reduced
temperatures were approached by Angell [25, 35] based on extension and extrapo-
lation by means of application of the VFTH viscosity equation.
Glass forming ability is noticeably related to the ease of the reverse process of
devitrification possibly evaluable on basis of the difference between crystallization
Fig. 4.1 Left: Plot of enthalpy, H, versus temperature, T (upper), which is accessible and thus
characteristic as an experimentally obtainable DTA/DSC curve (factually representing dH/dT DT).
Solid line indicates regions of stable gaseous, liquid and solid phases; dashed lines designate regions of
metastability (left: undercooling; upper: superheating). Thin line displays the unstable territory of
constrained state of glass. Equilibration and rapid liquid cooling (RC) can result to either equili-
brium or delayed crystallization (exothermic peak at T0 cr), or to non-equilibrium vitrification through
the step-wise glass transition (Tg). Under consequent reheating DTA/DSC shows exothermic crystalli-
zation (Tcr) below the melting temperature (Tm). These points are serviceable in the determination
of some material’s characteristics, such as reduced temperatures (Tg/Tm), or Hrubý coefficient:
KH ¼ (Tcr Tg)/(Tm Tg). A special meaning has the point TK (often called Kauzman temperature),
estimated by intersection of extrapolated line for the equilibrium liquid with that of equilibrium solid
(obtainable at the extrapolation limit of a fictitious null cooling rate). The distinctive amorphous phases
(obtained, e.g., by vapour deposition, VD; or by mechanical disintegration of the crystalline state, MD)
can behave differently because their enhanced reactive state is capable to promote (or catalyze) too
early crystallization, thus overlapping with glass transition (an often neglected or experimentally
misinterpreted effect). Right: typical traces depicted to illustrate a possible span of the glass transfor-
mation region distinctive for various dissimilar materials (oxides/non-oxides) and/or for different
heating rates (b2 > b1). If additional temperature treatment occurs, such glass gets pseudo-equilibrated
(vertical shift of its glassy state: horizontal dashed line) and such a process is called thermal annealing.
The DTA/DSC peaks responsible for glass crystallization (exotherms bottom left) can be of two-fold
character (bottom right) given by the simultaneous and/or consequent amalgamation of elementary
processes involved in either the nucleation-and-growth (JMAYK) or the normal-grain-growth (ANG)
kinetics
temperature Tcr (exothermal maximum) and the glass transition temperature Tg.
Various examples reveal that this difference Tcr – Tg varies repeatedly with compo-
sition reaching its maximum value in a composition range which appears to provide
best glasses. In order to make possible comparisons with glasses showing different
Tg some authors weighted this difference Tcr Tg by the reciprocal value of Tg
leading thus the dimensionless factor (Tcr Tg)/Tg. Even a more sensitive interre-
lation to the glass formation peculiarities can be found on basis of Hrubý coeffi-
cient, beforehand developed mostly for chalcogenide systems [38], which,
however, is typically available only upon physical preparation of a given type of
glass: KH ¼ (Tcr Tg)/(Tm Tcr), where Tcr is the crystallization temperature and
Tm is the melting temperature. This criterion was thoroughly analysed [39–41]
having almost the same meaning as the difference (Tcr – Tg) alone varying,
however, more rapidly when crystallization peak is shifted and taking into account
melting temperature, which may not be too significant advantage as Tg and Tm are
usually correlated. In order to make the criterion more sensitive, Poulain [42] took
into consideration the width of a DTA/DSC peak, i.e., the difference between the
onset of crystallization, Tx and its maximal value, Tcr, accounting, among other
features, that more stabile glasses exhibit broader isotherms and thus a larger
crystallization time and therefore a smaller crystallization rate. The new criterion
(Tcr Tx)·(Tcr Tg)/Tg owns units of [K] but able to be encoded dimensionless if
weighted by Tg2. It is clear that the evaluation move a step forward to further
sophistication providing more refined criteria for the use of DTA/DSC traces
toward the resolution of glass-formation region, which is the subject of recent
analysis [31, 35, 45–48].
It is worth noting, however, that the kind of crystallization kinetics may essen-
tially change the curve shape and thus its testifying character [43, 44]. For example,
see the differential scanning calorimetry (DSC) curves obtained for two Fe-based
metallic alloys of comparable composition and which are depicted for portrayal in
Fig. 4.1 (right column, bottom). The quenched alloy (Fe75Si15B10, with relative
atomic composition at.%) was produce as the fully amorphous ribbons and exam-
ined twofold: as-quenched and isothermally annealed, indicating a sharper (so called
‘Johnson–Mehl–Avrami–Yerofeev–Kolmogorov’ JMAYK-type of nucleation-
growth) crystallization curve [1, 43], which upon annealing shifts the peak position
(as depicted in Fig. 4.1: right column, bottom). For the analogous (but now already
nanocrystalline) ribbon of the comparable composition (Fe74Cu1Nb3Si13B9 at.%
again – notice a difference in a small contribution of Cu and Nb), a broader DSC
peak is obtained (indicating thus a different, so-called ‘Atkinson-normal-growth’
ANG-type crystallization kinetics), as depicted in Fig. 4.1 (bottom right), associated
with a nanocrystalline grain-structure formation [49] (often called FINEMET-type
alloys), which thermal annealing restrains that changes in the peak size, only.
Various connotations and alternative forms of various reduced quantities were
analysed in detail by Šesták [5, 43]. Several models and limitations towards clarifica-
tion of various features of vitrification were extensively described [25, 26, 45–49], just
mentioning Parthasarathy et al. [50], who presented glass transition as a transition
from ergodic to nonergodic behaviour and discussed the meaning of residual entropy.
4.6 Practical Aspects of Freeze-In Process Mostly Applied

to Metallic Alloys
For a general material outlook there subsists a widespread acquaintance with the
measurable reality that near the melting temperature, Tm, the melts of most ready-
to-crystallize solids possess viscosities around 0.1 Pa·s (1 P), while, for comparison,
the anomalous water has that of mere 103 Pa·s (1 cP) [7]. It is worth to remark that
metallic glasses do not show this characteristic reduction on viscosity; their melts
remain very fluid, which requests the application of extremely high quenching rates
(> 106 Ks1) in order to ever produce a noncrystalline solid. However, for the alloy
melt compositions in the neighbourhood of deep eutectics, such as 80% of metals
(Fe, Ni, Co, Mo, Cu, Cr) combined with 20% of glass-forming metalloids (B, Si, P,
C, Ge) the viscosities stand for a moderate melt quenching in order to produce
technologically beneficial glasses (often in quest for specific magnetic properties),
but a clear glass transition is seldom observed.
Increased quenching rates can diminish the clustering size for nano-crystals,
while increasing the chemical inhomogeneity, super-saturation and ease the forma-
tion of glassy state, which is usually achievable in such systems. The components
should possess reciprocal low solubility, the highest difference between their
melting points (of alloy and the pure components), a suitable ratio between their
atomic radii and also strong mutual interactions. An empirical relation in the form
of a power law holds for the dependence of a suitable characteristic distance (d) of
clustered dendrites on the local solidification time, t, or on the average cooling rate,
f, i.e., d ¼ afn ¼ a0 t n, where a, a0 and n are characteristic parameters and
d might well be taken as the initial side branch spacing of the dendrites [1, 43,
51–53]. The local conditions of solidification to form glasses by melt vitrification
gives up only its specific heat, whereas coupled crystallization is accompanied by
additional release of the heat of crystallization.
In order to reach a sufficiently high quenching rate, it is mandatory that the heat
transfer coefficient (at the boundary between the melt and the cooling substrate)
ought to be high enough, and the cooled melt layer sufficiently thin, so that the heat
can be adequately removed from the whole volume of the sample away to the
coolant substrate in a sufficiently short time. Therefore, the most suitable substrates
are those metals possessing higher values for the heat capacity, thermal conductiv-
ity, and surface heat transfer coefficient (often reduced in practice due to the
oxidation layer over most metal surfaces). The cooling rate is essentially influenced
by the heat transfer coefficient (l), by the thickness of cooled sample (w), and
relatively less, by its actual temperature. At the condition of ideal cooling, where
we assume infinitely high coefficient of heat transfer, the cooling rate is propor-
tional to 1/w2 while for Newtonian cooling controlled by real phase boundary,
f correlates with 1/w, only. In practice, we may adopt the power relation f ~ 1/wn
(where 1 n 2 is a experimentally determined exponent). For illustration we may
present the example of cooling, which is close to ideal, with the proportionality
coefficient, l ¼ 104 J m2 K1 s1, frequently exhibited for several real materials.
We can guess the minimum glass-forming quenching rates of 102, 106 and 1010
Ks1 for a critical sample thickness of 10, 5 102 and 103 mm, respectively.
The last value is very small indeed, hardly attainable even by intensive surface
laser glazing, which works with very thin layers and assures intimate contact of the
in situ melt with the entire surface of the solid coolant support [53]. It, however, lies
within the possible quenching rates assumed for vapour/gas deposition on a solid
surface, which can attain values as high as about 1010 Ks1.
Successful mastering the technology of forced cooling is long time known in
metallurgy where the meaning ‘rapid’ can be taken to imply a short-time interval
between initiation and completion of solidification with respect of propagation of
the advancing solidification front [53, 54]. It occurs either directly, as a result of
coupling between external heat extraction and the transport of latent and specific
heat required to advance the solidification front; or indirectly, during the recales-
cence that follows nucleation of solidification at large undercoolings. Experimental
evidence can help to compare various cooling rates approximately, estimated for
quenching of the melt of silicates down from the temperature of about 1,200 C,
which can achieve as much as 104 Ks1 when applying either the melt pressing
between two moving metallic surfaces (Fig. 4.2), which forms a ribbon with the
thickness of about 0.2 mm, or the melt crumbling to drops of about 0.5 mm in
diameter and their centrifugation and splashing against metallic walls. Pouring a
fibber into a water bath (with a diameter less than 0.5 mm) decreases the cooling
rate by more than one order of magnitude (to about 103 Ks1) and that would be
similar to the helium fast-flow cooling of thin layers or wires. When dropping
droplets of melt (~3 mm in diameter) into oil, a further decrease of cooling rate is
experienced, to about 102–103 Ks1, while melt-bulk self-cooling slows down the
Fig. 4.2 Some fast-quenching devices formerly used at the Institute of Physics. Left: a modified
twin-roller quenching device, comprising a thin metallic ribbon belt; the melt is poured and
squeezed between the belt and the opposing drum. This adjustment helps to assure prolonged
contact of the quenched melt with the belt’s coolant surface, thus avoiding supplementary
crystallization of the glass once it leaves the contact line between the two opposing revolving
drums. Middle: assembly for splat quenching; the melt is poured and spreads over the bottom
surface just before being quickly squeezed under the falling slanted copper plate. Right: device for
the ‘single roll technique’ used for the preparation of metallic ribbons [49]; the melt is continu-
ously poured and casted over the coolant rotating drum
cooling rate to the order of a few Ks1. Any cooling in liquid media is often
ineffective, due to the immediate creation of gaseous envelop upon immersing,
which obstructs the heat exchange (despite the coolant low temperature – often
liquid nitrogen).
Most common is the so called ‘twin roll technique’, forming the basis for the
continuous production of metallic glass ribbons with homogeneous thickness and
compositions, comprising as well smooth surfaces on either side of the ribbon.
A relatively short time of effective cooling at the contact line of the rolling wells
often causes the temperature of the departing (cooled) ribbons to remain high
enough to enable re-crystallization processes to evolve, or otherwise promotes
undesirable relaxation. That, together with other disadvantages, such as the difficult
synchronization of the outlet velocity of the melt with the tangential speed of both
wheels (to about 15–30 ms1), steered preference to the practical exploitation of
the single wheel quenching. These difficulties were, however, successfully counter-
acted by a specially designed set-up of the so-called continuous belt-running
method, which was developed in the laboratory of the Institute of Physics, as
shown in Fig. 4.2.
Of an upmost technological interest is the still lacking proper understanding
of the balance between thermal stability against micro-crystallization and nano-
crystallization for metallic glasses [5, 43]. For instance, soft-magnetic properties of
Fe-based ferromagnetic amorphous alloys might be significantly improved, or even
fine-tuned to special requirements, by a properly heat treatment schedule (encom-
passing a tuned crystallization process), since such properties are known to depend
strongly on the nano-crystalline structure. Therefore, the investigation of the
complexity of crystallization processes occurring in metallic glasses is important
to better understand the mechanisms involved when trying to produce designed
micro- and nano-structures aimed to enhance the required magnetic properties.
Among metallic glasses, the Fe–Si–B-based alloys produced by melt-spun tech-
nique attracted substantial recent investigation owing to their excellent soft mag-
netic properties (e.g. high magnetic permeability). These are capable to be modified
by properly chosen annealing schedules, so that they can be optimized aiming a
number of technological applications, as their inclusion in components for mag-
netic sensors or in information handling devices.
For example, the above mentioned Fe75Si15B10 alloy prepared by single roll
quenching exhibits a rather understandable process of crystallization when two
exothermic interconnected contributions are attributed to the crystallisation of
micro-crystalline a-Fe(Si), Fe3Si and self-possessed composite (the inner Fe3B
core with a a-Fe(Si) envelope). Further temperature increase is followed by the
transformation of metastable boride (Fe3B) to more stable one (Fe2B) and finally to a
a-Fe [55, 56]. When such a primary composition is adjusted under comparable
quenching by Cu and Nd melt doping, a novel internal order appears what makes
difficult to distinguish between non- and nano-crystalline states. The previous
thermally activated crystallization process is thus converted into a more multiface-
ted make-up mainly controlled by the particles’ nano-grain-growth and their inter-
face properties enabling thus to produce more specific magnetic behaviour.
Acknowledgements The study was supported by the following scientific foundations: GAČR:
P204/11/0964, MŠMT: 1M 06031 and MPO: FR-T11/335.
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Chapter 5
Basic Role of Thermal Analysis
in Polymer Physics
Adam L. Danch
5.1 Introduction: Misunderstanding on Thermal Analysis
‘Works in the field of calorimetry were very appreciated in the physics of the
nineteenth century but for decades are not a part of physics and belong to the
engineering science. . .’ [1], this sentence is the most nonsensical one which has
been ever written about calorimetry. One can easy find that although calorimetry
is a somewhat ‘primitive’ experimental technique, it, however, is the one which
does not disturb a sample physical state during the preparation process that is
necessary in polymer physics. The more complicated measurement apparatus, the
more the system under investigation is disturbed. Moreover, one can easy show
that there is a set of experimental techniques of thermal analysis (TA), which, if
applied correctly, give us a comprehensive description of the studied system
under study. There are only two questions: which methods of TA and how they
should be used. Certainly, it is not a problem for an experienced experimentalist
who understands the basis of thermodynamics and who is able to apply the basic
rules of physics in practice. It is true that some knowledge about the technical
aspects of the instrument construction is required. It means that we should hardly
work in our laboratories in order to improve our knowledge about the techniques
used. Some incidental experiment, performed by technicians, is not sufficient for
so called ‘theoreticians’ who try to involve in experimental comprehension. We
will not improve any theory if we do not understand experiments and, likewise,
we are unable to interpret measured parameters. There is no sense to ‘produce’
theories if they are not applicable, if they do not reflect reality. We also know that
it is not easy to find an adequate theory which is confirmed totally by an experi-
ment, especially, if we take into account ‘many-body systems’. Physics is not able
to describe completely (and without approximations) systems which include more
A.L. Danch (*)

Research and Development Center, STOMIX, 790 65 Žulová, Czech Republic

78 A.L. Danch
than three bodies. Therefore any theory or formula describing a polymeric system
will be only a more or less good approximation reflecting a real situation occurred
during an experiment.
In this chapter, it will be emphasised that only those methods of TA are useful
in the case of polymer physics, which are applied properly. It is high time we
understood thermal analysis as any experimental technique which gives information
about physical parameter with temperature changing. The key aspect of the chapter
is the relation between supermolecular structure and physical parameters of the
polymeric system. Also, structural heterogeneity of the amorphous phase in semi-
crystalline and nano-crystalline systems (the three-phase model) will be discussed
and new interpretation of the pretty old experimental data obtained for poly
(4-methyl-1-pentene) (PMP), as an example of TA proper using, will be presented.
Moreover, two very important (if not the most important) physical phenomena:
glass transition and a relaxation (structural relaxation) will be discussed on the
molecular level using new definition and new formula. Precise carrying out of the
calorimetric measurements and the proper interpretation of the calorimetric results
are the clue to the riddle of the both physical phenomena. The chapter shows how
the methods of TA can give a successful answer toward the fundamental questions
of polymer physics. Unfortunately, here, the potential reader attention will be
restricted to the chosen experimental methods only, however, the methods are
complementary.
5.2 Applicability of the Chosen Methods
5.2.1 Calorimetry
‘...Calorimetry means the measurements of heat...’ [2]. We may possibly classify

the calorimeters according to various criteria. Owing to the fact that there are a
large number of available calorimeters for the scientific, engineering or techno-
logical applications, one can find many different classifications in literature [2–4].
The most important feature of the instrument from the physics point of view
seems to be the most precise determination of heat effects or a phase situation of
studied object in a quantitative manner in order to compare the experimental
results with theoretical predictions. Basically, two types of DSCs are widely used
for polymers study: heat-flux DSC and power-compensation DSC. The principle
of the first measurement system is similar to that of DTA; instead DT differences
the apparatus is calibrated in terms of heat fluxes and the mathematical descrip-
tion remains equal to that used for DTA [4]. In order not to mislead both types, the
heat-flux DSC is named DTA in the following text. Both DTA and DSC are the
most generally applicable of all thermal analysis methods and it is not a purpose
of this chapter to discuss which one is better and why. It is worth noting, however,
5 Basic Role of Thermal Analysis in Polymer Physics 79
that only a proper application of both instruments done by a well educated and
experienced researcher exhibits the desired differences between them [4]. In other
case the ‘myths and legends’, advocated by some groups, are repeated credu-
lously. There are numerous problems in polymer physics which still require
further investigation. Most of them are strictly related to the proper using of
calorimetry which is the only one technique giving evidences on thermodynamics
of the polymeric systems.
The DSC/DTA curve may show an exothermic or endothermic peak which are
characterised by: position (i.e., start, end, extrapolated onset and peak tempera-
tures); size (related to the amount of material and energy of the reaction or the
phase transition); shape (which can be related to the kinetics of the process) [4].
The other feature of the curves is their run, especially, the jump reflecting the step
transition occurred in the studied system. The proper result analysis requires the
knowledge of the base line for the sample that is ignored very often in many
publications. Frequently, physicists and chemists, who are not strictly related to
TA business, treat the curves as a supplement and as a ‘nice picture’. They apply
mathematical tricks for the curve smoothing losing a lot of information about the
investigated system often employing the luxury of sophisticated TA instruments
capable to execute it alone. Moreover the second heating run is also taken into
consideration. The reason is the only one: the curve of the second run looks ‘nicer’
as compared with the curve of the first run. Such a sample treatment makes that we
obtain information about two various systems. The first run informs us about a
thermal history of the polymeric sample before the heating run. The second run,
which is always done after the cooling run is performed with the some cooling
rate, gives merely information about the sample phase situation occurred during
the specific cooling run. Nothing is wrong with this methodology when investi-
gators have knowledge about the difference between the first and the second runs.
Unfortunately, we can easy find in vast literature a lot of examples when the
investigators compare the results obtained by various techniques of TA studying
samples of different thermal histories. The results obtained for polyethylene (PE)
are presented as an example of various sample treatment, see Fig. 5.1 [5] (samples
were thermally modified). We can see that although all of them were prepared
from the same piece of polyethylene of low density, each of them exhibited
different thermal behaviour, it means different phase situation. It is especially
seen in the temperature range of the sample melting. This example shows that
there is no sense to compare results obtained for any polymeric samples if their
thermal histories differ. Therefore we should not say about thermodynamic para-
meters of polymer but we should say about thermodynamic parameters of the
polymeric system with some thermal history. Any comparison between our results
and the results presented in the databases makes no sense if the thermal history of
the sample is not precisely describe. Although DSC (DTA) seems to be a suitable
method for the quick and cheap structure analysis, we face one serious problem. It
is a question of material homogeneity and whether the results obtained for the
small part of the material can be extended on the whole final product. However,
80 A.L. Danch
Fig. 5.1 DSC traces of samples cut out from as produced (PE100p), drawn (PE(c/D)100p) and
electron irradiated (PE(c/E)100p) materials annealed at 373 K over 1 h: PE- commercial product;
PE(Ca)100 composite material annealed at 373 K over 1 h
this problem can be resolved by testing several pieces cut out from different part
of the same product. It is possible if we take into account that the weight of one
piece can be less than 1 mg for a high quality apparatus. It must be emphasised
that we do not describe the supermolecular structure of the polymeric system in
this case, at all. For this, DSC is not proper, as everyone has been able to easy find
out. We describe the relative changes of the structure of the PE products based on
the changes of the thermodynamic parameter and the general knowledge on the
possible PE morphology. The morphology description by means of DSC is
speculative as much as every description done for other experimental technique.
However, for the property description of plastic commercial products, we propose
to use very simple and cheap method (it is not time consuming), DSC or DTA,
against very expensive one. In conclusion, we should consider the influence of
some techniques on the obtained results at last [5].
Owing to the fact mentioned above, we usually obtained a set of glass transition
temperatures (Tg), specific heat changes at Tg (DCp(Tg)) or melting enthalpies
(DHm) for one polymer which formed various phase systems from the physical
point of view, where one Tg, one DCp(Tg) and one DHm reveal only the feature of one
thermodynamic system. The situation is more complicated if we take into account
the composites. A small amount of additive may perturb the polymeric system
drastically. Someone can give the question: ‘What is the sense to apply DSC/DTA
if the results are not univocal?’. DSC is one of the most sensitive methods which is
able to detect even small changes occurred in the investigated system and does not
disturb it. When we use DSC/DTA, thermal history of the sample should be kept in
mind. There are kinetic and thermodynamic contributions to the heat capacity value
in the transition range due to the fact that below Tg, the glass is trapped kinetically in
one thermodynamic metastable state and above Tg, the supercooled liquid may
explore all the configurations at equilibrium. Consequently, the heat capacity,
entropy (its temperature change is proportional to the measured DCp(Tg) value)
and any other thermodynamic quantity are dependent on the thermal history of the
system. Hence, the heat capacity posses a special importance because it is the
thermodynamic measure of temperature-induced structural changes in liquid [6].
5.2.2 Thermogravimetry
Thermogravimetry (TG) is a well-known thermoanalytical technique [4] in polymer

research. The mass of a material is continuously registered as a function of time or
temperature. Owing to the fact that polymers do not evaporate, the change of mass
provides information about low-mass molecular substances removal that may be
related to either the thermal degradation of the sample or some substance (solvent,
catalyst, initiator, monomer, etc.) evaporation. Not only the component variety but
also the structure heterogeneity can be detected by means of TG [7, 8]. Although the
material is homogenous from the chemical point of view, ‘different’ kind of mole-
cules can be found [9–11]. It is a result of physical heterogeneity, it means, the
variety of supermolecular structure of the studied system. The structure of the
polymeric matrix, which some solvent molecules are occluded in, influenced
the diffusion process of the molecules in such a manner that the boiling temperature
of solvent might be shifted towards higher temperature. TG is another one method of
TA which is able to study phase situation of the polymeric sample. This simple
technique may indirectly reveal the supermolecular structure complexity as well as
the more advanced one, which very often requires special sample treatment. The
ranges of the mass change are precisely determined from the first derivative of TG
signals (DTG). A simple fitting procedure (the Gaussian peaks) was proposed for the
DTG curve interpretation in order to find the mass loss occurred in each of the range
for studied PMP samples. The typical TG and DTG curves are presented in Fig. 5.2.
Although the TG signal reflects one step mass loss between 50 C and 250 C, the
DTG curve exhibits three processes distinctly [11].
Owing to the fact that two fractions of the amorphous phase of different
morphologies and one crystalline phase coexist in one polymeric system, we can
attribute the processes to the removal of the solvent occluded in each of the
morphologically different areas. This untraditional using of TG led to the descrip-
tion of the supermolecular structures of the polymeric systems. The experimental
results were used in a computer simulation that gave quite good agreement with an
analytical equation which was obtained from theory [12].
82 A.L. Danch
Fig. 5.2 A chosen example of the - - - – TG and ○ – DTG curves obtained for the studied
membranes. The dotted lines (Gaussian curves obtained from the fitting procedure of the DTG
signal) represent the amounts of the solvent occluded in different areas of the membrane; the solid
line is a fitting curve
5.2.3 Dilatometry and Positron Annihilation Lifetime

Spectroscopy
It is well known that every structural change is reflected in measurements of the

adequate physical parameters. One can easy find that if we measure specific
(dilatometry, DIL) or free (positron annihilation lifetime spectroscopy, PALS)
volume, we are able to estimate the glass transition temperature, Tg. The model
relationship between free (VF), occupied (V0) and specific (VS) volumes has been
presented/discussed in handbooks [13, 14] and papers [15, 16]. It is commonly
accepted that all of the volumes should increase with rising temperature. The model
relationship is presented in Fig. 5.3.
It is very difficult, due to strong anisotropy of polymeric systems, to perform
volumetric investigations. Moreover every technique requires some simplicity for
the evaluation of the parameters. PALS assumes the spherical shape of the cavities,
unoccupied places by the matter, and that the intensity of the measured relative
intensity of the longest lived component of positron lifetimes is proportional to the
number of the cavities [17]. In this way, indirectly, we receive information about a
free volume of the system. The volume increases with temperature rising, changing
a slope of the line representing the temperature function, VF! f(T). A similar
situation is in the case of the specific volume evaluated from dilatometric measure-
ments. However in this case we conclude indirectly about the thermal properties of
V
VS
VF
0 VO
VS
0
VO
I II
Tg T
Fig. 5.3 A general scheme of relation between VS, V0 and VF in two temperature regions, below
(I) and above (II) Tg
Fig. 5.4 Relative changes of the parameters obtained from PALS (left scale) and DIL (right
scale). The relative units, in both cases, are applied in order to better show the parameter changes
for PALS (R – diameter of the average cavity) and DIL (l – sample elongation). The obtained data
were scaled at 100 K for the better results comparison. It means that the relative values are zero for
both data at 100 K
the studied system only base on one dimensional test. The simplicities taken in the
both methods make the problem in data interpretation. It is very difficult to secure
the same sample orientation for the both techniques. Lack of the same orientation
may lead to the false conclusions. The selected results obtained from PALS and
DIL are presented in Fig. 5.4.
84 A.L. Danch
One can find more detailed description of our study in literature [17–19].
However it is worth noticing here that the effect of the cavities joining not only in
the glass transition zone takes place, when the cooperative motions occur, but also
below Tg the number of the cavities changes. It means that the free volume seems to
play a significant role for local relaxation, too. Different slopes of the DIL curve after
the b and g relaxations would mean that this technique is not only sensitive to
structural relaxation but also the local relaxations influence the thermal expansion
coefficient. It was found that for the adequate comparison of the absolute values of
the free and specific volumes new model giving the number of cavities should be
applied [18]. Moreover the comprehensive investigation ought to be performed with
using the samples prepared under the same condition. Especially, one must be
careful when the comparison between DSC and other techniques is done [5].
5.2.4 Dynamic Mechanical Thermal Analysis
Frequency and temperature dependent dynamic mechanical thermal analysis

(DMTA) is very important because of complexity of the relaxations in polymeric
systems. Although the physical basis of mechanical and dielectrical (DETA)
spectroscopy is different, the both thermal methods give direct information about
molecular fluidity and indirect information about a supermolecular structure
[20–23]. It must be emphasised that one must be careful in result interpretation
because some relaxations are stronger dielectrically than mechanically. Moreover
in many cases some of them cannot be observed by one of the techniques. It is
especially important for semi-crystalline polymers where a local dipole moment is
rather weak or does not exist. DETA is a ‘blind’ method then, e.g. for symmetrical
polyethylene (PE) chains where we are not able to study pure PE but only some
modification of PE [20, 21]. Unfortunately the modification might change the
supermolecular structure which, in many cases, differs from the structures of the
samples investigated by other methods. Therefore DMTA seems to be more useful
technique when we want to compare results of different thermal methods. Figure 5.5
presents the results obtained for different semi-crystalline polymers exhibiting two
a relaxations (ag and ac, [23]). Four samples prepared from four different polymers
PMP-poly(4-methyl-1-pentene), PA6- polyamide 6, LDPE- polyethylene of low
density, PVDF- poly(vinyl diflouride) exhibit various dependence of the ac relaxa-
tion on the degree of sample crystallinity.
5.3 Supermolecular Structure of Semi-Crystalline Polymers
The methods presented in Sect. 5.2 should be completed by another one very
important method, i.e. X-ray scattering, small (SAXS) or wide (WAXS) angle
X-ray scattering. It would not be possible to perform any structural study without
this method. Unfortunately, very often, it is impossible to prepare the sample exactly
Fig. 5.5 Tangent delta (tg ¼ E00 /E0 ) as a function of scaled temperature. The scaling was done to
the temperature of the ag relaxation (T[ag]) for the better results comparison
in the same way for WAXS/SAXS and other methods of thermal analysis, especially
like for DMTA/DETA or DIL. Therefore this method is only used in a restricted way
in a complementary study for polymer. X-ray scattering was applied by us in the
cases when the sample could be prepared at least in the same way as a one for
DMTA/DETA and PALS/DIL. As was mentioned above, DSC/DTA and TG can be
used always that makes them very attractive for experimentator. As we know, only a
small piece of sample prepared for other methods must be used. The complementary
methods of thermal analysis and comprehensive results gave a general picture of
supermolecular structure of semi-crystalline polymers. The structure is presented in
a schematic way in Fig. 5.6. The supermolecular structure of semi-crystalline
polymers can be described as a system of various phases (amorphous and crystalline)
interlocked by chain molecules which traverse the phases. It means that some part of
the chain is located in the amorphous region while the other part builds the crystal-
line domains [24]. It was shown; the domains of long-range order distinctly influ-
ence the arrangement of the chains within the amorphous regions [25, 26]. It resulted
in the appearance of two amorphous fractions in one polymeric specimen. The
fractions were named: ‘real’ and ‘ordered’ amorphous phases, RAP and OAP,
respectively [27]. The co-existence of the amorphous and crystalline phases resulted
in different properties of the ‘real’ and ‘ordered’ amorphous phases. It was shown
that the ‘ordered’ amorphous phase could be treated as a ‘fingerprint’ of the possible
crystallisation, when the crystallisation process is not completed due to fast cooling
regime. The experimental evidences showed that two fractions of the amorphous
phase were created in one polymeric material that is schematically presented in
Fig. 5.6. There are two possible scenarios of the morphology depended on the degree
86 A.L. Danch
Fig. 5.6 Phase situation taking place for semi-crystalline polymers with a different degree of
crystallisation
Fig. 5.7 The stages of the crystallites formation in terms of the polymer concentration in the
solution. Squares, rectangles and triangles represent the crystal unit-cells, OAP and RAP,
respectively. Dots mean that this area is supposed to contain the molecules of the solvent
of crystallinity of the polymeric sample. The left morphology is characteristic for

low crystallinity whereas the right one can be found in highly crystallised polymers.
The role of the crystal-amorphous regions was already discussed in 1962 [25]. The
interphase is necessary for the dissipation of the order existing on the crystal surface
because the long chains must traverse the ordered and disordered regions many
times creating some kind of network composed of crystalline, amorphous and
intermediate regions. Spectacular presentation of the interphase existence in real
systems was done for dielectric spectroscopy applied to liquids [28] and polar
oligomeric systems (polymers with a low molecular mass) [29]. The studied systems
were prepared as a glass (there was no sign of crystallites) in nanoporous media,
hence, biphasic nature of the supermolecular structures of the oligomers (only ‘real’
and ‘ordered’ fractions) could not be a result of the influence of the arrangement of
the chains built the crystal phase on the amorphous regions. However the similar
situation was found by us and described in the paper concerning formation of PMP
membranes [12]. We showed experimentally (using the methods of TA) and theo-
retically (crystallisation and lamellae aggregation processes) how the membrane
morphology varies with the degree of crystallinity (see Fig. 5.7). Two main topics
were addressed: a three-phase model (‘real’ and ‘ordered’ amorphous phases, and a
crystal phase), and factors affecting the supermolecular structure of the membranes.
Special attention was paid to lamellae perfection in the solution of different polymer
concentrations and its relation to the membrane morphology. The stages of the
crystallisation were proposed mainly in terms of the role played by the solvent
molecules.
5.4 Structural Relaxations and Glass Transition Temperatures
Semi-crystalline polymers exhibit the morphology of lamellar crystals located in an

amorphous matrix. The matrix is not homogenous in a morphological sense.
Although some fraction of the chains attains the mobility level of the liquid-
like state as temperature is increased above Tg, it has been shown, that a portion of
the amorphous phase (the interphase) remains still rigid above Tg [24, 27, 30, 31].
The crystalline phase reduces the segmental mobility of the chains located in the
interphase. The main consequence of this is that the glass transition of the interphase
is extended towards the high temperature and the second a relaxation appears. The
correlation between different results obtained by various techniques of TA is pre-
sented in Fig. 5.8. Now, Tg is defined as a temperature at which 50% of the mers
(segments) take part in the collective motion that is show schematically in the right
side of the picture. Such a definition correlates with the results obtained by mechan-
ical and/or dielectrical spectroscopy. The relation between the local (b) and the
structural (a) relaxations is shown in the diagram of relaxation frequencies as a
function of temperature (log f!f(T)). Also, the temperatures in this diagram corre-
late with the temperatures at which the adequate number of the mers is activated to
the collective motions that further is revealed as a step transition in the DSC curve. It
is worth noticing that the shape of the DSC curve is well reproduced by the new
formula discussed in our earlier paper [16, 30]. The formula is an alternative for
the formulae which readers can find in literature. It is the most important that the
parameters included in the formula possess physical interpretation and can be
evaluated by independent measurements. This empirical relationship combines
the Arrhenius and Vogel–Fulcher equations for the temperature dependence of the
relaxation time. It must be emphasised that the formula describes the dynamics of
one system, it means, the thermodynamic parameters, taken from the calorimetric
88 A.L. Danch
T4
TO~T1 T2 T3 = Tg
β relaxation α relaxation
T4 ~ 100 %
log f
T3 ~ 50 %
Temperature [a.u.]
1.0
T4
T2 ~ 15 %
nα / n1
0.5
T3 = TC = Tg(DSC)
T1 ~ 0 %
Temp.
T1 = TO(DMTA)
T2 = TO(DSC)
0.0
Temperature [a.u.]
Fig. 5.8 Comparison of various thermal methods: DMTA/DETA, DSC. For more detailed
description see [16, 30, 31]
study, must be exactly pointed out for the system which is the subject of the
mechanical or dielectric spectroscopy. The same must be true of the free volume
and the X-ray measurements. The new formula of the relaxation time exhibits the
existence of some correlation between thermodynamic and structural parameters.
Moreover, it distinguishes two fractions of the amorphous phase that gives better
description of polymer properties.
5.5 Concluding Remarks: ‘Myths and Legends’
It is very often called by some authors that PMP is unique due to its room-temperature
density of the amorphous phase exceeding that of the crystalline one. Among many
papers, these authors have cited the volume-temperature studies [32, 33]. It should be
mentioned that the densities of the PMP samples, prepared in highly specific and
different ways for various experimental methods, were determined either by the
capillary dilatometer or by the X-ray measurements of the lattice parameters. Reading
the original papers [32, 33], one can easy find that the conclusion concerning the PMP
unusual property was drown indirectly from the experimental data. Griffith et al.
determined the density of the pure amorphous sample, which was prepared under
some condition. It is commonly accepted now that the amorphous state, thus its
density and the thermodynamic parameters (e.g. Cp), strongly depend on thermal
sample treatment. It means that the densities of the pure amorphous and, especially,
the crystallised samples were not the properties of the amorphous and crystalline
phases of PMP, at all. Only the densities of some PMP samples were determined and
not the density of the polymer. One can suppose that various sample preparations,
however producing only the amorphous samples always, would have resulted in their
different densities. Very often in discussion, the density of the sample of 76%
crystallinity has been taken by some authors as a density of the crystalline phase. It
should be emphasised that the crystallinity in the original paper was obtained from the
density measurements taking the two-phase model for determination of the volume of
the crystalline phase. Griffith et al. showed only that the density of the PMP samples
was lower for the samples with higher crystallinity. However, this tendency was not
regular (see Table in original paper). Luck of the regularity in the density results might
be explained by the presence of the third phase: ‘ordered’ amorphous phase, OAP, and
the different ratio of both amorphous phases in the sample. It should be mentioned that
the three-phase model for polymer had been suggested, without experimental confir-
mation, in 1962 by Flory [25]. It was experimentally confirmed almost 20 years later
although the confirmation was not strictly observed by the structural study, performed
next 20 years later. Now, the usefulness of three-phase model is not disputed,
especially, that there are a lot of structural studies (NMR, X-ray) giving evidences
of the three-phase structure.
The second disputed problem concerning PMP is the high temperature relaxation
signed as the ac relaxation. Some authors have attributed this relaxation to the
motion of the chains within the crystalline phase. As a proof, the temperature
change of the lattice parameters, measured in X-ray study, is called. However,
other interpretation of this relaxation is given [23]. It was proposed that the ac
relaxation occurs due to the motion of the chains formed OAP and the second glass
transition at high temperature, related to this relaxation, was defined. Thus X-ray
study, presented by Ranby et al. [33], would give the proofs confirming the latter
idea. Let us assume that the three-phase model is correct for PMP supermolecular
structure. It was proposed [27], and recently showed [34], that the specific volume
of OAP exceeds the specific volume of RAP. Firstly, it would explain why the
density of the amorphous PMP samples exceeding that of the crystalline one, as was
discussed above. Secondly, the origin of the ac relaxation concerning the motion
within OAP would explain the thermal expansion of the lattice parameters. Taking
into account the difference in the activation of the large scale motion within RAP
and OAP, the change in the slope of the lattice expansion-temperature relationship
is understandable. The large scale motion of the chains (cooperative motion) is
activated above some characteristic temperature. Owing to the fact that the slope
change does not occur in the temperature range of the first glass transition (about
40 C), we can suppose that the crystallites are enclosed by OAP and not by RAP.
This would be a proof confirming the three-phase model importance for semi-
crystalline polymer.
90 A.L. Danch
References
1. Hołyst R (2007) The review report sent to Inst. Phys. of Silesian University (in Polish)
2. Mathot VBF (ed) (1994) Calorimetry and thermal analysis of polymers. Hanser, Munich
3. Zielenkiewicz W (2000) Pomiary efektów cieplnych (in Polish). Warszawska drukarnia
naukowa PAN, Warszawa
4. Šesták J (1982) Měřenı́ termofyzikálnı́ch vlastnostı́ pevných látek (in Czech). Academia,
Praha; (1984) Thermophysical Properties of Solids: their measurements and theoretical
thermal analysis. Elsevier, Amsterdam; (1988) Teoreticheskij termicheskij analyz (in Rus-
sian). Mir, Moskva
5. Danch A, Osoba W (2006) DSC monitoring of supermolecular structure damage of polyeth-
ylene products: academia and industry challenges. J Therm Anal Calorim 84:331–337
6. Danch A (2006) The glass transition-finite size effect. J Therm Anal Calorim 84:663–668
7. Saaoudi M, Chassaing E, Cherkaoui M, Ebntouhami M (2002) Hydrogen incorporation in
Ni–P films prepared by electroless deposition. J Appl Electrochem 32:1331–1336
8. Markovic N, Ginic-Markovic M, Dutta NK (2003) Mechanism of solvent entrapment within
the network scaffolding in organogels: thermodynamic and kinetic investigations. Polym Int
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9. Ngui MO, Mallapragada SK (1999) Mechanistic investigation of drying regimes during
solvent removal from poly(vinyl alcohol) film. J Appl Polym Sci 72:1913–1920
10. Janowska G, Rybiński P (2004) Thermal properties of swollen butadiene-acrylonitrile rubber
vulcanizates. J Therm Anal Calorim 78:839–847
11. Wolnik A, Borek J, Sułkowski WW, Żarska M, Zielińska-Danch W, Danch A (2007)
Thermogravimetric evidences of supermolecular structure variety of PMP membranes.
J Therm Anal Calorim 90:237–242
12. Kruszewska N, Danch A, Zielińska-Danch W, Wieczorek E, Sułkowski W, Gadomski A
(2009) Supermolecular structure formation of PMP membranes: theoretical argumentation in
terms of the experimental evidences. Mater Sci Eng B 163:105–113
13. van Krevlen DW (1990) Properties of polymers. Elsevier, Amsterdam
14. Ward IM (1971) Mechanical properties of solid polymers. Wiley, London
15. Richet P (2002) Enthalpy, volume and structural relaxation in glass-forming silicate melts.
16. Danch A (2003) On the influence of the supermolecular structure on structural relaxation in
the glass transition zone: free volume approach. Fibres Text East Eur 11:128–131
17. Danch A, Osoba W (2003) The temperature dependence of free volume in polymethylpentene
by positron annihilation. Radiat Phys Chem 68:445–447
18. Danch A, Osoba W (2006) Stability of supermolecular structure below Tg – a role of free and
specific volumes in local relaxations. J Therm Anal Calorim 84:79–83
19. Danch A, Osoba W, Wawryszczuk J (2007) Comparison of the influence of low temperature
and high pressure on the free volume in polymethylpentene. Radiat Phys Chem 76:150–152
20. McGrum NG, Read BE, Williams A (1967) Anelastic and dielectric effects in polymeric
solids. Wiley, London
21. Graff MS, Boyd RH (1994) A dielectric study of molecular relaxation in linear polyetylene.
Polymer 35:1797–1801
22. Danch A, Osoba W, Stelzer F (2003) On the alpha relaxation of the constrained amorphous
phase in poly(ethylene). Eur Polym J 39:2051–2058
23. Danch A (1998) Dynamic mechanical relaxation in the opaque and transparent PMP films.
J Therm Anal 54:151–159
24. Struik LC (1987) The mechanical and physical ageing of semicrystalline polymers: parts 1, 2,
3, 4. Polymer 28:1521–1533; (1987) 28:1534–1542; (1989) 30:799–814; (1989) 30: 815–830
25. Flory JP (1962) On the morphology of the crystalline state in polymers. J Am Chem Soc
84:2857–2867
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272:226–229
27. Danch A (2001) Effect of supermolecular structure changes on the glass transition of polymer.
28. Kremer F (2002) Dielectric spectroscopy – yesterday, today and tomorrow. J Non-Cryst
Solids 305:1–9
29. Schönhals A, Goering H, Schick C, Frick B, Zorn R (2005) Polymers in nanoconfinement.
J Non-Cryst Solids 351:2668–2677
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31. Danch A (2008) Some comments on nature of the structural relaxation and glass transition.
32. Griffith JH, Ranby BG (1960) Dilatometric measurements on poly(4-methyl-1-pentene) glass
and melt temperatures, crystallization rates, an unusual density behavior. J Polym Sci
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J 3Polym Sci 58:545–552
34. Dlubek G, Gupta AS, Pionteck J, Haessler R, Krause-Rehberg R, Kaspar H, Lochhaas KH
(2005) Glass transition and free volume in the mobile and rigid amorphous fractions of
semicrystalline PTFE: a positron lifetime and PVT study. Polymer 46:6075–6089
Chapter 6
Phases of Amorphous, Crystalline,
and Intermediate Order in Microphase
and Nanophase Systems
Bernhard Wunderlich
6.1 Solids, Liquids and Their Transitions
To describe matter, one can use two levels, the microscopic one, which requires
identification on a molecular scale, and the macroscopic one, which can make use
of the identification of the phase of the sample. The International Union of Pure and
Applied Chemistry, IUPAC, has provided a binding scientific definition of the
phase [1]. It is to be “an entity of a material system which is uniform in chemical
composition and physical state.”
Next, one should describe the state of the just defined phase [2]. For solids and
liquids, however, there seems to be no operational definition of the type suggested by
Bridgman [3]. Such would require a quantitative experiment, an operation, which can
answer the question whether a given phase is solid or liquid. The chosen experiment
should provide a simple yes or no result. Turning to the common meaning of the words
solid and liquid, one may turn to Meriam-Webster’s Collegiate Dictionary [4]. It
suggests a solid is “a substance that does not flow perceptibly under moderate stress,
has a definite capacity for resisting forces (as compression or tension) which tend to
deform it, and under ordinary conditions retains a definite size and shape.” A liquid, in
turn, is “a fluid (as water) that has no independent shape but has a definite volume and
does not expand indefinitely and that is only slightly compressible.” As scientific
definitions, these two statements are insufficient. Expressions like “. . . does not flow
perceptibly, . . . moderate stress, . . . definite capacity, . . . ordinary conditions, . . .
# US Government 2010. Created within the capacity of an US governmental employment

and therefore public domain. Published by Springer Netherlands.
B. Wunderlich (*)
The University of Tennessee, Knoxville, TN, USA
and
Rensselaer Polytechnic Institute, Troy, NY, USA

94 B. Wunderlich
Fig. 6.1 Today’s nine condensed phases of matter, their states and transitions. First suggested in
[7] and detailed in [5] and [6]
indefinitely, . . . slightly” are imprecise. To improve on these definitions, specific

limits need to be set.
When the molecular structure of matter was better understood, it became
common practice to link the solid state to the fully ordered crystal structure. It is
obvious, that the amorphous glass is also a solid, although its structure is that of a
liquid, i.e., structure alone cannot predict the solid or liquid nature of a phase. In
addition, over the last 150 years, a number of intermediate phases were discovered
[5, 6], the so-called mesophases. They are of intermediate order and also solidity or
fluidity. Figure 6.1 is an attempt to list the types of condensed phases [7]. In
addition, on the left side of the schematic, the solidity trends are indicated. The
further details in the figure are discussed in the bulk of the chapter.
The connections left and right of the phase boxes in Fig. 6.1 indicate the possible
transitions. The dictionary meaning of the word transition is a “passage from one
state, stage, subject, or place to another” [4]. In the present chapter, the two types of
transitions listed will be discussed, namely, the glass and ordering transitions.
Going from the liquid in Fig. 6.1 upward toward the crystal, the phases are listed
on the left as becoming “increasingly solid,” and the transitions describing the
changes to the upper solids are the glass transitions. This makes it reasonable to
choose the measurement of the glass transition temperature, Tg, as the operation to
define a solid. The glass transition, the crystal phase, and the ordering transitions are
discussed with their thermal behavior in the next six sections.
6.2 Phase Types, Distinguished by Their Sizes and Molecules

Lead to 57 Different Entities
Phases, as just defined, must be sufficiently large so that the inhomogeneity due to
the size of its constituent atoms is insignificant. Since atoms are smaller in diameter
than one nanometer, and the smallest phase that can be seen with the unaided eye is
6 Phases of Amorphous, Crystalline, and Intermediate Order in Microphase 95
bigger than 0.01 mm (¼ 10 mm ¼ 10,000 nm), the homogeneity is not endangered

by the molecular structure when working with ‘visible phases.’ To distinguish
phases of this size from smaller phases, to be discussed next, they will be called
‘macrophases.’ The thermal properties of the macrophases are represented by the
well-established thermodynamics, developed more than 100 years ago [8].
It already was recognized by early thermodynamicists that small phases may
have different properties than larger ones. It was proposed in Gibbs’ “theory of
capillarity [8]” that the “influence of surfaces of discontinuity upon the equilibrium
of heterogeneous masses” must be considered. Two observations can be clarified by
considering the effect of surfaces. One is the existence of ‘colloidal particles’ with
typical sizes of less than 1 mm. Today, phases of this size are called ‘microphases.’
Colloidal particles or droplets are kept in metastable dispersion by their surface
charge, which prohibits coagulation to a more stable, larger phase. The other
observation is a change in the overall thermodynamic quantities due to the surface
free energy. One can use the Gibbs–Thomson equation [9–11] to calculate the
lowering of the melting temperature, DTm, for known, small volumes, V, or in turn,
to calculate the surface free energy from the measured DTm:

DTm ¼ sTm A =ðDhf rVÞ; (6.1)
where s is the specific surface free energy; Tm, the bulk equilibrium melting
temperature; A, the surface area; Dhf, the specific heat of fusion (per gram); and
r, the mass density of the crystal. Equation 6.1 can easily be modified if more than
one specific surface free energy is found on a crystal, for different phase geome-
tries, and even for the presence of internal, non-equilibrium defects.
The lowering of the melting temperature due to microphase formation is of
particular importance for the understanding of semicrystalline macromolecules [2].
For a typical, 10 nm thick, laterally large, chain-folded lamella of a polyethylene
crystal, for example, DTm is 26 K [7]. In this case, only the two fold-surfaces of the
lamellae contribute significantly to the surface free energy. Clearly, when increas-
ing the lamellar thickness (¼ V/A) beyond that of the microphase dimension, let us
say to 10 mm (thicker than the micrometer limit of the microphase), the lowering of
the melting temperature, DTm, decreases to a negligible 0.026 K. Such phase is then
a ‘macrophase,’ practically unaffected in its thermal properties by the presence of
the surface.
In the last 20 years, it became customary to use the term ‘nanophase’ [12, 13] for
phases which approach a nanometer-size scale. For a long time, the development of
this terminology was not given an operational definition [14, 15]. Feynman when he
speculated about ‘very small phases,’ suggested in 1959 already that “on a small
scale we will get an enormously greater range of possible properties that substances
can have” [16]. This suggestion can be the basis for an operational definition.
In the field of flexible macromolecules (polymers), it is obvious that rather small,
disordered entities existed which are larger than typical crystal defects and smaller
than microphases. These defects were initially called ‘amorphous defects’ [7].
Ultimately, it became clear, that these amorphous defects behave like very small
96 B. Wunderlich
phases with different properties than the bulk-amorphous microphases. On hand of

many literature examples on phase separation of small and large molecules, an
operational definition was suggested which can distinguish nanophases from micro-
phases on the basis of its properties [14]: “In nanophases, the opposing surfaces of a
phase area are sufficiently close to interact.” While the microphase is also described
as a phase with a sufficiently large surface area to cause changes in the properties, it
can still be considered a bulk phase (with macrophase properties) enveloped by a
distinct surface layer.
The nanophase, in contrast to a microphase, has no remaining bulk phase. Its
properties change gradually from the outside to the center, without reaching the
plateau of the bulk phase observed in the microphase. The operation to distinguish a
nanophase from a microphase, thus, must involve the detection of the presence or
absence of bulk phase in their centers. An experiment most suited for this, is the
measurement of the glass transition temperature, Tg. The glass transition of a phase
is set by the properties around a ‘hole’ of perhaps 0.1–1.0 nm in diameter [17–19],
close to atomic dimensions.
Nanometer-sized structures were suggested in 1963 to account for certain
defects in semicrystalline fibers [20]. This structure was similar to the amorphous
defect proposed at the same time [7, 21]. Later it became clear these were nano-
phases.
In macromolecular nanophases the molecules are sufficiently long to cross the
phase boundary multiple times. Semicrystalline polymers are usually a globally
metastable aggregate of two or more phase types. Similarly, amphiphilic crystals, of
small, flexible molecules, synthesized out of two or more incompatible, chemically
different segments, can be considered as being molecularly coupled nanophases
[6, 14]. A crystal structure of alternating aliphatic and aromatic layers, for example,
was found for 4-n-octyloxybenzoic acid [22]. A number of such amphiphilic
crystals undergo separate solid–liquid phase transitions at different temperatures
in their different phase layers [5, 6].
To characterize a material one must know which of the phase or phases listed in
Fig. 6.1 are present and then specify their sizes and interconnections. In addition,
the ‘class of the molecules’ must be given. After the last class of molecules, the
flexible, linear macromolecules, had been recognized by Staudinger [23], it became
obvious, that there are three distinct classes of molecules, ‘small molecules,’
‘flexible macromolecules,’ and ‘rigid macromolecules’ [7, Vol. 3, pp. 4–5]. This
classification scheme is closely connected to the phase properties [24]. Rigid
macromolecules can only exist as solids. On liquefaction or evaporation, the strong
bonds defining the molecules are broken, destroying the integrity of the molecule.
Flexible macromolecules can be disordered without losing their integrity, so that for
many, liquid as well as solid states are possible (but no gaseous states). Small
molecules under proper conditions may exist in all three states, solid, liquid, and
gaseous. Examples of the three classes of molecules are found in all of the histori-
cally defined inorganic, organic, and biological molecules. It is now known that
none of these historically developed classes of molecules show unique character-
istics and, thus, do not help in the understanding of chemistry.
With the newly selected definitions, materials can now be identified as being
made up of three classes of molecules, three phase sizes, and ten phase types. Gases,
however, must be of small molecules, and because of the lack of self-sustaining
surfaces cannot be microphases or nanophases. Rigid macromolecules may not
become liquids or mesophases. Finally, mesophases may be coupled to specific
molecule types. This leaves 57 different possible condensed states in addition to the
gas [14].
Thermal analysis is the macroscopic tool to analyze these 57 condensed states to
be discussed next.
6.3 Measurement of Thermal Properties
With the description and classification of the molecule and phases, one can return to
Fig. 6.1 and consider the measurements that identify the properties listed on the
sides of the schematic. On the left, the changes when going from liquid to solid are
indicated. The thermal property of interest is the change in heat capacity, DCp
(at constant pressure, p, and composition, n), when becoming a solid at Tg. The heat
capacity, Cp, is equal to (∂H/∂T)p,n, where H is the enthalpy (¼ U + pV, the
internal energy, U, plus the product of pressure, p, and volume, V). The change in
H is equal to the measured ‘heat’ gained or lost by the system [1].
On the right of Fig. 6.1, the ordering transitions are indicated which have a more
abrupt change in enthalpy, H. This change is related to the change in entropy,
DS (¼ L/T), to be calculated for equilibrium transitions from the heat of transition,
DH, the latent heat, L [1].
To understand the experimental basis of Fig. 6.1, calorimetry, as the tool to
measure heat will be considered in this section and an interpretation in terms of
molecular structure and motion will be given thereafter. Today it is well known,
that ‘heat’ is a form of energy exchanged between systems [1] and has its micro-
scopic origin in molecular motion [2].
The measurement of unknown heat effects always involves its comparison to
known effects. The SI unit for energy, work and heat, is the joule (kg m2 s2) [25].
The most common calorimeters are the adiabatic calorimeter, differential scanning
calorimeter (DSC), temperature-modulated differential scanning calorimeter
(TMDSC) and quasi-isothermal, non-scanning version, TMDC. Classical, precision
adiabatic calorimetry starting with measurements at temperatures close to 0 K was
accomplished in the early twentieth century [26]. The total H is accessible by
measuring heat exchanges from 0 K to the temperature of interest. Increasingly
more automated calorimeters have been developed over the years [27–29].
Quantitative DSC and modulated calorimetry developed only in the second half
of the twentieth century. Since then, these more convenient techniques also have
reached considerable precision. An example of a calorimeter capable to perform
standard DSC as well as TMDSC and TMDC is shown in Fig. 6.2. The roots of
DSC are the qualitative cooling and heating curves of the eighteenth century [2].
98 B. Wunderlich
a b
Reference Constantan Sample
fastest q(t) on
K = 20 J / (Ks) Platform Body Platform
10
Temperature Increase (K)
modulation
<q> = 3.0 K / min = 7.26 K / min Chromel Area
AT = 1.0 K
(3) Tr
s qC T Detector
8 p = 60 s –1
ΔT =
K Ref.
s
ω = 0.105 rad s
AT = 1.155 K Smpl.
b
6
Ts Chromel
4 (5) Wire Tb
Tb Constantan
A Chromel
AΔ = TωC Wire
2 K
Wire
ΔT = Tb–Ts c
To AΔ
0 80 160 (7) mcp = K 1 + (τω)2
ATsω
Time (s)
Fig. 6.2 Differential calorimeter of type TA Instruments Q1000. (a) Graph of the change of
sample and body temperatures, Ts and Tb, during a heating scan as given by Eqs. 6.3 for DSC and
6.5 for TMDSC. (b) The measuring principle. The calorimeter assembly is placed in a tempera-
ture-controlled enclosure, filled with slow-flowing N2 gas free of turbulence, also kept at Tb.
(c) The TMDSC Eq. 6.7 for Cp (expressed by sample mass, m, in g, specific heat capacity, cp, in
J K1 g1, and the measured amplitudes A, in K at Ts, the temperature difference DT, ¼ Tr Ts,
the angular modulation frequency o, in rad s1, and the two calibration constants, K and t)
When inserting a sample into a bath of constant temperature, To, Newton’s law
allows to describe its measured temperature, T(t), as a function of time, t. The value
of T(t) exponentially approaches To:
dT=dt ¼ K ðTo T Þ: (6.2)
Over small temperature ranges, K is constant and accounts for the nature,
geometry, heat capacities, and thermal conductivities of sample and container.
The calorimeter in Fig. 6.2b can perform the modern version of such ‘Newton’s
Law’ measurement and then permits the extraction of the changes in H as a function
of temperature. The key to quantitative DSC is proper calibration and comparison
to a standard of known Cp, often sapphire (single crystals of Al2O3). The function of
the constant-temperature bath is taken over by the constantan body of temperature
Tb, changing linearly with temperature at the rate q ¼ dTb/dt. Figure 6.2a illustrates
that about 60 s into the measurement, steady state is reached, i.e., thereafter DT
changes parallel to the changes of Cp with temperature. The thin cylindrical walls
supporting the sample and reference platforms cause the major temperature lags of
the sample temperature, Ts, and reference temperature, Tr, relative to the constantan
body temperature, Tb.
As indicated in the figure, the sample (of typically 1–20 mg) is enclosed in a
sample pan (of high thermal conductivity, usually Al or Au). This configuration is
to keep the temperature gradient within the sample pan small (perhaps <0.5 K,
defining the error limit in temperature determination). The asymmetry of the plat-
forms must be established by calibration. Experience has taught, that extra time
spent on calibrations repays with increased precision. The heat capacity of sample
and pan, C (at Ts or time t) can then be extracted from Eq. 6.3 in Fig. 6.2a. By
performing DSC, i.e., also measuring the reference temperature, Tr, the Cp (¼ mcp)
of the sample can be obtained based on Eq. 6.3:
DT ¼ Tr Ts ¼ q mcp =K; (6.4)
where m is the sample mass and cp the specific heat capacity of the sample in J K1
g1.
The Newton’s law constant K needs a second calibration, namely the conversion
of the measured quantities (DT/q, in s) into Cp, in units J K1. This is done by
performing a separate run on a reference material of known Cp. This should be done
under identical conditions and with a similar magnitude of DT as the sample run.
Careful handling of the calorimeter and samples, carrying out the measurement and
calibrations, equalizing the pan weights, etc., are the main issues for a quantitative
DSC [2]. Unfortunately, qualitative runs, of value only for preliminary information,
still find their way into the literature. Under optimum conditions, accuracies in Cp
could be 1.0% or better. Data can easily be obtained from 100 K, using liquid N2
as a coolant, to temperatures above 1,000 K.
Standard DSC has been expanded in the last 15 years to TMDSC. Figure 6.2b
indicates that no new hardware is needed. The linear increase of Tb is now
modulated with a periodic change (commonly with an amplitude between 0.1 and
5.0 K) and a fixed period (usually between 10 and 500 s). The heating rate of
interest is the ‘underlying heating rate,’ < q>. In case the response of the calorim-
eter to the modulation is strictly linear, a sliding average over the time of one
modulation period yields the underlying quantities, indicated by the angular brack-
ets, < >. The TMDSC values of < q>, <Tr>, and < Ts > correspond to the
standard DSC values of q, Tr, and Ts. The dashed curve in Fig. 6.2a indicates that
the steady state of TMDSC is reached after 2 min, later than in the standard DSC
mode.
By subtraction of < T > from the instantaneous, modulated value of T, one can
extract the effect of modulation as a function of temperature (or time), usually being
called the ‘reversing temperature.’ Its analysis is done using a pseudo-isothermal
method since the underlying changes have been removed [30, 31]. The result is the
reversing heat capacity, C, indicated by the Eq. 6.5 of Fig. 6.2a. Changing, as
before, to a differential measurement with DT ¼ Tr Ts, the TMDSC equation
results:
mcp ¼ fAD =ðAT s oÞgK (6.6)
where o is the angular modulation frequency (in rad s1). If steady state and
linearity are preserved and the heat capacities computed from Eqs. 6.4 and 6.6
are identical, Cp is reversible. Complications arise in the transition regions, to be
discussed below. In the latter cases, the response is often non-linear. As long as
reversibility is not proven, the heat capacity by TMDSC must be called reversing
(and usually is time-dependent). The basic calibrations of TMDSC remain similar
100 B. Wunderlich
KΔT AΔ
(4) mcp = (6) mcp = K (7) K = K' 1+τ(m)2ω2
q ATsω
a b
1.25
Specific Heat Capacity (J K–1 g–1)
1.20
Polystyrene Polystyrene
DSC & TMDSC 1.15 TMDSC
1.10
1.05
TMDSC DSC
A = 1K 1.00 uncorrected cp (K' = K)
A = 2K corrected cp (τ = 3.2 s)
A = 3K 0.95
0 100 200 300 400 500 0 100 200 300 400 500
Period (s) Period (s)
Fig. 6.3 Comparison of DSC and TMDSC data [33]. The equations at the top correspond to the
standard DSC analysis, to the TMDSC analysis with K ¼ K’, and fitted to a constant t, as in
Eq. 6.7, suggested in Fig. 6.2c. For periods less than 10 s, t changes with frequency and mass, can,
however, still be calibrated by evaluating its change with o [34]
to that of the standard DSC, but gets more involved since the amplitude responses
are identical for positive and negative deviations, an effect which can be assessed
by considering the phase shift of the response [2, 32].
In order to correct for the frequency-dependence of K, an additional calibration
constant t is introduced in Fig. 6.2c by Eq. 6.7 [31, 33]. Figure 6.3 illustrates its
evaluation. In Fig. 6.3a, a comparison of heat capacity by DSC and TMDSC is
shown. In DSC, the measurement was made at constant q at the end of the indicated
time period and cp was calculated using Eq. 6.4. The reversing cp by TMDSC at the
indicated amplitudes of modulation was calculated with Eq. 6.6. As expected from
Fig. 6.2a, the standard DSC reaches steady state faster than the TMDSC. In
Fig. 6.3b, the TMDSC data for a 2.0 K modulation are extracted from Fig. 6.3a.
In addition, the corrections, as given in Fig. 6.3 by Eq. 6.7, are marked by the filled
squares. Periods as short as 10 s can generate acceptable data when properly
corrected. But even at much shorter periods, quantitative information can be gained
by calibration of t as a function of not only sample mass, but also frequency [34]. It
is important, that all calibration and measurement runs must be independently
corrected for frequency.
The quasi-isothermal mode, TMDC, is carried out at an underlying constant
temperature, i.e., the measurement is performed by modulation without scanning
(<q> ¼ 0,). The TMDC results are derived by similar procedures, as derived in
Figs. 6.2 and 6.3 [31] and can be extended to very long times to analyze the kinetics
of slow changes.
6.4 Interpretation of the Heat Capacity of Solids
In this section, an attempt will be made to link the macroscopically measured heat
capacity with its microscopic, molecular origin. The first success in this endeavor
was Einstein’s discussion of the possible vibrations in crystalline metals and salts
[35]. It was shown that the vibrations of each atom or ion are determined by the force
field of its 6–12 symmetrically placed neighbors. It was proposed then to approxi-
mate the force field with a spherical symmetry, giving each vibration in the solid the
same frequency, the Einstein frequency. Calorimetry revealed that this approxima-
tion was valid only at intermediate temperatures, and even then only for crystals
of the highest symmetry and coordination number for the atoms or ions. The problem
was resolved by replacing the single Einstein function [36] by a three-dimensional
Debye distribution [37, 38]. This distribution of frequencies was derived from a
macroscopic description of acoustic vibrations, extended to higher frequencies
until the maximum number of degrees of freedom of an atomic assembly [1]
was accounted for. This treatment described the heat capacities of many metals
and salts over wide temperature ranges by specifying only the end-frequency of
the spectrum, u(Debye), the Debye temperature Y3 is represented by hu(Debye)/k, in
kelvin (h ¼ Planck’s constant, k ¼ Boltzmann’s constant, 1 Hz corresponds to
4.8 1011 K). An extensive discussion with data comparisons is available in [39].
Solid linear macromolecules, however, do not fit such an analysis. Strong
deviations occur, starting at rather low temperatures. For polyethylene, for exam-
ple, only the crystalline solids yield the expected increase of heat capacity at low
temperature with a T3 temperature dependence, and even this, only up to about 10
K! Figure 6.4 illustrates a frequency spectrum for polyethylene, suitable to under-
stand IR and Raman spectra [40]. This spectrum fits Cp at higher temperatures, but
not at low temperatures.
Fig. 6.4 Vibrational spectrum of crystalline polyethylene, derived from normal-mode calcula-
tions based on a fit to the measured infrared and Raman frequencies [40]
102 B. Wunderlich
Fig. 6.5 Various approximations of the vibrations of crystalline polyethylene (CH2–)x [46]. The
repeating unit has nine normal modes of vibration. (a) The two skeletal vibrations (overall chain
torsion and bending in addition to the inter-chain acoustic vibrations) approximated by the three
Y-parameters of the Tarasov treatment [41]. (b) Five partial, coupled modes approximated by box-
distributions (mainly consisting of CH2 wagging, twisting, and rocking modes, total modes 2.4)
[46]. (c) The remaining eight partial and full modes of the group vibrations (The three highest
frequencies are the complete CH2 stretching and bending modes, total modes 4.6) [46]
Empirical equations for the approximation of low-temperature heat capacities for

linear and two-dimensional macromolecules were suggested by Tarasov [41] and
are shown in Fig. 6.5a. They were based on a three-dimensional Debye function
for the lowest-frequencies [38], starting with the acoustical vibrations. This is
followed by a two-dimensional and/or a one-dimensional Debye function to average
the rest of the so-called skeletal vibrations marked in Fig. 6.4 [42, 43]. The remain-
ing vibrations are group vibrations, known to change only insignificantly for
the same chemical grouping in different molecules. Their contribution to the heat
capacity can be computed from spectroscopic analysis of the molecule in question,
or even of model compounds. Because of the rather limited coupling between the
group vibrations, they are narrow local modes of vibration and can be either treated
as single Einstein modes [36] or approximated by a box distribution fitted at the
upper and lower frequency limit with a one-dimensional Debye function [44–46].
Figure 6.5a–c illustrate such a fitting for crystalline polyethylene in the different
frequency ranges. In Fig. 6.5a, the general Tarasov treatment for the two skeletal
modes with three Y-temperatures is shown [46]. The remaining seven group vibra-
tionsare approximated as five box distributions (b), and eight Einstein vibrations (c).
A comparison with the spectrum in Fig. 6.4 allows to judge the simplifications.
Figure 6.6a illustrates Cp (solid) and Cp (liquid), and Fig. 6.6b the contributions
from the skeletal and group vibrations for crystalline polyethylene. The difference
between Cp and Cv can be computed from information on compressibility
and expansivity [47, 48]. Below 200 K, this difference is negligible. Up to 150
K the Cv (Cp) is almost fully accounted for by the skeletal vibrations and calorim-
etry permits an easy fit to the approximate frequency spectrum in Fig. 6.5a.
a
50
Tm liquid
Heat Capacity
40
[J / (K mol)]
glassy Tg
30
amorphous
20
crystalline
10
0
0 100 200 300 400 500 600
Temperature (K)
b
60
Heat Capacity [J / (K mol)]
experimental Cp liquid
50 heat Capacity total Cp
40 Cp (crystal)
30
total Cv
20
skeletal
10
vibrations
group vibrations
0
0 200 400 600
Temperature (K)
Fig. 6.6 Measured and calculated heat capacities of glassy, liquid, and crystalline polyethylene.
(a) Measured data, extrapolated to 100% amorphous and 100% crystalline content, based on about
100 publications reviewed for the ATHAS Data Bank [49]. (b) Comparison Cp with the vibrational
heat capacity (total Cp) calculated from an approximate frequency spectrum
The agreement between measured and calculated data from the approximate
frequency spectrum of Fig. 6.5 is 3%. At the melting temperature (414.6 K), the
measured heat capacity of the crystal and liquid intersect.
When sufficient data on heat capacities of linear macromolecules were measured
[49] and their link to the vibrational motion was established, it was possible to
generate a reliable Advanced Thermal Analysis Scheme (ATHAS) to evaluate the
approximations of the skeletal vibrations [2, 50]. After conversion of Cp to Cv [47,
48], the group vibration contributions to Cv are subtracted, and the remaining
skeletal contributions are fitted to the proper Tarasov equation [45, 46]. Figure 6.7
illustrates the quality of one of the most complicated Tarasov fits yet attempted, that
for bovine a-chymotrypsinogen type II protein [51]. This molecule consists of 245
amino acid repeating units with a total molar mass of 25,646 Da and 3,005 skeletal
vibrations. The minimization of the error in the figure shows a unique solution and
allows a reproduction of the experimental data. Such data are now available for
more than 100 linear macromolecules in their solid states. A number of small
molecules, as well as rigid macromolecules have also been analyzed.
Overall, these skeletal frequency spectra reveal that the vibrations below 109 Hz
(Y-temperature 0.05 K), with a time scale larger than one ns (109 s), which
ultimately lead below 2 104 Hz to the acoustic vibrations, are negligible with
respect to their contributions to the integrated thermodynamic functions H, S,
104 B. Wunderlich
Fig. 6.7 Fit of the skeletal heat capacity of a-chymotrypsinogen with the ATHAS data using a
minimization algorithm [51]
and G. This means that in calorimetry, the heat capacity of solids is describable by
vibrations which react instantaneously to the changes in temperature. Any lags are
due to heat conduction delays and slow transitions.
Because of the great similarity of the weak intermolecular forces in polymers and
their strong C, N, O intramolecular backbone-bonding, the ATHAS Data Base can
also be used to estimate the Cp of samples which have not been measured yet. The
overall error is usually less than 5%. This scheme is valuable to assess the unlimited
numbers of proteins and synthetic copolymers [2]. All solid phases of the same
polymer have a closely similar Cp down to about 50 K. Below 50 K, Cp for glasses
yields a lower Y3-temperature. For glassy polyethylene, Y3 is 80 K, compared to 147
K for the crystals (see Fig. 6.5a, Y1 is identical for both, crystal and glass).
Liquid, flexible macromolecules have a long temperature-range of linearly
changing Cp [49]. In addition, they are additive with respect to their structure
units. To develop a more precise theoretical description, however, has proven
difficult because of problems to assess the large-amplitude motion in liquids with
a wide variety of intermolecular barriers to translation and rotation [52, 53].
6.5 Large Amplitude Motion
Besides the small-amplitude vibrational molecular motion about an equilibrium

position, there are a number of large-amplitude motions. Easiest is the description
of the three translational degrees of freedom known from the ideal gas theory via:
1=2Mv2 ¼ 3=2RT ¼ U; (6.8)

__
2
where M is the molar mass of the particle in question, v the mean square transla-
tional velocity. The left third of the equation represents the kinetic energy, linked to
the internal energy of the gas, U, on the right. The connection between energy and
temperature is made by the gas constant, R, in the center (¼ 8.314334 J K1 mol1).
The translational heat capacity at constant volume is then simply: Cv ¼ (∂U/
∂T)v ¼ 3/2 R. A similar expression can be derived for the rotational degrees of
motion. Both, translational and rotational energies refer to the molecule as a whole
and one does not expect either of these motions in the solid state without additional
potential energy contributions.
The intramolecular conformational rotation is the basic internal large-amplitude
motion of flexible molecules. It represents a hindered rotation of parts of a molecule
about covalent bonds. The different conformational isomers reached by this internal
rotation have usually several well-defined potential-energy minima and maxima
which define the symmetry of the motion.
Within crystals, the process of conformational motion can be simulated by large-
scale molecular-dynamics calculations [54]. In polyethylene-like solids, this main
motion involves a twisting of the backbone chain, ultimately producing defects
consisting of various combinations of gauche- and trans-conformations which leave
the chains largely parallel [55]. At room temperature, such defects have a lifetime of
the order of magnitude of 1012 s and a concentration of 0.5% [54]. The calcula-
tions substantiated that the deviations of Cp from the vibration-only value, seen in
Fig. 6.6b to start for the crystals at about 300 K, agrees with the defect formation [56].
In the amorphous glass, the first deviations are seen in Fig. 6.6a below 150 K.
Reasonable agreement of the computed concentrations of gauche conformations exists
also with measurements by IR spectroscopy on paraffins [57] and is discussed in [58].
The contribution to Cp of an isolated, internal rotation at low temperature is
similar to a torsional vibration. At higher temperature, when the potential energy
barrier to rotation into the next minimum can be overcome, it reaches a maximum,
and finally it drops to that of a free rotator with half the vibrational Cp [59]. The
internal rotations involving cooperative motion of neighboring molecules are
sufficiently slow to be measurable by DSC and TMDSC. Model calculations
made use of the hole model [18, 19]. It describes the configuration involved in
the cooperative, large-amplitude conformational as motion of a ‘hole’ with a 1-nm
or smaller radius and can also be used to describe the glass transition [17].
6.6 Ordering Phase Transitions
The integral calorimetric functions, H, S, and G, are summarized in Fig. 6.8 and
expressed there by Eqs. 9–11. They will be the basis for the description of the
ordering transitions. The data for polyethylene were taken from the ATHAS Data
106 B. Wunderlich
40
super-
30 cooled
liquid Ha
)
20 T
, TS ( mol
KJ
Hc (9) H = CpdT+ΔHf
10 Hg
glass 0
T
0 TS Cp
, G–HO
crystal
C
Gg (10) S = dT+ΔSf
–10 Gc 0
T
(11) G = H–TS
– 20
H–HO
C
Tg Tm Ga
– 30
– 40
237 K 414.6 K
– 50
0 200 400 600 800 1000
Temperature (K)
Fig. 6.8 The integral thermodynamic functions of amorphous (a), crystalline (c), and glassy
(g) polyethylene, based on calorimetric measurements
Bank [49]. Information on both, the fully crystalline and amorphous sample is given

in the figure, normalized to zero for the enthalpy of the crystalline state at 0 K, Hc .
The contribution to the enthalpy change, dH, during transition is represented by two
terms. The first is due to the heat capacity Cp {¼ (∂H/∂T)p,n}, the second to the
latent heat, L {¼ (∂H/∂n)p,T}:
dH ¼ ð@H=@T Þp;n dT þ ð@H=@nÞp;T dn (6.12)
In standard DSC experiments, one has to separate the two contributions from the
measured, apparent heat capacity, Cp# (¼ dH/dT). The second contribution to Cp#
depends according to Eq. 6.12 on dn/dT, the amount of phase transformations
during the change of temperature. This can be assessed by TMDSC with a proper
choice of frequency and underlying heating or cooling rate. It can be written as
(dn/dt)/(dT/dt) and introduces the time, t, in form of the ratio of rate of transforma-
tion and the rate of temperature change q ¼ dT/dt (see Figs. 6.2 and 6.3). Only in
case of continuous equilibrium is dn/dT time and frequency independent.
A schematic of the free enthalpy as a function of temperature is drawn in Fig. 6.9,
allowing the discussion of equilibrium states (dotted lines), as well as metastable or
unstable states of higher free enthalpy (continuous lines). The equilibrium melting
temperature, Tm, is easily recognized in Figs. 6.8 and 6.9 at the temperature were
Ga ¼ Gc. At this temperature Ha Hc represents the equilibrium latent heat of
fusion (L ¼ DHf) and the corresponding entropy of fusion (DSf ¼ DHf/Tm) can be
connected to the increase in disorder. The entropy contribution introduced during the
transition has predictable limits, as shown on the right-hand side of Fig. 6.1. The
various values have been established over the years [7, Vol. 3, pgs. 5–23], DSp is
Richards’ rule, DSo is Walden’s rule, and DSc was established based on the ATHAS
Data Bank. Also shown on the right-hand side of Fig. 6.1, are the possible connec-
tions between the various phases via order/disorder transitions. Besides the melting
and crystallization transitions, one can note partial ordering and disordering involv-
ing mesophases (at To and Td) and isotropization of mesophases (at Ti). The boiling
and sublimation, involving the gas phase at a fixed pressure are not further discussed,
they are also connected with a largely fixed entropy contribution, DSe 100 J K1
mol1 (Trouton’s rule).
The transitions characterized by an entropy of transition have a discontinuity in
the slope of G, ∂G/∂T ¼ DS, when progressing along the curve of Figs. 6.8 and
6.9, but not in G itself. Such transitions where were called by Ehrenfest ‘first order
transitions’ [60]. A first order transition was to be distinguished from a ‘second
order transition’ which has a discontinuity in curvature, ∂2G/∂T2 (¼ DCp/T), but
not in slope. These definitions apply for systems which stay in equilibrium through-
out the transitions, a condition which can be realized for systems of simple
structure. For flexible, linear macromolecules this formalism is, at best an approxi-
mation. All transitions marked on the right side of Fig. 6.1 have been analyzed by
assuming such a first-order formalism for the order/disorder transitions.
Only one metastable crystal is marked in Fig. 6.9, naturally many might exist.
A series of lamellar crystals, for example, distinguished by different lamellar
thicknesses would lead to parallel states with increasing metastability, fixed in
metastability by the decreasing lamellar thickness and calculated with Eq. 6.1. In
case the degree of order of the metastable crystal is different from the equilibrium
crystals, as in a mesophases, the slope of G {(∂G/∂T)p,T ¼ S}, would vary in
addition to the level of G. Under proper conditions, the metastable state may then
cross G of the crystal, as well as G of the melt and reach equilibrium at a limited
range of intermediate temperatures [2].
It is possible, to follow G of the metastable crystal in Fig. 6.9 during a transfor-
mation with the non-equilibrium Eq. 6.13 (given in the figure), which is linked to
the Gibbs–Thomson equation 6.1. Inspecting the point of non-equilibrium melting
marked zero-entropy-production melting, one notes that formally, this point is
similar to equilibrium melting. In case of folded-chain crystals, the degree of
metastability is set by the fold length and must at this point be identical to the
metastability of the supercooled melt.
The main issue in using nonequilibrium thermodynamics is to avoid the ever-
present possibility that the metastable states become unstable and change during
measurement [61]. For the analysis, unstable systems must be followed as a
function of time. Useful calorimetric techniques are then to follow the process
with TMDC until a new metastable state is reached for analysis based on the
observed changes [32]. The second technique is to speed up the analysis such,
that the change during the analysis is negligible, a technique which by now has
reached thermal analyses of up to 106 K s1 with superfast chip calorimetry [62].
While the lamellar crystals of linear, flexible macromolecules are frequently meta-
stable and melt quickly at the zero-entropy-production Tm, the superheated crystals
are usually unstable and their kinetics must be followed [63].
Above the glass transition of the surrounding amorphous phases, semicrystalline
macromolecules, being metastable, become increasingly unstable with increasing
temperature. On approach of the melting temperature, for example, a multitude of
108 B. Wunderlich
Fig. 6.9 Schematic of the free enthalpy of a system capable to display equilibrium and nonequi-
librium states. The equations are derived from the Gibbs–Thomson equation 6.1 expressed for
lamellar crystals with negligible side-surface effects and thickness ℓ. The latent heat effect on
fusion Dhf ¼ Dgf + TDsf. The lower-case letters signify specific quantities, subscript c refers to
crystals, the prefix ‘i’ indicates the “production” quantities (deviation from equilibrium). The glass
transition temperature is marked as Tg. The first law of thermodynamics forbids enthalpy produc-
tion (DiH ¼ 0), the second law upward motion in the diagram to reach a different phase line
(DiG 0, or DiS 0)
reorganization, irreversible melting, and recrystallization may occur. These effects

cause changes in Cp# of Eq. 6.12 with a much longer time scale than the fast
vibrations with frequencies in the THz region (1012 Hz), shown in Fig. 6.4 for
polyethylene. For the interpretation of the measured data, they must be compared to
the thermodynamic functions caused by vibrations only, which represent a hypo-
thetical, solid equilibrium crystal. A larger number of experimental data have been
collected and discussed in [32]. With the modern modulated calorimetry and the
ultrafast calorimetry for small sample mass, much progress is expected not only by
understanding the thermal behavior, but also by the link of mechanical properties
and large-amplitude molecular motion to thermal properties.
6.7 Glass Transitions
The glass transitions are marked on the left side of Fig. 6.1, producing a jump in
heat capacity, DCp, as can also be seen in Fig. 6.6a for glassy polyethylene. At Tg,
the function of G shows a change in curvature, but no change in its slope, as can be
seen in Figs. 6.8 and 6.9, i.e., there is a change in Cp, but no change in entropy, S at
the given temperature. Both of these observations are the requirements of a second
order transition [60], but the glass transition is not an equilibrium transition, rather
a kinetic transition. The glass transition temperature, Tg, is located best at the mid-
point of the change in Cp, at half-completion of the transition at the given heating or
cooling rate, q. It also depends on the thermal history of the sample [2]. An
empirical analysis of many glasses of flexible molecules suggests, that DCp depends
on the number of ‘beads’ that gain mobility at Tg, being linked to a number of
internal, conformational rotators.
Besides with calorimetry, the glass transition can also be identified by its jump in
thermal expansivity at Tg. Furthermore, the glass transition can be recognized by
the change it causes in response to simple mechanical tests. Based on these, the
glass transition has also been called the ‘brittle point,’ the ‘softening point,’ the
‘thread-pull temperature,’ the ‘maximum in the loss tangent,’ etc. All these point to
the glass transition as being an easy operation to distinguish solids from liquids, as
suggested in the Introduction. Of special interest is the observation, that the
viscosity of a liquid (which increases on cooling), rapidly approaches a value of
about 1012 Pa s at the glass transition temperature. Viscosity of such magnitude is
also observed, for example, in ice crystals close to their melting temperature. Based
on these experiments, a glass can be identified as a solid that changes on heating at
its transition temperature, Tg, to a more mobile phase, such as a liquid or a
mesophase.
The solidity of many crystals must next be questioned. Often, orienting or
ordering of the molecules increases the glass transition. Ultimately, this may
move the glass transition to the melting temperature. In such cases, melting and
devitrification or crystallization and vitrification may occur simultaneously. If this
is the case, the crystal is a solid. Not because it is ordered, but because its glass
transition is increased to the melting point.
The glass transition of amorphous polystyrene, PS, was one of the earliest
analyzed in detail by calorimetry [64]. Its kinetics could be linked to the hole
model of Hirai and Eyring, mentioned above [17]. An exponential decrease was
observed for Tg with decreasing cooling rate. This might suggest that at infinitely
slow cooling one may retain the Cp of the liquid to absolute zero. Such slow
experiments, however, are impossible to extend far below Tg and it is erroneous
to extrapolate the experimental, linear Cp of the liquid to temperatures below Tg to
assess the thermodynamic functions of a hypothetical, supercooled liquid far below
Tg. If such erroneous extrapolations are done, they result at sufficiently low
temperature in a lower entropy for the glass than for the crystal and yield the so-
called Kauzman paradox [65]. With better estimates of Cp of the liquid, it could be
shown, at least for polyethylene, that this paradox does not seem to exist [66]. Even
when avoiding the glass transition, the Cp of the liquid decreases sufficiently
quickly on cooling so that the amorphous solid and supercooled liquid have similar
Cps and the liquid retains a positive entropy at 0 K, in addition to the substantially
positive Ga, signaling its metastability.
Looking to the onset of the glass transition, one notes a similarity of glass and
crystal. For polyethylene, one can see in Fig. 6.6 that up to 150 K below Tg and Tm there
110 B. Wunderlich
are only vibrational contributions. As the transitions are approached, defect-based,

large-amplitude motion is noted for both the glass (at 150 K) and the crystal
(at 300 K). For the glass transition, close to Tg, it gradually turns into the character-
istic cooperative motion. For the crystals, melting intervenes before a glass transition is
reached. It was found, however, that for crystals of some nylons [67] and poly-
(oxymethylene) [68] the full glass transition can be reached before melting of the
crystals occurs, i.e. these polymers have a separate Tg and Tm [69].
Analyzing the glass transition of different polymers with TMDC using a simple,
first-order kinetics, based on the hole theory yields different relaxation times for the
different samples, accounting for the broadening of the transition when going from
quenched amorphous, to slowly cooled or annealed glasses, and finally to semi-
crystalline samples [70, 71]. In addition to the broadening of the glass transition, the
DCp at the glass transition decreases more than linearly with crystallinity. This
suggests that a sizable amorphous fraction exists that does not participate in the
measured glass transition. This fraction remains rigid on heating and shows a
separate glass transition at higher temperature. It was identified as a ‘rigid-amor-
phous fraction,’ RAF of nanophase dimension [32, 72]. Both crystallinity and RAF,
and their transition behavior must be known to judge the mechanical properties of
semicrystalline polymers.
6.8 Conclusions
The characterization of the phases between solid and liquid using thermal analysis
was begun with a review of the definitions and classifications. Of particular impor-
tance were changes suggested for the definition of the solid state, types of molecules,
and of small phases. A sample of condensed phases to be analyzed by thermal
analysis is suggested to be identified in terms of 1 of 57 types, based on three
molecule classes (small molecules, flexible macromolecules, and rigid macromole-
cules), the nine phase types of Fig. 6.1, and three phase sizes (macrophase, micro-
phase, and nanophase). In case the sample is heterogeneous, the global fitting of the
different phases must be identified by their shapes and possibly molecular coupling
across the interfaces, which calls for a rather extensive analysis program [2, 32].
Next, the new experimental tools of calorimetry which permit the measurements
of heat capacity and latent heat, have been summarized with Figs. 6.2 and 6.3.
Modern developments were detailed, and methods available to not only measure
equilibrium properties, but also to handle non-equilibrium and kinetic processes
were displayed. The conclusion is that the accuracy of the data in differential
calorimetry lies in the quality of the calibration.
Molecular motion was linked to Cp. The vibrational motion in the solid state
with a time scale shorter than 1 ps accounts for most of the enthalpy of the solid
state, as illustrated with Figs. 6.4–6.6, 6.8. The large-amplitude conformational
motion evolves at higher temperature out of torsional oscillations. Depending on
the molecular structure, it may begin with the creation of isolated, intramolecular,
vibrations only increasing large-amplitude motion

solid intermediate to liquid gas
crystal [Tg]
[Tg] Tsub
Tm
increasing meso- Tg mesophase
phase Ti gas or
order
glass Tsub vapor
Tg liqid or melt Tb Tsub
disorder glass
condensed dilute
immobile increasingly mobile
increase in temperature
Fig. 6.10 Schematic of the changes in molecular motion and structural order on going through the
various phase transitions indicated in Fig. 6.1
conformational defects. At this stage the large-amplitude motion may also have a
timescale in the picosecond range. The larger potential energy needed for the defect
creation is detectable by a gradual deviation of Cp beyond the vibrational level, as
shown in Fig. 6.6. At higher temperatures, the large-amplitude motion expands into
intermolecular, cooperative, liquid-like motion, starting when approaching Tg with
a high activation energy. In case the molecules are sufficiently small to undergo
rotation and translation, these additional large-amplitude motions also begin when
approaching the glass transition.
These conclusions are combined into the scheme of Fig. 6.10. Under the heading
vibrations only one finds the solid (molecularly) immobile, condensed phases. The
transition behavior changes when going from a disordered glass (bottom, left) to
increasingly ordered mesophase glasses and ultimately to the crystal (top, left).
Increasingly large-amplitude motion makes the condensed states (molecularly)
increasingly mobile, ending with the liquid or melt. The transformation of the
solid to the liquid (melt) occurs at Tg, where Tg may occur at lower temperature
or simultaneous with Td or Tm.
To complete the phase picture, the dilute gas (vapor) phase is also included in
Fig. 6.10. It is linked to all condensed phases, either at well-defined boiling
temperatures, Tb, or via the sublimation at the temperature ranges Tsub.
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Polym J 17:1–3
Chapter 7
Thermal Portrayal of Phase Separation
in Polymers Producing Nanophase
Separated Materials
Ivan Krakovský and Yuko Ikeda
7.1 Polymers
Differential scanning calorimetry (DSC) and other methods of thermal analysis

provide a lot of information about phase behaviour and physical properties of
heterogeneous systems. This information is usually supplied by information
provided by other methods, e.g., optical microscopy, X-ray and neutron diffraction,
etc. Advantage of methods of thermal analysis consists in small amount of material
necessary for the measurement, simple sample preparation and short measuring
time.
Polymers represent a class of materials in which methods of thermal analysis are
very popular. Today, a large variety of polymeric materials is available and used in
modern technologies. Synthetic polymers like polyethylene, polypropylene or
polystyrene are exploited intensively in everyday life. Polymers are also abundant
in nature, e.g., polysaccharides such as cellulose represent main constituents of
wood and paper. Other natural polymeric materials, e.g., caoutchouc have been
used by mankind for centuries. Proteins, nucleic acids are biopolymers which play a
crucial role in life processes.
Despite a great difference in their chemical composition, polymers are distin-
guished from other materials by the spatial structure of their molecules, namely, a
long linear sequence of atoms or groups of atoms which is referred to as polymer
chain or macromolecule [1]. In rubbers or resins, polymer chains are linked together
to give rise to one giant molecule of macroscopic dimensions – polymer network.
I. Krakovský (*)
Department of Macromolecular Physics, Charles University, V Holešovičkách 2,
180 00 Prague 8, Czech Republic
Y. Ikeda
Graduate School of Science and Technology, Kyoto Institute of Technology,
Matsugasaki, Sakyo, Kyoto 606-8585, Japan

116 I. Krakovský and Y. Ikeda
Fig 7.1 Illustration of the

analogy between the space
form of polymer chain
(polymer coil in 3D) and
random walk (in 2D)
There is something universal for all polymer chains: despite the details of their
structure which is reflected in flexibility, any sufficiently long polymer chain obtains
a form of an interwoven coil resembling a trail of a randomly flying object. As a
consequence, many physical properties of polymers can be explained exploiting the
analogy between polymer chain and random walk [2], see Fig. 7.1.
qffiffiffiffiffiffiffiffiffiffi
For example, the average size of a polymer coil can be estimated
2
from the mean-
square root of the end-to-end distance of the random walk, R :
qffiffiffiffiffiffiffiffiffiffi pffiffiffiffi
R2 ¼ b N (7.1)
where the number of steps, N (N>>1), and their length, b, correspond to the
number of (statistical) segments and persistent length of the polymer chain, respec-
tively [2].
Obviously, polymer coil, typically formed by a linear chain composed of
hundreds of statistical segments of the length of few nanometres has a characteristic
size of a few nanometres which explains interest in polymers in nanotechnology1.
Many typical properties of polymeric materials originate from the chain struc-
ture of their molecules, e.g.:
l Polymers are poor in configurational entropy.
l Main part of elasticity of polymers at temperatures above their glass transition
temperature is of entropic origin.
l In polymers there is a wide spectrum of processes – from very slow translational
and rotational dynamics of whole chains realized by means of torsional move-
ments of their segments of large amplitude to very fast vibrations of bond length
and angles of small amplitude.
Thermal properties of an amorphous polymer (i.e., polymer unable of crystallization)
resemble properties of any glass-forming substance. A big increase in viscosity and
response time to external perturbations is observed when the temperature is decreased
pffiffiffiffi
1
At the same time, the length of the same chain in fully stretched state, L, is: L ¼ bN>>b N for
N>>1.
7 Thermal Portrayal of Phase Separation in Polymers 117
Fig 7.2 Two possible ways of

enthalpy relaxation during heating of a H
polymer annealed for a time in the
glassy state (Adapted from [5])
a
b
LIQUID
GLASS (MELT)
Cp
b
a
a
Ta Tg T
below the glass transition temperature, Tg. The material is not able to attain its
equilibrium state in experimentally observable time (see Fig. 7.2). This state is
referred to as glassy state.
Despite many efforts, the exact nature of the glass transition has not yet been
satisfactorily clarified. In polymers, the reduction in configurational entropy of the
system seems to play an important role [3, 4]. If a polymer is cooled down at a
constant rate to a temperature below Tg and the system is annealed for a time, a slow
relaxation to an “equilibrium” state occurs which is reflected in a decrease of the
enthalpy, H. When reheated again at a rate used typically in DSC, enthalpy of the
system can evolve in two ways as shown in Fig. 7.2. A recovery peak is found in
heating DSC curves which represent temperature dependences of specific heat at
constant pressure, cp ¼ ð@H=@T Þp . The peak can occur either before glass transi-
tion (a) or (more often) it is superimposed on it (b).
7.2 Polymer Solutions and Blends
Polymer solutions and blends represent mixtures of two or more components and
exhibit a rich variety of phase behaviour. One special example of the phase diagram
for a binary mixture exhibiting upper critical solution temperature (UCST) is shown
in Fig. 7.3.
At temperatures higher than the critical temperature, Tc, the one-phase state of
the binary mixture is stable for all compositions, described by, e.g., molar fraction
ONE-PHASE LIQUID MIXTURE IS: G

T
p = const
critical 0 x2 1
point G
Tc
STABLE
0 x 2c x2 1
binodal
G
spinodal UNSTABLE
META-
STABLE
0 x2 1
0 x 2c x2 1
Fig. 7.3 Phase diagram of a binary mixture exhibiting upper critical solution temperature (UCST)
of the component 2, x2. Cooling of the mixture with a certain composition can bring
it into region where it is metastable. Separation of the system into two phases
separated by interphase is started and droplets of a new phase appear. In this case,
an energy barrier against diffusion of the components into new phases has to be
overcome. The curve allocating the onset of phase separation in the phase diagram
is referred to as cloud point curve or binodal line (Fig. 7.3). If viscosity of the
system is low as it is the case in polymer solutions, the droplets coalesce and the two
phases can be isolated. However, in polymer blends the viscosity of phases is
usually very high and full demixing would require unrealistic time. Eventually,
heterogeneous material with a particulate morphology which is in non-equilibrium
state is obtained.
A different situation occurs when the system is cooled rapidly into unstable state
which is marked out by spinodal line (Fig. 7.3). In unstable state, the energy barrier
against diffusion vanishes and the system spontaneously separates into two phases
by a mechanism known as spinodal decomposition. Similarly to the previous case,
the process can be again hindered by high viscosity of the system. Fixation of the
system in this state by freezing or a chemical reaction provides a way of preparation
of the heterogeneous materials with bicontinuous morphology.
Spinodals and binodals touch each other in the critical point where they have
also common tangent (Fig. 7.3).
For a binary mixture the binodal, spinodal lines and critical point in the phase
diagram can be determined from the Gibbs free energy of the mixture, G, as
mI1 ¼ mII1
binodal ðequality of chemical potentials in individual phasesÞ (7.2)
mI2 ¼ mII2
@2G
¼0 spinodal (7.3)
@x22
@2G @3G
¼ 0 and ¼0 critical points (7.4)
@x22 @x32
Therefore, if an expression for the Gibbs energy of a binary mixture as a function of

temperature and composition is available from a microphysical model the phase
diagram as well as its thermodynamic properties can be calculated. First model of
this kind for polymer systems was developed by Flory et al. almost 60 years ago
[6–8], see also [1]. The model is a lattice model: polymer chains and solvent
molecules are “inweaved” into a simple cubic lattice such as in Fig. 7.1 and the
sum over states of the system is calculated in the mean-field approximation. Final
expression for the Gibbs energy of the polymer solution derived by Flory reads
G ¼ N1 m01 þ N2 m02 þ kB T ½ðN1 þ rN2 Þwv1 v2 þ N1 ln v1 þ N2 ln v2 (7.5)
where N1, N2 are numbers of solvent and polymer molecules, m01 ,m02 their chemical
potentials in pure form, and v1, v2 their volume fractions. In discussion of the phase
behaviour of mixtures involving polymers volume fractions are preferred to molar
fractions due to high molecular weight of polymers.
In the derivation of Eq. 7.5 it is assumed that polymer chains consist of equal
number of segments, r, which are linked into a flexible array. The segment is
supposed to occupy the same volume as a solvent molecule. Interaction parameter,
w, represents a measure of readiness of polymer segments to mutual mixing with
solvent molecules.
Similar expression can be also derived for binary mixture of two polymers with
the numbers of segments r1 and r2, respectively:
G ¼ N1 m01 þ N2 m02 þ kB T ½ðr1 N1 þ r2 N2 Þwv1 v2 þ N1 ln v1 þ N2 ln v2 (7.6)
In the original treatment by Flory and Huggins, w is assumed to be a function of

temperature, only:
wH
wðTÞ ¼ wS þ (7.7)
T
where wS and wH are entropic and enthalpic part of the interaction parameter.
Generally, a large variety of phase diagrams found for polymer solutions and
blends can be explained by assuming following temperature dependence of the
interaction parameter [9]:
B C
wðTÞ ¼ A þ þ (7.8)
T T2
with three constants A, B and C.

Fig. 7.4 Compositional dependence of

the enthalpy and Gibbs free energy of a H
binary mixture at a temperature where the
system is partially miscible
ΔHdemix
0 x2 1
However, it was found experimentally that w may be also composition-dependent.

For example, Šolc et al. [10] expressed this dependence by
w
wðT; v2 Þ ¼ wS þ H þ av2 þ bv22 (7.9)
T
where a, b are constants. This enabled an explanation of peculiarities of phase

diagrams found in some systems, e.g., existence of double critical points in aqueous
solutions of poly(vinylmethylether) (PVME).
In polymer solutions, binodals can be determined by observation of cloud points.
For experimental location of spinodals methods like pulse-induced critical scattering
has to be used [11]. Calorimetry can be also exploited for determination of binodal
lines. The method is based on the measurement of the change of enthalpy that occurs
during demixing process induced by heating or cooling as illustrated in Fig. 7.4.
In metastable or unstable one-phase state the enthalpy of the mixture is larger
(thick curve in Fig. 7.4) than the enthalpy in two-phase state (thin line in Fig. 7.4).
Therefore, demixing is accompanied by an enthalpy jump, DHdemix , which can be
measured by a calorimetric method. This is illustrated in Fig. 7.5 where DSC traces
obtained in heating and cooling of an aqueous solution of PVME are shown.
Demixing in heating and remixing in cooling of the system is clearly visible. Note
that this system has lower critical solution temperature (LCST) unlike the phase
diagram with UCST shown in Fig. 7.3. Enthalpy of demixing for a polymer solution
ONE-PHASE TWO-PHASE
heating
heat flow, ENDO UP
at 5°C / min
cooling
at 5°C / min
2 mw
20 30 40 50 60
T, °C
Fig. 7.5 DSC scans of poly(vinylmethylether) aqueos solution (volume fraction of polymer,
v2 0:07) (Adapted from [12])
or blend can be also calculated from the Flory–Huggins formulas (Eqs. 7.5, 7.6 or
7.7) by virtue of the Gibbs-Helmholtz relation.
So far we dealt with phase behaviour of liquid binary systems – polymer solutions
or blends in liquid state. What will happen if these systems are cooled to lower
temperatures? In the case of the system with UCST, the components in individual
phases pass into glassy state eventually. The glass transition can be preceded by
crystallization if some components have a suitable regular molecular structure.
Systems with LCST which are one-phase liquids below the critical temperature
exhibit phase diagrams similar to those found for low-molecular-weight mixtures,
as illustrated in Fig. 7.6 by the phase diagram of the aqueous solution of Jeffamine
ED2003. This polymer is basically poly(oxyethylene) and crystallization (melting)
of water and polymer, glass transition of polymer and formation of the eutectic
mixture are found on DSC scans as shown in Fig. 7.7.
Actually, reheating of a system from its glassy state and determination of the
glass temperatures of phases is the simplest and most often way used for investiga-
tion of phase behaviour and miscibility of polymer blends.
An accepted unambiguous indication of one-phase state, i.e., that the compo-
nents are miscible, is a single Tg which is close to a value calculated from Tg ‘s of
the components by means of additivity rules [14, 15]. Detection of multiple transi-
tions, coincident with or shifted from those determined for the neat components,
proves that the system is in the multi-phase state.
Implementation of this procedure requires that glass transitions of phases are
separated by a sufficiently large gap, at least 10–20 C. The domains of individual
phases should also have a size bigger that a critical size to manifest a unique glass
transition. The critical size was estimated to be about 10–15 nm [16].
Fig. 7.6 Experimental phase diagram for the Jeffamine ED2003 aqueous solutions; (●) glass
transition, (□) water melting, (■) water crystallization, (D) polymer melting, (~) polymer crystalli-
zation, (*) eutectic. Lines are a guide to eye (Reproduced from [13] with the permission of Elsevier)
Fig. 7.7 DSC thermograms at a heating rate of 10 C/min for the Jeffamine ED2003 aqueous
solutions. The number on each curve represents the weight percentage of polymer in the solution.
The insert shows a detail of the glass transition region for one of the solutions with high water
content (Reproduced from [13] with the permission of Elsevier)
Enthalpy relaxation illustrated in Fig. 7.2 can be used in identification of

multiphase structure in cases when the difference in glass transitions of components
is small. The method is attractive due to its simplicity as illustrated in Fig. 7.8 where
thermal behaviour of the polystyrene (PS), poly(methylmetacrylate) (PMMA) and
their blend (67/33 % by weight) is shown [17]. The samples were first heated to
temperature 150 C which is higher than glass transition temperature of both poly-
mers (106 C and 126 C for PS and PMMA, respectively). Before the heating scans
shown in Fig. 7.9, the samples were subject to three different thermal histories:
annealing at 92 C for 24 h (Fig. 7.8a), annealing at 98 C for 320 h (Fig. 7.8b) and
annealing at 112 C for 24 h (Fig. 7.8c).
In the case of short annealing time (Fig. 7.8a), distinct enthalpy relaxation peak
is observed for PS during heating scan. The peak for PMMA is much smaller
because of higher Tg of PMMA and correspondingly much slower relaxation time at
the annealing temperature. This is also reflected in the heating scan of PS/PMMA
blend which has to be phase separated at 150 C. Longer annealing at somewhat
higher temperature makes the enthalpy relaxation peak of PMMA more distinct
a b c
PS PMMA
PS
PMMA
ENDO
ENDO
ENDO
PMMA
copol.
copol.
copol.
blend
blend
blend
70 110 150 70 110 150 80 120 160

T, °C T, °C T, °C
Fig. 7.8 DSC traces from polystyrene, polymethylmetacrylate, their blend (67/33 by weight) and
block copolymer: (a) annealed at 92 C for 24 h, (b) annealed at 98 C for 320 h, (c) annealed at
112 C for 24 h. Note that in this figure endotherms are oriented down (Reproduced from [17] with
the permission of The American Chemical Society)
(Fig. 7.8b). Annealing at a temperature between the glass transitions of PS and

PMMA for 24 h suppresses (Fig. 7.8c) the height of enthalpy relaxation peak of PS
and further sharpens the peak of PMMA.
7.3 Block Copolymers
A mixing of polymer chains of two different homopolymers results usually in a

two-phase blend which is heterogeneous on micrometer scale. If the pairs of
different homopolymer chains are linked covalently (giving rise to block copolymer
chains) the phase separation on micrometer scale is not allowed since it would
require splitting of the copolymer chains. Instead of that, the material separates into
domains of the size commeasurable with the characteristic length of the chain
blocks. The magnitude of this length can be ffiffiffiffiffiffiffiffiffiffi
qestimated
2 using the mean root square
of the end-to-end distance of chain blocks, R . As it was mentioned above, for
common polymers, the values of this parameter are in nanometre range and the
domains can be therefore referred to as nanodomains. The nanodomains obtain
various geometrical forms as shown in Fig. 7.9. Equilibrium morphology of the
system at given temperature and composition is that with minimal Gibbs free
energy. Three phenomena must be taken into account in the calculation of the
Gibbs free energy of the system: (a) interaction and mixing of the blocks analogical
to that in polymer blend, (b) stretching of the copolymer chains and (c) formation of
T one-phase gyroid
CPS CPS
spherical cylindrical
cylindrical
cylindrical
lamellar
spherical
spherical
0 0.5 1
xB
gyroid lamellar
Fig. 7.9 Morphologies and schematic phase diagram for linear AB diblock copolymer. CPS ¼ closest
packed spheres. xB denotes the molar fraction of B-block (Adapted from [18])
the new surface between (nano)phases, see, e.g. [18]. Of course, morphology of the
copolymer has to be identified by other method, such as X-ray scattering or
transmission electron microscopy.
7.4 Nanophase Separation in Polymer Networks
Polymer networks represent a system in which polymer chains are linked into one
molecule of macroscopic dimensions (therefore, “infinite” on the molecular length
scale). They can be prepared by cross- or end-linking of existing polymer chains.
Cross- or endlinking of one of the components of the (multicomponent) reaction
mixture is accompanied by change of the phase diagram of the system as illustrated
in Fig. 7.10.
With increasing molecular weight the binodals are shifted to higher temperature
and initially homogeneous mixture can become unstable in the course of the
reaction. This is illustrated in Fig. 7.11 where changes of structure during end-
linking of the mixture of poly(butadiene) diol (PBD) and poly(oxypropylene) triol
(POPT) by diphenylmethane diisocyanate (MDI) [19] were monitored by small-
angle X-ray scattering (SAXS). Similarly as in block copolymers, the size of phase
separation is restricted to nanometer level because of the formation of covalent
polymer network.
The phases can be identified using DSC by glass transitions of the components as
shown in Fig. 7.12 for a series of nanophase separated polyurethane networks.
increasing
r
Fig. 7.10 Change of the phase diagram

(shift of bimodal line) with increasing
molecular weight of polymer formed by
cross- or endlinking (r denotes number of
chain segments in the Flory-Huggins
model). The asterisk denotes the state of
the reaction mixture at the beginning of
the reaction 0 V2 1
8
7
6
5
[OH]PBD:[NCO]MDI:[OH]POPT = 1: 2: 1
4
224 min in 10 min intervals
3
105
I. a.u.
9
8
7
6
5
2 min
4
4
10
0.01 2 3 4 5 6 7 8 9 0.1 2 3 4 5
q, Å–1
Fig. 7.11 Time-resolved SAXS patterns from the formation of nanophase separated polyurethane
network by endlinking reaction of PBD and POPT with MDI (Reproduced from [19] with the
permission of Elsevier)
PUR 5
60
Tg,1
50 PUR 4
40
Heat Flow, a.u.
Tg,2
PUR 3
30
PUR 2
20
PUR 1
10
0
–100 –80 – 60 – 40 – 20 0 20 40 60 80 100
T, °C
Fig. 7.12 DSC traces (second heating scans) from the series of nanophase separated polyurethane
networks formed by endlinking reaction of PBD and POPT with MDI. The networks differ in
molecular weight of PBD which increases from PUR1 to PUR5. The arrows indicate phase transitions
of soft and hard segment nanophases (Reproduced from [20] with the permission of Elsevier)
Acknowledgements Financial support from the Ministry of Education of the Czech Republic
(project MSM 0021620835) is gratefully acknowledged.
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Chapter 8
Solid Forms of Pharmaceutical Molecules
Bohumil Kratochvı́l
8.1 Introduction
A drug discovery is characterized by two stages. The first in terms of time is called
“lead structure”, followed by a so called “drug candidate” stage. The lead structure
stage involves selecting the optimum molecule of the pharmaceutical, while drug
candidate stage means selecting the optimum solid form. Usually, five to ten candidates
pass to the drug candidate stage and the result is the selection of the final solid API
(Active Pharmaceutical Ingredience) for the ensuing formulation of the solid dosage
form. The lead structure stage concerns only the discovery of the original drug, the drug
candidate stage may concern also generics (a drug which is bioequivalent with original
and is produced and distributed after the patent protection of the original).
The choice of the optimal API for a specific solid drug formulation means the
optimization of its properties. The most important properties of API include its solubil-
ity, dissolution rate and permeability, which are closely related to the oral bioavailability
of the drug. Apart from these, there are other properties influencing functional and
technological parameters of the API and its patent non-collision status (Table 8.1).
For the selection of the optimal API, several dozens of solid forms may be
available from one molecule. An example is atorvastatin calcium, a drug used for
the treatment of high cholesterol, for which more than 60 solid forms are patented
[1]. Piroxicam, a non-steroidal anti-inflammatory drug was synthesized in more
than 50 forms [2] and more than 100 forms have been described for sulphathiazol
[3], a local antimicrobial agent. A review of possible chemical and physical types of
pharmaceutical solid forms is given in Table 8.2. In the case of multi-component
compounds the reduction in number of solid forms is given by the condition of
pharmaceutical acceptability of the fellow component (e.g. counterion in the case of
salts), see GRAS (Generally Recognized as Safe [4]).
B. Kratochvı́l (*)
Prague Institute of Chemical Technology, Technická 5, CZ-166 28 Praha 6, Czech Republic

130 B. Kratochvı́l
Table 8.1 The most

Solubility, dissolution rate
important parameters for the
Hygroscopicity
selection of optimum API
Crystal design or amorphous state
Chemical purity (including chiral purity) and physical purity
(polymorphism)
Physical a chemical stability
Powder flow
Static charge
Porosity
Robust manufacture reproducibility
Mechanical stress resistance
Taste acceptability
Must not corrode the tablet machine
Non-collision patent status (generic companies)
Table 8.2 Chemical and Crystalline forms

physical types of (all are potentially Semicrystalline Non-crystalline
pharmaceutical solids (API) polymorphic) forms forms
Anhydrates Semicrystalline Amorphous phases
phases
Multi-component Amorphous hydrates
phases:
Hydrates
(exceptionally
ethanol solvates)
Salts
Cocrystals
Glycosylated
derivatives
8.2 Polymorphs
Most pharmaceutical molecules are polymorphic. Polymorphism (from Greek:

polys – multiple, morfe´ – shape) is an ability of a chemical compound to
crystallize – depending on crystallization conditions – in different crystal structures
alias polymorphs. Molecules in the crystal structure of a polymorph are bonded by
weak interactions (H-bridges, Van der Waals forces, p-p interactions). Two general
categories of polymorphism are distinguished: packing polymorphism and confor-
mational polymorphism. Packing polymorphs which differ by molecules packing in
the crystal structure, are formed by a rigid molecule (e.g. sulphapyridine) while a
flexible molecule existing in various conformers forms conformational polymorphs
(e.g. L-glutamic acid).
8 Solid Forms of Pharmaceutical Molecules 131
In practice mixed types of polymorphism are often encountered. Labelling of

polymorphs is not unified (e.g. I, II, III . . .; A, B, C. . .; a, b, g) and it occasionally
happens that identical polymorphs are named differently by different discoverers.
The polymorphism of anhydrates (ansolvates) means that water (solvent) molecule is
not involved in the crystal structure of the polymorph. The polymorphism of hydrates
(solvates) is called pseudopolymorphism or solvatomorphism. Polymorphs may or
may not differ by their crystal shape (habitus). An ability of a compound to form
different crystal shapes, while its crystal structure remains the same, is not polymor-
phism, but crystal morphology (crystal design). Fundamental causes of polymor-
phism are not known. But a statement by W. McCrone from 1963 is ever confirmed
that if a molecule becomes a focus of attention, further polymorphs are discovered.
An example can be olanzapine intermediate, the so-called ROY (red-orange-yellow),
Fig. 8.1, which is already described in ten polymorphs [5]. On the other hand a very
well-known and many times crystallized molecule of sucrose is monomorphous.
Among pharmaceutical molecules, the most frequent case is dimorphism. A well-
known example is the patent litigation between pharmaceutical companies Glaxo and
Novopharm over two polymorphs of ranitidine hydrochloride [6], which decreases the
production of stomach acid, or the problems of the company Abbot Laboratories
concerning two polymorphs of ritonavir [7] – an inhibitor of HIV-protease. Since
polymorphs differ by their crystal structures, they differ by their properties, of which
solubility and dissolution rate are the most important. A typical ratio of solubility
(beware various definitions of solubility) of two polymorphs is less than two, but there
are exceptions, e.g. polymorphs of premafloxacin I/III or polymorphs of chloram-
phenicol A/B have this ratio larger than 10 [8]. Thus it can happen that a less soluble
polymorph does not even reach the minimum medicinal concentration in blood.
An unwanted polymorph in the mixture is called a polymorph impurity. In a
polymorph system only one polymorph is thermodynamically stable, the other are
unstable. The stable polymorph is characterized by the lowest Gibbs energy, the
lowest solubility in any solvent, the lowest dissolution rate and the lowest reactivity.
For a drug formulation the original companies usually choose a stable polymorph,
the generic companies then have to use even an unstable and less-lasting polymorph.
Uncontrolled phase transitions of unstable polymorphs into more stable ones are
a big problem of pharmaceutical industry. Two types of polymorphous transitions
are distinguished, the enantiotropic and the monotropic (Fig. 8.2). The enantiotropic
transition is characterized by the transformation temperature TA!B at which an
originally more stable polymorph A transforms into a finally stable polymorph B.
The enantiotropic transition is often reversible and well-defined. The monotropic
CH3
S
NH
NO2
Fig. 8.1 Molecule of “ROY” N
liquid B liquid
G G
A
A
B
TA-B Tm(B) T Tm(B) Tm(A)

T
Fig. 8.2 Enantiotropic (left) and monotropic (right) polymorphic transformations
Table 8.3 The critical

Temperature and pressure
parameters affecting the
Solution cooling rate
controlled crystallization of a
wanted polymorph Solution saturation grade
Solvent (precipitant) or a mixture of solvents
Water content in solvent
Impurities
Crystallization additives
Saturation rate
Standing of product in mother solution
Stirring intensity
Concentration and temperature gradients
Ultrasound, microwave, laser and other shocks
Solution pH
transition in solid state has no transformation temperature, so that the polymorph

transition passes over the liquid phase. In practice this means the crystallization from
a different solvent. Unfortunately, the polymorphous transitions of pharmaceutical
substances are more often monotropic than enantiotropic and moreover hysteretic.
Uncontrolled polymorph transitions in pharmaceutical manufacture may happen
during the final crystallization of API, during long-lasting standing of the product in
the parent solution, during drying, micronization, tablet pressing, during wet
granulation, or even in the tablet during storing. The most important for the
production of the wanted polymorph is the final crystallization and the monitoring
of all its parameters (Table 8.3) to prevent a potential creation of an unwanted
polymorph. Since there are many variable parameters and it is difficult to monitor
them all in cases of sensitive polymorph systems, a method of seeded crystallization
is often used. In this case of seeding the requested product certain nuclei are added
to the oversaturated solution. On them then the product grows.
For pharmaceutical companies, the problem of polymorphism is rather a block-
ing than a creative element. Sometimes the differences between two polymorphs
are tiny and tiny are the differences in properties (e.g. polymorphs of aspirin –
acetylsalycilic acid [9]). Nevertheless, polymorphism is closely watched by regu-
latory authorities and no pharmaceutical manufacturer can afford to ignore it.
8.3 Anhydrates and Hydrates
The first choice of API for a solid drug formulation is the anhydrate of active
substance (free acid, free base or neutral compound). Anhydrates together with salts
form the majority of all drug formulations. If the anhydrate for some reason is not
suitable (e.g. it is little soluble, unstable, has complicated polymorphism etc.), then
possible hydrates are monitored. The hydrate is most frequent a solvate containing
water molecules in its crystal structure. Water molecules can be incorporated in the
structure in a stoichiometric manner (stoichiometric hydrates) or non-stoichiomet-
rically (non-stoichiometric hydrates), Fig. 8.3. For the formulation stable stoichio-
metric hydrates in a lower stage of hydration are chosen in which water molecules
are bound to molecules of the active substance by H-bonds. The dehydration of a
stoichiometric hydrate often results in the collapse of the crystal structure and the
origin of an amorphous phase. Non-stoichiometric hydrates are not suitable for the
formulation because the water content in them changes with the partial pressure of
water vapour in the ambience and with temperature a thus they difficult to define. In
non-stoichiometric hydrates, water is not bound very firmly, it rather fills present
cavities in the structure, often without forming H-bridges. The dehydration of non-
stoichiometric hydrates does not result in the origin of an amorphous phase but a
crystalline anhydrate originates. An example of a non-stoichiometric hydrate is the
interstitial water molecules in the cavity of b-cyklodextrin [10]. Other solvates
(with the exception of ethanol solvates) are not used for the formulation but can be
used as important precursors. For instance polymorhs which are otherwise difficult
to attain can be obtained by their desolvation.
The stability of the system anhydrate/hydrate depends on the ambient relative
humidity. Many active substances form hydrates, often in a various degree of
hydration and stability. If the hydrate is the more stable in the system anhydrate/
hydrate then the hydrate has all available reliable proton donors and acceptors
better satiated compared to anhydrate (Etter0 s rule [11]). For instance ergot alkaloid
tergurid exists as an anhydrate, a twothird hydrate and a monohydrate, and the
stable phase is the monohydrate [12], Fig. 8.4. Tergurid tends to form hydrates
eagerly which results in taking up residual water molecules from acetone during
H H H H
H H H H H H H O O H H
O O O O O
O O H O
O H O H H H H H
H H H H
Fig. 8.3 Stoichiometric hydrate with a regular H-bond network (left) and non-stoichiometric
hydrate with water molecules in cavities (right)
O
H
N N CH3
CH3
H
N
CH3
H
terguride molecule
N
H
suspension in water suspension in water

terguride terguride.H2O terguride .2/3 H2O
Fig. 8.4 Transformation pathways among solid forms of terguride
crystallization. Formulations from hydrates are not very frequent and represent only
several percent of the total number of APIs (e.g. chloral hydrate, levofloxacin
hemihydrate, terpin hydrate and others). The reason is their thermal instability
and possibility of the potential dehydration during drying. Of excipients, much
used is the lactose monohydrate.
8.4 Salts
About a half of all APIs used today are salts. Salts represent a considerable
enlargement of the portfolio of solid forms of pharmaceutical molecules. Salts are
stable and well soluble in polar solvents (first of all in water), because they contain
ionic bond. A necessary prerequisite for the formation of salts is the presence
ionizable groups in the molecule (Fig. 8.5). A pharmaceutical substance then can
be in the API either in the form of cation (about 75% of pharmaceutical salts) or in
the form of anion (about 25% of pharmaceutical salts). The counterpartners must
comply with the pharmaceutical acceptability (see GRAS). At present 69 cations
and 21 anions comply [13].
The most frequent counteranion is hydrochloride, followed by sulphate and
hydrobromide. Only then occur organic anions, most often tartrate, mesylate
(methansulfonate), maleate and citrate. The most frequent countercation is sodium
ion, followed by Ca2+, K+ and Mg2+ ions, and only then comes the first organic ion,
meglumine (N-methyl-D-glucamine). Na-salts are mostly so well soluble that they
are used also in injection applications. There is one more essential advantage of
salts – their solubility is a function of pH. Since pH in the gastrointestinal tract
(GIT) vary between 1 and 7.5 (e.g. in stomach pH is 1–3, in small intestine it is
5–7), it is possible to optimize in GIT the location with the highest solubility by
selection of suitable salt. Each salt has a pHmax value with the maximum solubility.
O H3C CH3
H O HC H OH OH O
2
N N C
O NHC
N C C C O–
.Ca2+
H2 H2 H2
H +
H O–
N
CH3 HO
H
O F
HN 2
Fig. 8.5 Salts – terguride hydrogenmaleate (left) and atorvastatin calcium (right)
The choice of an optimum salt for the solid drug formulation does not mean only
finding a substance with the maximum solubility, but also with maximum stability.
With growing solubility, diffusibility rises and stability decreases. The substance is
easily diffusely dispersed in the organism and penetrates biological membranes. As
a result it is less specific as to the site of action and eliminates more readily.
Salts show polymorphism as well but not so effuse as in the case of free acid, free
base or neutral compound. The problem of polymorphism can be circumvented by
choosing a suitable salt. For instance the ergot alkaloid terguride crystallizes in
seven forms as a base, while converted to salt we obtain only one monomorphous
tergurid hydrogenmaleate monohydrate. The crystallization of API in the form of a
salt can be used for the separation of the active substance from the mixture or for its
purification. For instance a liquid valproic acid forms solid Na- and Mg-salts.
In a mixture of two or more API it is necessary to consider their mutual
interaction. For instance the analgetic proxyfen was originally formulated as a
hydrochloride and used together with aspirin in one formulation. But aspirin
decomposed easily in the presence of propoxyfen hydrochloride, it was unstable.
Only after re-formulation of propoxyfen into napsylate aspirin is stabilized (brand
name Darvocet, marketed by Elli Lilly) [14]. Moreover, propoxyfen napsylate is
more stable and less toxic compared to hydrochloride. Salts may also form hydrates
which can be also used for the formulation. The best known example is atorvastatin
calcium trihydrate (Sortis, Pfizer).
8.5 Cocrystals
Cocrystals are at present the most dynamically developing group of solid pharma-
ceutical substances. The definition of the term “pharmaceutical cocrystal” is still
under discussion, but essentially it is a multi-component compound that is formed
between a molecular or ionic API and a cocrystal former that is a solid under
ambient conditions [15], Fig. 8.6. Pharmacodynamically, cocrystal former is a
ballast molecule (the same applies to salts), and the GRAS rules apply. Neverthe-
less even a cocrystal former can be an active molecule.
carbamazepine - API
HN O
O
O H
O HN
S S
NH O
H O
O NH
O saccharin
-cocrystal former
Fig. 8.6 Cocrystal carbamazepin/saccharin (1:1), dottes lines are H-bonds
The stoichiometric ratio of API and cocrystal former in a pharmaceutical

cocrystal is mostly simple (1:1, 1:2, 1:3 or vice versa). Cocrystals are not necessar-
ily binary compounds, ternary and quarternary cocrystals are known. Cocrystals
can be divided into: cocrystal anhydrates, cocrystal hydrates (solvates), anhydrates
of cocrystals of salts and hydrates (solvates) of cocrystals of salts. The borderline
between salts and cocrystals is blurred and can be distinguished by the location of
the proton between an acid and a base. In salts, carboxyl proton is moved to the
hydrogen of the base while in cocrystals the proton remains on the carboxyl of the
acid. In cases when DpKa ¼ pKa (base) pKa (acid) ¼ 0–3, the transfer of proton
is ambiguous and we talk about the salt-cocrystal continuum [16].
The cocrystallization potential of some active molecules is studied in detail,
e.g. carbamazepine, itraconazole, piroxicam, norfloxacin, fluoxetin, caffein and
others [17]. The reason is to achieve a wide variation in solid-state properties of
APIs. These efforts stem from principles of supramolecular chemistry and crystal
engineering to affect the properties of API through the “bottom up” approach. This
is illustrated in the following examples. By the cocrystallization of antifungal drug
itraconazole with 1,4-dicarboxylic acids (succinic acid, L-tartaric acid or L-malic
acid) a modification of the dissolution profile is achieved compared to the amor-
phous form of itraconazole (Sporanox, Janssen-Cilag) [18]. A 1:1 carbamazepine/
saccharin cocrystal compared to polymorph III of carbamazepine (anticonvulsant
Tegretol, Novartis) shows no polymorphous behaviour and is not prone to hydration
[19]. The cocrystallization of pregabalin with S-mandelic acid separates from the
mixture of R and S isomers only the (1:1) cocrystal (S)-pregabalin/(S)-mandelic
acid. This technology is used by Pfizer in manufacturing dosage form Lyrica [20].
The cocrystals of paracetamol show an improved tablet formation ability than free
paracetamol, polymorf I (Panadol, GlaxoSmithKline) [21]. Caffein tends to form
hydrates at high RH (relative humidity) while its cocrystals with oxalic acid or
malonic acid do not have this unwanted property (never form hydrates) [21].
However, general trends of variation of properties during the transition from APIs
to their cocrystals are not so far evident because fundamental causes of cocrystalli-
zation are not known so far.
The preparation of cocrystals involves a number of techniques, in gas, liquid or
solid phase. The most important is the joint cocrystal growth from solution or joint
solid state grinding, often with the addition of a small amount of a “molecular
lubricant” (methanol, cyclohexan, chlorophorm etc.). Furthermore, cocrystals can
be synthesized by evaporation, sublimation, melting, sonication etc. It often holds
that identical starting components may not yield the same product under different
cocrystallization techniques.
Although cocrystals are intensively studied and patented by both academic
institutions and R&D departments of pharmaceutical companies, there is no medi-
cament on the market formulated from a cocrystal. Nevertheless it turns out that
some pharmaceutical salts should be re-classified as cocrystals. This is also impor-
tant for patent litigation.
8.6 Glycosylated Derivatives
Glycosylated derivatives (acetals of saccharides) are not usually ranked among

solid forms of pharmaceutical molecules in literature [22]. Certainly unjustly
because in natural materials the molecules of active substances are often bonded
to saccharides, e.g. digitoxin in the plant Digitalis lanata.
Glycosylated derivative can be obtained by adding saccharide (sugar) compo-
nent to the molecules of active substances through a glycosidic bond, Fig. 8.7. This
bond can be formed if a hydroxyl group is present in the molecule of the active
substance which is bonded to the hemiacetal group of a saccharide. The presence of
a saccharide component containing several OH-groups often increases solubility of
API in polar solvents.
Moreover, the glycosylation often improves also pharmaco-dynamic properties
of the active substance. A well-known example is the antibiotics vankomycin some
of whose glycosylated derivatives are 500 times more efficient compared to van-
komycin itself [24]. Apart from saccharides, it is possible to bond for instance
peptide, or protein to the molecule of active substance and thus to change dissolu-
tion profiles and pharmaco-dynamics of these derivatives.
8.7 Amorphates
Amorphous forms are thermodynamically metastable which results from the

disordering of their inner structure on molecular level. Compared to ordered crys-
talline phases, amorphates have better molecular mobility which results in a better
HO saccharide (b-D-glucopyranosyl)
O
HO O
HO
OH glycosidic bond
O CH2
HO O OMe
O
OH OH
API (silybin)
OH O
Fig. 8.7 Glycosylated derivative of hepatoprotectivum silybin. Solubility of silybin is very low
(430 mg/l). Silybin glycosides are 4–30 times more water-soluble [23]
dissolution profile and thus a better oral bioavailability. On the other hand this is
compensated by lower chemical and physical stability (shorter expiration) and by
greater demands on production and storing (e.g. protecting atmosphere).
An empirical rule applies to amorphates: the temperature of storing must be
50oC below the temperature of their glass transition Tg [25]. The amorphous state
has a higher energy than the crystalline state and therefore amorphous phases tend
to turn into crystalline ones. The crystallization of amorphates is facilitated by their
high hygroscopicity and absorbed water acts as a plasticizer increasing molecular
mobility. The transition between amorphous and crystalline phases is not sharp and
so called semicrystalline phases appear, e.g. atorvastatin calcium, V (Teva) [26].
Tiny differences between amorphous phases of one API (e.g. different methods
of synthesis) initiate discussion about polyamorphism (the ability of a substance
to exist in several different amorphous forms). Polyamorphism is well defined in
inorganic phases (e.g. six- and four-coordinated amorphous silicon) but no poly-
amorphates have been so far proved in pharmaceutical substances. Current formula-
tions from amorphous phases include asthma medicine, e.g. zafirlukast (Accolate,
Astra-Zeneca [27]), quinapril hydrochloride (Accupro, Accupril, Pfizer [28]), anti-
fungal drug itraconazole (Sporanox, Janssen-Cilag [29]) or non-steroidal anti-
inflammatory drug indomethacin. (Indocin, Merck [30]). In solid drug formulations,
amorphates are stabilized by suitable excipients (e.g. PVP, trehalose, sorbitol, etc.).
Depending on temperature and ambient relative humidity the water content in
amorphous phases varies. However, pharmaceutical phases denoted as amorphous
hydrates have been patented lately, e.g. amorphous esomeprazole hydrate [31],
amorphous cephalosporine hydrate [32] or amorphous imatinibe mesylate hydrate
[33]. Although a physical and chemical substance of the term amorphous hydrate is
debatable, we can admit that in certain cases a relatively stable amorphous phase
containing a defined amount of water may exist.
8.8 Conclusion
The portfolio of solid forms of pharmaceutical molecules is nowadays very wide

and somehow difficult to overlook. A further increase in number of new co-crystals,
or multi-component compounds generally, and their application in solid drug
formulations are expected in future. Progress in the theory of chemical bond,
prediction of crystal structures and the development of supramolecular chemistry
enable better understanding of the fundamentals of polymorphism and control of
crystallization processes. This will lead to a better orientation and targeted selection
of the optimum solid form of a certain pharmaceutical molecule with requested
technological and functional properties.
Acknowledgments This chapter was written in the framework of the project MSM 2B08021 of
the Ministry of Education of the Czech Republic.
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26. Teva Pharmaceutical Industries Ltd Patent WO 01/36384 A1
27. Accolate (2008) http://www.astrazeneca-us.com/pi/accolate.pdf
28. Accupro (Accupril) (2008) http://www.pfizer.com/files/products/uspi_accupril.pdf
29. http://www.janssen-cilag.com/product/filtered_list.jhtml?product¼none
30. http://www.merck.com/product/usa/pi_circulars/i/indocin/indocin_cap.pdf
31. http://www.faqs.org/patents/app/20080293773
32. http://www.freepatentsonline.com/7244842.html
33. Parthasaradhi et al Novel polymorphs of imatinib mesylate. Patent US2005/0234069A1
Chapter 9
Chalcogenide Glasses Selected as a Model
System for Studying Thermal Properties
Zdeněk Černošek, Eva Černošková, and Jana Holubová
9.1 Introduction
Chalcogenide glasses have been intensively studied from the seventieth of

twentieth century as the important new class of promising high-tech materials for
semiconducting devices and infrared optics. Chalcogenide glasses are formed by
chalcogens, stoichiometric chalcogenides, e.g. germanium and/or arsenic sulfides or
selenides or by non-stoichiometrics alloys whose composition (and physicochemical
properties) can be modified in broad ranges. They have unique optical properties –
low phonon energies as compared with oxide glasses, high refractive index, infrared
luminescence and so on. The advantage of many chalcogenide glasses is that they can
be obtained using very simple technologies.
Besides applicability in many areas outlined above chalcogenide glasses represent
excellent model materials for thermoanalytical studies. Extremely stable glasses and
undercooled melts can be prepared, as well as very temperature-sensitive unstable
ones. Glass transition temperature can be changed easily from subambient tempera-
tures (glassy sulphur, for example) up to temperatures over 500 C (germanium
disulphide or diselenide). This make chalcogenide glasses ideal candidates for differ-
ential scanning calorimetry (DSC) studies, because these apparatus operate in men-
tioned temperature region.
Z. Černošek (*) and J. Holubová

Faculty of Chemical Technology
Department of General and Inorganic Chemistry, University of Pardubice,
nám. Legiı́ 565, 53210 Pardubice, Czech Republic
E. Černošková
Joint Laboratory of Solid State Chemistry of Institute of Macromolecular Chemistry,
Academy of Sciences, Czech Republic and University of Pardubice,
Studentská 84, 53210 Pardubice, Czech Republic

142 Z. Černošek et al.
All chalcogenide glasses used in following studies were prepared by direct

synthesis from high purity elements (semiconductor purity – 5N elements) in evac-
uated quartz ampoules in a rocking furnace and quenched in air or in cold water. Other
glasses used (organic polymers, oxide glasses) were commercial products.
9.2 Differential Scanning Calorimetry
The development of differential scanning calorimetry (DSC) technique in last

2 decades was done by introduction of commercially available calorimeters with
temperature modulation, MDSC, by TA Instruments. The temperature of conven-
tional heat-flux DSC heating block is sinusoidally modulated and so the sample
temperature is modulated in the same manner about a constant ramp. The resulting
instantaneous heating rate varies sinusoidally about the underlying heating rate
(average heating rate). The average heat flow is called total heat flow. This one is
the only quantity that is available and hence it is the only quantity that is always
measured in conventional DSC experiments. The sample temperature and the
amplitude of instantaneous heating flow are measured and finally, using Fourier
transformation of the experimentally obtained data, the quantity termed reversing
heat flow is obtained. The nonreversing heat flow is the difference between the total
heat flow and the reversing heat flow and represents heat flow due to kinetically
hindered process. Process is called reversing if the system responds in a reversible
way on the timescale of the experiment (or faster) and nonreversing if the system is
either too slow to respond reversibly on the timescale of the experiment or if it is
irreversible altogether (on any timescale). In case of MDSC it means that reversing
process is in-phase with temperature modulation and nonreversing process with
some phase lag is out-of-phase.
Reversing isobaric heat capacity can be determined by MDSC using the magni-
tude of heat flow and heating rate obtained by averaging over one modulation
period. As a complex heat capacity has been defined, see [1], the nonreversing heat
flow recalculation to the nonreversing heat capacity has also been used. Detailed
information about MDSC one can found in [2–5] and references therein.
More recent and from MDSC essentially different technique, StepScan DSC by
Perkin–Elmer, is based on enthalpic method of isobaric heat capacity, Cp, determi-
nation adapted to the high sensitive power-compensated apparatus. This method
allows equilibration of the system after each step in a series of small step increases
(decreases) in temperature. The area under the resulting curve (the total enthalpy
change in the step) is evaluated and divided by the temperature step to give the heat
capacity at the midpoint of the temperature step. Enthalpic changes connected with
possible kinetic effects are recorded in the timescale during equilibration after each
one temperature step. StepScan DSC method allows obtaining not only Cp at the
midpoint of the temperature step but also enthalpic changes connected with slow
processes (compare to the time of temperature change) after temperature step. Two
curves are obtained as a result. The first of them is the temperature dependence of
9 Chalcogenide Glasses Selected as a Model System for Studying Thermal Properties 143
Cp (reversible part) and the second one is the temperature dependence of slow
processes’ enthalpy changes (irreversible part); these parts have been termed by
Perkin–Elmer as thermodynamic and kinetic ones, respectively.
The result obtained by StepScan DSC seems to be close to this one obtained by
MDSC, but two crucial differences should be stressed. Firstly, when TMDS is used,
the sample temperature is continually periodically changed, aside from the extent of
possible kinetic effects, whereas in the case of StepScan DSC the software-controlled
variable isotherm duration allows the sample to achieve the state close to the thermal
equilibrium at each temperature step. Secondly, no special mathematical operation,
like Fourier transformation, is needed to obtain results by StepScan DSC.
9.3 Glass Transition
9.3.1 Capability of Conventional DSC, Temperature Modulated

DSC (MDSC) and Stepscan DSC for the Glass Transition
Phenomenon Study
Bulk glass of As2S3 was used as the model glass. The power-compensated differential
scanning calorimeter Pyris 1 operated with Pyris software (both Perkin–Elmer)
capable of working in all three modes under study was used. Conventional DSC
mode was used with heating rates successively 1, 10, 20, 50 and 100 K/min. For
experimental curves, see Fig. 9.1.
DSC
a
b
c
heat flow
d
endo up
e
a - 100 K /min
b - 50 K /min (×1.5)
c - 20 K /min (×2.5)
d - 10 K /min (×7.2)
e - 1 K /min (×20)
180 200 220 240 260

T [°C]
Fig. 9.1 Conventional DSC results. Number in brackets is magnification factor

Dynamic DSC (DDSC) is the Perkin–Elmer version of MDSC. To avoid possible

confusion the MDSC will be used as a common mark for temperature modulated
DSC, despite of calorimeter manufacturer. Dynamic mode operated with saw-tooth
modulation was used with period 40 s, temperature amplitude 0.75 K and heating/
cooling rates 2/1, 4/2 and 10/5 K/min. These experimental conditions corre-
spond to underlying heating rate 0.5, 1.0 and 2.5 K/min, respectively. For tempera-
ture dependence of reversing CP, see Fig. 9.2.
StepScan DSC experiments were carried out with temperature step 1 K, heating
rates in the temperature step successively 1, 10 and 100 K/min and isotherm duration
either 60 s. or with maximal allowed heat flow difference 0.1 mW per approx. 2 s.
before next step. The experimental setup corresponds to average underlying heating
rate 0.50, 0.91 and 0.99 K/min, respectively. For results, see Fig. 9.3.
In the glass transition temperature range the influence of three available DSC
methods on the determination of glass transition temperature, Tg, was studied. Tg
was determined as a temperature of half-change of heat flow (DSC) or isobaric heat
capacity, DCp, (MDSC, StepScan DSC). Results are collected in Fig. 9.4. The Tg
dependence on the heating rate obtained by conventional DSC was significant as it
is well-known and is discussed elsewhere [6–14].
Results obtained by MDSC show still distinguishable dependence of Tg on
heating rate (more correctly on underlying heating rate) even though these rates
are slow at all. The Tg values are from 10 C up to 22 C higher comparing with
conventional DSC results at the comparable heating rates. Furthermore, it must be
stressed that with increasing underlying heating rate besides the glass transition
temperature also temperature dependence of isobaric heat capacity, Cp, has been
0.85
MDSC reversing heat capacity
saw-tooth modulation
0.80 modulation heating rates
underlying heating rate
0.75 2/–1 K/min
0.5 K/min
CP [J/(g*K)]
0.70
4/–2 K/min
1.0 K/min
0.65
10/–5 K/min
2.5 K/min
0.60
0.55
0.50
170 180 190 200 210 220 230 240

T [°C]
Fig. 9.2 Reversing CP dependence on T obtained from MDSC measurements. For details, see text
0.80 StepScan DSC

thermodynamic part
0.75
average heating rates

0.70
0.50K/min
CP [J/(g*K)]
0.91K/min
0.65 0.99K/min
0.60
0.55
0.50
170 180 190 200 210 220 230 240

T [°C]
Fig. 9.3 StepScan DSC thermodynamic (reversing) part at different average heating rates, see text
220
MDSC DSC
215
210
Tg [°C]
StepScan DSC
205
200
195
1 10 100
average heating rate [K/min]
Fig. 9.4 Heating rate dependencies of Tg, obtained by indicated methods
shifted up but without changing of isobaric heat capacity change at glass transition,
DCp, see Fig. 9.2.
From above mentioned follows that experimental MDSC dependencies have
been moved up in both axis when underlying heating rate increases. It means that
MDSC requires both careful calibration and choice of experimental set up. It is well
known that both Tg and Cp depend not only on frequency but also on amplitude of
temperature modulation (it means on mean rate of temperature change). It seems to

be clear that MDSC reversing heat flow is in fact not fully in phase with the
temperature change. The permanent periodical change of sample temperature
probably causes that sample is not close to thermal equilibrium, especially in the
case when reversing process is attended by some slow nonreversing one. The glass
transition is one of typical examples.
The values of Cp given by StepScan DSC are independent on the average heating
rate and in consequence of that Tg value remains unchanged, see Figs. 9.3 and 9.4,
and also [15].
Average heating rate is governed both by the temperature step heating rate and
duration of following isotherm. The isotherm duration is variable, depending on the
amount and average relaxation time of kinetic processes at the given temperature. It
means that the average heating rate of the one step can differ more or less from the
other one at every heating-isotherm step. It can be simply said that in every step the
StepScan DSC method will wait for termination of all processes being slower then
experimental time of the temperature step, of course within the instrument sensitiv-
ity. As follows, the heat flow of nonreversing (kinetic) process is effectively
separated from reversing (thermodynamic) one and so the temperature dependence
of isobaric heat capacity, and from it Tg, can be determined without influence of
both thermal history of glass and experimental conditions.
9.3.2 Enthalpic Relaxation and the Glass Transition
The glassy state is generally the non-equilibrium one and is characterized by an

excess of thermodynamic quantities (e.g. enthalpy, entropy, volume). The
as-quenched and thus non-equilibrium glass seeks to attain a lower energy metasta-
ble equilibrium especially if this one is held at temperature not too far below the
glass transition temperature. This time dependent variation in physical properties
following glass formation is called structural or enthalpic relaxation if the change of
enthalpy is the studied thermodynamic quantity [16]. While the glass transition has
been described as “fast” process associated primarily with the vibrational degrees
of freedom, the subsequent slow structural relaxation is connected with a change in
the frozen liquid structure [17]. So the relaxation kinetics of glasses is determined
not only by the thermodynamic temperature, T, but also by the instantaneous
structure of the glass, which is characterized by fictive temperature, Tf, firstly
introduced by Tool [18]. The fictive temperature is defined as the temperature at
which the observed value of an intensive quantity would be the equilibrium one.
During relaxation Tf approaches relaxation temperature Tr. In the metastable
equilibrium Tf ¼ Tr and the departure from equilibrium is measured by |Tf – T|.
The initial non-equilibrium state of glass is not unique but depends on the condi-
tions of glass formation and the relaxation process is strongly influenced by the
complete thermal history of glass.
Besides the great interest of structural relaxation the considerable attention has
been paid to the glass transition. Historically, the glass transition has been observed
in undercooled liquids and, therefore, is regarded as a characteristic property of
liquids. Later experiments, however, showed that this phenomenon is quite com-
mon for non-crystalline materials prepared by various methods other than tradi-
tional liquid cooling, see [19] and references cited in.
The glass transition temperature is “defined” by various inconsistent manners,
for example:
1. The glass transition temperature denotes a temperature for which relaxation time
in the supercooled liquid become longer than typical observation time. The ratio
between these two times, the Deborah number, is approximately unity for T ¼ Tg.
(Prophetess Deborah is claimed to have stated, “. . .the mountains flowed before
the Lord. . .”, Old Testament, Judges 5, verse 5.)
2. The glass transition temperature is the one at which the viscosity of the super-
cooled liquid reaches 1013 Poise. It is important to note that the viscosity is
continuous through Tg, exhibiting none of the discontinuities observed in heat
capacity [20] and thus this definition has no physical meaning.
3. The glass transition temperature is the one at which configurational entropy
vanishes during melt cooling.
Notwithstanding these “definitions” the glass transition is characterized by a
gradual break in slope of extensive thermodynamic quantities (enthalpy, entropy
and volume). The region over which the changes of slope occur is termed glass
transition region. This region is usually characterized by midpoint temperature
called glass transition temperature, Tg. Continuous change of extensive thermody-
namic quantities through the glass transition implies that there must be a disconti-
nuity in derivative variables at Tg, such as a heat capacity or a coefficient of thermal
expansion. Such differences are used to distinguish two classes of glass forming
liquids – strong and fragile [21]. For review on supercooled liquids and the glass
transition refer to [22] and references cited in.
It is well-known that Tg is not regarded as a material constant because when
measured for instance by DSC it depends on many parameters as for example
heating rate, q+, [6–8], the cooling rate, q, [8, 9] and the physical aging [7, 10, 11].
If the Tg is determined by heating the temperature obtained often differs from the
one from cooling measurement. These values of Tg may vary in the range of
10–20% depending on difference of cooling rates and heating rates.
The nature of the glass transition is very complex and poorly understood so far. It is
clear that regarding long structural relaxation time relatively to laboratory time scale
during measurement the material is out of thermodynamic equilibrium. Elimination of
this influence of scanning rate on determining of Tg was the main aim of some models.
Expression relating dependence of Tg on the cooling rate was derived by Kovacs [12].
More often the linear dependence of Tg on ln(q+) proposed by Lasocka [13] has been
used. Extrapolation of the experimental results to q ¼ 0 K/min in order to obtain the
“correct” glass transition temperature has been suggested in [23]. It must be noted that
logarithmic dependence lacks of physical meaning when q is less then 1 K/min or

limited to infinity and thus logarithmic model only hardly can be correct.
9.3.3 Enthalpic Relaxation – The Model
Enthalpic relaxation (physical aging, structural relaxation) of glassy materials has

been studied by a number of techniques, but in particular the differential scanning
calorimetry (DSC) has been used extensively to measure the kinetics of enthalpic
relaxation of glasses.
According to the Tool’s concept of fictive temperature, the specific enthalpy of a
glassy sample can be expressed as a function of fictive temperature, Tf, and
thermodynamic temperature, T:
ZTf ZT
H(T,Tf Þ ¼ H(To ;To Þ þ Cpm (T)dT þ Cpg (T)dT (9.1)
Tr Tf
where Cpm, Cpg are specific isobaric heat capacities of metastable melt and glass,
respectively, and To is an arbitrary sufficiently high reference temperature at which
the sample is in a metastable thermodynamic equilibrium. Narayanaswamy
generalized Tool’s model [24] by allowing for distribution of relaxation time and
obtained the following expression for the fictive temperature that can be calculated
for any thermal history:
Zt
dT
Tf (t) ¼ T(t) dt0 MH ½x(t) x(t’) (9.2)
dt t0
0
T is time, MH is a Kohlrausch–William–Watts (KWW) relaxation function:

MH ðxÞ ¼ exp xb (9.3)
b is the non-exponentiality parameter (0 < b 1), which is inversely proportional

to the width of a distribution of relaxation times of independent relaxation pro-
cesses. x is the dimensionless reduced relaxation time:
Zt
dt0
xð t Þ ¼ (9.4)
tð t 0 Þ
0
The contribution to the relaxation time t(T,Tf), simply t, from both the temperature
and fictive temperature is controlled by a non-linearity parameter x (0 x 1)
according to the Tool–Narayanaswamy–Moynihan (TNM) equation [9]:

xDh ð1 xÞDh
t ¼ t0 exp þ (9.5)
RT RTf
where t0 is a constant, Dh* is an apparent activation energy, R is the universal gas constant.
9.3.4 Enthalpic Relaxation
Perkin–Elmer Pyris 1 DSC calorimeter was used for enthalpic relaxation measure-
ments. All experiments were carried out without removing the sample from the
instrument. To ensure good thermal contact of glass and aluminium pan and to minimize
thermal gradient inside sample thin disks (thickness less than 1 mm) of glassy sample for
relaxation study was prepared directly in calorimeter. Encapsulated powder of bulk
glass (approx. 10 mg) was melted and equilibrated at 420 C (Tm(As2Se3) ¼ 375 C) and
subsequently cooled to 50 C with rate q ¼ 100 C/min. Glass prepared by such a way
was immediately heated by heating rate q+ ¼ +100 C/min onto relaxation temperature
Tr. After isothermal relaxation the sample was cooled down to the temperature 50 C by
cooling rate q ¼ -100 C/min. After this the DSC curve was recorded up to 420 C by
heating rate q+ ¼ +20 C/min. This scan was used for computer simulation. Glasses were
isothermally relaxed at temperatures 145, 150, 155, 160, 165 and 170 C with duration
between 15 min and 35 h. All in-instrument steps were computer controlled using Pyris
1 software.
Generally the relaxation enthalpy, DH, corresponds to area of so called over-
shoot on the DSC heating scan. The values of DH were obtained as a difference
between overshoot areas of relaxed glass scan and non-relaxed glass one. The
relaxation enthalpy, DH, increases with increasing time (or duration) of relaxa-
tion, tr, at every relaxation temperature, Tr, used for isothermal aging. Relaxation
enthalpy, DH, reaches its limit value, DHeq(Tf ¼ Tr) after the sufficiently long
time, tr, at each isothermal relaxation. This means that glass achieves a metastable
equilibrium at given temperature. The dependence of obtained values of DHeq on
relaxation temperature is shown in Fig. 9.5. When relaxation temperature
decreases the value of DHeq increases, but not linearly. At relaxation temperatures
sufficiently below Tg (Tr ~ Tg – 30 C) the enthalpy changes from that one of non-
relaxed glass to the enthalpy of metastable equilibrium of glass and achieves its
final value DHeqmax. This value does not change with further decreasing of Tr, see
Fig. 9.5. For As2Se3 glass the maximal enthalpic change is DHeqmax(As2Se3) ~ 6.4
kJ/mol.
DSC curves were normalized to pass from zero to unity as the sample goes from
glassy state to the equilibrium undercooled liquid state. When above mentioned
model of enthalpic relaxation was used and all normalised DSC scans were com-
puter simulated the complete set of parameters of TNM model was obtained for each
of relaxation. This set contains the parameter of non-exponentiality, b, non-linearity,
x, fictive temperature, Tf, and apparent activation energy, Dh*.
7
eq
ΔHmax = 6.4 J/g
6
ΔHeq βeq
ΔHeq [J/g]
4 Tr
[K] [J/g]
3
418 6.34 1.00
428 6.06 0.99
2
433 4.52 0.87
438 4.31 0.86
1 443 3.45 0.82
461 0.00 0.75
0
420 430 440 450 460 470
Tr [K]
Fig. 9.5 Dependence of total relaxation enthalpy, DHeq, on relaxation temperature Tr
Non-exponentiality parameter b was found not to be constant in both the time scale
of isothermal relaxation and the temperature scale of the set of Tr. That parameter
increases with increasing time of relaxation at every relaxation temperature used. The
time dependence of b at two different relaxation temperatures is shown in Fig. 9.6.
As one can see, after sufficiently long duration of relaxation (when Tf ¼ Tr) the
parameter b achieves its final value beq(Tr) corresponding to the metastable equilib-
rium structure of glass at Tr. Value of beq increases with decreasing Tr, see inset in
Fig. 9.5. Based on that one can conclude that the non-exponentiality parameter is both
time and temperature dependent, b ¼ f(tr, Tr).
It was found that for given relaxation temperature the value of beq(Tr) is indepen-
dent on the way in which the metastable equilibrium was reached, Fig. 9.7. The as-
quenched glass was subsequently completely relaxed at Tf ¼Tr¼ 165 C and the value
of beq ¼ 0.86. Another sample of glass was completely relaxed at Tf ¼ Tr ¼ 145 C
(beq ¼ 1.00) and after temperature jump it was completely relaxed again at
Tr ¼ 165 C. The beq was then found 0.87, within error the same as it was found in
previous experiment. It is necessary to emphasize that the first relaxation at 165 C is
the exothermic process and the second relaxation is the endothermic one, see Fig. 9.7.
In the case when the change of the relaxation enthalpy reaches its maximal value,
DHeqmax (as it was mentioned above) the value of beq reached its maximal value
beqmax ¼ 1.
Non-linearity parameter, x, increases as Tf is getting near Tr during isothermal
relaxation. This parameter was found in range 0.60–0.75 and these values reflect
relatively small influence of structure to relaxation time. During annealing this
influence still decreases.
1.00
βeq[418 K]
0.95
0.90
β
0.85
βeq[438 K]
0.80
0.75
0 50 100 150 200 250 300 350 400
tr [min]
Fig. 9.6 The time dependence of non-exponentiality parameter b
As2Se3
ΔH
βeq = 0.86
βeq = 1.00 βeq = 0.87
Tr(1) Tr(2) Tg Tm
146°C 165°C 188°C
Fig. 9.7 Qualitative concept of enthalpic relaxation. The values of parameter beq (for Tf ¼ Tr)
were obtained experimentally
The apparent activation energy is nearly constant and independent on both

temperature and time of relaxation, Dh*(As2Se3) ¼ 263 15 kJ/mol.
It was found that glass reached the metastable equilibrium at each of relaxation
temperature used. Corresponding limiting value of the enthalpy change, DHeq(Tr),
are indispensable lower than the expected values from linear extrapolation of melt
equilibrium enthalpy, see Fig. 9.8. At certain temperature, To, sufficiently below the
As2Se3
10 J/g
ΔH
max
Δ Heq
To
110 120 130 140 150 160 170 180 190 200 210 220 230
T [°C]
Fig. 9.8 Temperature dependence of equilibrium enthalpy of As2Se3 bulk glass. Full lines are
calculated from Cp measurement during glass formation and points (DHeq) reflect the set of
isothermal relaxation, see Fig. 9.5
glass transition temperature the enthalpy loss achieves its maximal value DHeqmax.
This one is invariant at temperatures lower than To for relaxed glass. For As2Se3
glass it was found To ~ 157 C and DHeqmax ~ 6.4 kJ/mol. The changes of H(T) of
fully relaxed glass at temperature lower than To bear on the changes of vibrational
enthalpy. These changes are the same as for crystal of the same chemical composi-
tion because of known fact that heat capacities for both the crystalline and glassy
states of most of materials are essentially the same [20, 25, 26], except at ultra-low
temperatures [25], and arise from vibrational contributions. As one can see in
Fig. 9.8, the curve of metastable equilibrium has the same slope as this one of
non-relaxed glass. It corresponds with finding that the specific heat is insensitive on
the thermal history of a glass, see below. All these facts confirm assumption that
metastable equilibrium is not identical with equilibrium linearly extrapolated of the
equilibrium enthalpy above Tg, see Fig. 9.8. This conclusion agrees with [26–28].
The obtained dependence of non-exponentiality parameter b ¼ f(tr, Tr) need to
be interpreted in two steps. Firstly the attention was focused on b ¼ f(tr), thus on
results obtained from isothermal relaxation (Tr ¼ const.).
The relaxation function, which is frequently simplified by KWW stretched
exponential Eq. 9.3, may be expressed by a sum of exponential terms of N
individual simultaneous relaxation processes [29]:
" 0 b #
X
N
t t
MH ¼ wi exp t exp (9.6)
i¼1
toi to
where wi are weighting factors, t0i are independent relaxation times and t is
duration of isothermal relaxation. In the right part of Eq. 9.6 the KWW parameter
to means relaxation time of all relaxation processes at actual time t’ and b reflects
the variation of weighting factors wi (the distribution of relaxation times) in this
time. From the theories describing structural relaxation it follows that the non-
exponentiality parameter is inversely proportional to the distribution of structural
relaxation times. b ¼ 1 corresponds to a single relaxation time and as b decreases
the distribution broadens. It is reasonable assumption that in the course of relaxa-
tion to the metastable equilibrium, Tf ! Tr, the number of independent relaxation
processes decreases in consequence of decreasing disorder. Therefore the experi-
mentally found growth of parameter b during the isothermal relaxation, Fig. 9.6,
may be interpreted as a consequence of restriction of relaxation times distribution
when structure becomes relaxed.
Dependence of non-exponentiality parameter on relaxation temperature, b ¼ f(Tr),
is interesting especially in case of its limit value beq, thus for Tf ¼ Tr, see inset in
Fig. 9.5. These values, inversely proportional to the distribution of relaxation times of
glass in the metastable equilibrium, have shown namely that with decreasing temper-
ature the metastable equilibrium structure approaches the state with only one relaxa-
tion time (beqmax ¼ 1 at the temperature Tr b To). This structure is characterized also
by a final relaxation enthalpy, DHeqmax, Fig. 9.8, see above. In contrast to our results
some researchers found, especially on organic polymers, that b decreases when
temperature decreases [30, 31]. These results are only hardly compatible with the
idea of structural relaxation. The metastable equilibrium structure becomes denser
when temperature decreases and the number of independent relaxation processes
decreases, as well. Consequently distribution of relaxation times becomes narrower
and thus b rises up. Also it has found that beq does not depend on fact whether
metastable equilibrium was reached by exothermic or by endothermic relaxation,
Fig. 9.7. Therefore non-exponentiality parameter of metastable equilibrium is path
independent.
It can be concluded that it would be better to express the parameter b dependent
on the structure of glass than on the time of relaxation tr. While the time increases
constantly from the beginning of process irrespective of relaxation extent, the
change of the structure of glass is finite. The change of the structure is described
by the change of fictive temperature, Tf. Then one may summarize that b depends on
thermodynamic temperature and simultaneously on fictive temperature, b(Tr, Tf).
9.3.5 The Description of Glass Transition
Conventional DSC measurements were carried out using of DSC 7 calorimeter

and stepwise technique StepScan DSC was carried on the Pyris 1 DSC (both
PERKIN–Elmer) with special software. Powdered glassy samples (weigh around
4 mg for conventional DSC and 10 mg for StepScan DSC measurements, see below)
were encapsulated into sealed aluminium pans. Conventional DSC scans were done
using heating and cooling rates q ¼ (1 – 20) C/min.
To distinguish results of conventional DSC and StepScan DSC, the glass transi-
tion temperature, Tg, and DCp measured by StepScan DSC are labelled by prime,
0 0
i.e., Tg , DCp .
Typical StepScan DSC traces of As2S3 melt cooling through the glass transition
region, as well as of glass heating are shown in Fig. 9.9. Reversible (thermody-
namic) component, Cp vs. T, and enthalpic change corresponding to irreversible
(kinetic) one are separated. Both exothermic peak, DH ¼ 3.2 J/g, on the kinetic
part of cooling scan and endothermic overshoot, DH ¼ +3.5 J/g, on heating scan are
seen. Reversible parts are identical for cooling and heating.
Important result shown in Fig. 9.9 clearly demonstrates that the Cp measurement
close to isothermal equilibrium removes completely both well-known hysteresis of
thermal capacity and shape difference during heating and cooling always obtained
by conventional DSC. Temperature dependence of Cp (StepScan DSC) is indepen-
dent on both heating/cooling rate and thermal history. Similar result was found also
for organic polymers [32]. In other words, the application of StepScan DSC
eliminates influence of thermal history of glass and also influence of heating or
0
cooling rate on the glass transition temperature, Tg . It can be easily shown that the
sum of thermodynamic and kinetic components is equivalent to the conventional
DSC scan at the same heating rate.
It is well known that conventional DSC traces obtained during cooling and
heating differ significantly in the shape and thus the value of glass transition
temperature, Tg, depends on heating and cooling rate as well as the specific heat
capacity change, DCp, e.g. [33–36]. With increasing rates (heating and/or cooling)
0.55
As2Se3 thermodynamic
heating
cooling
0.50
ΔH = +3.5 J/g
Heat flow [mW]
ΔCP [J/(g*K)]
0.45
'
Tg = 188°C
kinetic
ΔC'P = 0.185 J/(g*K)
heating
0.40
kinetic
cooling
0.35
ΔH = –3.2 J/g
130 140 150 160 170 180 190 200 210 220
T [°C]
Fig. 9.9 Typical results of StepScan DSC. For details, see text
190
188 T'g = 187.4 ± 0.4°C
186 Tglim 187°C

184
182
Tg [°C]
180
178
176
174
172
170
0 5 10 15 20 25
heating rate, q [K/min]
Fig. 9.10 Heating rate dependence of the glass transition temperature. Conventional DSC, Tg,
(full circles), StepScan DSC, Tg0 , (shaded stripe of 2*(Tg0 std. deviation) width)
the glass transition temperature increases, see e.g. [13, 34]. Results of conventional
DSC experiments carried out at different heating rates compared with StepScan
0
DSC result, Tg , are in Fig. 9.10. It should be stressed that dependence of Tg on
heating rate doesn’t need to be logarithmic contrary to Lasocka’s proposal [13]. The
application of two-phase exponential association equation (also known as pseudo-
first order association kinetics eq.) allows us to extrapolate the Tg values from zero
heating rate even to the infinity. The limit values of Tg obtained in this manner are
more realistic compared to application of logarithmic dependence.
According to the results there is directly proposed conception that in the glass
transition region the glass may be viewed as an equilibrium mixture – supercooled
liquid $ glass. Starting from the upper temperature end of a glass transition region
when temperature decreases this equilibrium moves towards the glass and at the
temperature To, see Fig. 9.8, the supercooled liquid completely disappears and vice
versa. Temperature dependence of isobaric specific heat in the glass transition
interval also supports this concept. In the case of studied glass this change of the
total quantity of DCp is also finished practically at the temperature To. The fact that
the overwhelming majority of studies of the relaxation have been done in the glass
transition region, e.g. [37], probably due to strongly increasing time-consumption at
lower temperatures is worthy of remark.
Conventional DSC measurements of the glass transition temperature showed
0
that the glass transition temperature Tg approaches StepScan DSC Tg in the case of
sufficiently high heating rates, Fig. 9.10. It is clear that the explanation of known
heating/cooling rate dependence of the glass transition temperature should be
searched in relaxation times of processes in the glass transition region. The temper-
ature dependence of reversible (thermodynamic) Cp, essentially the change of
vibrational amplitudes, is rapid enough in comparison with experimental time of
DSC technique and thus this reversible part cannot be influenced by the rate of
temperature changes. To elucidate the experimental results it is necessary to focus
attention on irreversible (kinetic) component, because of strong temperature and
structure dependent relaxation time t(T,Tf), simply t. One can expect that this fact
should influence considerably the shape of the non-isothermal DSC scans.
The kinetics of isothermal structural relaxation, T ¼ Tr ¼ const., can be
expressed:
dTf jTf Tj
(9.7)
dt t(T,Tf Þ
For non-isothermal relaxation kinetics this equation can be rewritten in the form:
q ¼ dT dTf 1 jTf Tj (9.8)

dt dT q t(T,Tf Þ
where q is a heating rate,q = DT dt

For the forthcoming discussion on influence of non-isothermal structural relaxation
on the shape of conventional DSC curve, and thus on the Tg and DCp values, refer to
Fig. 9.11.
Heating scan wil be discussed at first. Provided that (Tf > T)T<Tg, then the glass
relaxes exothermally toward the equilibrium structure at T. It manifests itself as
so-called undershoot on the non-isothermal DSC scan, e.g. [14]. On the other hand
when (Tf < T)T<Tg the relaxation is endothermic and its typical overshoot is found
at the temperature above conventional DSC glass transition temperature. In the
limit case of (Tf ¼ T)T<Tg the glass is in metastable equilibrium. It is important to
point out here that this is the case only when Tf crosses line T ¼ Tf. At this moment
exothermic relaxation changes to endothermic one, Fig. 9.11.
Because the relaxation time, t, increases exponentially with decreasing temper-
ature so at glass formation structural relaxation time is much longer than experi-
mental time, t >> t, for the temperatures not too lower than Tg (T ~ Tg – 10 C).
As a matter of fact the fictive temperature of non-relaxed glasses is practically
always substantially higher than thermodynamic temperature (Tf >> T). It results
in well-known fact that during glass heating the exothermic relaxation (undershoot)
can be observed in many cases. Its magnitude depends on the difference between
the rate of glass formation (the rate of cooling) and the rate of following heating. In
case of a low heating rates the equilibrium structure can be reached, (Tf ¼ T)T<Tg,
and crossed. In such case further increasing of temperature leads to departure from
equilibrium and subsequent endothermic process proceeds toward a new equilib-
rium. Thus an overshoot begins to appear at DSC scan. Very slow heating of
quickly cooled glass, represented by curve 2 in Fig. 9.11, leads to deep undershoot
and very small overshoot when conventional DSC is used. Resulting shape of DSC
scan is known as so-called pre-peak, or sub-Tg peak. Origin of this is unclear up to
now, see e.g. [16, 38]. When non-relaxed or only slightly relaxed glass is heated
Fig. 9.11 A schematic drawing of relation between fictive (structural) temperature, Tf, and
thermodynamic temperature, T. Circles: conventional DSC glass transition. Curves: 1 – cooling,
2 – slowly heated non-relaxed glass, 3 – quickly heated non-relaxed glass, 4 – quickly heated glass
fully relaxed at Tr, see text for details
with sufficiently high rate the exothermic undershoot decreases and at the same
time the endothermic overshoot shifts up to higher temperature because the equality
(Tf ¼ T)T<Tg is reached at higher temperature, Fig. 9.11.
With regard to conventional DSC cooling scan the explanation is not prima facie
so clear. During cooling of the melt the exothermic process (relaxation) takes place
in and below the glass transition region, see Fig. 9.9. Now it should be pointed out
that the conventional DSC doesn’t measure directly the specific heat but only the
heat flow and the later is higher in the glass than in the undercooled melt. Therefore
when melt is cooled and glass is formed the heat flow of exothermal changes is
subtracted from the growth of heat flow during glass transition, Fig. 9.12. It leads
consequently to erroneous lower values of both Tg and DCp obtained from conven-
tional DSC cooling scan, as it is demonstrated in Fig. 9.12.
The opposite sign of heat flow of the glass transition and of the exothermic
structural relaxation during cooling and, on the other hand, the same sign of changes
of both heat flow components, when the heated glass undergoes the glass transfor-
mation, causes the completely different shape of conventional DSC traces. These
differences led to erroneous conclusion that when the melt is cooled through the
glass transition region there is not exothermal counterpart to endothermic overshoot.
From the aforesaid it is obvious that the value of glass transition temperature
obtained by conventional DSC strongly depends on the facts that (1) relaxation
kinetic affects significantly shape of DSC scan, and that (2) glass transition
ΔCp difference
heat flow, endo up
kinetic
StepScan DSC
cooling scan
conventional DSC
thermodynamic
StepScan DSC
Tg difference
100 120 140 160 180 200 220 240 260

T [°C]
Fig. 9.12 Glass transformation region-the influence of exothermic process on the shape of
conventional DSC cooling scan [14]
temperature is actually determined on an ascending part of irreversible endothermic

overshoot added on the reversible Cp(T) dependence.
The heating rate dependence of the overshoot peak shift is widely used for
determination the apparent activation energy of relaxation. Heating rate depen-
dence of the glass transition temperature has been used to find the activation energy
of either the glass transition [39] or the activation energy of relaxation [40]. From
aforesaid results it is evident that both relaxation peak and Tg shift bear on
relaxation and thus it doesn’t surprise that the obtained activation energies of
relaxation and of glass transition are very close each other. Their difference is
caused only by the fact that in the first case the peak shift and in the second one the
shift of the ascending part of endothermic overshoot is used, but in all cases it is
only more less good estimation of activation energy of relaxation.
It’s clear that using conventional DSC it is possible only to approach more or
less correctly the values of Tgeq and DCpeq (characteristic values of reversible
changes).
Crucial question follows from obtained results – whether or not the glass
transition is the kinetic effect at all. To solve this question the StepScan DSC
heating scan was stopped in the glass transition region and after 30 min isotherm
(sufficient long time to reach thermal equilibrium) heating was continued. In the
case that experimental heat flow separation into reversing and nonreversing parts
represents only misleading software separation both reversing and non-reversing
parts should change during the isotherm. However, results show clearly that only
kinetic overshoot disappeared after isothermal dwell whereas the sigmoidally
shaped reversing part remains unchanged, Fig. 9.13.
This result, along with previous finding t hat reversible part (and consequently Tg)
depends only on the chemical composition of glass [14, 15], shows that the commonly
0.9
Kinetic heat flow
Kinetic heat flow, endo up

0.8
ISOTHERM
CP [J/(g*K)]
206°C/30 min
0.7
0.6
CP
0.5
160 180 200 220 240
T [°C]
Fig. 9.13 StepScan DSC of the glass transition of bulk As2S3 glass. Reversing parts are labelled
Cp, the nonreversing ones are labelled Kinetic heat flow, see text
used concept that glass transition is entirely kinetic process is probably not fully
realistic. It should be stressed at this moment that well known Tg dependence on the
thermal history of glass and on the experimental conditions, when conventional DSC
is used, can be caused by superimposition of the slow kinetic effects on the sigmoi-
dally shaped glass transition Cp change, for more details, see [14].
9.3.6 Glass Transition Modelling
Using StepScan DSC kinetic effects were separated and sigmoidal-shaped

curves corresponding to the changes of isobaric heat capacity in the glass transfor-
mation region (reversible part) were obtained for wide class of non-crystalline
materials, e.g. chalcogenide glasses (As2Se3, As2S3, GeS2, Ge4As4S92, S and
Se bulk glasses), oxide glass LiPbPBO (40Li2O:10PbO:10B2O3:40P2O5), lead-
silica glass NBS 711, poly(styrene-co-acrylonitrile), 75/25, PSA, from BASF and
poly(ethylen terephtalate), PET.
On the basis of above-mentioned experiment it can be further concluded that the
temperature T in the glass transition region can be considered to be the equilibrium
transformation temperature. It means that the reversible part of the glass transition
(Cp vs. T) may be referred to the temperature dependence of glass $ undercooled
melt equilibrium. This dependence after normalization represents the temperature
dependence of glass ! undercooled melt conversion a(T).
If temperature dependent transformation occurs randomly in the material and the
fraction dx of glass is transformed to undercooled melt, it is possible to write:
da ¼ ð1 aÞdx (9.9)
where a varies from zero to unity (the end of the transformation). Integration of this
equation yields to:
a ¼ 1 expðxÞ (9.10)
In case of the glass transition, the temperature dependence of the conversion a can
be expressed by the measurable values as a ¼ (Cp(T) – Cpg)/DCp. Cp(T) is the actual
value of isobaric heat capacity at temperature T, DCp is its total change during the
glass transition and Cpg is the heat capacity of glass at the lowest temperature of the
glass transition region. Substitution of x for (T/Tg0 )n yields to the following
equation:
!n !
T
a ¼ 1 exp 0 (9.11)
Tg
which describes well the experimentally obtained data. In this equation Tg0 is the
temperature of inflexion point of a vs. T dependence, and n is a steepness parameter.
The a vs. T form is more suitable for computer fitting then Cp vs. T because the use of
degree of conversion instead of isobaric heat capacities eliminates their temperature
dependencies out of glass transition region.
The applicability of Eq. 9.11 at the description of reversible part of the glass
transition was tested on many non-crystalline materials of a different chemical
1.0
Sulphur
experimental data
0.8
computer fit
conversion α
0.6
0.4
0.2
0.0
225 230 235 240 245 250 255 260
T [K]
Fig. 9.14 Normalized reversible part of the glass transition (a) of glassy S and its computer fit,
Eq. 9.11
1.0 n T'g [K]

Se 155 314
Se
0.8 PET 115 346 NBS 711
As2Se3 68 464
As2S3 57 484
conversion α
0.6
NBS 711 47 745
0.4
NBS 711
0.2 Se
0.0
0.92 0.94 0.96 0.98 1.00 1.02 1.04 1.06

T / T'g
Fig. 9.15 Normalized reversible parts of the glass transition of some glasses. All curves intersect
close to a ~ 0.63
nature mentioned above. The reversible parts of the glass transformation process
were normalized and fitted by Eq. 9.11. It was found that this equation fits the glass
transition region fairly well in all cases. As an example, see Fig. 9.14.
From the Eq. 9.11 it arises that in the inflection point (T ¼ Tg0 ) the conversion
must always be a ¼ (1 – 1/e) ¼ 0.632, where e is the base of natural logarithm.
Therefore when reduced temperature, T/Tg0 , is used, the conversion curves of all
glasses studied must intersect within an experimental error at a ~ 0.63. Experimen-
tal results are in the excellent agreement with this assumption, see Fig. 9.15. It
is evident that the reversible parts differ in the shape. The steepness of curves is
determined by the value of parameter n in Eq. 9.11. By differentiation of this
equation for T ¼ Tg0 the parameter n is obtained as n ¼ e*da/d(T/Tg0 ) and
represents the slope of the glass $ undercooled melt conversion curve in the
inflexion point. Values of n calculated for all materials studied are included into
Fig. 9.16.
From it follows that n decreases when Tg0 increases regardless of the chemical
composition of glass. It means that if glasses of different chemical composition
have close values of Tg0 than the shape of reversible part of glass transition will be
very similar.
The physical meaning of parameter n is not still clear. Its dependence on Tg0 is
noticeably close to the same dependency of Angell0 s fragility index m [21, 41].
Dashed straight lines with markedly different slopes crossing at approx. 150 C
divide the n vs. Tg0 into two regions, see Fig. 9.16. From both n and m dependencies
it follows that undercooled melts of glasses with glass transition temperature higher
200 T'g [K] n
FRAGILE
180 S 248 72
Ge4As4S92 296 170
160 Se 314 155
PET 346 125
140 PSA 381 92
As2Se3 463 70
120 As40S30Se30 470 52
n, m
As2S3 480 51
100 Ge18As18S64 598 47
LiPbPBO 617 60
80
NBS 711 745 47
GeS2 780 43
60
LR 836 40
STRONG
40 NCZ0 884 45
20
0
0 250 500 750 1000 1250 1500
T 'g [K]
Fig. 9.16 The dependence of the glass transition steepness parameter n (circles) and the fragility
index m (points) (From [42], on the glass transition temperature, Tg0 )
then approx. 150 C are “strong” (viscosity close to the glass transition obeys
arrhenian temperature dependency). However, further experiments are needed for
detailed n explanation.
9.3.7 Summary
From experimental results it follows that the glass transition can be regarded as a
temperature dependence of a glass $ undercooled melt equilibrium. The semi-
empirical two-parametric equation was proposed to describe the temperature
dependence of glass $ undercooled melt conversion. One of the parameters, Tg0 ,
determines temperature of inflexion point of sigmoidal shaped curve and the second
one, n, is the steepness at Tg0 . Applicability of proposed equation was tested using
various non-crystalline materials with very different chemical composition. All
experimentally obtained reversible parts were fitted fairly well and in agreement
with the proposed equation an inflection point at a 0.63 was found in all cases.
The steepness, n, was found to be inversely proportional to the glass transition
temperature. The temperature of inflection point, Tg0 , should be used as unambigu-
ously defined glass transition temperature.
Acknowledgements This work was supported continuously by the project of the Ministry of
Education of the Czech Republic MSM 0021627501.
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Chapter 10
Viscosity Measurements Applied
to Chalcogenide Glass-Forming Systems
Petr Koštál, Jana Shánělová, and Jiřı́ Málek
10.1 Introduction
Viscosity is an important physical parameter which determines the flow of material.

The knowledge of viscous behaviour is important for example for the process of the
material production. In the case of glasses and their undercooled melts, viscosity
influences also the processes of structural relaxation and crystallization. Structural
relaxation is in fact a very slow structural rearrangement of glass. This process can
be realized through viscous flow and therefore is influenced by it. Crystallization
process which may occur in undercooled melts is also influenced by the diffusion
coefficient in the glassy matrix and therefore by its viscosity. This chapter tries to
summarize the available viscosity data for chalcogenides and the basic measuring
methods which are mostly often used to determine them.
Generally, it should be mentioned that most of amorphous chalcogenides are
considered to be Newtonian fluids. Their viscosity coefficients are dependent only
on pressure and temperature. Nevertheless, the pressure dependence is often
neglected in the case of condensed phase. Measurements of the pressure dependen-
cies are for inorganic glass-formers complicated because the combination of a high-
pressure and high-temperature apparatus is needed. This difficulty, together with
small influence of pressure on viscosity at common pressures, caused that most
works dealing with the viscosity of inorganic glass-formers study only the temper-
ature dependence of viscosity.
P. Koštál (*), J. Shánělová and J. Málek

Faculty of Chemical Technology
University of Pardubice, Studentská 573, 532 10, Pardubice, Czech Republic

166 P. Koštál et al.
10.2 Measuring Methods
Most important measuring methods for determination of dynamic viscosity of

chalcogenide glass-formers are mentioned in Fig. 10.1. The approximate measuring
range for each method is also denoted. It is apparent that no method covers whole
viscosity interval from melt to glass. It should be mentioned that one method by
which is possible to measure this broad interval was introduced by Plazek [1]. But
his magnetic bearing torsional creep method is not widespread. The most wide-
spread methods for determination of higher viscosity of chalcogenide glass-formers
are penetration method followed by parallel-plate one. The dominance of penetra-
tion method is caused by the frequent use of it by Russian authors. Other two
methods for high viscosity region, rod elongation method and beam-bending
method are used only occasionally. Capillary and rotating cylinder methods are
the most popular for determination of dynamic viscosity in the region of lower
viscosity. Falling sphere method is used only rarely. Other popular method for
melts is torsion oscillating cup method [2] which is used for determination of
kinematic viscosity.
10.2.1 Capillary Method (C)
This method is based on measuring of time which a finite volume of liquid needs to
go through a narrow tube under a given pressure. The viscosity can be calculated
using the Hagen-Poiseuille equation [3] which presumes laminar liquid flow.
Fig. 10.1 Overview of the most typical measuring methods for chalcogenide glass-formers with
indication of their approximate measurement ranges
10 Viscosity Measurements Applied to Chalcogenide Glass-Forming Systems 167
pr 4 Dpt
V¼ ; (10.1)
8l
where r and l stand for the radius and the longitude of the capillary, respectively,
t stands for time, V stands for the volume of liquid, stands for viscosity and
Dp stands for pressure difference which is usually given by the hydrostatical
pressure of liquid column. This method is in practice commonly used as a relative
one. In this case the viscosity of measured liquid is determined by comparison of its
retentive time with retentive time of liquid with known viscosity.
10.2.2 Falling Sphere Method (FS)
This method is based on measuring the velocity of the falling sphere in measured
liquid [4]. The viscosity can be calculated by the use of Stokes law.
2gr 2 ðrs rl Þ
¼ ; (10.2)
9v
where rs and rl stand for the density of sphere and density of measured liquid,
respectively, v stands for the fall velocity, g stands for the gravitation constant,
r stands for the radius of the sphere and stands for viscosity. The non-newtonian or
non-transparent liquid can be measured by use of special setting of this viscometer.
In this case the sphere is connected by some rigid attachment to the movable arm
which can be weighted and the fall of sphere can be observed implicitly by
through it.
10.2.3 Rotating Cylinder Method (RC)
In the case of this method the measured liquid is placed between two defined
surfaces, usually concentric cylinders (so-called Couette viscometer). One of
these cylinders makes rotating motion with constant angular velocity o, the second
one is stationary. The moment of force M produced by viscosity of liquid is
measured by the use of torsion spring. Viscosity can be then calculated using
following equation [5]:

1 1 M
¼ 2
2
; (10.3)
r1 r0 4pho
where r1 and r0 stands for radius of inner and outer cylinder, respectively and
h stands for the height of the column of the sliding liquid. This equation was
deduced for laminar liquid flow and for the neglected end and edge effects. This
method is commonly used as a relative one.
10.2.4 Rod Elongation (RE)
This method is based on measuring of the rod or fibre elongation. The rod is made
from measured material. The elongation of rod is caused by constant load or only by
self-weight of the rod. Viscosity can be measured using equation:
Lmg
¼ ; (10.4)
3pr 2 v
where L stands for the length of the rod, r stands for the radius of the rod, m stands
for the weight of load and v stands for the velocity of elongation. The elongation of
non loaded rod investigated Littleton [6]. He heated 229 mm long rod with diameter
0.65–1 mm at constant rate (5–10 K/min). The temperature when the velocity of
elongation was 1 mm/min is softening point. This point which corresponds to
viscosity 106.6 Pa.s is often called as Littleton softening point.
10.2.5 Torsion Oscillating Cup Method (TOC)
This method is based on measuring of torsion oscillation damping of cylindrical

crucible filled with sample. This method was firstly described by Meyer [2].
The viscosity can be determined from following equation:
2 sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi 3
pffiffiffiffiffiffiffiffi 4 ðp lÞ3
2Ml ¼ rT 4R þ 2cR3 K 5; (10.5)
2
where M stands for the moment of inertia, T stands for the time of the oscillation, l
stands for the damping decrement, stands for viscosity, r stands for density, R
stands for the semi-diameter of the cylinder, 2c stands for the height of the cylinder
and K is proportional to the time of oscillation. This method in modified form was
widely used by Russian authors for determination of kinematic viscosity. Details
can be found for example in Ref. [7].
10.2.6 Penetration Method (P)
This method, firstly described by Cox [8], is based on measuring of penetration

depth or rate of indenter which is penetrated into sample by constant force.
The penetration method can be used to measure viscosity in the range of
107–1013 Pa.s. The indenter may have the any basic shape [9] but in most cases
only hemispherical and cylindrical indenters are used.
The cylindrical indenter was very popular for Russian scientists, especially for
Nemilov [10] and his co-workers. The general description of the penetration of
cylinder was not published until the Yang work [9]. He and his co-worker deduced
the general equation for calculating of viscosity:
F
¼ ; (10.6)
8Rðdh=dtÞ
where F stands for the applied force, R stands for the radius of indenter and dh/dt
stands for the rate of penetration.
The hemisphere is the second one mostly used shape of the indenter.
The equation which is needed for calculating viscosity and some theoretical and
practical aspects about this method can be found in the work of Exnar et al. [11]:
9 Ft
¼ pffiffiffiffiffiffi 3=2 ; (10.7)
32 2R h
where h stands for penetration depth and other symbols are the same as in previous
equation.
10.2.7 Parallel-Plate Method (PP)
This method is based on measuring the time dependence of the height of the sample
which is squeezed between two parallel plates. The parallel-plate method can be used
to measure viscosity in the range of 104–1010 Pa.s. The viscosity value can be obtained
from the following equation which corresponds to a cylindrical specimen [12]:
2pFd 5
¼ ; (10.8)
3Vðdd=dtÞð2pd3 þ VÞ
where F stands for the applied force, d stands for the height of specimen, V stands
for the specimen volume and t stands for time.
10.2.8 Beam-Bending Method (BB)
In the case of this method the bar sample is supported by two knife edges. Another
rod pushes in the middle of the sample from the upper side. The viscosity can be
calculated from the deflection rate of the sample by use of the following equation
[13].

gL3 rAL
¼ Mþ ; (10.9)
144 Ic v 1:6
where L stands for the support span, Ic stands for cross-section moment of inertia, v
stands for midpoint deflection rate of the sample bar, M stands for the applied load,
r stands for the density of sample and A stands for the cross-section area of bar.
10.2.9 Low-Temperature Torsion Viscometer (LV)
This uncommon viscometer is based on measuring of angular velocity o of rod

from measured material which is screwed by moment M. The viscosity can be
calculated by use of the following equation [5].
2LM
¼ ; (10.10)
pr 4 o
where L stands for length of the rod and r stands for radius of the rod.
10.2.10 “Eisenberg” Method (EM)
This indirect method to determine viscosity was introduced by Eisenberg and

Tobolsky [14]. Their apparatus is constructed to measured stress relaxation of
sample and viscosity is determined from Young modulus and relaxation time.
10.2.11 Magnetic Bearing Torsional Creep Method (TC)
This method was described by Plazek [1]. The creep experiment starts by fixed
stress on relaxed sample. The recoverable portion of deformation is subsequently
measured as a function of time after the removal of the stress. The permanent
deformation is indirectly proportional to viscosity which can be also determined
from this experiment.
10.3 Overview of Viscosity of Amorphous Chalcogenides
The overview of measured chalcogenide systems is summarized in the Table 10.1

(dynamic viscosity) and in the Table 10.2 (kinematic viscosity). The kinematic
viscosities are published only for melts. This work is primary aimed on the viscosity
of glasses and undercooled melts. Hence the kinematic viscosities and the dynamic
viscosities of melts are presented only for selected compositions and for completion
of general view on amorphous chalcogenides. Both tables contain four columns.
The first one includes the chemical formula of measured composition or the
schematic formula of measured system. The compositions of substances are
expressed in atomic percents but the steady formulas of some compounds are
respected. The tables are divided into three parts; each part includes the materials
based on one of three chalcogenide glass-formers (S, Se and Te). The substances
including more then one glass-former are placed in group of chalcogenide with
lower atomic weight. The first in each group is the pure glass-former followed by
substances sorted by alphabetical order. The important chalcogenides (as As2S3,
As2Se3. . .) have their own entry and are sorted in the front of group which belongs
to its alphabetical order. The second column comprises the measured range of
viscosity values. In all case only temperature dependence was looked at. The third
and fourth column includes measuring method and the source work, respectively.
Table 10.1 Overview of dynamic viscosity of amorphous chalcogenides

Range
Substance [Pa.s] Method Reference
S 101–102 RC [15]
As2S3 108–1015 RE [16]
As2S3 108–1012 P [17]
As2S3 1010–1012 BB [18]
As2S3 103–1012 P [19]
As2S3 108–1015 P [20]
As2S3 1012–1015 RE [21]
As2S3 104–1012 P [22]
As2S3 108–1012 P [23]
As2S3 104–1012 P [24]
As2S3-AsI3 104–1012 P [24]
As2Se3-S 105–1010 P [25]
As2S3-Tl2S 104–1012 P [26]
As-S 103–1012 P [19]
As-S 101–103 RC [15]
As-S 104–1012 P [22]
As-S 1010–1013 BB [18]
As-I-S 1010–1013 BB [18]
AsTlS2 1012–1014 RE [21]
AsTlS2 106–1012 P [27]
As-Tl-S 1010–1012.5 BB [18]
(continued)
Table 10.1 (continued)

Range
5 12
As-Tl-S 10 –10 P [23]
Ga-La-S 105–108 PP [28]
GeS2 1010–1012 P [29]
GeS2-Sb2S3 106–1013 P [30]
PP
Ge30S70 107–1010.7 P [31]
Ge-S 108–1013 P [29]
Ge-I-S 107–1010.5 P [31]
Se 100–101 RC [32]
108–1013 BB
Se 108–1012 P [33]
Se 1010–1014 RE [34,35]
Se 100–101 TC [36]
108–1012
Se 106–1012 P [37]
Se 100.5–100.5 C [38]
Se 101–100 FS [39]
Se 105–1012 RE [40]
101–100.5 C [41]
Se 104–1017 LV [42]
RE
RC
Se 100–102 C [43]
Se 105–1012 EM [44]
Se 101–100 RC [45]
Se 100–100.5 C [46]
Se 101–100.5 C [47]
Se 107.5–1010 EM [14]
Se 106–109 PP [48]
Se 105–1010 P [25]
Ag-As-Si-Te-Se 107.4 and 108.8 P [49]
As2Se3 108–1015.5 RE [16]
As2Se3 105–1012 P [24]
As2Se3 105–107 PP [50]
As2Se3 107.5–1012 PP [51]
(As2Se3)99Ag1 107.5–1014 PP [51]
As2Se3-AsI3 105–1012 P [24]
As2Se3-Cu 108.5–1013 P [52]
As2Se3-Te 105–1010 P [25]
As2Se3-Tl 105–1010 P [25]
As2Se3-Tl2Se 104–1012 P [26]
As2Se3-Tl2Se 105–1012 P [53]
AsSe-TlSe 105–1012 P [53]
As-Se 105–1010 P [25]
As-Se 103–1012 P [37]
(continued)

Range
10 12
As-Se 10 –10 See note [54]
As-Se 102–1012 TC [36]
As20Ge22Se58 1010–1013 PP [55]
As-Ge-Se 1010–1012 See note [54]
As-Ge-Se 105–107 PP [50]
As-Ge-Se 103–1012 P [56,57]
As-Ge-I-Te-Se 104–109 PP [58]
As-Ge-Te-Se 105–107 PP [50]
As-Ge-Te-Se 104–109 PP [58]
AsTlSe2 106–1012 P [27]
Cl-Se 100.5–100.5 C [38]
Cl-Se 101–100 C [46]
Ga2S3-La2S3 108.5–1011 P [59]
(GeSe2)-(Sb2Se3) 106–1013 P [60]
PP
Ge-Se 106–109 PP [48]
Ge-Se 103–1012 P [61]
Ge-Se 1010–1012 see note [54]
Ge-Sb-Se 106–109 PP [48]
Ge-Sb-Se 105.5–1012 P [62]
Ge-Sb-Se 105–107 PP [50]
I-Se 100–102 C [43]
P-Se 105–1012 P [63]
P-Se 105–1012 P [64]
P-Te-Se 105–1012 P [64]
Sb-Se 106–1012 EM [44]
Tl-Se 101–100 RC [45]
ZnSe 103 C [65]
As-Si-Te 107.4 and 108.8 P [49]
ZnTe 103 C [65]
CdTe
Note: These data were originally taken from other not so well accessible sources (e.g. Ph.D. thesis
or conference)
Table 10.2 Overview of kinematic viscosity of amorphous chalcogenides

Range
Substance [m2.s1] Method Reference
6.5 6
Ag2S 10 –10 TOC [66]
As2S3 105.5–103 TOC [67]
As-S 106.5–103 TOC [67]
AgSbS2 106.5–106 TOC [68]
Cu2S 105.5–105 TOC [69]
Cu2S-Cu2Se 106.5–105.5 TOC [70–72]
Cu2S-Cu2Te 106.5–105.5 TOC [70–72]
CuSbS2 106.5–106 TOC [68]
GeS 106.5–105 TOC [73]
PbS 107–106.5 TOC [74]
SnS 106.5–106 TOC [73]
Se 106–103.5 C [75]
Se 105.5–104 TOC [76]
Se 105.5–104 TOC [77,78]
Se 105.5–104.5 TOC [79]
Ag2Se 106.5–106 TOC [66]
As2Se3 105.5–104 TOC [79]
As2Se3 105–103 TOC [7]
As2Se3 105–102.5 TOC [80]
As2Se3-As2Te3 106–103 TOC [7]
As-Se 105.5–103.5 TOC [79]
As-Se 106–102 C [75]
As-Ge-Se 106.5–102 C [75]
AgSbSe2 106.5–106 TOC [68]
AsTlSe2 106.5–103 TOC [80]
Cu2Se 105.5–105 TOC [69]
Cu2Se-Cu2Te 106.5–105.5 TOC [70–72]
Cu-Se 105.5–105 TOC [81]
CuInSe2 106.5–106 TOC [68]
CuSbSe2 106.5–106 TOC [68]
GeSe 106.5–106 TOC [73]
Ge-Se 105.5–103 TOC [76]
Ge-Se 105.5–103. TOC [77,78]
PbSe 107–106.5 TOC [74]
Pb-Se 107–106.5 TOC [82]
SnSe 107–106.5 TOC [73]
Sn-Se 106.5–106 TOC [83]
Tl2Se 106.5–106 TOC [80]
TeSe 106.5–104.5 C [75]
Te 107–106.5 TOC [84]
Ag2Te 106.5–106 TOC [66]
As2Te3 106.5–104 TOC [84]
As-Te 106.5–105 TOC [84]
As20Ge10Te70 106.5–105 C [75]
AgSbTe2 107–106.5 TOC [68]
(continued)

Range
Substance [m2.s1] Method Reference
6.5 6
Cu2Te 10 –10 TOC [69]
Cu-Te 106.5–106 TOC [81]
CuGaTe2 106.5–106 TOC [68]
CuInTe2 106.5–106 TOC [68]
GeTe 107–106.5 TOC [74]
Ge-Te 107–106.5 TOC [85]
PbTe 107–106.5 TOC [74]
Pb-Te 107–106.5 TOC [85]
SnTe 107–106.5 TOC [74]
Sn-Te 107–106.5 TOC [85]
Acknowledgments This work has been supported by the Ministry of Education Youth and Sports
of the Czech Republic under project: LC 523 and the Czech Science Foundation under grant No:
104/08/1021.
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Chapter 11
Thermal Properties and Related Structural
Study of Oxide Glasses
Marek Liška and Mária Chromčı́ková
11.1 Introduction
Glass is accompanying people from the early times of mankind. First it was the natural
glass generated by the volcanic processes and the glass “produced” by the impact of
meteors on the earth. During formation of the earth, highly siliceous melts of rocks
froze to natural glasses such as obsidians. After some time the people start the glass
melting. Glass was first produced by man about 4,000 years ago in ancient Egypt.
From this time the need of the knowledge of glass composition, structure and proper-
ties is dated. These are the typical questions answered by the glass chemistry [1–6].
The aim of the present contribution is point out the mutual relationships between
the understanding of the glass structure and construction of the thermodynamic
models of glass. Finally the method of studying glass structure based on combined
statistical treatment of Raman spectra with the thermodynamic model will be
presented together with the example of its application on the chalcogenide glasses
from the pseudobinary system As2S3–As2Se3.
11.2 Thermodynamics of Glass Formation [7, 8]
The glass is commonly defined (e.g. [9]) as the non-crystalline solid obtained by
cooling the melt without crystallization. Despite the fact that glass can be produced
also by other ways, like by the sol–gel method or by the amorphization of crystalline
solid [6], it is worth noting the uncommon situation when the method of preparation
M. Liška (*) and M. Chromčı́ková

Vitrum Laugaricio, Joint Glass Center of Institute of Inorganic Chemistry
(Slovak Academy of Sciences) and Alexander Dubček University of Trenčı́n
and RONA, j.s.c. glassfactory, Študentská 2, Trenčı́n SK-911 50, Slovak Republic

180 M. Liška and M. Chromčı́ková
becomes a part of the definition of some kind of substance-material. This indicates the
importance of the kinetic factors connected with the glass formation. On the other
hand the kinetics – namely the kinetics of nucleation and crystal growth – is deter-
mined by the (under-cooled) melt structure. The typical course of the glass formation
from the melt can be seen in Fig. 11.1 where the temperature dependence of the (single
component) system volume, enthalpy and entropy are plotted against temperature.
The melt is in the state of the true thermodynamic equilibrium (corresponding to the
global minimum of the Gibbs energy at isothermal-isobaric conditions) at the melting
temperature Tm. In case of the multi-component system the melting temperature is
replaced by the liquidus temperature, Tliq, and during crystallization the temperature
gradually decreases tracing the binary, ternary. . . eutectic lines of the particular
equilibrium phase diagram until the multi-component eutectic is reached at the
temperature Teut (obviously Teut < Tliq). The true thermodynamic equilibrium of the
single-component system under the Tm temperature is then represented by the crystal-
line state. In case of multicomponent system the equilibrium mixture of crystalline
phases and the melt corresponds to the true thermodynamic equilibrium in tempera-
ture ranging from the liquidus temperature to eutectic temperature. The mixture of
crystalline phases (i.e. without melt) represents the equilibrium state under the eutectic
temperature.
The equilibrium state represented by the equilibrium mixture of crystalline
phases is termed the Crystalline Reference State (CRS) by Conradt [8]. It is worth
noting that the knowledge of the particular equilibrium phase diagram is sufficient
for the knowledge of the composition of the CRS. Thus mole fractions of individual
thermodynamically stable crystalline phases in the CRS can be simply calculated
from the particular phase diagram, namely from the coordinates of particular
eutectics (non-variant points of the phase diagrams).
When the crystallization is avoided (due to sufficiently high cooling rate) the
metastable equilibrium state represented by the under-cooled melt is reached below
the Tm/Tliq temperature. Depending on the cooling rate the system follows the
metastable equilibrium until the glass transition region (the curved part of the dashed
line) where the increase of the viscosity and thus the structural relaxation time leads
Volume, Enthalpy (Entropy)
Melt
Supercooled
melt
Glass
Crystal
Tg Tm Temperature (log T)
Fig. 11.1 The temperature dependence of volume during cooling of the single component melt
11 Thermal Properties and Related Structural Study of Oxide Glasses 181
to freezing in of the structure. Under the glass transition region characterized by the
glass transition temperature Tg the glass is obtained (the dotted line). The kinetic
character of the glass transition is expressed by the fact that decreasing the cooling
rate (but avoiding the crystallization) shifts the glass transition to lower tempera-
tures. Thus the glass structure depends on the cooling rate, i.e. on its thermal history.
It is worth noting that the Tg temperature is in fact not strictly defined. On one side it
depends on the cooling rate but also on the method of its determination (thermo-
dilatometry, DSC, . . .). The structure of the glass can be thus characterized by the
temperature at which the metastable equilibrium structure was frozen in. This is the
fictive or structure temperature Tf introduced by Tool. In the simplified situation of
linear volume temperature dependence presented in Fig. 11.1 the glass transition
temperature coincides with the Tool’s fictive temperature. In fact the V(T) linearity
can be generally assumed with some reasonable accuracy in limited temperature
range. This situation may be reached supposing the temperature independent value
of the volume thermal expansion coefficient:

1 @V
b¼ (11.1)
V @T P
and replacing the exponential volume temperature dependence resulting from the
Eq. 11.1 by the linear approximation:
V2 ¼ V1 exp½bðT2 T1 Þ ffi V1 ½1 þ bðT2 T1 Þ (11.2)
Thus the slopes of linear dependences plotted in Fig. 11.1 are simply related to
the particular thermal expansion coefficients. It is worth noting, that the thermal
expansion of glass can be well approximated by the thermal expansion of the CRS.
In both cases the volume change induced by temperature increase is connected only
with the increase of population of higher vibrational states. The real experimentally
obtained temperature dependence of volume (length) obtained by the thermodilato-
metric measurement is plotted in Fig. 11.2. In the right part of the figure the
experimental result of measurement performed on axially loaded sample during
zig-zag cyclic time temperature regime is plotted. In this case the thermal expan-
sion is combined with the structural relaxation (represented by the hysteresis) and
viscous flow (represented by irreversible shortening of the sample). Such type of
experiment can be used for numerical analysis possessing simultaneously the
information of thermal expansion, structural relaxation (e.g. the parameters of
Tool-Narayanaswamy-Moynihan/Mazurin model) and viscosity [10].
Similar picture can be obtained for the temperature dependence of the system
enthalpy, H. The slope of lines in the H(T) line is then given by the isobaric heat
capacity CP:

@H
CP ¼ (11.3)
@T P
–10
–20
106 * ε
–30
–40
Tg
– 50
300 350 400 450 500
T / °C
–10
106 * ε
– 20
– 30
– 40
300 350 400 450 500
T/ °C
Fig. 11.2 Top: Thermodilatometric cooling curve (cooling rate 5 C/min) of the NBS711 viscosity
standard glass. Bottom: Results obtained for the same glass during cyclic zig-zag time temperature
regime. Points – experimental values, line – model accounting for thermal expansion, structural
relaxation and viscous flow [10]
Like in the case of the thermal expansion coefficient the temperature independent
values of heat capacity can be assumed in the plotted temperature range. Moreover,
using the same reasoning as in the case of thermal expansion, the same value of heat
capacity of glass and those of the CRS can be assumed. It is also obvious that the value
of the heat capacity/thermal expansion coefficient of metastable melt is higher than
those of the glass. It is of academic importance only, that assuming the extremely low
cooling rate we can reach the hypothetic situation when the volume/enthalpy of
the metastable melt will be lower than those of the CRS. Taking into account the
logarithmic temperature dependence of the entropy:
dqrev
dS ¼ ¼ CP d ln T (11.4)
T
the same picture will result when entropy is plotted against lnT. Here the situation
when extremely slow cooling would lead to lower entropy of metastable melt than
of the CRS is paradoxical. This situation is known as the Kauzmann paradox. The
point where the entropy of metastable melt equals to the entropy of the CRS is
considered as an ideal glass. The glass close to this state can be obtained by
amorphization of some zeolites [6].
To describe the thermodynamics of the glass state we have first to discuss the
fact that glass itself is not in the equilibrium state and its structure depends on the
kinetics factors, e.g. on the thermal history or the cooling rate when the glass was
prepared from the undercooled melt. However, following the reasoning of Conradt
[8, 11], we can with some acceptable tolerance accept the glass as a system with
definite (mean) values of thermodynamic quantities.
In analogy with melting where we define the melting difference, Dfus, of any
property as the difference between the melt and crystal at the temperature Tm and
we define the vitrification change, Dvit, as the difference between the glass and
crystal state at T. Once again in many component incongruent systems, the crystal is
replaced by CRS and Tm by Tliq (or an effective mean temperature between the
Tliq and Teut). Due to the assumption CP,glass ¼ CP,CRS that results in the parallel
course of enthalpy temperature dependence the vitrification enthalpy is constant
below Tg, i.e.:
Dvit HðT; T Tg Þ ¼ Dfus HðTg Þ (11.5)
The temperature dependence of the enthalpy of melting can be calculated from

the known (from calorimetry experiment) enthalpy of melting at Tm assuming the
temperature independent heat capacities:
Dfus CP ¼ CP;melt CP;CRS ¼ CP;melt CP;glass ¼ Dvit CP ¼ DCP (11.6)
and consequently:
ZT
Dfus HðTÞ ¼ Dfus HðTm Þ þ DCP dT 0 ¼ Dfus HðTm Þ þ DCP ðT Tm Þ (11.7)
Tm
The entropy of melting at Tm, DfusS(Tm), can be obtained from the equilibrium
condition:
Dfus GðTm Þ ¼ Dfus HðTm Þ Tm Dfus SðTm Þ ¼ 0 (11.8)
and for the temperature dependence of the melting entropy we obtain:
ZT
Dfus HðTm Þ T
Dfus SðTÞ ¼ Dfus SðTm Þ þ DCP d ln T 0 ¼ þ DCP ln (11.9)
Tm Tm
Tm
Using the same reasoning as in the case of vitrification enthalpy, we obtain:
Dvit SðT; T Tg Þ ¼ Dfus SðTg Þ (11.10)
Taking into account Eqs. 11.5 and 11.10 we can conclude that we have described
the thermodynamics of vitrification by the thermodynamic quantities related to
crystallization. Obviously, the driving force for isothermal isobaric devitrification
(by crystallization) is represented by the positive value of the vitrification Gibbs
energy Dvit G(T):
Dvit GðTÞ ¼ D vit HðTÞ T Dvit SðTÞ (11.11)
or

Dfus HðTm Þ Tg
Dvit GðTÞ ¼ Dfus HðTm Þ þ DCP Tg Tm T þ DCP ln (11.12)
Tm Tm
that can be rewritten as:

T Tg
Dvit GðTÞ ¼ Dfus HðTm Þ 1 þ DCP Tg Tm T ln (11.13)
Tm Tm
Because of the positive value of the melting enthalpy and the relationship Tg < Tm it
can be seen from the above equation that the thermodynamic driving force towards
crystallization (i.e. the opposite to vitrification) increases with decreasing temperature.
The following rules of thumb are frequently used in the glass science [8, 11]
1 1 Dfus HðTm Þ
Dvit S ¼ Dfus SðTm Þ ¼ (11.14)
3 3 Tm
3 3 Dfus HðTm Þ
DCP ¼ Dfus SðTm Þ ¼ (11.15)
2 2 Tm
These rules, although almost never correct in detail, give reasonable estimates of
the true values. Inserting the Eqs. 11.14 and 11.15 into the Eqs. 11.9 and 11.10 we
obtain the equation:
1 3 Tg
Dvit S ¼ Dfus SðTm Þ ¼ Dfus SðTm Þ þ Dfus SðTm Þ ln (11.16)
3 2 Tm
leading to the simple relationship between Tg and Tm:
2
Tg ¼ Tm expð4=9Þ ¼ 0:641 Tm ffi Tm (11.17)
3
Moreover, inserting the Eqs. 11.17 and 11.15 into the Eqs. 11.5 and 11.7 we obtain
simple approximate relationship between Dvit H and Dfus H:

3 Dfus HðTm Þ 2
Dvit H ¼ Dfus HðTg Þ ¼ Dfus HðTm Þ þ Tm Tm (11.18)
2 Tm 3
or
1
Dvit H ¼ Dfus HðTm Þ (11.19)
2
Finally, inserting the Eqs. 11.14 and 11.19 into the Eq. 11.11 we obtain the
temperature dependence of the affinity to glass crystallization:

1 1 Dfus HðTm Þ 1 2
Dvit GðTg Þ ¼ Dfus HðTm Þ Tg ¼ Dfus HðTm Þ
2 3 Tm 2 9
5
¼ Dfus HðTm Þ (11.20)
18
and
1
Dvit Gð0Þ ¼ Dfus HðTm Þ (11.21)
2
The above equations are of especial importance because the enthalpies of melting
of crystalline compounds are well experimentally determined and can be obtained
from many sources including various thermodynamic databases [12].
11.3 Glass Structure
What is the structure [1–5] of glass and how to describe it? In contrary to the
crystalline substances where the 3D translational symmetry takes place the struc-
ture of glass cannot be quantified giving a small number of numeric data. Due to the
3D translational symmetry the structure of any crystalline substance is given by
specifying the basic cell and giving the fractional coordinates of all atoms located in
the basic cell. Positions of all other atoms are then simply given by superposition of
translations in the three dimensions. Following this concept the structure of glass
would be given by specifying Cartesian coordinates of all atoms – i.e. about ~1025
data for 1 mol of glass.
On the other side the relatively uniform coordination polyhedra, like SiO4, AlO4,
BO4, BO3 etc., can be found in the oxide glass. Therefore the glass structure has to
be seen in different scales. The uniform coordination polyhedra correspond to the
short-range order (SRO) or the nearest neighbour scale. Going to the next nearest
neighbour we can distinguish between various types of coordination polyhedra
according to their structural position within the glass network. So the SiO4 tetra-
hedra can be classified according to the number of bridging oxygen atoms, con-
necting them with the neighbouring polyhedra. For instance Qi represents the SiO4
polyhedron with i bridging oxygen atoms, i.e. Si(-O-X)i(-O)4-i, where X stands for
any other networkforming atom (Si, Al, B, P,. . .). Going to the next nearest
neighbour (and next-next nearest neighbour) we can reach more detailed structural
description corresponding to the medium range order (MRO). The long range order
(LRO) structural information concerns the large extent of the polymerized 3D
network. Different glass properties are structurally influenced in different extent
of structural arrangement. So some optical properties are defined by the SRO,
mechanical, electrical and thermal properties depend on the MRO and LRO struc-
ture.
On the other hand, the usefulness and applicability of any kind of the structure
description/quantification is limited by the experimental methods enabling its
quantitative determination. So the nearest neighbour and next nearest neighbour
description of networkforming coordination polyhedra is possible mainly due to the
experimental techniques like EXAFS, XANES, NMR and Raman vibrational
spectroscopy.
The most important structural theory of inorganic glasses was developed by
Zachariasen and Waren [13, 14]. According to the Zachariasen-Warren Continuous
Random Network (CRN) theory the following rules are valid for the formation of
glass from simple compounds like SiO2, B2O3, P2O5, GeO2, As2S3, As2Se3, BeF2,
ZnCl2 etc.:
1. An oxide or compound tends to form a glass if it easily forms polyhedral groups
as the smallest building units.
2. Polyhedra should not share more than one corner.
3. Anions (like O2, S2, Se2, F, Cl, . . .) should not bind more than two central
atoms (in simple glasses anions form bridges between two adjacent polyhedra).
4. The number of vertices of polyhedron should be less than six.
5. At least three vertices of a polyhedron must be shared with neighbouring
polyhedra.
These rules can be well understood when we think about the consequences of their
violation. The first rule is in some extent equivalent to the assumption of covalent
(or polar covalent) bonding between cations and anions. In another words the
covalency implies the sufficient strength of the 3D backbone. The violation of

second rule results in more regular (more crystal like) structure and thus the
crystallization of the melt can be expected at least when common cooling rates
are applied. The same reasoning can be applied in the case of violation of the next
rule. The fourth rule can be understood in two different ways. On one side the six
(and more) coordinated polyhedra form more regular structures. On the other side
the high coordination numbers are typically found in ionic compounds, i.e. in case
of electropositive atoms like alkaline and alkaline-earth atoms. The last rule assures
the formation of three-dimensional network. In case of sharing only two vertices the
chain (or cyclic) structure is formed and the covalent percolation of the melt bulk is
not reached.
Zachariasen classified the cations in a glass as follows:
1. Network-formers (NWF, e.g. Si, B, P. . .) with the coordination number 3 or 4.
2. Network-modifiers (NWM, e.g. Li, Na, K, Ca, Sr, Ba, . . .) with coordination
numbers generally greater or equal to 6.
3. Intermediates that may either reinforce the 3D network by cross-linking (coor-
dination number 3 or 4) or weaken the network by depolymerization (coordina-
tion number 6–8). Moreover the intermediate cations cannot solely form the
single component glass.
In case of silicate glasses the NWM oxides (e.g. Na2O) depolymerize the network of
SiO4 tetrahedra by disrupting the oxygen bridges (bridging oxygen – BO) and
creating the non-bridging oxygen atoms O (NBO):
Si O Si þ Na2 O ¼ 2 Si O þ 2Naþ (11.22)
The lack of experimental information about the structure of glass and the
difficulties in describing the polymerized structure in the LRO extent can be
partially solved by the concept of atom-specific structure elements (ASEs) devel-
oped by Sprenger [15–17].
11.4 Deducing the Structure from Stoichiometry
11.4.1 Silicate Glasses
The structure of silica glass is formed by mutually 3D interconnected SiO4 tetrahedra.

Each tetrahedron is sharing four oxygen atoms with neighbouring tetrahedra, i.e. the
structure is on the SRO level composed from Q4 structural units. When alkaline or
alkaline earth oxide is added to silica glass the 3D silica network is gradually
depolymerized due to the reaction (Eq. 11.22). According to the ratio between the
molar amounts ox oxygen and silicon atoms, R ¼ n(O)/n(Si), the structure can be
roughly characterized as composed from the mixture of Qi and Qi+1 structural units
(Table 11.1). In case of specific glass compositions listed in Table 11.1, the glass can
be considered as composed from single type of Q-units.
It is obvious, that when the assumption of the structure formed by only two
successive Q-units (say Qi and Qi+1, where 0 i 3) is applied, the relative amount
of individual Q-units can be simply calculated from stoichiometry. It is worth
noting that this very simple model can provide very important information, e.g. in
the field of bioglass [18, 19]. Let us consider the glass of composition given by the
formula xR2O˙yR’O˙(1–x–y)SiO2, where 0 <x, y < 1, and x+ y < 2/3. Then the
i value is determined from Table 11.1 by the inequality:
x þ y þ 2ð1 x yÞ 2 x y
Ri ¼ Riþ1 (11.23)
1xy 1xy
Then the mole fractions, x(Qi), of particular Q-units are calculated from the mass
balance equations:

ð1 x yÞ xðQi Þ ði=2 þ 4 iÞ þ xðQiþ1 Þ ði=2 þ 7=2 iÞ ¼ 2 x y (11.24)
xðQi Þ þ xðQiþ1 Þ ¼ 1 (11.25)
Unfortunately, the above approach can be used for the rough orientation purposes
only. In fact, Q-units disproportionate and the Q-distribution is given by the
equilibrium of the disproportionation reactions of the type:
2Qn $ Qnþ1 þ Qn1 ; n ¼ 1; 2; 3 (11.26)
Nevertheless even the very simple approach considering the coexistence of only two
successive Q-units, can successfully explain some experimental property – composi-
tion relationships. It is worth noting, that the Q-units distribution represents the SRO
only. Going to the next neighbour the interconnectivity between various Q-units
(MRO) is taken into account. These level of structure description is especially
important for rationalization of the so-called mixed alkali effect, residing in the
Table 11.1 Structural units of silicate glasses and glass compositions of alkali silicate and
alkaline earth silicate corresponding to the R value
Structural unit Ri Coordination formula Glass composition
Qi R ¼ Li, Na, K, Rb, Cs, Fr
R’ ¼ Mg, Ca, Sr, Ba, Ra
Q4 2 SiO4/2 SiO2
Q3 2.5 [SiO3/2O1/1] R2O˙2SiO2, R’O˙2SiO2
Q2 3 [SiO3/2O1/1]2 R2O˙SiO2, R’O˙SiO2
Q1 3.5 [SiO3/2O1/1]3 3R2O˙2SiO2, 3R’O˙2SiO2
Q0 4 [SiO4/1]4 2R2O˙SiO2, 2R’O˙SiO2
non-monotonous dependence of various physical and chemical glasses and melt

properties on the degree of equimolar substitution of one alkaline (or alkaline
earth) oxide by the other.
11.4.2 Other Oxide Glasses
When compared with the silicate glasses the structure of borate glasses is more
complex namely due to the fact that both trigonal BO3 and tetrahedral BO4 poly-
hedra form the 3D network. The pure B2O3 glass is formed from BO3 triangles
(BO3/2) ordered in six-membered boroxol rings. Due to the equilibria between the
three- and four-coordinated boron, the compositional dependence of various physi-
cal properties of alkali-borate and alkaline earth-borate glasses is not monotonous.
This fact is known as the boron anomaly. The structure of borosilicate glasses
where the SiO4 Q-units are interconnected with the BO3 triangles and BO4 tetra-
hedra is even more complex.
Similar complexity is found in the structure of aluminosilicate glasses. The
crucial point determining the structure is the ratio between the molar amount of
alkali and alkaline earth oxides and alumina, i.e. [n(R2O)+n(R’O)]/n(Al2O3)]. In
the peraluminous region where this ratio is less than 1, the substantial amount of
octahedral AlO6 units is found in the network. In the peralakaline region where
sufficient amount of alkalis is present the tetrahedral [AlO4/2]1 units are formed by
the reaction:
Al2 O3 þ O2 ! 2[AlO4=2 (11.27)
The borosilicate an aluminosilicate glasses are presented here as an example

illustrating the possible complexity of the SRO glass structure. Obviously the
distribution of various types of coordination polyhedra cannot be obtained from
the stoichiometry even at the crudest simplifying assumptions. Some results may be
obtained by the purely statistical method assuming the purely stochastic formation
of connection between various structural units. It is in some respect equivalent to
maximizing the configurational entropy of the glass. However the decisive role of
the enthalpy (roughly speaking the energy of various bonds) is completely
neglected by such treatment.
11.5 Thermodynamic Models of Glass
The crucial point of each thermodynamic model is the definition of atomic groupings
that will be considered as components of the system. This definition implies the
structural range described by the particular model. On the SRO level the components
of the system are defined as the particular coordination polyhedra (like Q-units).
The system entropy can be then described by regular mixing of system components
while the enthalpy can be calculated by summing the bond energies. The equilibrium
composition of the system is then obtained by the minimization of the Gibbs energy
constrained by the stoichiometry of the system. Such type of models is critically
reviewed in the works of Gurman and Conradt [8, 11, 20]. As an example of very
simple thermodynamic model of silicate glasses the equations of simultaneous
Q-units disproportionation can be presented (Eq. 11.26). The model is represented
by the values of the equilibrium constants, Kn, of reactions 11.26 – i.e. by the Gibbs
energies of different Q-units.

D r;n Go aðQn1 ÞaðQnþ1 Þ xðQn1 ÞxðQnþ1 Þ
Kn ¼ exp ¼ ffi ; n ¼ 1; 2; 3 (11.28)
RT o ½aðQn Þ2 ½xðQn Þ2
where Dr,nGo is the standard reaction Gibbs energy of Qn-unit disproportionation,

To – the standard temperature, a(Qn) – the activity of Qn unit in the glass (melt) that
is (supposing the standard state of pure substance at standard pressure and temper-
ature) commonly approximated by the mole fraction x(Qn). The values of equilib-
rium constants are calculated from the Q-speciation that is commonly determined
by the 29Si NMR and Raman spectroscopy [4, 5]. However, as far as the energetic
and structure of the ionic bonds formed by NWM cations is not included in the
model, the Kn values are dependent on the type of NWM cations.
MRO structure is reflected in the thermodynamic models based on the (at least
stoichiometric) definition of components as compounds. The computational
complexity of the model depends on the number of components. In the model
of Conradt [8, 11], the components are defined as having the stoichiometry of
crystalline substances forming the CRS. The definition CRS implies that only
the coexisting phases are taken into account. Thus the concentrations of all compo-
nents are straightforwardly defined by the mass balance equations and can be obtained
by solving a set of linear equations. As an example we can present the molar
volume of Na2O–SiO2 glass at room temperature. According the equilibrium phase
diagram the CRS consists – depending on the glass composition – of eutectic mixtures
of: SiO2↔3Na2O8SiO2; 3Na2O8SiO2↔Na2O2SiO2; Na2O2SiO2↔Na2OSiO2;
Na2OSiO2↔3Na2O2SiO2; 3Na2O2SiO2↔2Na2OSiO2; 2Na2OSiO2↔Na2O.
Taking one mole of (1–z)Na2OzSiO2 glass and supposing it is formed by the mixture
of iNa2OjSiO2↔kNa2OlSiO2 we can calculate the molar amount, n, of both
compounds from:
l kþl
nðiNa2 O jSiO2 Þ ¼ z (11.29)
i:l j:k i:l j:k
j iþj
nðkNa2 O lSiO2 Þ ¼ þ z (11.30)
i:l j:k i:l j:k
It was shown by Conradt [21, 22] that the application of his computationally simple
model could explain the dependence of chemical durability of glasses including those
used for radioactive waste vitrification. The rate of the glass dissolution in aqueous
corrosive media has been found correlated with the hydration change of the Gibbs
energy calculated as the sum of the hydration energies of all components of the CRS.
Shakhmatkin and Vedishcheva proposed the associated solutions thermodynamic
model of glasses and glassforming melts [23–30] that could be considered as the
extension of the Conrad’s model. This model considers glasses and melts as a solution
formed from salt-like products of interaction between the oxide components and the
original (unreacted) oxides. These salt-like products (also called associates, groupings
or species) have the same stoichiometry as the crystalline compounds, which exist in
the equilibrium phase diagram of the system considered. The model does not use
adjustable parameters; only the standard Gibbs energies of formation of crystalline
compounds and the analytical composition of the system considered are used as input
parameters.
Obviously, contrary to Conradt’s model [22, 23] the number of system components
is greater than the number of oxides. Thus the equilibrium composition cannot be
obtained on the basis of mass balance equations. That is why the authors present a
calculation of the equilibrium system composition based on the values of particular
equilibrium constants that are obtained from the Gibbs formation energies by the
standard thermodynamic way. More generally, the constrained minimization of
the systems Gibbs energy constrained by the overall system composition has to be
performed with respect to the molar amount of each system component to reach the
equilibrium system composition [31]. The total Gibbs energy is expressed supposing
the state of the ideal solution:
, !
X
N X
N XN
Gðn1 ; n2; ::: nN Þ ¼ Df Gm;i þ RT ni ln ni nj (11.31)
i¼1 i¼1 j¼1
where N is the numberr of components, ni is the molar amount of i-th component,

T is the system temperature (i.e. the glass transition temperature, Tg, for particular
glass) and DfGm,i is the molar Gibbs formation energy of pure i-th component at the
pressure of the system and temperature T. The system components are ordered such
way that Xi (i ¼ 1, 2,. . . M < N) are pure oxides and Xi (i ¼ M + 1, M + 2, . . . N) are
compounds formed from oxides by reversible reactions
X
M
Xi $ ni;j Xj ; i ¼ M þ 1; M þ 2; ::: N (11.32)
j¼1
Let us suppose the system composition given by the molar amounts of pure
unreacted oxides n0,i (i ¼ 1, 2,. . . M). Then the mass balance constraints can be
written in the form:
X
N
n0;j ¼ nj þ ni;j ni ; j ¼ 1; 2; :::M (11.33)
i¼Mþ1
The molar Gibbs formation energies of the melts of pure components may be used
in more advanced version of this model. However these thermodynamic data are
relatively scarce that prevents routine application of the model to the study of
multicomponent systems. On the other hand the errors caused by substituting the
melt by the crystalline state are partially compensated when the reaction Gibbs
energy, DrGm,i is calculated according:
X
M
Dr Gm;i ¼ Df Gm;i ni;j Df Gm;j ¼ RT ln Ki ;
j¼1 (11.34)
i ¼ M þ 1; M þ 2; :::N
where Ki is the equilibrium constant of the i-th equilibrium reaction described by

the Eq. 11.32.
Recently, the thermodynamic model of Shakhmatkin and Vedishcheva and ab
initio molecular dynamics were used for the structural study of nonsilicate binary
calcium aluminate glass xCaO·(1 x)Al2O3, where x ¼ 1/3 (abbreviated as CA2)
1/2 (CA), and 2/3 (C2A) [32]. Both methods provided mutually comparable quanti-
tative results in a reasonable agreement with the accessible experimental data and
previous results of classical MD simulation. The obtained compositional trends
were in agreement with the concept of the increase of Al/O coordination number
(accompanied with formation of Al-triclusters) with the decreasing CaO content in
the per-aluminous region.
When the crystalline state data are used the model can be simply applied to most
multicomponent glasses including the nonoxide once. Especially the application of
the model to the multicomponent industrially produced glasses can be very impor-
tant. Taking into account that the common praxis resides in expressing most of the
multicomponent glass properties in the form of (mostly) additive functions of the
glass composition expressed in percents (even weight and not molar!) of pure
oxides [33–35] using the thermodynamic model unambiguously represents the
significant progress.
The contemporary databases of thermodynamic properties (like the FACT com-
puter database [12]) enable the routine construction of the Shakhmatkin and Vedish-
cheva model [31] for most of important multicomponent systems. It is worth noting
that other methods of thermodynamic modelling of glasses and glassforming melts
(not discussed here, e.g. [5, 36, 37]) do not posses the possibility of routine applica-
tion to multicomponent systems.
11.6 Quantitative Raman Spectroscopy

and Thermodynamic Modelling
Raman spectroscopy is commonly used for study of the glass structure allowing the
SRO and MRO structural units present to be inferred [4, 5, 38–40]. As a typical
example the Qn distribution in silicate glasses can be mentioned. The Raman spectra
are after the background subtraction and thermal correction [39] deconvoluted
typically to Gaussian peaks assigned to various structural groupings. From the
corresponding peak areas the relative abundance of particular structural units is
obtained using the NMR calibration. Sometimes [40] the direct proportionality
between the ratio of peak areas and molar amounts of various structural groupings
is assumed. Relating purely formally the Raman spectroscopy to the absorption
optical spectroscopy the non-validity of the Lambert–Beer’s law is the main mathe-
matical difference between both methods.
Recently Zakaznova and Malfait [41–43] proposed a new method of numerical
treatment of Raman spectra. The basic assumption of this approach is that the
Raman spectra are a sum of partial Raman spectra (generated by individual species)
multiplied by the abundance of the species. Thus a set o Raman spectra obtained for
series of glasses with different composition spans a linear vector space with the
dimensionality given by the number of independent species (i.e. species that
independently vary their abundance) with different PRS. Each spectrum is recorded
with an arbitrary scaling, i.e. it is known with the exception of any multiplication
factors. Principal component analysis (PCA, [44–47]) is then used to find the
number of independent components. Following statistical treatment based on
proper thermodynamic model results in finding the unknown equilibrium constants.
Zakaznova and Malfait use the proposed method for analysis of the binary
K2O–SiO2 glassforming melts with the aim to estimate the temperature dependence
of the disproportionation constant K3 (see Eqs. 11.26 and 11.28). The resulting
values of K3 and reaction enthalpy were in perfect agreement with independent
results obtained by 29Si NMR spectroscopy.
The approach of Zakaznova and Malfait [42] can be mathematically formulated as:
AP ¼ EC (11.35)
where the matrix formalism is used where A(Nw/Ns) is the matrix of Raman spectra
with Nw rows corresponding to Nw wavenumbers and Ns columns corresponding to
Ns samples/spectra, P(Ns/Ns) is the square diagonal matrix with the unknown
coefficients each multiplying one particular Raman spectrum, E(Nw/Nc) is the
matrix of PRS stored columnwise (Nc equals to the number of independent compo-
nents), and C(Nc/Ns) is the matrix with abundances of Nc individual components in
Nc samples. Replacing the product AP with another matrix Acorr we obtain the
equation formally equivalent to the Lambert–Beer’s equation of optical absorption
spectra – here Acorr is the absorbance matrix, E – the matrix of molar absorption
coefficients and C the concentration matrix.
Let us suppose that the C matrix is known from the solution of the thermody-
namic model. Then the non-linear least squares problem can be formulated:
" #2
X
Ns X
Nw X
Nc
FðP; EÞ ¼ Ai;j Pj;j Ei;:k Ck;j ¼ Fmin ¼ min (11.36)
j i k
1.0
0.8 As2S3
As2Se3
0.6
n i / S nj
0.4
Se
As2S2
0.2
AsSe
0.0
0.0 0.2 0.4 0.6 0.8 1.0
1–x
Fig. 11.3 Results of thermodynamic model of the xAs2S3·(1 – x)As2Se3 system
4
As2Se3
As2S2+ Se
As2S3
3
PRS / a.u.
0
100 200 300 400 500 600
Wavenumber / cm–1
Fig. 11.4 Partial Raman spectra of the As2S3–As2Se3 glasses
Without loss of generality we can set P1,1 ¼ 1. Then the unknown Pi,i multiplication
factors are obtained together with the unknown E matrix of PRS by solving the set of
(Ns 1 + Nw Nc) linear equations. Minimizing the Fmin value with respect to some
parameters of the thermodynamic model this method can be used for finding some
values of missing thermodynamic data.
In our recent paper [48] the structure of chalcogenide glasses of the pseudo-binary
system As2S3–As2Se3 was investigated by comparison of the results of the thermody-
namic model of associated solutions with the results obtained by the above analysis of
Raman spectra of xAs2S3·(1 – x)As2Se3 (x ¼ 1; 3/4; 1/2; 2/3; 1/4; 0) glasses. The
results of thermodynamic model are presented in Fig. 11.3. On the basis of experi-
mental values of Tg published in [49] the following linear approximation of Tg
dependence on the glass composition was obtained

Tg K ¼ 478; 85 23:087 x (11.37)
reproducing the experimental DTA with the standard deviation of approximation

sapr ¼ 1.6 K. For each glass composition plotted in Fig. 11.3 the system temperature
was set to the Tg value obtained from the Eq. 11.37.
The PCA method identified three independent components in the studied spectral
series. On the other hand, the thermodynamic modelling resulted in four components
with significant abundance in the studied glasses, i.e. Se, As2S2, As2S3 and As2Se3.
Finally, the correlation analysis proved the strong (correlation coefficient of 0.97)
linear dependence between the concentrations of Se and As2S2. Thus the results of
Raman spectra analysis were in harmony with the thermodynamic model. Solving
the Eq. 11.36 led to the set of PRS plotted in Fig. 11.4.
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Chapter 12
Oxide Glass Structure, Non-bridging
Oxygen and Feasible Magnetic Properties
due to the Addition of Fe/Mn Oxides
Jaroslav Šesták, Marek Liška, and Pavel Hubı́k
12.1 Non-bridging Oxygen and the Structure of Oxide Glasses
To a large extent, the physical and thermodynamic properties of glasses are con-
trolled by their inner structural make up within the so called short range order (SRO)
and its extended viewing as modulated structures identified as medium range order
(MRO) [1–5] often adjacent to nano-crystalline arrangements. Study of physical
nature of nano-scale in-homogeneities in glasses (and in their melts) [6, 8] provides
glass inventors with basis for elaboration of glasses of a required state, from
extremely homogeneous glasses (optical fibre drawing) to nano-crystallized and/or
porous-containing glasses suitable for various application (sorbents, molecular
filters, bioglasses, zero-expansion glass-ceramics, matrixes for nano-scale crystals,
etc.). Thus structural information is essential for material scientists to predict their
thermal, magnetic and other properties.
Over the past 20 years the structural investigation conducted by nuclear magnetic
resonance (NMR), Raman infrared spectroscopy (RIS) [4–7, 9] and various other
techniques of thermophysical measurements (e.g., methods of thermal analysis) have
established that silicate melts and glasses are combination of a relatively small number
of building species though the glass can be perceived as a continuous inorganic
J. Šesták (*)
M. Liška
Vitrum Laugaricio, Joint Glass Center of Institute of Inorganic Chemistry
(Slovak Academy of Sciences) and Alexander Dubček University of Trenčı́n
and RONA, j.s.c. glassfactory, Študentská 2, Trenčı́n SK-911 50, Slovak Republic
P. Hubı́k
Institute of Physics, v.v.i., the Academy of Sciences of ČR, Cukrovarnická 10,
CZ-16200 Praha 6, Czech Republic

polymeric material. The basic structural unit (analogous to organic mers in

polymers) are regular polyhedrons AOn (such as SiO4, GeO4, AlO3, AlO4, BO4,
BO3, PO4, etc.). By help of Niggli’s coordination-substitution formulae [10–12] the
thorough state of completely interconnected netting can be described in accordance
with the Zachariesen’s theory [13] as AOn/2 if the bridges are formed by all n atoms of
oxygen and if oxygen is bridged with two central cations, A- (e.g. {SiO4/2}). In the
case when i atoms of oxygen become bridged with A by a double bond (so called
terminal bonds), such as single component glass composed by phosphorus oxides
containing –mers of {O ¼ P(–O–)3} the drivable coordination formula ensues as
{AOi/1O(ni)/2}, i.e., {PO1/1O3/2}, corresponding thus the stoichiometry of P2O5. In
the analogy with organic polymers the group {AOi/1O(ni)/2} can be considered as
(ni)-functional –mer.
Until now the single component glasses were discussed, which can be extended
in the sense of the Zachariesen’s theory [13] of a randomly interconnected web
(continuous random network – CRN, see also Fig. 12.1) to more complex systems
containing supplements of electropositive elements (such as alkaline oxides, M2O,
or oxides of metals and alkaline earths, M0 O) often called modifying oxides. Their
additions to a single-component netted glass result in the breakdown of bridging
bonds A–O–A and creation of so called non-bridging oxygen (NBO), which can be
described by the equations:

M2 O ¼ 2Mþ þ O2 (12.1)
Fig. 12.1 Two-dimensional illustration of a continuous random network model (CRN) for the
corner-sharing tetrahedral oxides (left) fitting the structure of AO2-type glass (such as typically
SiO2). A-type atoms (Si) are shown as solid small circles while the bridging atoms (O) as open
circles. The modified random network (MRN) correspond to the structure of a modified silicate
glass where Si atoms are shown again as small open circles and filled circles refer to modifiers
(alkalis or alkaline earth cations). BO atoms are located within the network and NBO atoms along
the modifier channels (left middle). A compensated continuous random network (CCRN) model is
represented by an alumino-silicate glass where all O atoms are bridging (Al atoms are shown as
small bold open circles, right middle). Far right is a portrayal of a two-dimensional depiction of
the random network model of a AO3 structure (such as B2O3 glass consisting of B3O6 boroxol
groups and BO3 triangles). B and O atoms are shown as open and filled circles, respectively.
12 Oxide Glass Structure, Non-bridging Oxygen and Feasible Magnetic Properties 201

M0 O ¼ M0
2þ
þ O2 (12.2)
A O A þ O2 ¼ 2A O (12.3)
First two equations are responsible for the dissociation concerning a single mole-
cule of modifying oxides while the third describes breakdown of bridging bond
A–O–A. In the case of typically modifying oxides the equation equilibrium
12.1–12.3 is shifted toward the right-sided products and the structural information
is straightforwardly accessible from glass initial stoichiometry. Interestingly, there
is an apparent analogy with organic polymers mentioning the so called mean degree
of netting [14, 15]. Structural motives, Q, which are appearing throughout glass, is
possible to characterize by a coordination formula {AO(i+j)/1O(nij)/2}, where j is
the number of bridging oxygens associated with a single central atom being ripped
away by the action of oxygen produced through the dissociation of modifying
oxides (j ni). In the case of silica glasses (i ¼ 0, n ¼ 4) there is a direct link
between the concept of the so called Q-notation (i.e., Qk, k ¼ 0, 1, 2, 3, 4) a and
coordination formula, Qk {SiO(4k)/1Ok/2}.
A most common parameter characterizing quantitatively the degree of netting is
the ratio of molar amounts of the oxygen atoms and that of cations in the net-forming
oxide. In the case of silica glass with the composition of {xM2O·yMÓ·(1 x y)
SiO2}, where apply both {0 x, y} and {x + y 1}, it reads:
nðOÞ 2 x y
r¼ ¼ (12.4)
nðSiÞ 1 x y
The value of r ¼ 2 fully corresponds to 100% networking where (in the terminology
of Q-motives) the system is composed exclusively by the structural units Q4. On the
other hand, when the value reaches 4, the system is composed of isolated anions
[SiO4]4, i.e., by mere units of Q0 matching up to the zero netting. At the fully
interconnected web (100% netting) the number of bridging bonds is equal to the
double of compound amount of the silica atoms, i.e., {2(i x y)}. Certainly, it is a
hypothetical reference state in which the oxygen atoms created by the dissociation of
modifying oxides are NOT employed to split the Si–O–Si bridges. In fact, however,
the number of bridges (identical to the compound amount of bridging oxygens) is
equal {2(1 x y) x y ¼ 2 3x 3y}. In this light, the degree of netting
can be defined by the percent of maximum networking, i.e.:
2 3x 3y 2
P ½% ¼ 100 ; xþy (12.5)
2 2x 2y 3
The state of zero interconnected web are represented by glasses with an orthosili-
cate stoichiometry {2/3(M2O, MÓ)·1/3SiO2} or in a more common notation
{2(M2O, MÓ)·SiO2}. From Eq. 12.5 follows that a 100% netting is attainable for
pure quartz glass, only, i.e., in the case of {x + y ¼ 0}.
In contrast to the momentary look of an apparently limited applicability, the

above description is, in fact, useful for a generalized description of a variety of
glasses containing multiple glass-forming and modifying oxides. The only condi-
tion is the internal stability of theirs internal coordination spheres, i.e., values i a n
emerging in coordination formula {AOi/1O(n-i)/2} of a glass formed by mere pure
glass-forming and thus net-forming oxide. Moreover, the basic significance of
netting parameter r, gives a possibility to correlate its value with various techno-
logically important properties; for example increasing r correlates with the increas-
ing viscosity, chemical durability and/or decrease of Tg while lessening an
associated value of thermal expansion. It is clear that such an approach cannot be
fully applied to such oxides which do not possess a clear glass-forming and/or
modifying status thought it is even applicable for anionically mixed glasses, such a
oxynitride glasses [7]. A specificity of alkali aluminosilicate glasses it can be
mentioned as the trivalent aluminium cation does not always act as a network
former. The structural configuration depends upon the r (¼Al2O3/R2O) ratio.
Apparently, if the parameter r becomes greater than one the Al3+ goes into the
network having a tetrahedral coordination. Like (BO4) group, the excess of unit
negative charge on (AlO4) group is satisfied by alkali ion in the neighbourhood.
Thus, the further addition of an aluminium ion to a silicate glass removes one NBO.
At the ratio equal one there is no NBO in the structure. For the further additions of
Al3+, when the ratio r becomes greater than one, the Al3+ cations enters the network
as a modifier in the tetrahedral coordination and the formation of (AlSiO6) groups
turn out to be unlikely due to the packing difficulties. Presumably three of the
oxygens are then non-bridging and three remaining (already) bridging, which
favours the formation of triclusters, where an oxygen is shared between three
tetrahedrons (one AlO4 and two SiO4 or vice versa). The first type of tricluster is
electrically neutral while the second one requires an associated alkali cation. In
principle, the triclusters appear equivalent to an Al3+ cation in the form of a
modifying ion and are bonded to three NBO.
In other melts of the ternary system, such as CaO–TiO2–SiO2, silica oxide acts
always as the network-forming oxide while calcium oxide takes always action as
the modifier of the poly-anionic network. The role of TiO2 can be twofold again
acting either as a modifier or as a complementary associate undertaking thus the
function of the network-forming oxide. Depending on the behaviour of TiO2 in the
melt, the structure and thus also the activities of the present components of the melt
change revealing variously possessed NBO. The structural role of Ti4+ in titanium
silicate melts is accordingly a complex function of several variables, namely TiO2
and SiO2 concentrations, type and content of modifying cations [8] as well as
temperature. Recently, the structural characteristics of many important glasses
and melts (including silicates, borates, aluminosilicates, halides and chalcogenide)
are drawn in additional details using results of the recent spectroscopy [7] and
scattering experiments by Greaves and Sen [2] and the quantitatively applied
Raman spectroscopy as introduced by Malfait et al. [9].
12.2 Reflection on Volume of Ionic Sites in Silicate Glasses

and the Applicability of NBO Concepts
As mentioned above various physico-chemical properties of silicate glasses can be

correlated with the concentration of certainly modelled structural units. Properties,
such as molar volume, refractive index, molar refraction, thermal expansion and
even some magnetic properties can then be practically described by additive
relations. In these relations a specific factor can be used for each structural unit.
The factor depends on the type of property under consideration. The obtained
factors could successfully be used to calculate the magnitude of those physical
properties in binary alkali (or alkaline earth) silicate glasses and in other multi-
component glasses. Molar abundant data of alkali and alkaline earth silicate glasses
have been recently used to calculate the free volume [14] associated with the
presence of BO (bridging oxygen) and NBO as well as modifier ions. The volumes
of voids in the structure are of special importance for the transport properties. The
mobility of movable ions is affected to a great extent by the openness (nature) of the
glass matrix. Such an “open matrix”, exhibiting higher concentration of NBO ions,
is characterized, e.g., by higher electric conductivity than a closed one. Different
spectroscopic studies indicated that up to about 33 mol% of alkali oxide (R2O) so
called Q3 units are formed at the expense of Q4 units where Q3 units are SiO4
tetrahedra having one NBO ion per tetrahedron, whereas Q4 units are SiO4 tetra-
hedra without NBOs. For more than 33 mol% of R2O about 50 mol% of Q3 units
converts into Q2 units the latter representing SiO4 tetrahedra with two NBOs for
each tetrahedral [3, 4]. Results of Raman spectroscopy revealed that the conversion
process continues along with the increasing R2O content, from Q2 to Q1 (for > 50
mol% R2O) and finally from Q1 to Q0 (for >60 mol% R2O) where Q1 and Q0 refer
to SiO4 tetrahedra having, respectively, three and four NBOs per each Si4+ cation.
In the light of these findings some relations could be estimated which describe the
concentration of structural units as a function of modifier oxide concentration in
binary alkali or alkaline earth silicate glasses.
The relations were modified to calculate the concentration of structural units in
mixed alkali silicate glasses on basis of the molar volume (Vm) of a glass, which can
be given in the form of an additive relation, such as Vm ¼ Nu Vu, where Nu is the
number of the structural units u per mole of glass and Vu is the volume of this unit
[14]. On the basis of the structural unit distribution in alkali silicate glasses and the
volumes that the constituting ions occupy in the matrix (VSi, V’, VR and VO), the
volumes of individual structural units can be given as follows:
V4 ¼ VSi þ 2V’ ; V3 ¼ VSi þ 1:5V’ þ ðVO þ VR Þ;

(12.6)
V2 ¼ VSi þ V’ þ 2ðVO þ VR Þ;
V1 ¼ VSi þ 0:5V’ þ 3ðVO þ VR Þ and thus V0 ¼ VSi þ 4ðVO þ VR Þ: (12.7)

Here VSi, V’, VO and VR are, respectively, the volumes occupied by Si4+, BO (’),
NBO (O) and alkali ion (R). The volume occupied by an ion is the volume of ion
itself and its associated space (its free volume) in the matrix. These relations
can be used to calculate V’ and VO. Thus on the basis of above equations we may
write Vm ¼ Ni Vi with Ni being the number of the ions i per mole of glass and Vi is
the volume occupied by that ion in the given glass. The last above relation can be
reformed to Vm ¼ NSi VSi + N’ V’ + NO VO + NR VR, where NSi, N’, NO and NR
are, respectively, the number of Si4+, BO, NBO and alkali ions per mole of glass.
The radius of Si4+ ion in oxides is ~0.26 108 cm whereas that of O2 ion in
silicate units is 1.2 108 cm. Thus the volume of Si4+ ions in vitreous SiO2 and
then in any modified silicate glass is ~0.5% of the volume of O2 ions. Therefore, in
the first approximation, the first term can be neglected with respect to the other
terms Vm N’ V’ + NO VO + NR VR and further accepting that NO ¼ NR, we
obtain Vm N’ V’ + NO (VO + VR). Any NBO ion is always bound to an alkali ion
(or a half alkaline earth ion) and therefore the term in the brackets can be looked as
an undividable quantity that can be labelled by VB, namely VB ¼ VO + VR It
follows that Vm ¼ N’ V’ + NO VB which equation can be solved simultaneously
for two values of Vm close to each other to get V’ and VB.
As the modifier oxide content increases the total contribution of BO ions (N’ V’)
decreases, whereas that of the NBO bindings (NOVB) increases. The decrease in
(N’ V’) is related to the decrease in the SiO2 content. Up to 33 mol% of the modifier
oxide, the values of (N’ V’) are mostly the same for all types of modifier ions. This
behaviour reveals that V’ is not affected by the type of modifier ion up to one NBO
ion per SiO4 tetrahedron. Above this concentration (N’ V’) varies slightly with the
type of modifier oxide. On the other hand, (NOVB) increases when increasing the
modifier oxide content. There is a marked difference between the values from one
type of modifier to another showing that Vm of a glass decreases with increasing
modifier oxide concentration for |d(N’ V’)/dC| > d(NO VB)/dC and vice versa. The
increase in (NOVB) for a constant modifier concentration and a change of its type
(such as from Li2O–SiO2 to Cs2O–SiO2) reveals that the volume VB becomes
greater with the field strength of the modifier.
The cooperatives of the field strength are expressed as q/r2, where q is the charge
of modifier ion and r is its radius. It is observed that in all cases the dependence of VB
on field strength can be roughly expressed by linear dependence on r2/q, namely by a
relation VB ¼ s(r2/q) + 13.737 1024 cm3. It follows that VO has a constant value
and that the increase in VB with increasing VR is related to the size of the alkali ion.
A greater alkali ion size means lower field strength and weaker bond with the NBO
and this leads to a greater VB value. With reference to the size of the O2 ion in
silicate units (~7.24 1024 cm3) it can be said that on average each NBO is
associated with a space of ~6.50 1024 cm3. By neglecting the volume of Si4+
ion it can be concluded that, in this region, the average associated space is
15.39 1024 cm3 per each BO ion.
It was concluded [14] that the free volume associated with the BO is almost
constant (15.39 1024 cm3) for all modifier ions below 33.3 mol% of addend
oxide. In the case of alkali or alkaline earth silicate glasses it decreases with the
increasing number of NBO ions per a structural unit and/or radius of the modifier
ion. In all cases the NBO ion is associated with a constant free volume and the
modifier ions are associated with a free volume that increases with increasing
number of NBO ions per a structural unit and/or radius of the modifier ion. The
above model explores the change in the free volume due to changing the concen-
tration of alkali oxides in mixed alkali silicate glasses where the free volume is
always related to a certain type of alkali oxide and intensifies with its increasing
content.
It is also in agreement with ref. [15], which showed that the partitioning of NBO
in silicate melts is not identical to the segregation of Ca, Mn, Mg, and Fe divalent
cations [8, 15] between solid (e.g. olivine) and melt, which was revealed as a non-
equivalent presence of NBO in the main structural units of Q4, Q3, and Q2 type.
For melts with high Q3/Q2-abundance ratio the increasing ratios of Na/(Na + Ca)
and/or Na/(Na + Ca + Mn + Mg + Fe) result in a systematic decrease of the parti-
tion coefficients because of ordering of the network-modifying Ca, Mn, Mg, and Fe
among NBO in Q3 and Q2 structural units. This decrease is more pronounced at the
smaller value of ionic radius of the cation. With decreasing Q3/Q2 abundance ratio
(e.g., less-polymerized melts) this effect becomes less pronounced. Activity vs.
composition relations among network-modifying cations in silicate melts are,
therefore, governed by availability of energetically nonequivalent NBO in individ-
ual Qn-species in the melt. As a result, any composition change that enhances
abundance of highly depolymerized Qn-species will cause partition coefficients to
decrease.
This concept of NBO was applied for various cases and treated under different
theories [15–19] as well as for the determination of oxygen states in iron-rich borate
glasses [19] (see next paragraph). In the forthcoming text we would like to present
two examples of analysis regarding the material properties and the role of NBO
with respect to the behaviours of matrix glasses. As for the soda–lime–silica glass
system, the correlation between the structural parameters characterized by the
anionic constitution and the bioactivity has been investigated by Koga et al. [17].
As a simple way for describing the glass composition, Steevel’s parameters [18],
X and Y, were employed, which indicate respectively the mean number of NBO
and BO ions per polyhedron in the glass lattice. These Steevel’s parameters [17, 18]
can be plainly calculated from the molar composition of glass assuming the
following equations, X ¼ 2R Z and Y ¼ 2Z 2R where Z and R denote the
mean number of all types of oxygen per polyhedron and the ratio of the total
number of oxygens to the total number of glass-forming cations in glass, respec-
tively. As for the soda–lime–silica system, the pure silica glass SiO2, pseudo-binary
Na2O–2SiO2 glass and pseudo-ternary CaO–Na2O–2SiO2 glass are characterized
by (X, Y) ¼ (0, 4), (1, 3), and (2, 2), respectively. With X > 2 and Y < 2, the
concentration of BO ions is appreciably large and the glasses in this compositional
region are commonly called as “invert glasses” (typically X ¼ Y). Some further
data [20] insinuated a rather good bioactive characteristic for similar borate and
phosphate glasses accentuating their potential use as a sympathetic template for
analogous strategy in bone-tissue formation.
During the last several decades numerous compositions of alkali borate glasses
were studied showing the glasses structure with composition (B2O3)12-x(R2O)x
where (R ¼ Na, Li, Rb, K) discriminative toward the B–O network, built up from
planar three coordinated and tetrahedral four coordinated boron atoms. Pure B2O3
contains only three coordinated boron atoms, which glass network is almost
completely made up of randomly connected boroxol web but if alkali oxide is
added some of these units are transformed into four coordinated tetrahedral origi-
nally suggested by Krogh-Moe [21, 22]. Adjacent BO3 and BO4 groups are linked
by bridging oxygen atoms, building the glassy network. At higher alkali oxide
concentration (often greater than 20 mol%), the formation of non-bridging oxygen
(NBO) is suggested to amplify providing that the boroxol rings in these glasses are
transformed into rings incorporating one or more four coordinated boron atoms.
The presence of magnetic cations such as Mn3+/Mn2+ or Fe3+/Fe2+ in such glasses
involves their interactions with surrounding oxygen, which has been intensively
studied for behaviour (redox potential of iron oxides as a particular additive in silicate
melts [23–29]). It is widely believed that a similar behaviour can be expected in the
other glass-forming mixtures. The details of these interactions depend on the type of
oxygen polyhedral around ferric and/or ferrous cations. If, for example, Fe3+ is
considered in tetrahedral (VI) coordination (Fe3+(IV)/O22) and Fe2+ is in octahedral
(VI), we can compose a following relation (Fe3+(IV)/O22) , 4Fe2+ + O2 + (2O22).
However, if the (2O22) anions in the melt are under the affect of the other structural
units co-existing in the melt, further associated processes, mostly depolymerization,
may occur. An alternative is that both Fe3+and Fe2+ are octahedrally coordinated
providing thus optional relation 4(Fe3+(VI)/O22) + (2O22) , 4Fe2+ + O2, which is
adjacent to opposite process of polymerization. Certainly, it is plausible that both
Fe3+and Fe2+ cations may undergo coordination transformation simultaneously,
which would result in structural changes touching all variables as illustrated by the
relation (Fe3+(IV)/O22) , (Fe3+(VI)/O22) + (2O22). Thus any glass property of
iron-bearing mixtures can be related to the ratios of Fe3+/Fe2+ and/or Fe3+/SFe [7] the
latter being also controlled by other glass-modifying admixtures such as CaO, Na2O,
K2O with positive and MgO or Al2O3 with negative correlations towards the redox
data and thus affecting the level of NBO. Simply saying, it implies that the Fe3+/Fe2+
ratio decreases with increasing NBO in bulk melt.
12.3 Magnetic Properties of Non- and Nano-crystalline

Splat-Quenched (Fe,Mn)2O3–B2O3
Clearly, the action of alkali ions as modifiers in borate glasses is more complex than
the one in silicates where the NBO concentration increases almost linearly with the
alkali content. On the other hand, in borate glasses the modifier may act according
to three specific varieties of mechanisms [21, 22], the one prevailing depends on the
modifier content, possibly defined on basis of the stability of polyborate groupings,
which may similarly occur in borate crystals. However, the presence of magnetic
cations turned into the centre of investigation [29–37].
For example, let us present our experimental work, which was based on nontradi-
tional glasses prepared by melting raw material (mixed from Fe2O3, MnO2, SiO2,
Al2O3, B2O3 and K2B4O7) and adjusted to the base composition of 31Mn1.5Fe1.5O4 +
69B2O3 (marked as 0) and with the addition of 3% K2O (K), Al2O3 (Al) and/or SiO2
(Si) as well as the mixture 2% K2O and 2%Al2O3 (K + Al). After melt temperature
equilibration (~1100 C) and splat quenching between two copper plates, with the
estimated cooling rate of about 102 K/s [19, 33–36], a solid specimen (of about 1.5
mm thick) is formed. Its glassiness was examined by XRD and SEM and the given
cation content was approved by wet chemical analysis. Furthermore, thermal beha-
viour was measured by differential thermal analysis (DTA) [35], electric conductivity
[37] and magnetic susceptibility (by a modified Faraday method using an inhomoge-
neous field in the temperature range from 4.2 up to 270 K) [19, 36]. Determination of
the hydrostatic sample density r and the well-defined knowledge of composition can
be further used to provide the average volume per cation, Vc, or the average volume
Vmg per magnetic cation. The cubic roots of volume give us an estimate of the average
distances, i.e., ac (amg) ¼ {(M/r) u (1/n)}1/3, where n is the number of magnetic
cations in the formula units. Similarly we can determine the average volume per an
oxygen atom, Vox ¼ {(M/r) u (1/nox)} where nox is the number of oxygen atoms in the
formula unit. These data are summarized in Table 12.1.
Basic explorative interest was pointed towards magnetization curves from which
typical profile it is apparent that at higher temperatures the reciprocal susceptibility
1/w is approaching a linear dependence that can be extrapolated to high negative
temperatures (of the order of 102 K). Relatively strong interactions among the
present magnetic moments can be deduced preferring their antiparallel orientation.
However, there is no trace of anomalous behaviour at low temperatures bearing
witness on an expected ordering of an antiferromagnetic or ferrimagnetic type.
On the other hand, the 1/w temperature dependence displays a downward curvature
at low temperature, which can be explained by a simplified model of coexistence of
Table 12.1 Properties of unconventional glasses with magnetic moments. Tg is the glass-
transformation temperature [ C] and stability indicates a relative ratio (Tc Tg) with respect to that
of the undoped sample (0). Similarly is given the relative values for peak area of crystallization and that
for related activation energy. The sample density [g cm3] is measured by a hydrostatic method while
the average distance between the magnetic cations amg [in 108 cm] is calculated. Moreover, the
average volume of oxygen anions Vox is also determined (181024 cm3). It worth noting that the
oxygen volume is about 5% higher than that often exploited from tables (17 1024 cm3) and even
much higher in the case when assuming the volume of bridging oxygen depicted in the first section
(15.34 1024 cm3), which is likely caused by the specificity of borate matrix involved
Sample Tg stability Area Energy density dist. amg vol. Vox
0 528 (1) (1) (1) 3,251 4.033 18.42
K 515 0.64 1.0 1.39 3.215 4.096 18.80
Al 525 1.15 1.0 0.42 3.104 4.147 18.15
Si 531 1.0 1.07 0.82 3.338 4.054 17.73
K + Al 520 0.91 0.97 0.89 3.198 4.122 18.74
two kinds of magnetic moments. Certain amount of moments, with a relative

concentration t is not exposed to any appreciable interactions from their neighbours
and can be treated as paramagnetic whereas the remaining (1 t) amount behaves
like antiferromagnetic nano-clusters characterized by a paramagnetic Neel temper-
ature, Y, see the Table 12.1.
Introducing an additional assumption that both these kinds of moments have the
same average magnitude an expression for the temperature dependence of recipro-
cal susceptibility can be easily derive in the form
1=w ¼ fT þ ð1 tÞYg=c t=fT=ðY þ tÞgfð1 tÞY=cg (12.8)
Here c is the Curie constant, T is the absolute temperature and the meaning of t and
Y was shown above. The main features of this dependence reasonably agrees with
our experimental data so that we could convincingly determine from them the
model parameters such as the Curie constant c, the paramagnetic Néel temperature
Y, and the concentration t. In order to do that let us first note, that the asymptotic
behaviour at high temperatures is only governed by the first term of Eq. 12.8 and the
extrapolated Y0 corresponds to (1 t)Y, the slope being equal to 1/c. Getting an
estimate of t from Eq. 12.8, we calculated temperature T 0 at which the full
dependence of 1/w is equal to three-fourth of the first term linear in T. The
concentration t of paramagnetic moments is then given by
t ¼ fT 0 ðT 0 þ Y0 Þg=ð3Y02 þ T 02 Þ (12.9)
After t is calculated we can determine Y from Y0 /(1 t). All relevant data are
summarized in Table 12.2.
The Curie constant c may be further used to calculate the average magnetic
moment, m0 per an atom of transition metal using the resolved chemical composition
of our sample, i.e.,
cg ¼ Ng m02 =ð3kT Þ ¼ NA am02 =ðMkT Þ (12.10)
Here the subscript in cg stresses the fact that we are using susceptibilities and
consequently Curie constants per gram (g), Ng is the number of magnetic moment m0
in one gram and NA is the Avogadro number and 3a is equal to the number of
magnetic atoms in the formula unit (see Table 12.2).
Table 12.2 Magnetic moment-related properties of nontraditional glasses. For details see text
Sample Y0 t Y cg (m0 /mB)2 (m0 /mt)
0 140 0.16 167 2.22 22.74 0.83
K 115 0.125 131 2.25 24.3 0.86
Al 77 0.17 93 1.89 20.1 0.78
Si 130 0.105 145 2.56 27.35 0.91
K + Al 121 0.15 121 2.13 22.92 0.83
Magnetic properties consist of an extrapolated temperature Y0 [in K] and the

paramagnetic Neel temperature, Y [K] estimated for a given concentration of
antiparallel ordered magnetic moments (1 t). The value cg is the Curie constant
per gram [102], m0 is the average magnetic moment per atom of transition metal
yielding the revoking squares of average moments (m0 /mB)2. Using a theoretical
value of mt equal to 5.76 mB we can utilize it for the evaluation and consequent
comparison of experimental data in the form of ratio (m0 /mt).
The squares of the average moments derived from Eq. 12.10 are listed in Table 12.2.
In order to calculate the expected average magnetic moment of the present cations we
suppose that equilibrium between various valencies of manganese and iron does not
deviate in the glass from that stoichiometry found in the standard Mn-Fe spinels with
the same Mn3+/Fe3+ ratio, i.e., Fe1.53+Mn0.53+O4 [35, 36]. We then ascribe to each
cation a single spin-only value of
0
mt2 ¼ g2 sðs þ 1Þm2B (12.11)
with g ¼ 2, s is the quantum spin number, and mB is Bohr magneton. Assuming

squares of the moments in accordance with Eq. 12.11 we arrive at a theoretical
value of mt ¼5.76 mB which is further used for comparison with the experimental
values in the last column of Table 12.2.
It is worth noting that DTA was measured on few pieces of glass buried in the
powder of fine silver particles placed inside the DTA sample-cell because similar-
sized glass pieces were used in all other measurements. Moreover, powdering of
glass changed its properties slightly decreasing Tg (for sample 0: ! 524 C) but
doubling crystallization heat (A/Ao 2.1) due to the increased surface (a slight
increase of the activation energy E/Eo ¼ 1.2 was infertile negligibly enhanced by
anticipated surface crystallization).
Glass-forming abilities and associated cation compatibilities with various levels
of B2O3 shown a decrease from Mn3+ through Mn2+, Fe3+ to Fe2+ and, consequently,
we can expect that the transition metal ions will be incorporated into the glass
network along this sequence. This idea was corroborated by our findings about
crystallization [35], which for boron glasses containing iron and manganese cations
crystallization yields the crystal phase enriched in Fe with the remaining glass
matrix augmented of Mn (than that corresponding to the average Mn/Fe ratio
[36]). The stability of glasses with respect to the different admixtures can be
analyzed on the basis of DTA data, see Fig. 12.2. The ratio of the differences
between the temperature of glass crystallization and transformation of the doped
glass to the original one (o) may be taken as a measure of the relative glass stability.
It is equal to 1 for SiO2 admixture, which is in accordance with the standard concept
that SiO2 tends to form a separate network within B2O3 matrix so that the original
matrix remains essentially unaffected. On the other hand Al2O3 tends to enter B2O3
matrix and to span its network into three dimensions, which results in an apparent
gain in the relative glass stability. Potassium cations with a relatively high ionic
radius deform in their vicinity the B2O3 network, which may thereafter act as
Fig. 12.2 Left: DTA (Netzsch instrument) curves of glasses and resulting data applicable to their
stability related to Tg (as the front step-wise change) and Tc (as the onset of the exothermal
crystallization peaks), cf. Table 12.1. Right: Temperature dependence of the reciprocal magnetic
susceptibility, 1/w, extrapolated to negative temperatures of Neel temperature, Y0 , see text and
Table 12.2
potential sites for nucleation and crystallization. In consequence the glass stability
decreases. All that is also in accordance with the change in activation energy whose
high value for K2O admixture indicates an easier crystallization process started from
a large number of ready-to-grow nuclei while its lower value for Al2O3 indicates
rather slower process controlled by diffusion.
Let us turn now our attention to the magnitude of magnetic moments given in
Table 12.2. From the last columns it can be seen that for the basic glass (without
admixtures) this value is considerably lower than the moment expected for free
ions. Various admixtures bearing the magnetic moments are able of further chang-
ing the moment per atom of transition metal and we believe that both these
phenomena are symptoms of the number and type of incorporation into the net-
work. The reasons may be at three-fold:
1. Increased interaction of incorporated transition metal ions via the intermediating
oxygen, which may result in their antiferromagnetic pair (or even small cluster)
ordering thus substantially lowering (or even excluding) the contribution of
these moments to the Curie constant.
2. The spin moment of covalently bound cations, e.g., Fe3+, may be lowered due to
the transition to low-spin state. These effects are usually described in terms of
strong crystal fields revealed by some compounds supportive of these cations
though not so common in oxides.
3. To a large extent, the orbital contribution to the magnetic moment is affected by
covalent bonding but in our quantitative estimates we only capture into account
the spin moment so that this influence cannot be weighted up in a simplified way.
In any cases it seems that the incorporation of either Mn (or less probably Fe) ions into
the glass network can only lower its magnetic moment. The number of ions
incorporated will be given by the equilibrium of the reactions discussed in the
introductory paragraphs, Mn2+ + O2 ¼ Mn + O and/or 2Mn3+ + 3O2 ¼ 2Mn+
+ 2O + O2 ¼ 2Mn + 3O , where the number of primes denotes the multiplicity of
the bond of the given atom in the network. The surface properties, however, may
become effective (strongly related to the extent of interfaces in nano-crystalline
system [41], which is not subjected herewith).
Concluding on basis of DTA data and magnetic moment determination we
suggest the following mechanism for the influence of modifying admixtures. SiO2
enters the B2O3 matrix as (Si4+ + 2O ), which likely increases the concentration of
BO [29]. The NBO equilibrium is thus shifted to the left hand side, i.e., Mn and/or
Fe cations are released from the network. The addition of Al2O3 has the opposite
effect [1, 38], because it prefers the incorporation in the form of AlO4 groups
whose negative charge is compensated by bonding transition metal ions into the
network, which means a shift of equilibrium to their right hand side. The expected
effect of K2O admixture as the donor of O2 should be even stronger than that of
Al2O3 and point in the same direction. Our magnetic measurements show, however,
a minor influence though the DTA displays rather significant changes. Similarly,
the introduction of K2O into borate glass would change the B2O3 matrix itself so
that we can expect both the softening of the glass structure and a smaller effect
exerted upon the state of the transition metal ions.
The strength of magnetic interactions can be estimated from the value of Y as
revealed in Fig. 12.2. This quantity Y actually gives the lower limit for the entire
interactions. In a rough approximation, the effect of various admixtures can be
explained by the average distance between magnetic ions presented. In quantitative
agreement along our expectations, the value of Y smoothly decreases with the
increasing distance. Let us finally comment on the magnitude of this concentration,
which was calculated for the accepted model on the basis of Eqs. 12.8 and 12.10, and
given in Table 12.2. The moments, described here as paramagnetic, do not have a
sufficient number of magnetic cations as their nearest neighbours and, for an assumed
random distribution, the number dependence on the average concentration of mag-
netic atoms turn up to be an increasing function for low values attaining a maximum
(and again decreasing). The composition of our glasses clearly belongs to the latter
part of this dependence, which explains the seemingly contradictory behaviour of the
t-value with various admixtures. Namely Si releases transition metal atoms from the
network, which factually decreases the concentration t and the effect of Al is laying
just on the opposite direction. For describing magnetic susceptibility and approving
consistency of our model, we plotted in Fig. 12.2 the concentration t against the
relative magnetic moment m0 /mt (see Table 12.2). In agreement with our discussion,
admixtures increases the number of transition metal atoms incorporated into the
network, which decreases the average magnetic moment and increases the concentra-
tion t and vice versa. Antiparallel ordering was also indicated conforming that the
temperature of magnetic ordering (TN) is proportional to the square of mean number of
interacting neighbours and the Neel temperature (Y) lies lower than that for analogous
polycrystalline ceramics. Particularity of ferromagnetic or speromagnetic properties

(of disordered systems with canted spins) were previously identified in metallic glassy
alloys [43], which various compositionally different systems found already practical
applications [42–44].
12.4 Specific Case of Speromagnetic Behaviour of Rapidly

Quenched and Laser Melted (Fe,Mn)2O3–(B,Bi)2O3
The substitution of Bi2O3 for B2O3 [39] increases, however, the upper glass-forming
limit for Fe2O3 to about 20 mol% (such a composition was still vitrifiable by standard
splat quenching method at the cooling rate of ~102 K/s). In the contrast with the
simple (Fe, Mn)–B–O system, the substitution of Fe by Mn in the Bi2O3-rich matrix
did not improved the glass-formation but only decreased the Curie temperature.
Substitution of B for Bi in Fe–B–Bi–O system changed the phase relation substantially
enhancing crystallization tendency of crystalline borates on account of previously
precipitated crystalline phases of Fe4Bi2O6 and FeBiO3 leaving behind glassy matrix
with higher magnetic moments.
However, the Fe2O3-rich composition (such as the end compound FeBiO3)
required for its vitrification much powerful quenching than is a basic splat cooling
used above. In some cases it was necessary to exceed rates above 103 K/s. Such a
rapid freeze-in of melts could only be attained by a specially developed techniques
usually aided by fast laser melting and consequent melted drop pressing in a
specially modified coolers, such as twin-rollers [31, 37, 40] being worth of a more
detailed description.
These quenching options radically extended the range of vitrified compositions,
though the glassy samples were very tiny and difficult to become fully reproducible.
From magnetic susceptibility measurements, the temperature dependence of (Bi–B)
(Fe–Mn)–O glasses revealed certain evidence of stronger interaction of antiferro-
magnetic types [19, 32]. The composition containing not only Bi but simulta-
neously B, exhibited a definite Curie-Weiss behaviour (Fig. 12.3). Samples with
Bi and Mn probably contained cations’ multivalency as a result of their broader
distribution, showing their various degree of incorporation into the glass network.
Only difficult to prepare glassy FeBiO3 provided indication of magnetic measure-
ments explainable on the basis of weak ferromagnetism, i.e., so called speromag-
netism, probably caused by canted spins in the antiferromagnetic sub-lattice, which
was early suggested to take possibly place in the Fe–Bi–O system and which
magnetic ordering was already experimentally noted in metallic glasses [43].
The type of incorporation of cations into the Bi–B–glass network and the
formation of NBO predictably affects the resulting magnetic moment. Presumably,
the addition of Bi2O3 to the B2O3 matrix prefers to undertake web incorporations in
the form of BiO33 groups, their negative charge being compensated by pushing
transition metals to bond within the network. Thus the concentration of bridging
Fig 12.3 (a) Magnetization curves of the antiferromagnetic-like as-quenched Fe–Mn–Bi–O glass
viewing the experimental curves and their temperatures of measurements from upper curve at 4.2
K proceeding down with the increasing stepwise temperature changes along 24.5, 50.0, 75.0,
100.0, 125.0, 150.0 175.0, 200.0 up to the final 157.0 K. (b) Temperature dependence of the
reciprocal magnetic susceptibility, 1/w, portraying various magnetic behaviour, starting from
paramagnetic (arbitrary ordering of magnetic moments "↖#↘←) for Fe0.5Mn0.5Bi0.5B0.5O3 to a
mixture of paramagnetic and antiferromagnetic (↖#"#"↗) phases for Fe0.5Mn0.5BiO3 or MnBiO3
exhibiting a Neel temperature Y in the order of 100 K. A very special (almost extraordinary)
behaviour of so called speromagnetism is displayed by the extremely rapid quenched (ffi106 K/s)
glassy specimen of FeBiO3 showing not completely compensated moments (i.e., not fully antipar-
allel moment ordering, where arrow orientation "#"# is mutually little angled, so called canted
spins)
oxygen is thus decreased, i.e., equilibrium of Eq. 12.1 is shifted to the right. This
effect may be similar to that caused by Al2O3 but apparently stronger due to the
higher deformability of the larger radius of Bi–ions.
Magnetic glasses became practically relatable in various applications [42–45]
recently as a glass ceramics based on ferroan (wollastonite-like and e-(Fe,Ca)
SiO3-like phases) containing Fe2+ ions, which lead to two magnetic phases with the
different coercive forces applicable as thermo-seeding for cancer treatment by
hyperthermia [46].
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silicates are not equivalent. Geochim Cosmochim Acta 69:2861
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1:129–152; Activities of ions in silica melts. Trans Metal Soc AIME 224:878–887); Masson
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bio-compatible glass-ceramics for bone tissue substitution. J Therm Anal Calorim 71:927
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the bioactivity of silicate glasses. J Mater Sci- Mater Med 13:1221–1225; Liang W, R€ ussel C,
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and aluminosilicate glasses: the effect of network-modifying cations. Am Mineral 70:332–343
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49:228–229
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B2O3 glasses between 400 and 1000 K. J Non-Cryst Solids 30:375–378
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magnetic properties of the splat-quenched system of laser melted (Fe, Mn)2O3-(B, Bi)2O3.
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Synthesis of magnetic glass-ceramics in the system SrO–Fe2O3–Al2O3–B2O3. J Magn Magn
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(Fe, Ca)SiO3 solid solutions. Chem Mater 14:64–70
Chapter 13
New Approach to Viscosity of Glasses
Isak Avramov
13.1 Apparent Activation Energy
The most widespread assumption is that viscous flow is controlled by activation

energy barrier because it changes sharply with temperature:

EðTÞ
¼ o exp (13.1)
RT
Actually, E(T) is the apparent free activation energy. Here, the word apparent is
very important, because of the existence of direct experimental indication that E(T)
is not just a free energy barrier, although it is related to it. This was proven [1] by
comparing the equilibrium and the non-equjournaltilibrium viscosities at the break
point as shown in Fig. 13.1, where data [2–4] on viscosity of xNa2O.yCaO.(100-x–y)
SiO2 glasses are plotted against 104/T.
In the following, we mark with Tf the temperature at which the structure of the
system is becoming frozen. We use this notation because it is convenient to choose as
Tg the temperature at which viscosity of equilibrium system is lgZg ¼ 13.5 [dPa.s].
In this way Tg is always within the glass transition interval and could serve as
thermodynamic definition of the glass transition temperature. With this definition Tg
never deviates considerably from To of the onset of the changes, i.e. Tg To 1.%.
Angell [5, 6] formulated the steepness index (also known as fragility index m) as

d lg
m¼ : (13.2)
d Tf =T
T¼Tf
I. Avramov (*)
Institute of Physical Chemistry, 1113 Sofia, Bulgaria

218 I. Avramov
Fig. 13.1 Viscosity of xNa2O.yCaO.(100-x-y)SiO2. The equilibrium viscosity is given by the solid
points. Lines are according to Eqs. 13.14, 13.17. □ – 21Na2O.7CaO.72SiO2; ■ – 21Na2O.9CaO.70-
SiO2; D – 19Na2O.9CaO.72SiO2
Here derivative is along the equilibrium viscosity curve. In analogy one can
formulate the non-equilibrium steepness index mf as the same derivative, but along
the non-equilibrium curve. Note that Eq. 13.1 leads to the astonishing result that
these two steepness indices must be equal, m ¼ mf. Indeed, by definition the
activation energy is the difference between the energies of certain active state E*
and the ground state E, so that.

1 H HðTÞ S SðTÞ
lg ¼ lg o þ : (13.3)
2:3 RT R
Here H* and S* are the enthalpy and the entropy of the active state. Under the
assumption that non-equilibrium viscosity corresponds to a system with structure
fixed at T ¼ Tf, i.e. with constant enthalpy Hf and constant entropy Sf, the differ-
ence m-mg becomes:
0 1
1 @ 1 dHðTÞ dSðTÞ A
m mf ¼ : (13.4)
2:3R T d Tf =T d Tf =T
T¼Tf T¼Tf equilibrium
However, by definition, the term in brackets of Eq. 13.4 must be zero so that
m ¼ mf provided E(T) is either a single free activation free energy or a sum of
several free activation energies. At first sign, this result seems absurd, because of
13 New Approach to Viscosity of Glasses 219
the strong experimental evidences that m > mf. This result is obtained for many
systems, including organic substances [7], phosphate glasses [2, 8] and silicates
(see [2–4, 9]). Thus, it can be shown, that for a standard soda-lime silicate glass
NBS710 the experimental data [3, 9] lead to mf ¼ 0.36m.
This is the reason why in the following discussion we discuss only models in
which the temperature function E(T) in the exponential term of viscosity equation is
not a free energy, although it can be a result of the role of certain energy barriers.
13.2 Mean Jump Frequency and Apparent Activation Energy
To move, the molecules have to overcome activation energy barriers [10] created
by the resistance of the surrounding molecules. Due to the existing disorder barriers
of different height could appear. The jump frequency is thermally activated so that
for a given height E of the barrier the frequency is:

E
nðEÞ ¼ no exp : (13.5)
RT
If f(E) is the probability distribution function that activation energy barrier of height
E will appear, then, in continuous case, the average jump frequency can be
determined [11, 12] as:
ZEmax
h ni ¼ nðEÞ f ðEÞ dE: (13.6)
0
Since n(E) decays exponentially with E, of significance for the integral is only the
low energy part of the probability distribution function. Therefore, a sufficiently
accurate result can be obtained easily. The reason is that most of the tails of the
probability distribution functions are getting together away from the maximum,
although they could differ near the maximum. If the jumps are considered as a
sequence of independent events the probability distribution function is represented
by Poissonian law, so that f(E) is a function of the dispersity s as follows:

exp EEs max
f ðEÞ ¼ ; E Emax : (13.7)
s 1 expðÞ Emax s
In this way the average jump frequency is

E
1e max ðRT1 s1Þ

n;o e
Emax
<n> ¼
s
Emax
s : (13.8)
RT 1 1e s
220 I. Avramov
For RT < s < Emax, the term to the left of no, as compared to the exponential
term on the right-hand side, is a weak temperature function of the order of unity.
Therefore, one can use the approximation:
RT
<n> n1 e
Emax
s ; n1 ¼ n o : (13.9)
s
Equation 13.8 is really useful when the dispersion s is expressed through

entropy S.

2 S Sg
s ¼ sg exp : (13.10)
ZR
Here sg is the dispersion at the reference state with entropy Sg and Z/2 is the
degeneracy of the system, i.e. Z is the number of escape channels available for the
moving particle and each channel can be used in two directions. Taking into
account that viscosity is inversely proportional to the mean jump frequency the
viscosity can be expressed through Eqs. 13.9 and 13.10 as:

g 2 S Sg
lg ¼ lg 1 þ lg exp ; (13.11)
1 ZR
where lg Zg is viscosity at the reference state. Note that lg 1 is larger the preexpo-
s
nential constant lg o determined in other models. The reason for this is a term RT
coming from Eq. 13.9. For this reason it is expected that lg 1 lg o þ 1:5.
Equation 13.11 is the main viscosity expression [11, 12]. It permits to follow the
temperature and pressure dependencies of viscosity as well as the dependence on
how viscosity changes if system is not in equilibrium. It is sufficient to introduce in
Eq. 13.11 the dependence of entropy on the corresponding variables. It is quite
natural to try to express S as logarithmic function of temperature and/or pressure.
Thus, the temperature T dependence of entropy can be presented as:
ZT

SðTÞ ¼ Sg þ Cp dln T : (13.12)
Tg
So, we apply the most frequently used approximation that heat capacity is
temperature independent, i.e. Cp is the average value for the interval between Tg
and T. Under this assumption, the entropy of a melt in metastable equilibrium is
becoming:

T
SðTÞ ¼ Sg þ Cp ln : (13.13)
Tg
With these expressions the temperature dependence of viscosity becomes

a
Tg
lg ¼ lg 1 þ A ; (13.14)
T
2C
where the “fragility” parameter a stands for: a ¼ ZRp .
Note that A is not adjustable parameter, instead, it is well defined through lg 1

as: A ¼ lg g 13:5 10%. When a ¼1 viscosity gives a straight line in Arrhenian
1
coordinates, indicating that glass is strong. The larger is a the more fragile is the
glass. There is a simple relationship between the Angell’s steepness parameter m
and the fragility parameter a, namely m ¼ A a. Therefore, Eq. 13.14 can be
reformulated in terms of m as follows:
mA
Tg
lg ¼ lg 1 þ A : (13.15)
T
Only lg 1 and a, play role of adjustable parameters in Eqs. 13.14 and 13.15
because the parameter A is well defined. The best test of applicability of
Eqs. 13.14
a
and 13.15 is to plot experimental data in coordinates lg Z against TTg as this is
shown in Fig.13.2 for different systems (lead-silicate [3, 13], diopside, anortite [14,
15], garnet and basalts [16]).
The experimental data [2, 3, 6, 8, 11] on relationship between the Angell’s
steepness parameter m and fragility parameter a are shown in Fig. 13.3. It is seen
that with sufficient accuracy m ¼ 13.5a.
The pressure dependence of viscosity was already discussed in [12, 17] by
introducing into Eq. 13.11 the pressure dependence of entropy.
Note that certain temperature function appears in Eqs. 13.11, 13.14, 13.15,
however this function is not just free energy, although it is determined by the
presence of many free energy barriers. Therefore, this model is able to describe the
break in viscosity curve at the point where system moves out of equilibrium.
13.3 Non-Equilibrium Viscosity
Below the glass-transition region the structure is fixed because the relaxation time is
too large as compared with the time of observation. In this case the viscosity
equation is derived in terms of the temperature Tf at which the system with this
fixed structure will be in equilibrium. In terms of Eq. 13.11 this means that the
entropy of the non-equilibrium system depends on both the actual temperature T and
222 I. Avramov
a b
14 14
33PbO 67B2O3
12 12
10 10
8 8
lg η
lg η
6 6
anortite
4 4
2 2
diopside
0 0
–2 –2
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
2
(Tg / T)
2 (Tg / T)
c d
14 Gamet Mg3AI2Si3O12-Ca3Al2Si3O12 14
12 12
10 10
8 8 Basalt
lg η
lg η
6 6
4 4
2 2
0 0
0.0 0.2 0.4 0.6 0.8 1.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
2
(Tg / T) (Tg / T)2
Fig. 13.2 An illustration how well the existing experimental data on different systems (lead-
silicate [3, 13], diopside, anortite [14.15], garnet and basalts [16]) give straight lines in coordinates
corresponding to Eqs. 13.14, 13.15
on Tf. Basically, the entropy of undercooled melts splits into two parts: the equilib-
rium entropy S(Tf), and the entropy change while temperature changes from Tf to T
with a fixed structure. The corresponding heat capacities are Cp and Cgl so that:

Tf T
SðTÞ ¼ Sg þ Cp ln þ Cgl ln : (13.16)
Tg Tf
Taking into account Eq. 13.16 the nonequilibrium viscosity is given by:
a g
Tg Tf
¼ 1 exp A : (13.17)
Tf T
The dimensionless power g is proportional to the ratio of the heat capacity Cgl of the
glass and the heat capacity of the undercooled melt Cp.
140
120
100
80
m
60
40
20
0
0 1 2 3 4 5 6 7 8 9 10
α
Fig. 13.3 Relationship between the Angell’s steepness parameter m and fragility parameter a.
■ – silicates; □ – borates; D – phosphates and organic substances. The straight line is according to
m ¼ 13.5 a
Cgl
g¼a : (13.18)
Cp
Note that usually Tf Tg is a reasonable approximation. The discussed here

jump frequency model predicts, in agreement with experimental evidence that
mg Cgl
¼ ; (13.19)
m Cp
so that the ratio of the two slopes is in agreement with the existing experimental
evidences and the activation energy paradox disappears. This is because the role of
the jump frequencies instead of activation energies was considered to be of primary
importance. In this way a sort of apparent activation energy appeared, accounting in
addition to the real activation energies also to the contribution of different frequen-
cies to the overall process.
13.4 Preexponential Constant
The preexponential constant is proportional to the reciprocal of the vibration

frequency molecules.
224 I. Avramov
G
o ¼ : (13.20)
no
According to Maxwell the coefficient of proportionality G is equal to the

elasticity modulus G1, i.e.
G ¼ G1 : (13.21)
On the other hand, according to Frenkel’s equation, G is expressed through the

molar volume Vm, the temperature T and the ideal gas constant R as follows:
RT
G¼ : (13.22)
Vm
Experimental data [3] on glasses near the glass-transition temperature give for the
elasticity modulus a value of G1 ~ 10 GPa while from Eq. 13.22 a little bit lower
value of G ~ 1 GPa is expected.
The main problem is how to define the vibration frequency no. The widespread
assumption is that it is determined by the Planck’s formula. The alternative is to
consider that the vibration frequencies of all atoms constituting the building unit
vibrate according to Planck’s formula. The vibration frequency of each of them is
slightly different. Therefore a ‘beat’ of the molecule appears. An illustration of this
is given in Fig. 13.4 where interactions of two oscillators vibrating with 3%
Fig. 13.4 The ‘beat’ result (thick solid line) when two oscillators with equal amplitude and 3%
different frequencies interact
different frequency and equal amplitudes are shown. The resulting ‘beat’ frequency
is shown with a thick solid line. It is seen that the vibration period of the molecule
could be considerably larger as compared to the periods of constituting atoms.
References
1. Avramov I (2009) Non-equilibrium viscosity and activation energy. J Non-Cryst Solids

355:1769–1771
2. Mazurin O, Startsev Yu, Potselueva L (1979) Sov J Phys Chem Glass 5:504 (Engl Transl)
3. Mazurin O, Streltsina M, Shvaiko-Shvaikovskaya T (1985) Handbook of glass data. Elsevier,
Amsterdam (1985); SciGlass 6.5 Database and Information System (2005), http://www.
sciglass.info/
4. Lillie HR (2006) Viscosity of glass between the strain point and melting temperature. J Am
Ceram Soc 14:502–512
5. Angell C (1991) Relaxation in liquids, polymers and plastic crystals—strong/fragile patterns
and problems. J Non-Cryst Solids 131–133:13–31
6. Böhmer R, Angell CA (1992) Correlations of the nonexponentiality and state dependence of
mechanical relaxations with bond connectivity in Ge-As-Se supercooled liquids. Phys Rev B
45:10091–10094
7. Debendett P (1996) Metastable liquids. Princeton University Press, Princeton
8. Gutzow I, Streltsina M, Popov E (1966) Compt. Rend Acad Bulg Sci 19:15–17
9. Yue Y (2009) The iso-structural viscosity, configurational entropy and fragility of oxide
liquids. J Non-Cryst Solids 355:737–744
10. Gladstone S, Laider H, Eiring H (1941) The theory of rate processes. Princeton University,
New York, London
11. Avramov I (2005) Viscosity in disordered media. J Non-Cryst Solids 351:3163–3173
12. Avramov I (2007) Pressure and temperature dependence of viscosity of glassforming and of
geoscientifically relevant systems. J Volcanol Geoth Res 160:165–174
13. Nemilov S (2007) Structural aspect of possible interrelation between fragility (length) of glass
forming melts and Poisson’s ratio of glasses. J Non-Cryst Solids 353:4613–4632
14. Taniguchi H (1992) Entropy dependence of viscosity and glass-transition temperature of
melts in the system diopside-anortite. Contrib Mineral Petrol 109:295–303
15. Behrens H, Schulze F (2003) Pressure dependence of melt viscosity in the system NaAlSi3O8-
CaMgSi2O6. Am Mineral 88:1351–1363
16. Neuville D, Richet P (1991) Viscosity of pyroxenes and garnets melts. Geochim Cosmochim
Acta 55:1011–1019
17. Avramov I, Grzybowski A, Paluch M (2009) A new approach to description of the pressure
dependence of viscosity. J Non-Cryst Solids 355:733–736
Chapter 14
Transport Constitutive Relations, Quantum
Diffusion and Periodic Reactions
Jiřı́ J. Mareš, Jaroslav Šesták, and Pavel Hubı́k
14.1 Introduction
In this contribution we are discussing a class of linear phenomenological transport

equations and in some cases also their relation to microphysical description of
corresponding effects. Interestingly enough, in spite of practically identical forms
of these constitutive relations there are large differences in their physical content;
just such a large diversity of natural processes behind the same mathematical form
should serve as a serious warning before making superficial analogies. On the other
hand, besides quite obvious analogies there may be found also those much deeper
and sometimes quite astonishing. Lesser known or even new aspects of this kind the
reader can find especially in paragraphs dealing with Ohm’s law and with statistical
interpretation of generalized Fick’s law. The congruence of the last one with the
fundamental equation of quantum mechanics, the Schrödinger equation, opened the
possibility to interpret the rather enigmatic “quantum” behaviour of periodic
chemical reactions as a special kind of diffusion.
14.2 Fourier’s Law of Heat Transfer and Analogous

Constitutive Relations
There is a class of essentially linear equations describing the transport of substance-

like indestructible quantities through the homogeneous medium. Historically the first
J.J. Mareš (*) and P. Hubı́k

Cukrovarnická 10, 162 00 Praha 6, Czech Republic
J. Šesták
New Technologies Research Centre, University of West Bohemia,
Univerzitnı́ 8, 30614 Plzeň, Czech Republic

228 J.J. Mareš et al.
known law of this type is famous Fourier’s law [1] controlling the transfer of thermal
energy through the conductor of heat. Strictly speaking, it is no law of Nature but an
approximate linear constitutive relation which can be, with a certain degree of
generality, written in a differential form as
q ¼ l grad T, (14.1)
where q is the local current density of thermal energy, l the coefficient of thermal
conductivity and T the Kelvin absolute temperature. (We do not consider here the
cases where the conductor is anisotropic or where l is not continuous throughout
the conductor. The corresponding generalizations are straightforward, nevertheless
they are not free from controversies [2].) According to empirical evidence, the
terms in Eq. 14.1 have an additional property which may be expressed in the form
of constitutive inequality
q grad T 0: (14.2)
The physical meaning of this condition is obvious; the current vector q has to
have everywhere the component opposite to the direction of grad T representing the
local driving force of energy transfer. In order to solve concrete problems, rela-
tion 14.1 is, as a rule, completed by a pair of phoronomic equations, namely by
restricted equation of continuity
div q ¼ 0 (14.3)
which expresses the conservation of substance-like quantity (in this case of thermal
energy) during its transfer. Notice that in this case the substance-like quantity is not
considered to be only indestructible but that it is not created either. The second
phoronomic equation, sometimes called equation of discontinuity then reads
qn ¼ 0; (14.4)
where qn is the component of current vector which is normal to the surface of

heat conductor. This equation is assumed to be valid on all surfaces of the heat
conductor except its terminals where the current source and drain are placed. Putting
aside the cases where leakage currents or external current sources are present (qn ¼
6 0),
Eqs. 14.1, 14.3 and 14.4 may serve as a representative pattern for a wide class of
problems of mathematical physics connected with the transport of energy, electricity
or matter.
Relations 14.1 and 14.3 describe the steady state of the field represented e.g. by
the scalar quantity T. In order to describe also the time evolution of this field the
equation of continuity can be no more used in its restricted form 14.3. Instead, it has
to involve also a term characterizing the time dependence of accumulation or
depletion of the said substance-like quantity which may be represented by the
time derivative of the scalar quantity T at a given point, namely
14 Transport Constitutive Relations, Quantum Diffusion 229
b ð@T=@tÞ þ div q ¼ 0 ; (14.5)
where b is a constant coefficient ensuring the dimensional homogeneity of the

equation. Taking then into account Eq. 14.1 and assuming that l is in a certain
closed region constant, we obtain immediately
@T=@t ¼ ðl=bÞ div grad T; (14.6)
which is usually called the “second law” conjugated to the “first law” of type 14.1.
Returning back to the description of steady state, which may be now characterized
by the condition @T/@t¼0, we obtain from 14.6 the relation
div grad T ¼ 0; (14.7)
i.e. well-known Laplace’s equation. The solutions of this equation are called
harmonic functions, which are in a particular case of one dimension reduced to
the linear change of variable T along the axis x.
It is worth noticing that the most difficult part of the establishment of Fourier’s
and other similar constitutive relations was not finding out of their mathematical
form (which is very simple) but the definition and the physical interpretation of the
quantities involved or even the proof of their plain existence [3]. Empirically
determined pre-factor in 14.1 is thus very often decomposed into the product of
quantities having more straightforward or already known physical interpretation.
For example the thermal conductivity is usually written in the form
l¼a=ðcp rm Þ; (14.8)
where a means the thermal diffusivity introduced by Kelvin as an analogue of

diffusion constant, cp specific heat capacity at constant pressure and rm the density
of the material.
14.3 Darcy’s Law
As another example of linear transport constitutive relation may serve so called

Darcy’s law [4] describing the flow of fluid through the porous medium brought
about by pressure drop. This relation controlling e.g. the movement of groundwater
through the aquifer [5] or behaviour of petroleum in oil-deposits thus plays an
extraordinary role in geology. It may be written as
j ¼ ðk=ZÞ grad p; (14.9)
where j means the vector of filtration velocity (which differs from the real velocity
of liquid in pores) and p the pressure. Notice that the pre-factor is in this case
composed from two independent coefficients, one characterizing the porosity and
tortuosity of the porous medium, permeability k, and the second one characterizing
the flow of liquid, dynamic viscosity Z.
14.4 Ohm’s Law
The outstanding role among linear relations of type 14.1 plays so called Ohm’s law
controlling the transport of electricity in metals and semiconductors. This “law”
being the cornerstone of modern electronics is probably the most exploited physical
relation which has ever been discovered. Its differential form convenient for the
description of charge transport in an isotropic conductor reads
i ¼ g grad K, (14.10)
where i is the local current density vector, g the electrical conductivity and grad K
the force driving the electric charge. Of course, Eq. 14.10 has to be accompanied
with the phoronomic relations div i ¼ 0 and in ¼ 0, quite analogous to Eqs. 14.3 and
14.4. Originally the driving force was identified by Ohm with the electroscopic
force (Elektroskopische Kraft) measured by a mechanical action of the conductor
exerted on a small insulated body placed in the vicinity of its surface [6].
Obviously, the direct use of such a definition in the interior of the conductor was
impossible. As, however, the electroscopic force was by many savants considered
to be a measure of the density of electric charge dwelling on the surface of the body
it was quite natural to identify the quantity K simply with the local electric charge
density r. It seems to be very likely that Ohm was aware that such an assumption
results for the limiting case i¼0 to the condition r ¼ const. which is in contradic-
tion with Coulomb’s law, the fundamental theorem of electrostatics. He even
correctly claimed that [6, Cf.7] “...wenn Gleichgewicht sich hergestellt habe,
nach den Versuchen von Coulomb und nach der Theorie, die Elektricit€at an die
Oberfl€ache der Körper gebunden sei, oder durch eine unmerkliche Tiefe in das
Innere eindrige.” (“...if equilibrium is established, according to the experiments of
Coulomb and according to the theory, the electricity is bound on the surface of the
body or penetrates through the tiny depth into its interior”.) Nevertheless, he did
not provide any definite solution of this puzzling problem which was only due to
Kirchhoff who identified the force responsible for the charge transport with the
gradient of electrostatic potential j [8]. Such an assumption reconciled the dis-
crepancy between relation 14.10 and the laws of electrostatics. Indeed according to
Kirchhoff’s arguments we can compute from Eq. 14.10 div i ¼ g div gradj.
Taking then into account the fact that at any point in the interior of the conductor
steady state condition div i ¼ 0 must be valid, we immediately obtain equation div
gradj ¼ 0, which is nothing but the above mentioned Laplace’s equation
describing behaviour of electrostatic potential j in the neutral region (r 0).
In other words, it means that in the case where K j, there is no net space charge
in a current-carrying conductor and, vice versa, for any homogeneous conductor

where the space charges are present, the application of Kirchhoff’s form of Ohm’s
law cannot be fully justified. Of course, in the cases where the transport is
controlled by the regions containing space charge, e.g. in Schottky diodes, p-n
junctions and in the vicinity of charge injecting contacts, the violation of Ohm’s
law is a well-known effect having enormous application impact [9]. It may thus be
somewhat astonishing that the space charges must be inevitably present, in con-
trast to Kirchhoff’s proposition, in any transport of electricity via conductors. The
indispensable role of the space charges played in conduction was for a long time
overlooked in spite of the obvious empirical fact that transport through the wires is
to a large extent independent of the arrangement of its surrounding. In order to
suppress, namely, the long range electromagnetic interaction between charge
carriers in the conductor and external disturbing electric fields, the presence of
stable screening charges distributed in the conductor is quite inevitable. Such a
necessity of the existence of surface charges on the current-carrying conductor was
pointed out, e.g. in Ref. [10]. Accordingly, the surface charges not only prevent the
electric flow from escaping from the conductor but also provide, inside the
conductor, an appropriate field distribution ensuring the constancy of the total
current flow throughout any cross-section of the conductor regardless of its
complicated topology (e.g. in knots on the wire) and external electric fields. The
quantitative theory of this effect is practically lacking, however, a relatively
simple approximate formula for local charge density s dwelling on a free-standing
conductor having no loops may be written as:
s ¼ it ðee0 =gÞ bð1=d1 þ1=d2 Þ; (14.11)
where it is the local tangential component of the current density, ee0 the permittivity
of outer space, b the linear distance from the ground and d1 and d2 the principal radii
of curvature at a given point of the surface. For example, for the straight vertical
copper wire of diameter d1 ¼ 103 m with one end earthed, carrying the total
current of 1 A and for a point lying on it at the distance b ¼ 10 m from the ground
(other needed parameters are: ee0 8.85 1012 F/m, g 6.4 107 S/m, d2 !1)
we obtain from formula 14.11 that s 1.76 109 C/m2. It is an extremely low
value of surface charge density, especially because of high value of g. Nevertheless,
regardless of the smallness of this effect we can conclude that in conductors, the
presence of surface charges is a non-separable part of the steady state electric
current flow. It is further clear that the concept of finite charge strictly confined to
the geometric surface of the conductor is only an abstraction, while in a real case,
this charge must be deposited somewhere in the bulk. Interestingly, essentially the
same conjecture was expressed by Ohm in his quotation above. An adequate
mathematical formulation of this idea may be achieved by the following slight
modification of Ohm’s law [11]. Taking first into account the fact that for the
characterisation of the local electric state we have only two independent intensive
quantities at our disposal, i.e. potential j and charge density r, we suggest
completing of quantity K containing purely electrostatic term j by a chemical
(or diffusion related) term linearly depending on charge density r, resembling

original Ohm’s concept of “Elektroskopische Kraft”. In such a case it should be
K ¼ j þ r d2 =ee0 ; (14.12)
where d is a length parameter not specified yet, added in order to ensure the
dimensional homogeneity of both terms. The resulting form of Ohm’s law thus reads
i ¼ g grad ðj þ r d2 =ee0 Þ: (14.13)
Solving this equation with respect to the boundary condition in ¼ 0, we find that the
net charge density should decrease exponentially with increasing depth n under
the surface of current-carrying conductor, i.e. as r(n) ¼ r0 exp(n/d) where the
pre-factor can be obviously expressed as r0 ¼ s/d. Putting, moreover, i ¼ 0
identically, we obtain from Eq. 14.13 a usual electrostatic screening formula,
namely d2r/ee0 ¼ j0 j, playing an important role in the description of numerous
contact phenomena near the equilibrium. From all these relations, it is evident that
the parameter d has a physical meaning of the screening length, in metals, particu-
larly, of the Thomas–Fermi screening length [12]. In order to have a more specific
idea of the significance of the chemical term we can estimate its upper bound for the
above mentioned case of straight wire using Eq. 14.11. Accordingly it follows
d2 r0/ee0¼ sd/ee0 (it/g) (bd/d1). Simultaneously we can determine, by means of
Davy’s formula, the potential drop along this wire, j ¼ ib/g. As it i, we thus
immediately obtain for the ratio of chemical and electrostatic term j an estimate
d/d1. In ordinary metallic conductors used in electronics (e.g. Cu wire where
d ¼ 5.5 1011 m, and d1 104 m) this parameter attains the value 5.5 107.
Evidently, because of the smallness of this parameter the correction to Ohm’s law
due to the chemical term is absolutely negligible there having only theoretical
significance. In contrast to bulk metals, however, the situation may be rather
different in semiconductor-based structures in which d typically ranges from 106
to 109 m and where one of the dimensions of the conductor is confined to
nanometre scale. In such a case the original current-carrying neutral bulk region
which was perfectly screened against the influence of external fields by a surface
charge layer is appreciably reduced giving thus rise to qualitatively new effects
generally, but not quite correctly, connected with the so called “quantum confine-
ment” [11].
14.5 Fick’s Law
The spontaneous transport of dispersed substance from the region of high concentra-
tion to the one of lower concentration through a material medium is called diffusion.
There are a lot of combinations of species which may take part in such a process.
The pioneering systematic studies in this field were performed by Scottish professor of
chemistry T. Graham who formulated the first quantitative principles controlling the
diffusion of gases into another gas and the diffusion of salts in aqueous solutions [13].
Similar experiments were made somewhat later by a young Swiss pathologist A. E.
Fick who in his fundamental article [14] established the constitutive relations satisfac-
torily describing the process of diffusion in general. For the analytical form of his law
Fick used with awareness Fourier’s law of heat conduction (and very likely also
Ohm’s law) as a pattern, while for its physical interpretation he exploited consequently
the molecular hypothesis. The resulting first Fick’s law in its simplest form may thus
be written as
J ¼ D grad n; (14.14)
where J is the density of diffusion current (flux), D the coefficient of diffusion and n
is the local concentration of the diffusing species. As was later recognized, such a
form of this constitutive relation is related only to the case where we have to do with
rarefied gases or with the so called ideal solutions. For more complicated compound
systems the driving force of the diffusion is not simply proportional to the gradient
of concentration n but to the gradient of chemical potential m of particular species.
The relation 14.14 must then be rewritten as
J ¼ ðDn=RTÞ grad m; (14.15)
where R is the universal gas constant and T the Kelvin absolute temperature. It is
necessary to note that there was in fact only a rather vague connection between the
phenomenological relation 14.14 and Fick’s molecular model. In accordance with
the obsolete modification of molecular hypothesis currently used in the middle of
the nineteenth century, namely, the molecules consist of ponderable atoms sur-
rounded by a dense aether atmosphere. It was believed that the thermal agitation of
these two components was responsible for thermal dilation of bodies and for
movement of molecules within the bodies as well. Due to the high abstractness of
such ideas, however, the arguments are somewhat teleological and the causal
derivation of relation 14.14 was practically impossible. It is therefore a remarkable
fact that both these ingredients appearing in Fick’s approach i.e. molecular structure
and thermal agitation became essential for the construction of modern microscopic
(statistical) models describing diffusion and allied phenomena. The first model of
this kind was developed by W. Sutherland [15] and another one, very similar, a year
later by A. Einstein [16]. Accordingly, the diffusion constant must be given by the
formula
D ¼kB T= x; (14.16)
where kB is the Boltzmann universal constant (kB ¼ 1.38 1023 J/K) and x the
coefficient of friction affecting the movement of an individual molecule through the
medium. Useful approximation of x is that using the Stokes formula, namely,
x ¼ 3pZa, where a is the diameter of the molecule [15, 16]. Very soon after the
appearance of these theories it became quite clear that there was a close relation
between the diffusion and the so called Brownian motion. Within the frame of the
mathematical theory of Brownian motion and other fluctuation phenomena worked
out by M. von Smoluchowski [17] and R. F€ urth [18] it was possible to show that the
process of diffusion may be described as follows. Every diffusing molecule is
simultaneously submitted to the influence of force of friction characterized by the
coefficient x and to the random impacts due to the neighbouring thermally agitated
molecules. Under such conditions it can be rigorously proved that the statistical
shift of ensemble of diffusing molecules must be controlled by Eq. 14.14 (or 14.15)
with the diffusion constant given by Eq. 14.16. Careful consideration of the second
form of Fick’s law conjugated to Eq. 14.14 (cf. also Eq. 14.6), i.e. of the equation
@n/@t ¼ D div grad n; (14.17)
defining the relation between continuous phenomenological quantity n and its time
derivative, may lead to paradoxes which may be removed only by careful reconsid-
eration of concepts used. For example, for continuous n(x,t) the “speed of diffu-
sion”, which is intuitively associated with the speed of molecules, is not well
defined or it has to be assumed to be infinite. This odd statement can be elucidated
by the following argument [19]. If the concentration n of a substance at time t ¼ 0 is
finite only in a certain bounded region (e. g., n ¼ const.), being identically zero out
of this region, the equation implies that after an arbitrarily small time interval dt the
concentration at any point of the whole space is non-zero, so that the transport of
matter to any distant point would be instantaneous, i.e., with an infinite speed. On
the other side, taking into account the discrete molecular structure of ordinary
matter, the concentration at a given point should remain zero till it is reached by
the first diffusing particle (molecule), i.e., the velocity should be finite in any case.
Very similar unpleasant discordance between mathematical solution and common
sense arguments was much earlier discovered also by J. Stephan [20] who studied
the time dependent transfer of heat controlled by Fourier’s law 14.1. This paradox
which was shown to be intrinsic to the mathematical assumptions used by the
derivation of relations 14.14 and 14.1 may, as will be shown below, serve as an
important key to physically meaningful definitions of “speed of diffusion” or
“speed of heat transfer”.
14.6 Diffusion and Stochastic Quantum Mechanics
Second Fick’s law in the form 14.17 describes the process of diffusion only in the
case where the external forces are absent. According to laws of classical mechanics
the diffusion in an external field can be formally decomposed into a superposition
of movement of the centre of mass of the diffusing swarm of particles under the
influence of external force and of the diffusion without the external field. Therefore
the resulting formula has to contain beside the right side of Eq. 14.17 extra additive
terms corresponding to various types of external forces. As was pointed out by
F€urth [21], such a generalized formula is fully congruent with the fundamental
equation of quantum mechanics, Schrödinger equation1. These equations may be
mapped one onto another by substituting for the diffusion coefficient the value
(F€urth’s Ansatz)
D ¼ iDQ ¼ i
h=2M; (14.18)
where i is the imaginary unit i¼√(1) and ћ1.051034 Js Planck’s universal

constant. This very fact together with the feeling of dissatisfaction with some basic
quantum concepts going against the common sense leads to the attempts to construct
unified statistical theory treating the quantum motion as a kind of a stochastic process
(see e.g. [22–24] and references therein). Accordingly, the source behind the assumed
stochastic quantum process was tentatively identified with the universal noise gener-
ally known as “zero-point” fluctuations of vacuum (more correctly “temperature
independent” fluctuations of vacuum). As can be shown this assumption is consistent
with the structure of F€
urth’s diffusion constant DQ which differs essentially from that
of Sutherland and Einstein 14.16. Indeed, it is clear at first glance that the coefficient
DQ is temperature independent so that the diffusion of quantum particle can be really
considered to be a “zero-point” effect. Moreover, we cannot attribute any finite
friction coefficient analogous to x to the movement of particle through the vacuum
space because it would be then possible, in contrast to the Principle of Relativity, to
experimentally distinguish coordinate systems in absolute rest from that in uniform
motion. This requirement is also evidently fulfilled; DQ does not really contain
explicitly any friction coefficient. Taking now into account the fact that the large
macroscopic bodies do not appear to exhibit “quantum” behaviour, we can speculate
that the diffusion coefficient DQ is inversely proportional to the mass M of the body.
A special interest deserves the presence of imaginary unit in F€urth’s Ansatz 14.18.
The necessity to use the imaginary unit there is connected with the fact that the
quantum mechanics similarly to the analytical mechanics is formulated in the phase
space while von Smoluchowski’s theory describes the Brownian motion and diffu-
sion in the configuration space. As the cardinality of phase space is two times higher
than that of the configuration space related to the same physical problem, the existing
one-to one correspondence between solutions of generalized diffusion equation and
Schrödinger equation is ensured just by the implementation of complex numbers
effectively doubling the cardinality of the real space. The attempts to interpret
quantum mechanics as a stochastic theory, however, bring about further serious
problems. The classical Einstein–von Smoluchowski description of diffusion (i.e.
of a special case of Brownian motion of a small particle) is essentially a description of
Markovian stochastic process, i.e. a process in which the following steps are abso-
lutely non-correlated. Any stochastic process in the phase space assumed to underlie
motion of a small quantum particle cannot be, however, Markovian, because, by

definition, its state at t < 0 determines the probability of states at any later time t [25].
In other words, the quantum particle has “memory”. That is the reason why e.g.
advanced Uhlenbeck-Ornstein-Wang theory [26, 27] which is based on stationary
Markovian stochastic process characterized by measure-preserving flow in the phase
space is inevitably mathematically incompatible with the formalism of quantum
mechanics.
A famous controversial proof of von Neumann’s theorem [28] on the impossi-
bility of entering of “verborgene Parameter” (hidden variables) into description of
the quantum processes, is also based on practically the same grounds, i.e. on the
discrepancy between cardinality of various spaces of variables used for the descrip-
tion of quantum object. On the other side, as will be shown below, the “naive”
theory of von Smoluchowski and F€ urth constructed in the configuration space and
operating with the concept of intermittent measurement can provide a satisfactory
description of the quantum process. Intermittent measurements, namely, performed
in the configuration space reduce repeatedly the wave packet of a particle and may
thus cause the “memory loss” of the particle so that the resulting process can be
treated as Markovian. Such a compatibility of von Smoluchowski’s approach and
quantum mechanics is in very convincing way manifested below by the fact that
Hausdorff’s fractal dimensions of Brownian and quantum motions in the configu-
ration space are identical (d¼2).
14.7 Periodic Reactions and Quantum Diffusion
As an interesting example, on which the continuous transition from classical

diffusion to the domain of quantum physics can be demonstrated, may serve so
called periodic chemical reactions. These reactions, known from the second half of
the nineteenth century [29], perform a curious class of reactions generating marvel-
lous macroscopic patterns periodic both in space and time (see Fig. 14.1). They are
mostly considered to be spectacular manifestations of self-organization due to the
non-equilibrium nature of thermodynamic processes involved. As these reactions
violate traditional view on chemical kinetics characterized by the natural tendency
to reach the equilibrium by the shortest way, they have been interpreted as a
precursor of life processes [30]. In the 1930s, besides the fact that the kinetics of
periodic reactions is controlled by diffusion (so called Nernst–Brunner kinetics),
another peculiar and somewhat enigmatic feature of these reactions was discovered
[31, 32] which may be concisely expressed as
Mv ‘
h=2; (14.19)
where M is the molecular weight of precipitate, v the speed of spreading of reaction

fronts and ‘ the length parameter of reaction patterns. For a particular configuration
of the system in which reaction takes place the left-hand side of Eq. 14.19 should be
Fig. 14.1 The record of evolution of the so called Liesegang’s rings on gelatinous substrate. An
example of a regular pattern resulting from the periodic reaction and revealing the features of
quantum diffusion
completed by a geometric factor (e.g. 2 for three- and 1/p for two-dimensional case)
and by tortuosity characterizing the detailed topology of the system. As a rule, the
resulting factor is of order unity.
14.8 Speed of Diffusion
Taking now into account Sommerfeld’s criterion, according to which any effect
belongs to the scope of quantum physics just if the corresponding relevant quantity
of action is comparable with quantum of action, ћ [33], we can claim that the
diffusion-controlled periodic reactions fulfilling Eq. 14.19 may be interpreted as
quantum effect. What we, however, urgently need for constructing the corresponding
“relevant quantity of type action” is the definition of something like the instant
“speed of diffusion”, already mentioned above as a rather controversial concept. If
we, for the sake of simplicity, confine ourselves only to one dimension, the diffusion
can be described by the second Fick’s law 14.17 in the form
@n=@t ¼ D ð@ 2 n=@x2 Þ: (14.20)

The meaningful definition of “speed of diffusion” can be then made even under
the assumption that the concentration n (x,t) is continuous. Indeed, let us assume
that at time t¼0 there are N particles concentrated in the plane x ¼ 0 (source layer).
In this case the solution of Eq. 14.20 reads:
p
nðx; tÞ ¼ N=ð2 pDtÞ expðx2 =4DtÞ: (14.21)
Since the times of Fourier it has been a well-known property of solution 14.21
(known as a source–integral) that the time record of concentration taken in a
neighbourhood of a certain fixed point x has a local maximum. The mathematical
condition for this maximum reads @n/@t ¼ 0. This is, however, according to
Eq. 14.20, equivalent to the condition (@ 2n/@x2) ¼ 0 (for constant D 6¼ 0). The
second space derivative of solution 14.21 gives then the expression:
p
@ 2 n=@x2 ¼ fN=4 pðDtÞ3 gexpðx2 =4DtÞf x2 =2Dt 1g: (14.22)
Using now the above-mentioned condition for extreme, we obtain immediately

relation (Einstein-von Smoluchowski’s relation)
x2 ¼ 2Dt, (14.23)
the time derivative of which provides
x u ¼ D, (14.24)
where u ¼ @x/@t has evidently physical meaning of the instant speed of transfer of
concentration maximum. As the quantity u, in fact, represents the movement of the
most numerous swarm of diffusing molecules, it is quite reasonable just to call u the
“instant speed of diffusion”. It is a remarkable circumstance that Eqs. 14.23 and
14.24 are practically the same as the equations describing random walk of a single
Brownian particle (molecule) [16, 17]. The only differences are that there x is no
more the position of the concentration maximum but the mean-square-root √hx2i of
the position of a particular Brownian particle at time t and u has a meaning of its
mean-square root of stochastic speed √hU2i. If we start, namely, from the one-
dimensional Fick’s law 14.14 in a probabilistic notation, i.e., from
Uw ¼ D ð@w=@xÞ; (14.25)
where the probability density is defined as w ¼ n/N, U is the stochastic speed and
(Uw) has the meaning of the probability flux, we obtain for the mean-square of the
stochastic speed the expression (the integrals here are taken over the range from
1 to +1)
p R R
U2 ¼ ðU2 w dx ¼ D2 ð1=wÞð@w=@xÞ2 dx: (14.26)
In consequence of evident
R inequality {(@w/@x)/w + x/hx2i}2 0, one obtains
after a simple algebra that (1/w) (@w/@x) dx 1/hx2i and therefore eventually
2
p 2 p 2
x U D; (14.27)
where equality in this “uncertainty relation” takes place for the probability distri-
bution corresponding just to the source-integral 14.21. Because Eqs. 14.23 and
14.24 describe the same physical process of diffusion, the diffusion constants D
must naturally be identical for the microscopic as well as for the macroscopic cases
and simultaneously the relations
p p 2
u¼ U2 and x ¼ x (14.28)
must be valid. We can thus conclude that a typical “average” Brownian particle
follows the position of the concentration maximum or in other words that the most
significant packet of diffusing molecules consists of “average” Brownian particles.
As we believe, this is just the way how Planck’s universal constant can in
principle enter essentially macroscopic Eq. 14.24. Namely, if the microscopic
movement of a Brownian particle of mass M is controlled by a purely quantum
process, where the diffusion constant in three dimensions should have F€urth’s
limiting value of DQ ¼ ћ/2M, then Eq. 14.24 will formally attain the same form as
empirical Eq. 14.19, i.e.
Mux¼
h=2; (14.29)
provided that the experimentally observed quantities v and ‘ are identified with
u ¼ √hU2i (speed of diffusion) and x ¼ √hx2i (distance spanned by diffusion),
respectively.
14.9 Resemblance of Quantum and Brownian Motion

in a Configuration Space
It seems thus plausible that to prove the quantum nature of Eq. 14.19 it is enough
to make clear conditions under which the numerical value of diffusion constant D
attains the F€urth’s value DQ. Unfortunately, realization of this task is by no means
trivial, mainly because the frequently stressed analogy between quantum and Brow-
nian motions [34–36] is rather incomplete. On the other side, there is an important
common characteristic of these two types of stochastic processes which makes them
identical in a certain sense, namely their Hausdorff’s dimension in the configuration
space [37, 38]. To make clearer the relation of this useful mathematical concept to
the present problem we must go behind the continuous approximation of diffusion
represented e.g. by Eq. 14.23. Extrapolating the validity of this formula from the
experimentally verified range to arbitrarily small scales, we can use it, however, for
the construction of a more realistic model of movement of a Brownian particle in the
following way.
Let us make intermittent observations of total duration t, sampling every (t/k)
seconds the position of a Brownian particle, where k is an arbitrary integer. Every
time interval (t/k) involves some delay and time necessary to determine the
position of the particle. Such a measurement will provide in one dimension a
sequence of intervals l1, l2,.., lk, which define the apparent length of the path passed
through as:
Lk ¼ l1 þ l2 þ . . . þ lk (14.30)
As the movement along every of these intervals is, according to our assumption,
controlled by law 14.23, for a sufficiently large k instead of 14.30 we can write:
p 2
Lk ¼ k 1 k; (14.31)
where index k means the averaging over all k intervals in 14.30. It is simultan-
eously clear that the length√hl2ik defines for a given k also the length resolution
Dlk ¼ √hl2ik of the measurement, because the sampling by time intervals (t/k)
evidently ignores the details of the actual path of the Brownian particle finer than
Dlk. Average speed determined from the same experiment as k Dlk/t must, more-
over, fulfil the relation 14.27 in the form (reduced to equality):
Dlk ðk Dlk =tÞ ¼ D: (14.32)
It is obvious that the more frequent measurement with a better resolutionDlk will
reveal more details of motion of the Brownian particle. As a result, with increasing
k the number of recorded abrupt changes on the Brownian path will increase and
also Lk will increase simultaneously. For very large k’s (theoretically for k ! +1)
the shape of the Brownian path will resemble a continuous, at every point non-
differentiable curve. As was shown by Hausdorff [39] such a complicated mathe-
matical object may be, without ambiguity, characterized by introducing its (Haus-
dorff’s) measure L and generalized dimension d as follows:
L ¼ Lk ðDlk Þd1 ; (14.33)
where dimension d should (and can) be chosen in such a way that L is independent
of k. Putting then relations 14.32 and 14.33 together, we obtain:
L ¼ ðDt=Dlk ÞðDlk Þd1 ; (14.34)
from which, due to the said independence of L on k, it immediately follows that

Hausdorff’s dimension of the Brownian motion is d ¼ 2 (cf. e.g. [37]).
As was shown by L.F. Abbott and M.B. Wise [38], just the same Hausdorff’s
dimension in the configuration space (i.e. d ¼ 2) has to be ascribed to the jiggling
movement (‘Zitterbewegung’) of a quantum particle. This can be proved very easily
using, instead of Eq. 14.32, common Heisenberg’s uncertainty relation in a
(reduced) form
Dlk ðM k Dlk =tÞ ¼

h=2; (14.35)
preserving the previous meanings of all quantities involved. The corresponding

“quantum” expression for Hausdorff’s measure then reads:
h t=2M Dlk ÞðDlk Þd1 ;

L ¼ ð (14.36)
This formula gives the same value for d ¼ 2 as Eq. 14.34 and can be obtained
from it by a formal substitution of DQ for D. Because both quantum and Brownian
motions have in the configuration space exactly the same Hausdorff’s dimension
revealed, e.g., by the intermittent measurement described above, the quantum
jiggling can be, from the phenomenological point of view, considered as a continu-
ation of the Brownian motion down the smaller scales. This circumstance enables
us to treat the diffusion of a particular molecule together with its quantum jiggling
movement as a single stochastic process, formally described by a convenient
combination of classical stochastic and quantum diffusion constants, DS and DQ,
respectively. Using analogy with the composition rule for independent mobilities
well known from electrochemistry, we can tentatively write:
D ¼ DS DQ =ðDS þ DQ Þ: (14.37)
Then quantum limit is represented by the inequality DS > > DQ, which ensures
that D DQ. The quantum effects should prevail in the case, where DS attains a
very high value, or in other words, if the diffusing particle is decoupled from all
stochastic sources in environment which are not of quantum nature. We claim that
just this inequality, i.e.
DS >> DQ (14.38)
with the accompanying physical meaning mentioned above is the condition we are
looking for. If this takes place, namely, Eq. 14.29 and consequently Eq. 14.9 are
valid, satisfying simultaneously the quantum criterion.
To assess the range of validity of inequality 14.38 it is necessary to evaluate
stochastic diffusion constant DS. Somewhat crude estimate for ball-like particles
(molecules) without observable persistency in motion can be provided by a classi-
cal Einstein-von Smoluchowski’s formula [16, 17] the use of which is justified
rather by practical than physical reasons. Then condition 14.38 reads:
kB T=3pZa >> h=2M; (14.39)

where Z is the dynamic viscosity of environment, T the absolute temperature and

a the characteristic dimension of diffusing particle (molecule). To find out among
various aqueous solutions at room temperature molecular systems for which
the “quantum” behaviour is to be expected, we put in 14.39 T ¼ 300 K and
Z ¼ 103 kg m1 s1. The resulting condition is
8:4 1015 >>a=M; (14.40)
where a is in meters and M ¼ (1.67 1027 molecular weight) in kilograms.

Taking for a the ionic diameter [40], we can see that, e. g., sodium, calcium and
silver, for which ratios in 14.40 have values 6.0 1015, 3.4 1015 and 9.0 1014,
respectively, are good candidates for “quantum” Brownian particles. For H+ ions
(i.e. protons) which are the most mobile ions in aqueous solutions condition 14.38 is
also valid in spite of the fact that estimate 14.38 (with the ionic diameter a 1011 m)
provides rather a high value ~1.2 1016. It can be accounted for by the fact that the
system of protons in water being a Fermionic system requires a consequent quantum-
theoretical treatment (involving e.g. the Pauli Exclusion Principle), which is essen-
tially non compatible with classical formulae 14.39 and 14.40.
Summarizing, different linear transport constitutive relations controlled by the
equations congruent with Eq. 14.1 were compared. Among the most interesting
achievements a new form of force driving the electric current in Ohm’s law was
introduced. Another interesting item was the statistical interpretation of classical
diffusion. Basing further on the so called F€ urth Ansatz enabling one-to-one
mapping between the Schrödinger and generalized Fick’s law, it appear to be
possible to extent the statistical approach also on quantum phenomena. As an
example, the case of diffusion-controlled periodic chemical reactions was analyzed
in detail. It has been shown that in the configuration space and by intermittent
observations, which resemble the actual observations performed on periodic pat-
terns, the classical and quantum stochastic processes are practically indistinguish-
able. This remarkable fact enabled us to formulate in terms of the classical and
quantum diffusion constants the condition where the quantum stochastic process
should prevail. It has been shown on the basis of this criterion that it is very
probable that ions in aqueous solutions can possess macroscopically observable
quantum behaviour.
Acknowledgments This work was supported by Institutional Research Plan of Institute of

Physics No AV0Z10100521.
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Chapter 15
In-Situ Investigation of the Fast Lattice Recovery
during Electropulse Treatment of Heavily Cold
Drawn Nanocrystalline Ni-Ti Wires
Petr Šittner, Jan Pilch, Benoit Malard, Remi Delville, and Caroline Curfs
15.1 Introduction
Shape memory alloys (SMA) such as the near equiatomic Ni-Ti alloy [1] have
attracted considerable attention for their unique functional thermomechanical prop-
erties as superelasticity or shape memory effect deriving from the martensitic
transformation. Ni-Ti wires are being produced from extruded bars by multiple
hot working passes finished by a final cold drawing. In this so called “cold worked”
(as-drawn, hard, etc.) state, the alloy possesses a heavily deformed microstructure
resulting from severe plastic deformation [2] consisting of mixture of austenite,
martensite, and amorphous phases with defects and internal strain [3]. In this state,
the wires do not show any functional property (Fig. 15.1 left)
As-drawn Ni-Ti wires need to be heat treated so their cold worked microstruc-
ture changes into an annealed austenite microstructure for which the wire shows the
desired functional properties. At the same time, if the shape of a SMA element is
constrained during this final heat treatment, it acquires a new “parent shape”. The
final thermomechanical treatment thus has two purposes – setting the functional
properties and setting the new shape of the wire.
P. Šittner (*) and J. Pilch

Institute of Physics, Na Slovance 2, 182 21 Praha, Czech Republic
B. Malard
Institute of Physics, Na Slovance 2, 182 21 Praha, Czech Republic
and
Now at SIMaP, Domaine Universitaire, BP 75 38402 Saint Martin d’Hères, France
R. Delville
EMAT, University of Antwerp, Groenenborgerlaan 171, B-2020 Antwerp, Belgium
C. Curfs
ESRF, 6 rue Jules, Horowitz 38043, Grenoble, France

246 P. Šittner et al.
Fig. 15.1 Microstructures, electron diffraction patterns and tensile stress–strain response of thin
Ni-Ti wires just after cold drawing (left) and after electropulse heat treatment 125 W/12 ms [10]
Conventionally, this final heat treatment is performed in an environmental

furnace [4–6]. Depending on the alloy (chemical composition, cold work) and
desired application, heat treatment conditions in the range of temperatures
400–500 C and time 10–60 min [4] are applied. If the shape of the wire is
constrained during the heat treatment [5], the stress generated in the wire affects
the functional properties. This is the reason why the tensile force applied during the
commercial straight annealing treatment of superelastic Ni-Ti wires is a very
important technological parameter of the Ni-Ti wire production process.
Recently, the relatively long time of the conventional heat treatment of Ni-Ti
wires became an obstacle for emerging technology of textile fabrics knitted or
woven using continuous Ni-Ti filaments. Maximum respooling speed of ~1 m/min
achievable with straight annealing treatment in conventional ~6 m long tubular
electrical furnaces is still painfully slow for this purpose. To solve this problem
the possibility to treat continuously long thin Ni-Ti filaments by passing electric
current through it during respooling has been investigated as an alternative method
to the conventional treatment. The method has been developed based on a series of
dedicated studies [7–10] and called “Final Thermo Mechanical Treatment by Elec-
tric Current”/FTMT-EC/. Further experimental details can be found in Refs. [8, 9].
As reported in related works [7–10], thin superelastic Ni-Ti filaments heat
treated by the FTMT-EC method display excellent functional properties due to
the specific nanosized microstructures found by TEM in the treated wires. This
suggests that the recovery processes responsible for the functional property setting
(polygonisation, crystallization form amorphous, recrystallization, grain growth,
plastic deformation, etc.) are capable to change the cold worked microstructure
(Fig. 15.1 left) into the annealed one (Fig. 15.1 right) very fast .
Major difference with respect to conventional furnace heat treatment is that the
heat comes from inside the thin wire and that the temperature can rise and fall very
quickly. The time of heat treatment is in the order of milliseconds instead of
minutes. The opportunity to control the fast evolving sample temperature and
tensile force by the FTMT-EC method (Fig. 15.2b) has opened the way for detailed
investigations of the progress of the recovery processes closer to the rate at which
they naturally proceed at high temperatures. This motivated us to perform dedicated
15 In‐Situ Investigation of the Fast Lattice Recovery during Electropulse Treatment 247
Fig. 15.2 (a) Parameters describing the DC power pulse applied in the FTMT-EC treatment,
(b) temperature profiles T ¼ T(t) achieved in pulses with parameters P ¼ 2, 3, 4, 5, 6 W;
t2 ¼ 0.9 s and P ¼ 10 W, t2 ¼ 0.18 s
experimental studies during the electropulse treatments by combination of in-situ

tensile force measurement, electrical resistance measurement and high speed syn-
chrotron X-ray diffraction with the aim to obtain direct experimental information
on the progress of the recovery processes forming nanocrystalline microstructures
at heating rates of the order of ~5,000 C/s.
15.2 Experiment and Method
15.2.1 Heat Treatment
All experiments were performed on Fort Wayne Metals #1 superelastic as-drawn

Ni-Ti wires (56.0 wt.% Ni) having a diameter d ¼ 0.1 mm. The wire is first
mounted on the miniature deformation rig especially designed and built for efficient
testing of functional thermomechanical properties of thin Ni-Ti filaments in ten-
sion. The rig consists of a stepping motor, a 100 N load cell, electrically isolated
grips, a Peltier furnace, a laser micrometer for strain measurement and special
electronics allowing to send controlled electric power pulse to heat the Ni-Ti wire
up to the melting point and perform simultaneously electric resistance measure-
ment.
The initial length l0 (~50 mm) and electrical resistance r0 of the wire at room
temperature were first evaluated. The wire was then preloaded to a reach starting
values of the mechanical constraint s0 and e0. In the present experiments, the wire
was preloaded to 400 MPa and its length was fixed. The wire was than heated by a
controlled DC power pulse P (Fig. 15.2a). It is essential that the electronics system
is capable of controlling the desired power P(t), even if the electric resistance of the
wire drastically changes during the Joule heating event. Evolution of the wire
temperature, T(t), as a function of time (Fig. 15.2b) is calculated according to
Eq. 15.1, taking into account the Joule heat supply P and the ambient temperature
losses.
d
ðTðtÞ CÞ ¼ P h ðTðtÞ Text Þ e s A T 4 (15.1)
dt
The heat capacity, C, is assumed to be temperature independent, s is a Stefan-

Boltzman constant and A is the surface area of the wire. The specific heat transfer
coefficient, h, describing the heat dissipation into air per unit time and the NiTi
wire emissivity, e, needed for the calculation of the radiation heat loss per unit
time were indentified from series of calibration experiments. Other effects
influencing the wire temperature such as heat conduction losses into grips and latent
heats were neglected. In some experiments described below, two parameters of the
power pulse (maximum power P and pulse duration t_2) are used to represent the
temperature history T ¼ T(t) the wire is exposed to. In other experiments, the temper-
ature profile T(t) is directly set by controlling the P(t) and in accordance with Eq. 15.1.
As the temperature of the wire rises and falls during the treatment (Fig. 15.2b),
thermally activated recovery processes are triggered and proceed with their charac-
teristic intrinsic kinetics which changes with temperature. The electric resistance
of the wire, macroscopic tensile force and X-ray diffraction signal varying in
response to the progress of the recovery processes are evaluated. Finally, after the
treatment is finished, superelastic response of the treated wire in 10 tensile cycles at
room temperature is evaluated using the same stress rig. The parameters determined
from the superelastic stress–strain curves and their stability during cyclic tensile
loading serve as measures of the achieved functional properties of the treated wires.
15.2.2 Synchrotron X-Ray Diffraction
Synchrotron radiation enables to extend the X-ray measurements from the static to
the dynamic regime, thanks to its unique time structure and very high flux even at
high energy, which reduces considerably the data collection time. Very fast time
resolution down to the picosecond regime is achievable [11] with stroboscopic
studies of reversible phenomena. In case of the irreversible microstructure evolu-
tion, the X-ray data have to be acquired on a single shot basis [12] requiring high
flux source, very fast and sensitive data acquisition system and a high speed data
transfer.
The present experiment was performed on ID11 diffractometer at the European
Synchrotron Radiation Facility (ESRF) in Grenoble. A monochromatic X-ray beam
with energy of 45 keV (l ~ 0.27552 Å) is obtained with a Laue monochromator.
The beam is focussed down to 1 mm in vertical direction by bending the Laue
crystal and down to 100 mm in horizontal direction. Frelon2K 2D camera with taper
has been chosen as a fast detection system [12]. In order to speed up the data
acquisition for the targeted 10 ms time resolution only a radial slice of the 2D
detector (Fig. 15.3a) is used.
The thin Ni-Ti wire mounted between the grips of the stress rig is positioned
vertically in the beam (Fig. 15.3a). The heat treatment experiment is performed
Fig. 15.3 (a) Setup of the in-situ high speed synchrotron X-ray experiment during the heat
treatment by electric current. The FReLON camera reading was optimized for high speed data
acquisition (only part of the detector – strip of 2048 64 pixels – was used to increase the time
resolution to ~10 ms); (b) Evolution of the {110} austenitic peak measured during heat treatment
experiments with P ¼ 2, 3, 6 W/0.9 s and P ¼ 10 W/0.18 s
with synchronized pulse, force, electrical resistivity and diffraction measurements

(Fig. 15.4). A strip of 2048 64 pixels is acquired and 64-binned in order to obtain
a line of 2048 64 pixels. Then, this line is read out of the CCD and stored before
next image is acquired. Afterwards, 300 lines are put together into a single 2D
binary image which represents the evolution of the diffraction patterns versus time,
as illustrated in Figure 15.3b. To minimise the time needed to read out the line, the
64 active pixels have to be chosen at the bottom edge of the camera. The part of the
detection area, which is not active, is masked by a lead mask. By using such kinetic
mode of the data acquisition by the FReLON camera, it has been possible to acquire
Fig. 15.4 Synchronisation between the electric power pulse and X-ray measurements
Fig. 15.5 Quantitative phase analysis of the diffraction patterns to determine the evolution of the
height, position and FWHM of the {110} austenitic peak (a) Ni-Ti powder; (b) Ni-Ti wire before
heat treatment; (c) Ni-Ti wire after heat treatment
100 diffraction patterns per second with a readout time of less than 1 ms between
2 images.
In order to obtain a diffraction pattern of the intensity versus the diffraction
angle for the kinetic mode, a calibration was performed. A very fine capillary of 300
mm with LaB6 powder was placed at the Ni-Ti wire position and 2D diffraction
pattern was acquired. The position of each LaB6 peak in pixels was measured using
DASH [13] and the corresponding diffraction angle was calculated. The calculated
calibration function relating the diffraction angle to the pixel number was used to
transform each line of the experimental pattern (intensity versus pixel) into a
diffraction pattern (intensity versus diffraction angle). Since the beam centre is in
the middle of the detector, the right side of the diffraction pattern is added to its left
side to increase the statistics.
In order to obtain an etalon for stress-free Ni-Ti diffraction pattern, Ni-Ti
powder of similar composition as that of the wire was placed in the LaB6 container
and diffraction pattern was acquired. Since the Ni-Ti powder existed in a mixture of
austenite and martensite phases at room temperature, the diffraction pattern
contained both austenite and martensite diffraction lines. The Ni-Ti powder gives
diffraction pattern with much better resolution (Fig. 15.5a) than the thin as-drawn
Ni-Ti wires (Fig. 15.5b). This is due to the complex microstructure of the thin Ni-Ti
wires consisting of a mixture of heavily deformed austenite, R phase, martensite,
amorphous phase with frozen in internal stresses. After heat treatment yielding
ideal superelastic properties, the microstructure of the wire is essentially austenitic
(Fig. 15.5c). The diffraction lines were analyzed for height position and FWHM of
the {110} austenite peak using the LAMP software [14] as well as the GSAS
software [15] considering the structure of the austenite phase Pm-3m, R phase
P-3 and martensitic phase P21/m [1].
15.3 Experimental Results
15.3.1 Heat Treatment Experiments – Macroscopic Results
The heat treatment experiments were performed using different power P ¼ 2, 3, 4,

5, 6 W (t2 ¼ 0.9 s) and 10 W (t2 ¼ 0.18 s). Same experiments were performed twice
with identical results – once with simultaneous in-situ X-ray diffraction once
without. The results of 3 selected experiments are presented in Fig. 15.6 showing
the variations of the supplied electric power, temperature, tensile stress and electric
resistivity during the FTMT-EC pulse on the left side and the obtained superelastic
Fig. 15.6 Evolution of power, temperature, tensile stress and electric resistance (left) of the Ni-Ti
wire during FTMT-EC treatments with maximum power P ¼ 3, 6, 10 W/100 mm and resulting
superelastic response and electric resistivity records of the treated wires (right)
stress–strain response with superimposed variation of the electric resistivity of the

wire on the right side. The observed evolution of tensile stress and electric resistiv-
ity in response to the prescribed temperature evolution during the treatment
(Fig. 15.2b) is analyzed below.
The tensile stress evolves with time (temperature) due to the several mutually
competing processes: (1) relaxation of residual stress, (2) thermal expansion, (3)
plastic deformation processes, (4) reversible phase transformations. The tensile
stress starts to increase with increasing temperature right after the onset of heating
(Fig. 15.6). This is due to the unlocking of elastic deformation held by internal
stresses in the heavily cold worked microstructure of the as-drawn Ni-Ti wire
coupled with reverse transformation of small fraction of the martensite phase
which retransforms back to the austenite phase upon heating. The stress increases
with the increasing temperature up to ~450 C, where it reaches a maximum of ~690
MPa (Figs. 15.6 and 15.7b) and falls ultimately down to zero if the maximum
temperature reached in the pulse is high enough. This is due the plastic deformation
and thermal expansion processes prevailing at high stress and temperature. Upon
cooling, the stress varies simply due to thermal expansion.
The electric resistivity starts to decrease when the temperature reaches ~200 C
(Figs. 15.6 and 15.7) and decreases monotonically during heating until it reaches a
plateau at ~75% of its starting value. The electric resistivity changes with the
temperature due to: (1) intrinsic thermal dependence of the resistivity of a metallic
wire, (2) reversible phase transformations and (3) progress of the recovery pro-
cesses causing irreversible microstructure changes. If an already fully heat treated
Ni–Ti wire is subjected to the same FTMT-EC pulse [7], the electric resistivity
Fig. 15.7 Comparison in experiments with maximum power P ¼ 2, 3, 4, 5, 6 W/0.9 s and 10 W/

0.18 s of (a) the evolution of the tensile stress (left) and the electrical resistivity (right) with time
(b) the evolution of tensile stress (left) and electrical resistivity (right) with temperature
monotonically increases with increasing temperature and returns to its original

value after cooling back to room temperature. This is a simple proof that the electric
resistance decrease is caused by the recovery processes (3). Upon cooling, the
electrical resistivity decreases due to intrinsic thermal dependence of the electric
resistance of a metal (Fig. 15.7). Overall, the total decrease of the wire electric
resistance due to microstructure recovery reaches ~40% – from 1.45 to 0.88 Omm
for the 6 W/0.9 s treatment.
15.3.2 Heat Treatment Experiments - In-Situ X-Ray Diffraction

Results
Figure 15.3b shows the evolution of the diffraction pattern near the {110} austenitic
peak as measured by the 2D detector during the experiments using pulses with
power P ¼ 2, 3, 6 and 10 W (see also the synchronization in Fig. 15.4). It evolves
from the broad diffraction pattern corresponding to the complex microstructure of
the as-drawn wire to the well-defined narrow peak of the heat treated wire. The
intensity of the peak increases, the peak shifts left and right and its FWHM
decreases during the electric pulse treatment. Figure 15.8a shows the evolution of
the height of the {110} austenitic peak during the experiments. The higher the
temperature reached in the treatment, the larger the peak height is. The shift in the
onset of the increase of the peak height to shorter time with increasing P is due to
the fact that the temperature rises faster for more energetic pulses (Fig. 15.2b).
Figure 15.8b shows the results of the analysis of the evolution of {110}
austenite peak position recalculated into radial strain (Eqs. 15.2–15.4) of the
{110} austenitic peak for treatment with P ¼ 2, 3, 6 and 10 W pulses. Radial
strain means elastic strain in transverse direction. The axial strain would also be
of interest but it could not be evaluated due to the geometry of the diffraction
experiment (Fig. 15.3a). Using the Bragg law (Eq. 15.2) and the definition of
strain (Eq. 15.3) an expressionfor the radial strain of the {110} austenitic peak
ɛ110 is given by Eq. 15.4.
2dhkl : sin yhkl ¼ n:l (15.2)
dhkl d0;hkl Ddhkl

ehkl ¼ ¼ (15.3)
d0;hkl d0;hkl
sin y110
e110 ¼ 1 (15.4)
sin y0;110
y110 is the value of the Bragg angle of the {110} austenitic peak in the wire during the
heat treatment and y0;110 is the value of the Bragg angle {110} austenitic peak
measured on the powder. Because the radial strain is strongly negative before the
heat treatment experiment (Table 15.1), it means that the {110} austenite lattice of the
Fig. 15.8 Evolution of (a) the height, (b) the position (radial strain), (c) the FWHM of the
austenite given by the {110} austenitic peak during experiments at P ¼ 2, 3, 6 W/0.9 s and
10 W/0.18 s
as-drawn wires experienced a tensile stress along its axis. Assuming a Young modulus
E ¼ 60 GPa and a Poison ratio of 0.33, the stress is evaluated to 2,290 MPa.
Subtracting the 400 MPa external tensile stress, the tensile internal stress (corresponds
to 3.15% tensile elastic strain) existing in the as-drawn wire prior the heat treatment
comes down to 1,890 MPa. If the as-drawn wire is heated in stress free conditions,
Table 15.1 Key features of the evolution of the peak position in heat treatment experiments
Power 2W 3W 6W 10 W
Onset of the peak position change observed at (ms) 1,260 1,224 1,116 1,020
Maximum radial strain observed (ms) 1,920 1,716 1,188
Radial strain value before treatment (mstrain) 12,600 12,600 12,600 12,600
Maximum radial strain value (mstrain) 1,140 1,055 7,290
Radial strain after treatment (mstrain) 6,225 5,175 2,755 2,145
it becomes ~3% shorter and the radial strain equals to zero after the treatment. As the
temperature increases during the heat treatment, the austenite lattice expands in radial
direction due to two processes (1) isotropic thermal expansion and (2) directional
decrease of the internal tensile stress. Recall that the wire is exposed to oscilla-
ting external tensile stress (Fig. 15.7a) which affects the radial strain as well. The
radial strain increases and decreases but does not return to its original starting value
12600.106 mstrain in any of the treatments (Table 15.1).
Figure 15.8b evidences how internal tensile stress frozen in the wire after the
final cold drawing reduction becomes relaxed during the FTMT-EC treatment.
The radial strain 2145.106 mstrain measured after the 10 W/0.18 s treatment
(Table 15.1) gives a tensile stress of 390 MPa which nearly equals the external tensile
stress. This suggests that the internal tensile stress does not exist in the 10 W/0.18 s and
6 W/0.9 s treated wires but it still partially remains in the wires treated with 2 W/0.9
s and 3 W/0.9 s pulses.
Figure 15.8c shows the results of the analysis of the evolution of the width of the
{110} austenitic peak (FWHM) for experiments with P ¼ 2, 3, 6 and 10 W pulses.
FWHM is equal to 0.35 before the heat treatment. It decreases with increasing
temperature mainly due to the recovery of the crystal defects and related strain
fields existing in the cold worked microstructure, crystallization of amorphous and/
or due to the increase of the subgrain size. While in case of the P ¼ 10 W and 6 W
heat treatments, the decrease of the FWHM from 0.35 to ~0.1 corresponds to well
annealed microstructure, the decrease to only 0.2 in case of the 3 W treatment,
suggests that this microstructure probably still contains many defects and related
strain fields. In case of the P ¼ 2 W/0.9 s treatment, the FWHM almost does not
change suggesting that the defects and strain fields essentially remained in the
microstructure.
15.4 Discussion
The recovery of the cold worked microstructure of the Ni-Ti wire takes place as the
temperature increases from 200 C to 700 C during the heat treatment. The question is
whether it is possible to control the progress of the lattice recovery processes with a
sufficient precision. In conventional furnace treatment, the lattice recovery processes
occur in uncontrolled manner as soon as the wire enters the pre-heated furnace.
Obviously, precise control of the progress of the lattice recovery processes having fast
kinetics (~ms) is not possible by environmental furnace treatment. In the FTMT-EC
treatment, the chance is better since the temperature profile T(t) is prescribed.
In addition to the recovery processes, there are diffusion processes characterised
by much slower kinetics (min) such as precipitation or dissolution of precipitates
which may proceed during the exposure of the sample to elevated temperatures and
affect the functional properties of the wire as well [6]. Hence, in conventional
furnace treatments, it is not possible to find out whether the change of functional
properties is due to recovery processes or/and to diffusion processes. Since the
activity of the diffusional processes is largely suppressed by the short time FTMT-
EC treatments, it is possible to establish the heat treatment parameters – micro-
structure – functional property relationship for heat treated Ni-Ti wires [7, 10].
Obviously, the principal technological goal was to find out the parameters of the
FTMT-EC treatment which leads to optimum superelastic functional properties of
the treated Ni-Ti wires. It comes out that, among the performed treatments, the
optimal ones would be the 5 W/0.9 s or 10 W/0.18 s. The 3 W/0.9 s treatment is not
sufficient and the 6 W/0.9 s treatment results in a loss of stability of the superelastic
behaviour due to plastic deformation accompanying the stress induced phase trans-
formation during tensile cycling. Much more detailed results concerning the func-
tional property setting of Ni-Ti wires were reported in [8]. Detailed TEM
investigation of microstructures in FTMT-EC treated wires confirmed that the
functional properties of Ni-Ti wires can be very well correlated with the micro-
structures [10] and that slip deformation leading to unstable cyclic response takes
place during tensile cycling of overtreated wires [16]. The microstructure
corresponding to optimum superelastic response of the wire is a partially polygo-
nized/recrystallized microstructure with grain size 20–50 nm (Fig. 15.1 right). Such
microstructure was found in a wire treated by 125 W/0.012 s pulse [10]. The 5 W/0.9
s and 10 W/0.18 s treated wire are assumed to contain a very similar microstructure
although there was no direct observation.
Five recovery processes (Table 15.2) are expected to become subsequently
active during the heat treatment of as-drawn Ni-Ti wires. Though the same pro-
cesses take place also during conventional heat treatments in a furnace, there are
following differences that need to be emphasized: (1) fast rate of the FTMT-EC
treatment possibly leading to overheating which differently affects the recovery
processes with different kinetics, (2) mechanical stress action on the recovery
processes, (3) the possible direct action of passing electrons on the recovery
processes. It is assumed that these three FTMT-EC specific features assist the
formation of the desired polygonized/recrystallized nanograin microstructure [7,
10] in the FTMT-EC treated Ni-Ti wires.
The goal of this work was to obtain more detailed information on the lattice
recovery processes with the help of the high speed synchrotron X-ray diffraction
experiments. Particularly, the goal was to interpret the apparently curious in-situ
electric resistance-time and stress-time responses (Figs. 15.6 and 15.7) in terms of
the activity of various recovery processes subsequently taking place during the heat
Table 15.2 Recovery processes expected to occur during electropulse treatment of Ni-Ti wires
take place in sequence I–V as the temperature increases and those dominating in given temperature
range are in bold
Temperature
Recovery process range
I Residual stress relaxation and reverse martensitic transformation 20–500 C
II Polygonization and crystallization from amorphous phase and subgrain 200–700 C
growth
III Recrystallization and grain growth and plastic deformation 500–900 C
IV Plastic deformation and grain growth > 800 C
V Grain growth > 1,000 C
Fig. 15.9 In-situ macroscopic and diffraction results of the P ¼10 W/0.18 s experiment plot
together in dependence on (a) time, (b) temperature
treatment. To synthesize the obtained results, the macroscopic and diffraction

results from 10 W/0.18 s treatment were plotted together in Fig. 15.9.
The tensile stress (curve 2) increases from the onset of heating and electric
resistance (3) starts to fall at 200 C before any change of the diffraction signal can
be detected. However, one has to admit that the experimental error related to {110}
peak analysis at temperatures up to 300 C (Fig. 15.5b) is too large to determine the
peak parameters with sufficient precision. The increase of the tensile stress is thus
taken as a main evidence for the recovery process I. This process is largely reversible
if the maximum achieved temperature remains relatively low (see the stress-
temperature response during the 2 W/0.9 s treatment – curve a in Fig. 15.7). It can
be deduced that the process I dominates over the linear thermal expansion up to
~450 C, otherwise the stress would have to decrease with increasing temperature
due to thermal expansion. Upon further heating, the electrical resistivity (3) falls,
peak height (6) and radial strain (4) starts to increase at ~360 C. It is assumed that the
decrease of electrical resistivity starting at ~200 C evidences the beginning of the
irreversible microstructure change due to recovery of lattice defects through migra-
tion, redistribution and annihilation of point defects and migration of dislocation
dipoles into cell walls called polygonization, crystallization from amorphous phase
and growth of polygonized domains (recovery process II).
At ~450 C, the thermal expansion and/or plastic deformation accompanying the
recovery process II takes over the recovery process I and tensile stress (2) reaches a
maximum and starts to decrease. Right after that, at about 600 C, together with the
falling tensile stress (2), the FWHM (5) starts to decrease suggesting the accelerating
defect annihilation probably due to start of the recovery process III dominated by
dynamic recrystallisation. The alloy is extremely susceptible to plastic deformation
at this stage. At ~700 C, while the temperature still increases, the rate of the decrease
of electric resistivity suddenly changes. This is considered to be an important
threshold point in the microstructure evolution which can be roughly associated
with the termination of process II. It can be easily recognized as the knee point on the
electrical resistivity response. Upon further heating, the recovery processes III and
IV (FWHM decreases, austenite volume fraction increases) continue. The tensile
stress had already reached nearly zero terminating the wire plastic deformation. It
shall be noticed that, after cooling down to room temperature, the wire has the same
length as it had before the test (the tensile stress levels before and after the treatment
are similar) (Figs. 15.6 and 15.7). On the other hand, recalling that the free as-drawn
wire becomes 3% shorter after the 10 W/0.18 s heat treatment, it is assumed that the
plastic deformation did occur even if the wire length did not change. It compensated
the relaxed internal elastic strains due to internal stresses and/or martensite phase
strains present in the as-drawn microstructure which disappeared during the treat-
ment. The responses upon cooling are much simpler – tensile stress (2) increases and
radial strain (4) decreases due to linear thermal contraction taking place under the
condition of the constant sample length, electric resistivity (3) decreases linearly due
to conventional linear dependence on temperature. As the temperature decreases
below ~70 C, the stress (electrical resistivity) starts to decrease (increase) again
resulting in local maxima (minima) recorded at temperature 50 C on the respective
responses in Figs. 15.7 and 15.9. This is due to the B2-R transformation taking place
upon cooling in the already heat treated wires [8]. The situation upon cooling is
somehow more complicated in case of lowest power treatments which did not result
in complete relaxation of internal stresses (Fig. 15.7).
Although it was possible to follow the progress of the sequential lattice recovery
processes at heating rates reaching up to 5,000 C/s, it is difficult to discuss the
kinetics of individual lattice recovery processes, since these are still fast enough to
nearly follow the prescribed T(t) profile. Nonetheless, the fact that individual
responses in Fig. 15.7 do not follow same path upon heating is a clear experimental
evidence that the intrinsic kinetics of individual processes matters. In case of the
125 W/0.012 s treatment [10], in which the heating rate is ~80,000 C/s, the intrinsic
kinetics of the lattice recovery processes plays a much more important role.
15.5 Conclusion
Superelastic functional properties of Ni-Ti wires can be precisely set by the recently
developed nonconventional electropulse treatment. In order to learn about the
recovery processes responsible for that, variations of tensile force, electrical resis-
tance and synchrotron X-ray diffraction signal from 0.1 mm thin as-drawn Ni-Ti
wire prestrained in tension were recorded simultaneously during the short time
electric pulse treatment. The data were used to obtain direct experimental informa-
tion on the phase fractions, internal stresses and defects in the microstructure fast
evolving in response to the prescribed temperature and tensile stress in the treated
wire.
Acknowledgments The authors acknowledge the support of ESRF for performing the in-situ
synchrotron experiment (MA-358) and support from projects AV0Z10100520, IAA200100627.
References
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superelasticity of a nitinol stent. Mater Charact 59:402–406
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Microstructure and functional property changes in thin Ni–Ti wires heat treated by electric
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Chapter 16
Emanation Thermal Analysis as a Method
for Diffusion Structural Diagnostics of Zircon
and Brannerite Minerals
Vladimı́r Balek, Iraida M. Bountseva, and Igor von Beckman
16.1 Emanation Thermal Analysis of Solids
Emanation thermal analysis (ETA) [1–3] based on the measurement of the radon
release from samples, is one of the methods used in the diffusion structure diag-
nostics of solids. Changes in surface morphology and microstructure of solids
during their thermal treatments and changes due to chemical, mechanical or radia-
tion interactions can be studied by the emanation thermal analysis method.
As most of the solids to be investigated do not naturally contain atoms of radon it is
necessary to introduce the radon atoms in the samples prior to the ETA measurements.
To introduce the radioactive trace 220Rn into solids, the samples are labelled by
parent radio-nuclides 228Th and 224Ra, serving as a quasi-permanent source of
radon atoms 220Rn. The used specific activity of the parent radionuclide 228Th is
in the order 105 Bq g1 of the sample.
16.1.1 Radon Atoms Implantation into Solids by the Recoil

Energy of a-Decay
Atoms of the 220Rn radon radionuclide are formed by a spontaneous a-decay of

228
Th and 224Ra radio-nuclides according to scheme Eq. 16.1
V. Balek (*)
Nuclear Research Institute Řež, plc, 250 68 Řež, Czech Republic
I.M. Bountseva and I. von Beckman
Faculty of Chemistry
Moscow MV Lomonosov State University, Moscow 199234, Russia

262 V. Balek et al.
a a a
228
Th ! 224 Ra ! 220 Rn ! (16.1)
T1=2 ¼1:9y T1=2 ¼3:8y T1=2 ¼55s
and the 220Rn atoms can be introduced into the solid owing to the recoil energy of
the spontaneous a-decay (85 keV/atom). The samples can be labelled by using an
adsorption of traces of 228Th as nitrate from a solution.
Due to the energy of the spontaneous a-decay of 228Th and 224Ra radio-nuclides
the atoms of 220Rn can penetrate into the sample several tens of nanometres from
the surface depending on the composition of the materials.The values of the
maximum penetration depths of 220Rn were determined by the Monte Carlo method
using TRIM code [4], e.g. for SiO2: 65.4 nm, for zircon (ZrSiO4): 60 nm and
brannerite mineral (U1xTi2+xO6 ): 60 nm.
Radon atoms can be trapped in solids at structure defects such as vacancy
clusters, grain boundaries and pores. The structure defects in the solids can serve
both as traps and as diffusion paths for radon atoms.
16.1.2 Mechanisms of the Radon Release from Solids
The radon formed by the spontaneous a-decay of 224Ra may escape from the solid
either by recoil energy ejection or by diffusion. The term emanation rate, E, has
been used to express the release of radon from solids. It is defined as the ratio of the
radon release rate to the rate of radon formation by the spontaneous a-decay of
228
Th and 224Ra in the investigated solids.
It has been determined experimentally (in relative units) as E ¼ Aa/Atotal, where
Aa is the a-radioactivity of radon released in unit time from the labelled sample and
Atotal is the total g -radioactivity of the labelled sample. The Atotal value is propor-
tional to the rate of radon formation in the sample.
In the evaluation of the radon release from solids several mechanisms have been
supposed, namely the radon release by recoil mechanism, the diffusion in open
pores, and the volume diffusion mechanism.
The experimentally obtained values of the emanation rate, E, can be considered as:
E ¼ EðrecoilÞ þ EðporesÞ þ Eðsolid) (16.2)
The emanation rate due to recoil, E (recoil), can be expressed as
EðrecoilÞ ¼ K1 S1 (16.3)
where K1 is a temperature independent constant, proportional to the penetration

depth of recoiled radon atoms in solids investigated and S1 is external surface area
of sample particles. The path of recoiled atoms of radon is dependent on the
“nuclear stopping power” of the sample material.
16 Emanation Thermal Analysis as a Method for Diffusion 263
The emanation rate due to diffusion in pores, E (pores), is expressed as
EðporesÞ ¼ K2 S2 (16.4)
where K2 is a constant that depends on temperature and S2 is internal surface area of

the sample depending on the surface of open pores, cracks and intergranular space.
The emanation rate due to volume diffusion mechanism, E (solid), is expressed
as
EðsolidÞ ¼ K3 expðQ=2RTÞS3 (16.5)
where K3 is a constant related to the atomic properties of the lattice, Q is the

activation energy of Rn diffusion in the solid, S3 is surface area, R is molar gas
constant, and T is temperature.
The growth of the emanation rate values, E (T), may characterize an increase of
the surface area of interfaces, whereas a decrease in the E(T) may reflect processes
like closing up structure irregularities that serve as paths for the radon migration,
closing pores and/or a decrease in the surface area of the interfaces [3–6].
16.2 Application of the Emanation Thermal Analysis

in the Diffusion Structural Diagnostics of Solids
The equipment for the emanation thermal analysis (ETA) was developed in the
1960s [1, 2]. Since that time the ETA method was used in various investigations,
e.g. the re-crystallization of solids, annealing of structure defects and changes in the
defect state of both crystalline and amorphous solids, sintering, phase changes, the
characterization of surface and morphology changes accompanying chemical reac-
tions in solids and on their surfaces, including the thermal degradation, solid–gas,
solid–liquid, and solid–solid interactions [7–11]. The ETA made it possible to
reveal even fine changes in poorly crystalline or amorphous solids. Differences in
the morphology and behaviour of samples prepared by the sol–gel technique under
different conditions were revealed by the ETA.
Changes in defects annealing and pore sintering of the samples were character-
ized by using the ETA results under in situ conditions of their heat treatments. The
determination of optimized conditions for the preparation and thermal treatments of
advanced ceramic materials was achieved [10, 11]. By this way the ETA results
contributed to the solution of practical tasks in the materials technology.
Recently, this method made it possible to characterize the thermal stability of
ceramic materials designed for the immobilization/encapsulation of high level
radioactive waste [12]. Moreover, the thermal stability of self- irradiated amor-
phous minerals that serve as natural analogues of the ceramic matrices was eval-
uated by using the emanation thermal analysis.
264 V. Balek et al.
In the study of the self- irradiated metamict materials the ETA measurements
were carried out by using modified NETZSCH DTA-ETA equipment, Type 404.
Details of the measurements and the data treatments are described elsewhere [2–6].
During the ETA measurements the samples were heated at the rate of 6 K min1 in
air (zircon sample) and argon (brannerite sample). The specific activity of the
labelled samples was 105 Bq g1.The used amounts of the samples were 0.02 and
0.1 g respectively. During the ETA measurements, a constant flow of the carrier gas
(air, nitrogen, or another gas) has been used to take the radionuclide of radon of
220
Rn released by the sample into the detector of a-activity of radon (semiconductor
detectors).
16.2.1 Thermal Behaviour of Natural Zircon Mineral
Natural zircon mineral (general formula ZrSiO4), containing an average concentration

up to 0.4% of uranium and 0.2% of thorium, has attracted much interest from both
fundamental and technological view points. The a-particles and heavy recoil nuclei
released during the decay of radioactive impurities (typically 238U, 235U and 232Th)
interact with the surrounding crystalline matrix displacing atoms from their equilib-
rium positions [13]. Over geological periods of time this process disrupts the crystal-
line order to such a point that specimens covering all the stages from fully crystalline
to amorphous can be found, depending on the uranium/thorium content.
Understanding the radiation effects in crystalline zircon and the determination of
the structure of the aperiodic state are essential to ensure the reliability of zircon
based ceramics for nuclear waste disposition [13, 14]. During nuclear disintegra-
tion, the emission of the a-particle is accompanied by a recoil nucleus. Amorphiza-
tion taking place in natural zircon is called metamictization. The a-particles have
energy of 4–6 MeV, and almost all the energy is dissipated by the ionization
processes. It is believed that various isolated defects, such as Frenkel pairs, are
formed along their paths. A number of studies have been devoted to structural
changes of zircon under irradiation, in particular to understanding the amorphiza-
tion and/or metamictization process [15]. This process can lead to an increased
solubility and fracturing [16].
Ceramic forms used in the encapsulation of nuclear waste are subjected to a
similar transformation, with the corresponding variation of their physical and
chemical properties. An understanding of radiation effects in crystalline zircon
and a determination of the structure of the aperiodic state are essential to ensure
the reliability of zircon and related ceramics for nuclear waste disposition [13, 14].
Zircon ceramics can incorporate significant amount of UO2, PuO2 or ThO2 in a
solid solution with ZrO2. The zircon undergoes an amorphization promoted by
a-decay events of radiogenic elements. During the nuclear disintegration, the
emission of an a-particle is accompanied by a recoil nucleus and ballistic collisions
of the recoil nucleus cause displacement cascades. A number of studies have been
devoted to the evolution of amorphous zircon under irradiation, in particular to

understanding of the metamictization process [15].
Natural zircon mineral sample characterized by ETA was from the locality Sri
Lanka. The sample was X-ray amorphous [16].
Figure 16.1 shows ETA results of the zircon mineral sample measured on
heating (curve 1a) in air flow in the temperature range 20–1,100 C and subsequent
cooling (curve 1b). The increase of the emanation rate, E, observed in the tempera-
ture range of 170–250 C characterized the diffusion mobility of radon atoms along
surface cracks and other subsurface defects, the subsequent decrease of the E values
in the range 250–420 C can be ascribed to healing the surface and subsurface
defects.
We supposed that the increase of the emanation rate, E, in the range 420–750 C
is due to the radon diffusion along structure irregularities in the amorphous zircon.
The phase transformation of initially amorphous zircon was characterized by the
decrease of the emanation rate values E in the range 750–950 C. From ETA results
of the amorphous zircon mineral sample measured on heating to 1,200 C and
subsequent cooling to room temperature it followed that the microstructure changes
taking place in the sample on heating were irreversible.
The results of DSC measured on a parallel sample of amorphous/metamict
zircon are demonstrated in Fig. 16.1 as the full line curve. The transformation of
amorphous zircon to the crystalline zircon was characterized by a DSC exothermal
effect with the maximum at 918 C.
0.20
1a
0.15
ETA
E / rel. units
+ exo
0.10 ΔT
DSC
– endo
0.05 1b
0 200 400 600 800 1000 1200

Temperature / °C
Fig. 16.1 ETA results (points) of natural zircon mineral sample measured on heating (curve 1a)
and subsequent cooling (curve 1b) in air in the range 20–1,100 C. The DSC results measured on
the sample heating are depicted as the full line curve
266 V. Balek et al.
16.2.2 Thermal Behaviour of Natural Brannerite Mineral
Brannerite mineral (general formula U1xTi2+xO6) has been found in nature as

amorphous due to a-decay damage caused by high content of U, Th. The formula of
natural brannerite can also be written (U, Th)1xTi2+xO6. The natural brannerite
generally contains impurity elements like Pb, Ca, Th, Y and rare earth elements
(REE) on the U-site and Si, Al and Fe on the Ti-site. The brannerite is a minor phase
in titanate-based ceramics designed for the geological immobilization of surplus Pu
[17, 18]. Therefore, it was of interest to investigate the thermal behaviour of the
metamict brannerite mineral as a natural analogue of the brannerite ceramics to be
used for immobilization of hazardous radioactive elements.
The diffusion structural diagnostics based on the results of emanation thermal
analysis (ETA) made it possible to characterize the annealing of the structure
irregularities in the brannerite mineral sample on heating to various temperatures
up to 1,200 C. Natural brannerite mineral was from the locality El Cabril mine near
Cordoba, Spain. The sample was X-ray amorphous and contained Ca, Pb and other
impurity elements [17].
Figure 16.2 shows the ETA results of the metamict brannerite mineral measured
during heating in argon in the range 20–1,200 C and subsequent cooling. The
increase of emanation rate, E, observed on the sample heating in the range of
40–300 C characterized the diffusion mobility of radon atoms along surface cracks
and other subsurface defects to depth of 60 nm.
The slight decrease of E(T) observed in the temperature range of 400–500 C
(curve 1a, Fig. 16.2) was ascribed to healing surface cracks and voids. The decrease
Fig. 16.2 ETA results of natural brannerite mineral sample measured on heating (curve 1a) and
subsequent cooling (1b) in argon in the range 2–1,200 C
of the emanation rate E(T) observed on the ETA curve in the range 800–880 C,
corresponding to the healing microstructure irregularities, was considered as a first
step of the formation of crystalline brannerite. The increase of E(T) observed in
range 900–965 C followed by the sharp decrease of E(T) in the range 970–1,020 C
indicated the formation of the crystalline brannerite phase, as confirmed by XRD
spectroscopy [17, 19]. From ETA results of the brannerite mineral sample measured
on heating up to 1,200 C and subsequent cooling it followed that the microstructure
changes on sample heating are irreversible.
The release of CO2 was detected by mass spectrometry of evolved gases in the
temperature range 700–800 C [17] due to the thermal degradation of minor car-
bonate containing components of the sample. The release of CO2 gave rise to the
sample porosity [17]. It was of interest to investigate the self-irradiated metamict
brannerite mineral during “step by step” heating and subsequent cooling of the
sample to the temperatures of 300, 550, 750, 880, 1,020 and 1,150 C, respectively.
Results of ETA measured by the ”step by step” heating runs (Fig. 16.3) made it
possible to compare the annealing of microstructure irregularities of the sample in
the selected temperature intervals.
As it follows from the ETA results in Fig. 16.3, the “step by step” heating of the
sample to these temperatures caused a decrease of the amount of structure irregula-
rities serving as radon diffusion paths.
A good reproducibility of the ETA results measured on heating from 20 C to
300 C is obvious from the comparison of the results in Fig. 16.3, curves 2a and 1a.
0.10
1a
2a 2b
E / rel. units
0.05 3b
3a
4b
4a 6a 6b
5b
5a 7a 7b
0.00
0 200 400 600 800 1000 1200
Temperature / °C
Fig. 16.3 ETA results of natural brannerite mineral sample measured on heating and subsequent
cooling in argon in the range 20–1,150 C: curve 1a corresponds to the “as received” sample
measured during heating from 20 C to 1,150 C, curves 2a/2b, 3a/3b, 4a/4b, 5a/5b, 6a/6b and 7a/7b
were measured with a parallel samples pre-heated to the temperatures of 300, 550, 750, 880 and
1,020 C, respectively
268 V. Balek et al.
The ETA curves 3a/3b, 4a/4b and 5a/5b characterized the thermal behaviour of the
metamict brannerite sample pre-heated to 300 and 750 C, respectively. The
increase of the emanation rate, E, in the temperature range of 20–360 C, due to
the diffusion of radon along micropores in the sample, was followed by the decrease
of E, characterizing the partial healing of voids and structure irregularities that
served as diffusion pathways for radon.
The ETA curves 6a/6b in Fig. 16.3 characterized the thermal behaviour of the
sample pre-heated to 880 C. As already observed by curve 1a the amount of
structure irregularities serving as radon diffusion paths further diminished in the
sample pre-heated to 880 C. The decrease of the emanation rate on sample
observed on heating in the range of 970–1,020 C indicated the next step of the
formation of crystalline brannerite. A good reproducibility of the ETA measure-
ments can be seen from the temperature coincidence of the effects on the curve 1a
and curve 6a in Fig. 16.3.
From curves 7a/7b characterizing the thermal behaviour of the sample pre-
heated to 1,020 C, it is obvious that after the pre-heating the sample to this
temperature an irreversible crystallization of amorphous self-irradiated brannerite
mineral took place.
From Fig. 16.3 it is obvious that the amount of structure irregularities serving as
radon diffusion paths further diminished and the radon permeability in the pre-
heated brannerite samples decreased with the temperature used for pre-heating of
the samples.
Values of the emanation rate, ERT, measured at room temperature before and
after each heating run were used for the assessment of the relative changes of the
surface area affected by the heat treatments used. The ERT values summarized in
Table 16.1 are in agreement with our considerations of the annealing of surface area
and subsurface irregularities.
From the temperature dependences of the emanation rate, E(T), measured during
heating to selected temperatures and subsequent cooling, the decrease in the
amount of radon diffusion paths was assessed. To this aim we used the parameter
x defined in Eq. 16.6 as:
Table 16.1 Microstructure defects characteristics of natural self-irradiated brannerite mineral

sample pre-heated to various temperatures
ETA curves measured on Temperature of sample Defect amount ERT [rel. Dx**
heating/cooling pre-heating characteristics x *
units] [%]
Curves 1a/1b, Fig. 16.2 As received 38.1 0.026 100
Curves 2a/2b, Fig. 16.3 As received 0.41 0.023 1.08
Curves 3a/3b, Fig. 16.3 300 C 3.82 0.017 10.02
Curves 4a/4b, Fig. 16.3 550 C 10.26 0.015 26.93
Curves 5a/5b, Fig. 16.3 750 C 13.62 0.014 35.75
Curves 6a/6b, Fig. 16.3 880 C 6.30 0.005 16.54
Curves 7a/7b, Fig. 16.3 1,020 C 0.98 0.001 2.57
TR
max TR
max

xðTmax Þ ¼ EðTÞheating dT EðTÞcooling dT
Dx ¼ xxn1 100 ½%
Tmin Tmin
ZTmax ZTmax
xðTmax Þ ¼ EðTÞheating dT EðTÞcooling dT (16.6)
Tmin Tmin
Moreover, values of Dx (see Eq. 16.7) were calculated with the aim to compare the
amounts of the annealed microstructure defects during the “step by step” heating of
the sample. The difference of integrals used for the assessment of the amount of the
microstructure defects can be expressed as Dx defined as
xn
Dx ¼ 100½% (16.7)
x1
As it followed from values of x and Dx summarized in Table 16.1, the most

significant decrease of the structure irregularities serving as diffusion paths for
radon diffusion was annealed prior to the crystallization of the sample in the range
of 970–1,020 C.
Figure 16.4 depicts a comparison of the relative amount of structure irregula-
rities, expressed by parameter x, that were annealed during heat treatments to the
selected temperatures.
It was shown that the emanation thermal analysis revealed differences in the
amount of structure irregularities that served as radon diffusion paths in the brannerite
Fig. 16.4 Relative amounts of micro structure irregularities in natural brannerite sample healed in
the heating runs to temperatures 20–300, 20–550, 20–750, 20–880, 20–1,020 and 20–1,150 C.
Parameter x was used to characterize the amount of structure irregularities of the following
samples: preheated to 300, 550, 750, 880 and 1,020 C respectively
270 V. Balek et al.
samples. Additional information about thermal behaviour of self-irradiated metamict

minerals was obtained by using the diffusion structural diagnostics.
Acknowledgments Authors thank to the Ministry of Education, Youth and Sports of the Czech
Republic for the support (Project MSM 2672244501).
References
1. Balek V (1978) Emanation thermal analysis. Thermochim Acta 22:1–156

2. Balek V (1991) Emanation thermal analysis and its application potential. Thermochim Acta
192:1–17
3. Balek V, Šubrt J, Mitsuhashi T, Beckman IN, Györyová K (2002) Emanation thermal
analysis: ready to fulfil the future needs of materials characterization. J Therm Anal Calorim
67:15–35
4. Ziegler JF, Biersack JP, Littmark U (1985) The stopping and range of ions in solids.
Pergamon, New York
5. Beckman IN, Balek V (2002) Theory of emanation thermal analysis XI. Radon diffusion as
the probe of microstructure changes in solids. J Therm Anal Calorim 67:49–61
6. Emmerich WD, Balek V (1973) Simultaneous application of DTA, TG, DTG, and emanation
thermal analysis. High Temp-High Press 5:67
7. Balek V, Tölgyessy J (1984) Emanation thermal analysis and other radiometric emanation
methods. In: Svehla G (ed) Wilson and Wilson’s comprehensive analytical chemistry, Part
XIIC. Elsevier Science, Amsterdam
8. Balek V, Brown ME (1998) Less common techniques. In: Brown ME (ed) Handbook on
thermal analysis and calorimetry, vol 1. Elsevier Science BV, Amsterdam, pp 445–471
9. Balek V (1989) Characterization of high-tech materials by means of emanation thermal
analysis. J Therm Anal 35:405–427
10. Balek V, Šesták J (1988) Use of emanation thermal analysis in characterization of super-
conducting YBa2Cu3Ox. Thermochim Acta 133:23–26
11. Balek V, Pérez-Rodriguez JL, Pérez-Maqueda LA, Šubrt J, Poyato J (2007) Thermal beha-
viour of ground vermiculite. J Therm Anal Calorim 88:819–823
12. Balek V, Zhang Y, Zeleňák V, Šubrt J, Beckman IN (2008) Emanation thermal analysis study
of brannerite ceramics for immobilization of hazardous waste. J Therm Anal Calorim
92:155–160
13. Rı́os S, Boffa-Ballaran T (2003) Microstructure of radiation-damage zircon under pressure.
J Appl Crystallogr 36:1006–1012
14. Devanathan R, Corrales LR, Weber WJ (2004) Molecular dynamics simulation of disordered
zircon. Phys Rev B 69:064115(9)
15. Carrez P, Forterre Ch, Braga D, Leroux H (2003) Phase separation in metamict zircon under
electron irradiation. Nucl Instrum Methods B 211:549–555
16. Wang LM, Ewing RC (1992) Detailed in situ study of ion beam-induced amorphization of
zircon. Nucl Instrum Methods B 65:324–329
17. Balek V, Vance ER, Zeleňák V, Málek Z, Šubrt J (2007) Use of emanation thermal analysis to
characterize thermal reactivity of brannerite mineral. J Therm Anal Calorim 88:93–98
18. Lian J, Wang LM, Lumpkin GR, Ewing RC (2002) Heavy ion irradiation effects of brannerite-
type ceramics. Nucl Instrum Methods B 191:565–570
19. Zhang Y, Lumpkin GR, Li H, Blackford MG, Colella M, Carter ML, Vance ER (2006)
Recrystallisation of amorphous natural brannerite through annealing: The effect of radiation
damage on the chemical durability of brannerite. J Nucl Mater 350:293–300
Chapter 17
Scanning Transitiometry and Its Application
in Petroleum Industry and in Polymer
and Food Science
Jean-Pierre E. Grolier
17.1 Introduction
Liquid–solid phase equilibria in asymmetric binary mixtures are not only of general
interest to explore phase equilibria in three-phase (gas, liquid, solid) systems but
they play a major role in understanding and monitoring the pT-behaviour of petro-
leum fluids. Such fluids present a vast variety of compositions in terms of their
respective constituents from light gases and liquids of various molecular sizes to
macromolecular solids. Nowadays, the lack of thermodynamic data on asphaltenic
fluids prevents the large scale exploitation of heavy oils in deep deposits. The main
concern is the uncontrolled precipitation/flocculation of heavy fractions (asphal-
tenes, waxes) which causes obstruction and plugging of underground as well as
surface installations and pipes. Research in polymer science continues to develop
actively while the concepts of thermodynamics and kinetics together with polymer
chain structure enhance the domain of polymer development and transformation.
In many industrial applications, during extrusion processing or as all purpose
materials, polymers are usually submitted to extreme conditions of temperature
and pressure. Furthermore, most of the time they are also in contact with gases
and fluids, either as on-duty materials (containers, pipes) or as process intermediates
(foaming, molding). Since such materials are often used in special environments or
under extreme conditions of temperature and pressure, their careful characterization
must be done not only at the early stage of their development but also all along their
life cycle. In addition, their properties as functions of temperature and pressure must
be well established for the optimal control of their processability. This also stands for
phase transitions; ignorance of a phase diagram, particularly at extreme conditions
of pressure, temperature, and of chemical reactivity, is a limiting factor to the
J.-P.E. Grolier (*)

Laboratoire de Thermodynamique des Solutions et des Polymères Université Blaise Pascal,
24, Avenue des Landais, Clermont Ferrand 63177, Aubière Cedex, France

272 J.-P.E. Grolier
development of an industrial process, e.g., sol–gel transitions, polymerization under

solvent near supercritical conditions, micro- and nano-foaming processes. Natural
and bio-polymers constitute an important class of components largely used in food
science. Among the numerous such polymers, starch serves to illustrate the com-
plexity of state equilibria of systems containing other species like fibers, fat,
proteins, and extended ranges of water percentages. In food science, industrial
processing of such systems, for example during cooking extrusion, requires in
depth thermodynamic as well as thermophysical characterization of the systems to
process. All above fields to cite a few, in oil industry and in polymer and food
applications, necessitate the acquisition of key data.
Undoubtedly, thermal and calorimetric techniques are essential in this respect.
In relating thermal as well as mechanical behaviour to materials’ structures these
techniques are perfectly adapted to provide accurate data in wide ranges of temper-
ature and pressure. Typically, thermophysical properties feature the most important
information expected when dealing with materials submitted to thermal variations
and/or mechanical constraints. The properties of interest are of two types, bulk
properties and phase transition properties. The bulk properties are either caloric
properties, like heat capacities CP, or mechanical properties, like isobaric thermal
expansivities aP, isothermal compressibilities kT, and isochoric thermal pressure
coefficients bV. Two main thermal properties concern the first order transitions,
fusion and crystallization, and the glass transition. All these properties are now
accessible thanks to recent progress in various technologies which allow measure-
ments in the three physical states over extended ranges of p and T, including in the
vicinity of the critical point. In this respect, knowledge, i.e. measurements, of the
thermophysical properties of polymers over extended ranges of temperature and
pressures and in different gaseous environments is absolutely necessary to improve
the use and life-time of end products made of such polymers. The purpose of this
chapter is to demonstrate the contribution of the new technique, scanning transitio-
metry, in providing accurate information to meet the demand for the different data
pointed out. Examples have been selected in three main domains, oil exploitation
and transport, polymer foaming and modification, and starch-water systems. As a
matter of fact, these examples are directly connected to industrial activities: the
petroleum industry, the insulating material industry, and the food industry. In many
cases, gases and polymers of different types and from different origins (synthetic,
natural) are intimately interacting under external conditions of temperature (T) and
pressure (p). In the subsequent examples the gas/polymer systems are either selected
for a targeted industrial purpose i.e. foaming materials and materials processing, or
are polymeric materials in contact with gas/liquid systems, i.e. pipes or tanks in gas
and petroleum industry. The foaming materials industry is a rapidly growing area
where constant innovation and added value products are key factors for economic
success where international competition is high. The mastering of polymer degra-
dation (typically blistering) by high pressure dissolved gases is another key issue. In
what follows, in a first section the newly developed technique will be described. In a
second section selected examples will illustrate how such technique is providing
valuable data for significant progresses in different fields.
17 Scanning Transitiometry and Its Application in Petroleum Industry 273
17.2 Scanning Transitiometry
Certainly, calorimetry is a major technique to measure thermodynamic properties of

substances and to follow phase change phenomena. In most applications, calorimetry
is carried out at constant pressure while the tracked phenomenon is observed on
increasing or decreasing the temperature. The possibility of controlling the three
most important thermodynamic variables (p, V and T) during calorimetric measure-
ments makes it possible to perform simultaneous measurements of both thermal and
mechanical contributions to the thermodynamic potential changes caused by the
perturbation. Calorimetric techniques provide valuable additional information on
transitions in complex systems. Their contributions to the total change of thermody-
namic potential not only leads to the complete thermodynamic description of the
system under study, but also permits investigation of systems with limited stability or
systems with irreversible transitions. By a proper external change of the controlling
variable the course of a transition under investigation can be accelerated, impeded or
even stopped at any degree of its advancement and then taken back to the beginning,
all with simultaneous recording of the heat and mechanical variable variations. In
what follows the main characteristics of scanning transitiometry are reviewed.
The seminal presentation by Randzio [1] of thermodynamic fundamentals for the
use of state variables (p,V,T) in scanning calorimetric measurements has open the
path [2–4] from p,V,T-calorimetry to the now well established scanning transitiome-
try technique [5]. With this technique the simultaneous determination of thermal and
mechanical responses of the investigated system, perturbed by a variation of an
independent thermodynamic variable while the other independent variable is kept
automatically constant, allows the determination of thermodynamic derivatives over
extended ranges of pressure and temperature, impossible to obtain by other known
techniques. Four thermodynamic situations are thus possible to realize in the instru-
ments based on such technique, namely, pVT-controlled scanning calorimeters or
simply scanning transitiometers, since they are particularly adapted to investigate
transitions by scanning one the three thermodynamic variables. The four possible
thermodynamic situations (Fig. 17.1) are obtained by simultaneous recording of both
(∂V / ∂P )T kT
p = f(t) (∂V / ∂T )p
TRANSITIOMETRY
T = cst ap
V = f(t) Mechanical (∂V / ∂P )T = –(∂V / ∂T )p
SCANNING
T = f(t) (∂P / ∂T )V
P = cst bV
(∂S / ∂V )T = (∂P / ∂T )V
T = f(t) (∂H / ∂T )P CP
V = cst Thermal
(∂U / ∂T )V CV
Fig. 17.1 Thermodynamic scheme of scanning transitiometry showing the four possible modes of
scanning. Each of these modes delivers two output derivatives (mechanical and thermal) which in turn
lead to four pairs of the different thermomechanical coefficients, namely: aP, kT, bV, CP, and CV.
274 J.-P.E. Grolier
a stirring device
heat insulation
REAGENTS
reaction calorimetry
heating measuring cell
shield
sample Diff.
TDIFF T TSECURITY meas.
unit
Temp. 80 W 300 W
Calorimetric
ULTRACRYOSTAT control Heating
signal
Transitiometer
Pt100
PC
RS232
PCI-MIO-16XE-50
dry step motor
cooling
air control
jacket
flow
pressure high pressure pump

detector
high pressure calorimetric calorimetric
measuring cell detector block
Calorimetric block
Piston pump with

step motor control
Pressure programmer
Cell
Temperature
programmer
Fig. 17.2 (a) Detailed schematic representation of a scanning transitiometer setup for in situ
simultaneous determination of the thermal and mechanical derivatives. For convenience, two
heat flow (thermal output) and the change of the dependent variable (mechanical
output).
Then, making use of the respective related Maxwell relations one readily obtains
the main thermophysical properties as follows: (a) scanning pressure under iso-
thermal conditions yields the isobaric thermal expansivity aP and the isothermal
compressibility kT as functions of pressure at a given temperature; (b) scanning
volume under isothermal conditions yields the isochoric thermal pressure coeffi-
cient bV and the isothermal compressibility kT as functions of volume at a given
temperature; (c) scanning temperature under isobaric conditions yields the isobaric
heat capacity CP and the isobaric thermal expansivity aP; (d) scanning temperature
under isochoric conditions yields the isochoric heat capacity CV and the isochoric
thermal pressure coefficient bV.
A detailed description of a basic scanning transitiometer is given elsewhere [6].
A schematic representation of the instruments (from BGR TECH, Warsaw, Poland)
used in the present applications to polymers, and constructed according to the princi-
ple of scanning transitiometry, is presented in Fig. 17.2. It consists of a calorimeter
equipped with high-pressure vessels, a pVT system, and a LabVIEW based virtual
instrument (VI) software. Two cylindrical calorimetric detectors (ext. diameter
17 mm, length 80 mm) made from 622 thermocouples chromel-alumel each are
mounted differentially and connected to a nanovolt amplifier. The calorimetric detec-
tors are placed in a calorimetric metallic block, the temperature of which is directly
controlled with an entirely digital feedback loop of 22-bit resolution (~104 K), being
part of the transitiometer software. The calorimetric block is surrounded by a heating-
cooling shield connected to an ultracryostat (Unistat 385 from Huber, Germany) and
the temperature difference between the block and the heating-cooling shield is set
constant (5, 10, 20 or 30 K) as controlled by an analogue additional controller. The
whole assembly is placed in a thermal insulation enclosed in a stainless steel body and
placed on a stand, which permits to move the calorimeter up and down over the
calorimetric vessels. The actual operating ranges of scanning transitiometry are
respectively 173 K < T < 673 K and 0.1 MPa < p < 200 MPa (or 400 MPa).
Actually, transitiometry is at the centre of different types of utilization since with
such technique, bulk properties, transitions as well as reactions (for example poly-
merization) can be advantageously studied. In the case of a non-reacting system
which remains in a homogeneous state, both the mechanical and thermal outputs as
explained before give straightforward access to pairs of the thermomechanical
coefficients. When the system or the material sample evolves through a chemical
reaction or a phase change, the recorded information yields the corresponding heat
ä
Fig. 17.2 (continued) types of cells are shown: on the left-hand side is the standard high pressure
cell and on the right-hand side is a reaction type cell which can accommodate various accessories
(stirrer, reagents feeding, capillaries, optical fibers/probes for UV/Vis/near IR spectroscopic
analysis). (b) Photography of a standard scanning transitiometer (from BGR TECH, Warsaw).
The calorimetric detector which can be moved up and down over the measuring and reference cells
(in twin differential arrangement) is shown in the upper position. In this position the cells which
are firmly fixed on the stand table are then accessible for loading
276 J.-P.E. Grolier
and pVT characteristics. In the case of polymer synthesis, a scanning transitiometer

was used as an isothermal reaction calorimeter, the advancement of a polymeriza-
tion reaction being accurately monitored through the rigorous control of the thermo-
dynamic parameters [7, 8]. The thermocouples composing fluxmeters serve as a heat
conduction path between cell walls and the block. To gather additional information
on a reaction, the reaction can be coupled with other analytical devices (e.g., on-line
FTIR, particle sizing probes, turbidity probes, pH or other ion selective probes) [9].
A photographic presentation of a transitiometer is given in Fig. 17.2.
17.3 Selected Results
Performances and advantages of scanning transitiometry are well demonstrated by

typical applications in several important fields: (1) asymmetric fluid mixtures and
petroleum fluids; (2) transitions of polymer systems under various constraints
(temperature, pressure, gas sorption) including first-order phase transitions
[10, 11] and biopolymer gelatinization [12–14]; (3) polymer thermophysical prop-
erties [15] and influence of gas sorption [11, 16]. In what follows illustrative
examples have been selected, namely: in the petroleum industry, in polymer science
and in food science.
17.3.1 Petroleum Industry
The oil industry, where petroleum products and associated fluids of different nature
with multicomponent and complex compositions present a large variety of phases
and phase equilibria, is certainly the domain by excellence for scanning transitio-
metry applications. The ongoing determinations of the thermophysical properties
(CP, aP, kT) over extended p and T ranges of newly developed fuels (including
biofuels) will not be reported here. Instead, two other completed studies are worth
to report: (1) appearance of the solid phase in asymmetric binary systems and (2)
precipitation of heavy cuts in asphaltenic fluids under p and T conditions of deep
underground reservoirs.
The investigation of asymmetric systems i.e. binary mixtures of two components
having large difference in the molecular size is of interest in relation with the solid
precipitation or flocculation of heavy components in high pressure reservoir fluids
containing large concentrations of light components like methane. Typically these
systems exhibit a three-phase equilibrium curve (solid–liquid-vapor) with a high
temperature segment. Scanning transitiometry allows to precisely detecting up to
high pressures the transition through the three-phase line in both directions by
varying any of the state variables (p, V, T). The method was tested [6] with the
system {tetracosane + methane} by comparing with the reference data measured
a
200
180
160
140
120
p/MPa
100
80
60
40
20
0
315 320 325 330 335 340 345
T/K
b
140
Exo
130
120
1st expansion
Heat flow (a.u.)
110
100
2nd expansion
90
80
70
4th expansion
60
37 42 47 52 57 62 67
Pressura (MPa)
Fig. 17.3 (a) Phase equilibria in the system {tetracosane + methane}.~, Our work on the three-
phase equilibrium [6]. ○, Three-phase equilibria data of Flöter et al. [17]. □, Second critical
endpoint. ■, Our work for the high pressure equilibrium (solid + fluid + liquid) [6]. Note that the
three (open triangles) points correspond to a near critical liquid–vapor isopleth at 0.04 mole
fraction of tetracosane. (b) Thermograms obtained after cycling successive decompressions and
recom-pressions. During the first expansion the exothermic effect which would correspond to the
precipitation/flocculation of asphaltenes clearly appears; it is slightly visible for the second
expansion and completely disappears after the third one. The shape of the forth expansion
thermogram is similar to what is observed for a simple fluid [4]
using the conventional visual method [17]. The Fig. 17.3a shows the very good
agreement of data obtained with scanning transitiometry and the indirect method
based on the visual observation of phase boundaries.
278 J.-P.E. Grolier
Precipitation or flocculation of asphaltenes is a major concern for different

activities in the petroleum industry such as extraction, production and transport. Due
to their complex molecular structures, asphaltenes constitute large aggregates which
contribute to a large extent to the stability of crude oils. Asphaltenes are identified by
their insolubility in n-alkanes and their solubility in aromatic solvents like toluene.
Their particular molecular and thermodynamic properties are such that under slight
changes of p and T asphaltenes can flocculate in the crude oil causing the formation of
heavy deposits. Therefore it is essential to document the thermodynamic comportment
of asphaltenes undergoing temperature and pressure differences between in-well and
surface conditions. To this end scanning transitiometry was used to investigate the
thermodynamic behavior of asphaltenic fluids under in-well p and T conditions. The
study of real (live) fluids was a challenge [18] as regards the introduction of an
asphaltenic fluid (provided in a high pressure cylinder by TOTAL France) into the
transitiometric cell under isobaric conditions from the high pressure cylinder. Effec-
tively, the fluid has been collected and kept in the cylinder under the in-well
conditions, thus the isobaric transfer must be carefully made to prevent any drop in
pressure which would inevitably cause precipitation/flocculation of asphaltenes.
A special setup was designed to insure the isobaric transfer of the fluid into the active
calorimetric detector [18]; this was facilitated by the use of mercury as hydraulic fluid
to pressurize the whole (transfer setup and calorimetric cell) system and push the fluid
into the calorimetric cell during the operation of transfer. It was then possible to bring
the fluid sample in the calorimetric cell to the nominal p, T in-well conditions. Cycles
of compression/decompression could be performed over extended time periods
in order to allow the system to relax and return to equilibrium and observe
possible precipitation/flocculation of asphaltenes. The isothermal (at 430 K) thermo-
grams obtained with a given asphaltenic fluid (61 MPa and 430 K respectively) are
presented in Fig. 17.3b. The shallow exothermal maximum shown for the first
expansion would correspond to the precipitation/flocculation of asphaltenes; for the
second decompression (after recompression) only a small effect is visible and for the
fourth decompression under the same conditions no more such effect appears. It can be
concluded that after few decompression/re-compression the original asphaltenic fluid
behaves as a “normal” fluid [4] since the asphaltenes have precipitated and were not
redissolved by successive recompressions during the time frame of the experiment.
These preliminary investigations have shown the advantage of scanning transitiome-
try to characterize real (live) oils and systematic studies are underway on heavy oils
from different geological origins.
17.3.2 Polymer Science
As multipurpose technological materials, polymers must be perfectly characterized.

In particular, among the thermophysical properties the isobaric thermal expansiv-
ities, aP, and the isothermal compressibilities,kT, are key properties to document
over extended ranges of T, p, and crystallinities. Also, when dealing with polymer
materials, the glass transition must be unambiguously established in particular with

respect to its dependence with temperature, pressure and plasticizers, especially
high pressure gases. Although the following examples might appear as simply
relevant of “applied” science, they imply fundamental approaches in terms of
developing specific instruments and associated methodologies to determine ther-
mophysical properties and to investigate the glass transition temperature Tg which
is the pivotal transition to understand and control for the proper processing of
polymeric materials. Herein, an account of the influence of the crystallinity and
p on the isobaric thermal expansivities aP is reported; also the influence on Tg of p,
T and gas solubility is illustrated.
The thermodynamic principle of scanning transitiometry is based on the Max-
well equality

@V @S 1 dQ
¼ ffi : (17.1)
@T p @p T T dp T
Thus, if a sample of a polymer of a mass ms is placed in the calorimetric vessel

and is submitted to a pressure variation dp, then the heat exchanged in such a
process, dQpl, is defined by the following equation

@Vs
dQpl ¼ ms T dp: (17.2)
@T p
On the other hand, if the substance contained in the calorimetric vessel is in the
fluid state and the pressure is exerted through the fluid itself then the real mass of
the fluid sample contained in the calorimetric vessel is changing along with the
pressure variation and is equal to VE/Vs, where VE is the active internal volume of
the calorimetric vessel accessible for the fluid and Vs is the specific (or molar)
volume of that fluid. Thus, in this case the thermal effect, dQfl, associated with the
pressure variation is defined by the following equation

VE @Vs
dQfl ¼ T dp ¼ VE Tap dp; (17.3)
Vs @T p
where ap¼1/Vs(∂Vs/∂T)p is the isobaric thermal expansivity of the fluid. Then, if a

polymer sample is placed in the calorimetric vessel and is compressed or decom-
pressed by intermediary of a fluid like a gas or mercury, the total thermal effect will
be composed of the main three following terms: compression of the solid (Eq. 17.2),
compression of the fluid phase (Eq. 17.3) and “pure” interaction of the fluid with the
polymer. Of course it is assumed that there are no state or phase transitions in both
the fluid and the polymer within the experimental p, T range.
The thermal calibration (energy and temperature) was done with the use of
benzoic acid. The thermomechanical calibration, especially the determination of
the internal active volume VE (Eq. 17.3) was done with the use of nitrogen, for
which the thermal expansion is known from its equation of state.
280 J.-P.E. Grolier
17.3.2.1 Isobaric Thermal Expansivities of Polyethylenes with Various

Crystallinities over Extended p and T Ranges
As a matter of fact thermal expansivity aP as well as heat capacity CP, both second
derivatives of the thermodynamic potential G (the free enthalpy) are key thermo-
physical properties. The knowledge of CP as a function of T allows to evaluate the
temperature effects on thermophysical properties, similarly, the knowledge of aP as
a function of p permits to access the effects of pressure on thermophysical proper-
ties. However, direct measurements of aP, especially of polymers, are rather scarce.
Contrary to fluids (gases and liquids) the thermal expansivity of polymers presents a
specific (theoretical) aspect because like in solid substances thermal expansion
results from anharmonic lattice vibrations. The particularity of polymers is that
they usually are constituted of partially crystal phases. Therefore, this property of
both fundamental and engineering interests needs to be documented by experimen-
tal measurements taken over extended p and T ranges for various crystallinities.
We conducted the first systematic series of direct measurements along this line
[15, 19]. For this, we used a pressure controlled scanning calorimeter (PCSC),
actually later called Scanning Transitiometer (ST). Remarkably, scanning transi-
tiometry is perfectly designed to measure aP, in the same way temperature con-
trolled scanning calorimetry (TCSC), usually named DSC, is the technique by
excellence to measure CP. In our measurements [15, 19] mercury was used as
inert hydraulic fluid enveloping the polymer sample. Isothermal linear pressure
scans were performed from where aP’s of polymer samples were determined
through the procedure detailed in Refs. [15, 19]. Data for two different types of
low and high density polyethylenes (respectively LDPE and HDPE) are presented
on Fig. 17.4 as smooth isotherms of aP’s versus pressure. One observes that there
are small differences between the four sets of data which show the characteristic
converging trend at elevated pressures.
17.3.2.2 Glass Transition Temperatures of Elastomers Under High Pressure
The glass transition temperature is affected by pressure since an increase of pressure

causes a decrease in the total volume then an increase of Tg is expected due to the
decrease of free volume. This result is important in engineering operations such as
molding or extrusion, when operations too close to Tg can result in a stiffening of the
material. Investigation of the glass-transitions of polymers under pressure is not a
simple problem, especially in the case of elastomers of which Tg’s are usually well-
below the ambient temperature. In the case of scanning transitiometry the traditional
pressure-transmitting fluid, mercury, must be replaced since its crystallization
temperature is relatively high, i.e. 235.45 K. Then the choice of the replacement
fluid is again a challenge [20] because it should be chemically inert with respect to
the investigated sample. Also, values of its thermomechanical coefficients, com-
pressibility, kT, and thermal expansivity, ap, should be smaller than those of the
investigated sample. An additional difficulty in the investigation of second order
a 1.10
a 1.00
LDPE-A HDPE-A
1.00
362.5 K 393.0 K
0.90 0.80
αp (10–3 K 1)
αp (10–3 K–1)
0.80 362.5 K
–
333.0 K
0.70 0.60
0.60 302.6 K 333.0 K
0.50 0.40 302.6 K
0.40
0.20 0.20
0 50 100 150 200 250 300 0 50 100 150 200 250 300
Pressure (MPa) Pressure (MPa)
b 1.20
b 1.00
LDPE-B HDPE-B
1.10 362.5 K
393.0 K
0.00 0.80
αp (10–3 K–1)
0.90
αp (10–3 K 1)
362.5 K
–
0.80 333.0 K
0.60
0.70 333.0 K
0.60 302.6 K 302.6 K
0.40
0.50
0.40
0.20 0.20
0 50 100 150 200 250 300 0 50 100 150 200 250 300
Pressure (MPa) Pressure (MPa)
Fig. 17.4 Isobaric thermal expansivities as functions of pressure at various temperatures for four
polyethylenes (PE) with different densities (r in g cm1), crystal phase volume fractions (Fc), and
crystal phase mass fractions (wc). On left-hand side low density PE: LDPE-A (r ¼ 0.921, Fc ¼ 0.46,
wc ¼ 0.42), LDPE-B (r ¼ 0.936, Fc ¼ 0.51, wc ¼ 0.55). On the right-hand side high density PE:
HDPE-A (0.73¥), HDPE-B (r ¼ 0.957, Fc ¼ 0.64, wc ¼ 0.80¥). ¥N.B. from enthalpimetric
measurements; all other values from volumetric measurements
type transitions is the relatively weak effect measured. It is well-known that the
amplitude of the heat flow at the glass transition Tg increases with the temperature
scanning rate while the time-constant of heat flow type calorimeters, like scanning
transitiometers, imposes temperature scan rates which are slow compared to typical
DSC scan rates.
For the present measurements silicon oil was used instead of mercury as the
hydraulic pressurizing fluid, and the polymer sample was placed in a lead (soft
metal) ampoule. Test measurements were made on polyvinyl acetate for which the
DTg/Dp coefficient was found to be 0.212 0.002 K MPa1 in good agreement
with the literature value 0.22 K MPa1 [21]. The calorimetric traces obtained with
the same method for a poly(butadiene-co-styrene) vulcanized rubber [22] during
isobaric scans of temperatures ranging from 218.15 to 278.15 K at 0.4 K min1 are
shown in Fig. 17.5. This Figure shows also the evolution of Tg at different pressures,
at 0.25, 10, 30, 50, and 90 MPa, respectively: Tg increases linearly with pressure
with a DTg/Dp coefficient of 0.193 0.002 K MPa1. It should be noted that Tg is
expressed as the temperature corresponding to the peak of the first derivative of the
heat flux (i.e. the inflexion point of the heat flow).
282 J.-P.E. Grolier
Fig. 17.5 Illustration of the scanning transitiometry technique for the investigation of polymers
glass transition temperature at low-temperature and high pressure. The typical thermograms (heat
flow vs T) for the transition domain of a vulcanized rubber are shown for different pressures. The
pressure coefficient of the glass transition temperature is given in the inset
17.3.2.3 Glass Transition Temperature of Polystyrene Modified by High

Pressure Methane
There is not much information available in the literature on calorimetric study

of plasticization of polymers at high pressures, above say 50 MPa, induced by
gases. Plasticization is well characterized by the shift of the temperature of the glass
transition, Tg. Actually, when pressure is induced by a gas, both plasticization
and hydrostatic effects contribute to the shift of Tg. If plasticization tends to
lower Tg because of the gain of mobility of the polymeric chains, the hydrostatic
effect raises it in diminishing the free volume. Methane (CH4) is assumed to be a
non-plasticizing gas but, our results show that, at higher pressures, plasticization
overtakes again the hydrostatic effect, due to a probably higher solubility of the gas
in polystyrene (PS) at higher pressures; this kind of behavior has been suggested for
high enough pressures [23]. The plasticization of PS using CH4 seems to be possible
but it is necessary for this to apply high pressure, i.e. 200 MPa, in order to obtain
approximately the same shift of the Tg as with ethylene (C2H4) under 9,0 MPa! In
this respect CH4 cannot really be considered as a good plasticizing gas.
17.3.2.4 Shift of the Glass Transition Temperature

by High Pressure Gases
An important aspect of polymer foaming is certainly the “easiness” of the blowing

agent to enter, to dissolve and to diffuse into the polymer matrix. Two parameters,
T and p, are essential to control these phenomena. The nature and properties of the
polymer and of the fluid play evidently a major role. In this context, the physical
state of the polymer must be appropriately modified to undergo plasticization; this
optimal condition for having the “blowing” effect taking place depends upon the
glass transition temperature Tg. Plasticization depends on all the thermodynamic
variables and parameters listed above. In particular, it is necessary to know to what
extent Tg is advantageously decreased in order to optimise the foaming process.
From a practical point of view the DTg shift should be accurately determined or
predicted. Moreover, many properties can be correlated with the glass transition
temperature depression DTg due to plasticization. In order to predict the DTg the
model of Chow [24] was selected. The calculations using the model of Chow were
made using experimental data of solubilities directly measured with a new tech-
nique combining a vibrating wire (VW) weight sensor and a pVT setup [25].
Chow has proposed a relation based on Gibbs and Di Marzio principle (the
entropy of the glassy state is zero) to account for the change in Tg due to the sorbed
component as follows:

Tg
ln ¼ b ½ð1 yÞ lnð1 yÞ þ y ln y; (17.4)
Tgo
where
zR Mp o
b¼ ;y ¼ ;
Mp DCp z Md 1 o
Tg and Tgo are the glass transition temperatures for the polymer-gas system and the
pure polymer respectively, Mp is the molar mass of the polymer repeat unit, Md is
the molar mass of the (diluent) gas, R is the gas constant, o the mass fraction of the
gas in the polymer, DCp is the heat capacity change associated with the glass
transition of the pure polymer and z is the lattice coordination number. All para-
meters of the model have physical meanings, except the number z. The value of this
parameter may change according to the state of the diluent: z ¼ 2 when the diluent
is in the liquid state and z ¼ 1 when it is gas.
In order to compare the model calculations with experimental calorimetric data,
polystyrene (PS) samples were modified in a transitiometer used in that case as a
small reactor to modify under equilibrium conditions the polystyrene in presence of
a chosen fluid. Modifications of polystyrene have been done in presence of N2 and
CO2, along isotherms at a given pressure. For these two fluids, a final temperature of
398.15 K and a final pressure of 80 MPa have been attained. The glass transition
284 J.-P.E. Grolier
temperatures Tg’s of modified and non modified PS samples were determined by

Temperature Modulated DSC (TMDSC). The solubilities of the different gases
were measured using the VW-pVT sorption technique [25, 26] along different
isotherms and the mass fraction of the gas in the polymer was then determined
with the following equation:
s
o¼ ; (17.5)
sþ1
s being the solubility of the fluid in the polymer, in mg of fluid/mg of polymer.

Using the values of o determined for each system PS/gas, the Chow equation
(Eq. 17.4) has allowed to estimate the variation with pressure, D Tg, of the
temperature of the glass transition this, along the different isotherms of the sorption
measurements. The use of the Chow model is then rather delicate since the choice
of the value of z, that is to say in fact, the state of the diluent influences significantly
the results. The Tg-shift under CO2 pressures is spectacular showing the high
plasticizing effect of CO2. The good agreement of the literature data for PS/CO2
with the calculated values [23] as seen in Fig. 17.6 can certainly be explained by the
state of the diluent which is most likely in the critical state in the ranges of T and
p considered.
0
PS / CO2- 338.22 K-z = 2
PS / CO2- 362.50 K-z = 2
++
–20 PS / CO2- 383.22 K-z = 2 ++ +
+
PS / CO2- 402.51 K-z = 2 ++ +
PS / CO2- 338.22 K-z = 1 ++
–40 ++
PS / CO2- 362.50 K-z = 1 +
PS / CO2- 383.22 K-z = 1 +
DTg / K
–60 PS / CO2- 402.51 K-z = 1

+ O’Neill & Handa [28]
+ Chiou et al [29]
– 80
+ Zhang & Handa [30]
–100 0 2 4 6 8 10
–120
0 10 20 30 40 50
P / MPa
Fig. 17.6 Variation of the glass transition temperature with pressure for the system polystyre-
ne–CO2. Calculations have been made for 338.22, 362.50, 383.22 and 402.51 K. Full symbols
represent results for z ¼ 1 and empty symbols for z ¼ 2. Literature values are represented by
crosses in the zoom of the graph (the same scale of temperature being kept). Lines are hand drawn
through the points
Effectively, the critical temperature Tc and critical pressure pc of CO2 support

the hypothesis of the gas being in the near critical region. As a matter of fact,
depending on the experimental conditions in the vicinity of the critical point, the
fluid can exist in one or the other state (gas or liquid) or even in both. In the present
case, literature data [28–30] for the PS/CO2 system have been obtained under a
pressure p pc and at a temperature T Tc for CO2; then two phases of the diluent
can coexist in different proportions. Despite the difficulty to determine exactly the
variation of Tg, particularly under supercritical conditions of a diluent fluid, the
model of Chow is actually a useful guide in order to predict the variation of the
glass transition of a polymer modified by a high pressure fluid. However, the exact
determination of the glass transition depression, D Tg, becomes more difficult when
the pressure increases, specially near and above the critical point of the diluent
fluid. This means that when plotting DTg as a function of pressure, the temperature
of measurement plays a major role. If we do not take into account this temperature,
it is preferable to represent DTg as a function of the mass fraction of the fluid in the
polymer.
Compared to polar CO2 and because of its non-polarizability, N2 should be a
weaker plasticizing agent although, as shown in Fig. 17.7, it induces significant
shifts of Tg with increasing pressures [27]. However, N2 which should be also a
good foaming agent is not used in the foaming industry because of the need of too
high a pressure to attain the desired depression in Tg.
PS / N2 - 313.11 K
PS / N2 - 333.23 K
–10 PS / N2 - 353.15 K
ΔTg / K
–20
–30
–40
0 10 20 30 40 50
P/ MPa
Fig. 17.7 Variation of the glass transition temperature as a function of pressure for the system
polystyrene-N2. Calculations have been made for 313.11, 333.23 and 353.15 K, using z ¼ 1. Lines
are hand drawn through the points
286 J.-P.E. Grolier
17.3.3 Food Science
Recent and fast developments in food science result from the large scale use of
extruders to process different types of products from biscuits, crackers, breakfast
cereals, flours, to more elaborate culinary components and pet food. Actually, food
materials are extruded as other materials like polymers. Extrusion processes shape
the final products in terms of structural organization (fibre like crystallisation, foam,
soft or hard species) in combining elevated temperatures and pressures.
Optimization of extrusion processes requires a detailed knowledge of the proper-
ties of the starting ingredients. In this respect, the properties of starch which is a
major component of food systems are essential to document, particularly over
extended pressure and temperature ranges as well as water content. In this context,
the contribution of scanning transitiometry to investigate starch-water systems has
been recently demonstrated [14, 31]. Figure 17.8 presents an example of a transitio-
metric study of a 56% water suspension of wheat starch. Temperature scans have
been performed at various pressures while recording simultaneously two output
signals, heat flow and the thermal expansion. Interestingly, the endothermic main
transition (positive enthalpy) corresponding to gelatinization is associated with a
negative volume change, in complete agreement with the Clapeyron equation
characterizing the transition.
17.4 Concluding Remarks
New developments in calorimetric techniques like Temperature Modulated DSC,

(TMDSC), which permits to determine unambiguously glass transition tempera-
tures [32], and in associated techniques like the VW-pVT technique [26] which
allows measuring simultaneously the amount of gas entering a polymer sample and
the subsequent volume change of the polymer, have contributed to notably broaden
the area of experimental thermodynamics, with incursions in several major
domains. In addition, the field of calorimetric techniques has witnessed an impres-
sive impetus with the concept of scanning transitiometry. The main characteristic of
scanning transitiometry is its great versatility in the sense that all physical states,
homogeneous as well heterogeneous systems can be thoroughly investigated.
A special feature is the possibility it gives to take full advantage of the four possible
modes of scanning. Remarkably, it is possible after loading the measuring cell to
activate either one of the four scanning modes and to shift from one to another
without removing or reloading the cell. The possibility to use different hydraulic
fluids to pressurize the investigated sample or system is undoubtedly another great
advantage. The hydrostatic effect of a neutral fluid like mercury can serve as a
reference against which to compare the hydrostatic/plasticization effects of other
fluids (liquids or gases). Furthermore, a scanning transitiometer can be used as an
instrumented reactor to perfectly control the modifications induced by T, p and the
–1.5 1.4
–2.0 10 MPa 1.3

1.2
–2.5
1.1
–3.0
1.0
–3.5
0.9
–4.0 0.8
–4.5 0.7
–5.0 0.6
310 320 330 340 350 360 370 380 390 400 410
–1.5 1.3
–2.0 60 MPa 1.2
(dV / dT)p (mm3 g–1 K–1)

–2.5 1.1
qp(T) (mW g–1)
–3.0 M 1.0
–3.5 0.9
–4.0 A N 0.8
–4.5 0.7
ENDO
–5.0 0.6
310 320 330 340 350 360 370 380 390 400 410
–3.5 1.2
–4.0 100 MPa 1.1

–4.5 1.0
–5.0
0.9
–5.5
0.8
–6.0
0.7
–6.5
–7.0 0.6
–7.5 0.5
310 320 330 340 350 360 370 380 390 400 410
TEMPERATURE (K)
Fig. 17.8 Transitiometric traces (thermal and mechanical outputs per gram of dry starch) obtained
simultaneously in situ by scanning temperature at the rate 2.5 mK s1 at three different pressures
for a starch-water suspension (56 mass% total water content). The middle graph allows distin-
guishing between the heat flow qp (thermal) thermogram and the volume change (dV/dT)p
(mechanical) trace
288 J.-P.E. Grolier
pressurizing fluid as for example for polymer foaming [33] or for self assembling of
nanoscale molecular structures [34–36]. The possibility to use supercritical fluids to
transmit pressure adds a new feature to the technique which becomes ideally suited
to investigate state transitions in various thermodynamic situations. A scanning
transitiometer can also be used as a reaction calorimeter in which additional devices
(for example reagents feeding capillaries, stirrer, pH and spectroscopic probes)
allow to collect complete information on a reacting medium [8, 9, 37, 38]. Among
other possible fields of applications, biology and biochemistry are important fields
where scanning transitiometry should certainly contribute to provide original
results.
This technique plays an important role in defining the most probable thermody-
namic path to follow in order to in depth investigate a special region of interest in a
system undergoing imposed changes or self developing modifications kinetically
dependent. In making accessible new data, often impossible to obtain with other
known techniques, scanning transitiometry contributes to reinforce the place of
rigorous thermodynamics in providing key information to develop theoretical
models; a typical illustration being for example the use of recently obtained
thermophysical (isobaric thermal expansion) data on fluids to design new equations
of state [39, 40].
References
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variable: definitions and some metrological problems. Thermochim Acta 89:215–241
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measurement of isobaric expansivities and isothermal compressibilities of liquids by scanning
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20:937–948
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8. Grolier J-PE, Dan F (2007) Advanced calorimetric techniques in polymer engineering.
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9. Dan F, Grolier J-PE (2004) Spectrocalorimetric screening for complex process optimization.
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10. Randzio SL (1999) Transitiometric analysis of pressure effects on various phase transitions.
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the starch-water systems. Macromolecules 35:8852–8859
13. Randzio SL, Flis-Kabulska I, Grolier J-PE (2003) Influence of fiber on the phase transforma-
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14. Orlowska M, Randzio SL, Grolier J-PE (2003) Transitiometric in situ measurements of
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pressure methane. Polymer 42:1653–1661
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38. Grolier J-PE, Dan F (2006) The use of advanced calorimetric techniques in polymer synthesis
and characterization. Thermochim Acta 450:47–55
39. Randzio SL, Deiters UK (1995) Thermodynamic testing of equations of state of dense simple
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Chapter 18
Constrained States Occurring in Plants
Cryo-Processing and the Role
of Biological Glasses
Jiřı́ Zámečnı́k and Jaroslav Šesták
18.1 Unique Properties of Water Affecting Plant Life
The freezing temperatures well below 0 C [1] are common and there are several
mechanisms to assure life survival. Processes associated with water freezing (particu-
larly in conjunction with its supercooling) have been intensively studied [2–4] for
many years because their significance in the bionetwork of both plants [5] and living.
In human activity they play an important role in various production from a plain ice
making to the complex foodstuffs freezing [6, 7] and pharmacy finishing. Even more
important role they play in the viability of plants in natural overwintering and in
controlled cryopreservation of plants.
Water is a compound, which exhibits some extraordinary uncommon and amazing
properties and strange behaviour. It concerns a relatively high boiling-point, excep-
tionally large specific heat capacity and surface tension, and anomalous ability to
dissolve both ionic and polar compounds. When water is left standing for a longer
period, it tends to develop thixotropic properties, which implies a fragile but charge-
containing (pH-variation) macrostructure (OH–/H+ assembling), curiously capable to
even store and release amounts of preintroduced charge [8]. Impurities dissolved in
water decrease both its melting and boiling temperatures. Recent studies, done via
molecular dynamics, identified experimentally water clusters [2–4, 9], which grow in
size and become more compact as temperature decreases. Their size can be character-
ized by a fractal dimension consistent with patterns common in natural world, having
J. Zámečnı́k (*)
Molecular Biology Department, Plant Physiology and Cryobiology Laboratory
Crop Research Institute, Drnovská 507, CZ-161 06 Prague 6, Czech Republic
J. Šesták (*)
Division of Solid-State Physics, Institute of Physics, v.v.i., Academy of Sciences of CR,
Cukrovarnická 10, CZ-16200 Prague 6, Czech Republic

292 J. Zámečnı́k and J. Šesták
the correlation length proportional to the configurational entropy [10]. Upon cooling,
ice-like crystals were more easily transformed from the smaller clusters of (H2O)n
with n up to 20, more likely existing at temperatures >5 C. The larger clusters (n>20)
can undergo supercooling more readily to alter to glassy structures at low tempera-
tures. The decrease in the region of glass transition temperature with the increasing
cluster size was experimentally observed to be much less operative than the
corresponding change of melting temperatures. The mutual order of the melting and
glass-transition temperatures were found to be reversed compared with that observed
for bulk water.
Plants, tolerating ice crystals in their tissues possess several overall strategies
to remain alive during temperatures below zero (Fig. 18.1). The first living strategy
is to avoid nucleation while supercooled. Many vegetation and plant tissues
are capable to overcome freezing by adjusting certain supercooled status [4]
where the level of supercooling may go down to below 40 C [11]. There are
multiple examples in different plant organs, such as parenchymatic cells [12], whole
organs as generative buds of Ribes [13], Malus [14] or vegetative buds of Abies [15].
The second living strategy of plants is based on tolerating the extracellular
freezing of water [13, 15–18]. Survival of such plant cells and/or tissues is based
on their acceptability of excessive dehydration of the protoplast (Fig. 18.2). It is
worth noting that quite a few of plant tissues can survive naturally temperatures
down to 40 C, however, with the attuned techniques used for cryopreservation of
plant genetic material they can survive even the liquid nitrogen temperatures [19].
0°C ~ –2°C ~ –5°C –10°C > +20°C
Cooling Extra-
cellular
Ice rate Alive
1-5°C h–1 ice
nucleation
formation
Intra-
cellular Lethally
ice injured
formation
Cell
with
nucleus
Supercooling Alive
Quenching
>100 ºC min–1
Biological
Alive
glass
Fig. 18.1 Natural plant behaviour while exposed to cooling explained by diagram of the freezing
process in plant tissue. Freezing process is sorted according to the cooling rate and the degree of
the ice crystal formation. Ice crystal inside the cell formation is predominantly lethal for plant
18 Constrained States Occurring in Plants Cryo-Processing 293
Fig. 18.2 Cells from garlic shoot tip of dormant bulbils. Samples were quenched directly in liquid
nitrogen, fractured and etched. Left is a cross-section of the fractured vitrified cells (*) after the
process of plant vitrification (Plant Vitrification Solution No. 2 – treatment, magnification
10,000) Right is non-vitrified cell with the visible ice-crystal (+) structure inside the protoplast
(magnification 3,000) [24]
The third strategy towards an enhanced survival during sudden cooling is called
as an “extra-organ” freezing [14, 20] when the whole plant organ (for example bud)
stays protected against nucleation and ice spreading inside the organ. Extra-organ
ice formation causes frost dehydration of inner bud meristematic tissues resulted in
their deep supercooling [21, 22]. Above mentioned survival strategies of plant
species in their tissues are commonly witnessed such as the woody plants can
exhibit extra-organ freezing in their buds, extracellular freezing in their bark tissues
and supercooling in their parenchymatic cells of xylem rays [23].
However, a question remains what is the state of water or the state of protoplasm
in the plant cells subjected to subzero and even to lower temperatures. Supercooled
liquid can eventually switch into the form of non-crystalline solid, called glass. Such
a water vitrification was treated within the concept of polymeric-polymorphic
structure [4, 25]. The inherent glass formation takes place at a narrow temperature
interval called “glass transition” (and abbreviated Tg) [26], which, fortunately, does
not possess the volume change as it is associated with the transformation of ice. For
example, the glassy state found in dormant twig of a poplar tree [2, 23, 27] offers the
justification of what a curious state of solid water can be found in the frozen tissues.
The process of vitrification is [28], however, closely associated with the anomalous
behaviour of liquid water [29] and its apparent tendency to pentameric netting at
falling temperatures. Worth noting is possible interaction of liquid water with plant
cells, which structures possess fractal and self-affinity architecture [15] yielding thus
focal sites for compulsory nucleation enhancing and/or inhibiting ice formation.
Therefore, it seems to be essential to reiterate some basic data about the structure of
liquid water mainly of its configurationally quasi-periodicity, which seems be crucial

for the formation conditions of quasi-crystalline nuclei and their capability to outline
the state of either biologically optimal glass or hazardous ice.
18.2 Glass Forming Components in Plants
18.2.1 Supercooled Water
Any commence of a state diagram for water relies, at least, on two sources of data:
l Variation of glass transition temperature [26] as a function of water content;
l Curve-based determination of a freezing point depression [30] (often completed
up to the intersection with the Tg curve).
Temperature of both curves for homogenous and heterogeneous nucleation is
depending on water concentration. A state diagram cannot be created without a
precise knowledge of water content and the corresponding value of glass transition
temperature, Tg, which must be defined experimentally – Tg for hyper-quenched
water is generally believed to lay at about 133 C to 138 C [31]. Note the highest
heat capacity water has and the same applies for ice, at temperatures below zero
(Fig. 18.3), in comparison with other substances occurring in plants [32].
Water supercooling and ice formation have been theoretically analysed [12]
within a traditional nucleation theory and the ice formation can be conventionally
described by homogeneous nucleation if no foreign (nucleation extraneous) centres
Fig. 18.3 Heat capacity (Jg1 K1) of water and ice. The main organic substances and ash from
plants. Data calculated according published equations [40]. Heat capacity line for protein and fat
represents the same line. Note the abrupt change of heat capacity at 0 C of ice
are present. However, this is a rare case in nature, because microscopic inhomo-
geneities or biological interfaces (e.g. bacteria) are always present in water
(together with the outer-bordering surfaces) acting thus as nucleation sites and
triggering irresistible heterogeneous nucleation. Under normal atmospheric pres-
sure, the ordinary liquid water can be easily supercooled down to about 25 C,
with some further requirements (purity) as low as 38 C and with an enhanced
supercooling (such as in small droplets of ~5 mm diameter) down to lowest 40 C.
The bottom temperature limit for water supercooling (also known as the homoge-
neous freezing point) is achieved for water activity equal one and the associated
freezing point depression [30] is close to 0 C. Where salts or hydrophilic solutes are
present, the homogeneous freezing point reduces about twice (as much as the
melting point). However, some sugar solutions have very low glass transition
temperatures and the associated time for ice formation [26] becomes almost
immeasurable.
The intracellular ice-crystal formation is in every case lethal for plant survival
due to the inherent volume expansion of newly formed ice in comparison with the
original volume of liquid (Fig. 18.2). One way how plants can withstand the low
temperatures in the nature is their tolerance to movement of intracellular water to
extracellular domains, which, in result, brings a higher tolerance to cell dehydration
[4, 33–35]. However, the supercooled states frequently possess no dehydration
effects or ice-crystal formation, but this state is unstable. The exceedingly low
viscosity at rapidly cooling conditions of ‘freeze-in’ states give often birth to a new
non-crystalline state of a rigid state of glasses, and remaining once again, such a
process of vitrification is not associated with any dangerous volume changes. The
freeze-in states can nearly hinder any diffusion of molecules, preventing thus
biochemical transformations and, accordingly, excluding also any genetic changes.
From a comparison of the elements and inorganic compounds forming glasses
[36–38] in plants it is not clear to derive a strict relationship of glass formability
in plants.
18.2.2 Carbohydrates
Organic compounds, such as sucrose, glucose, glycerol fructose and proteins occur in
higher concentration in plants and it is not clear how to derive a strict relationship of
glass formability in a wider organic disposition. A certain exception can be seen in
carbohydrates, mainly in the region of high concentration of sucrose. The levels of
various organic and inorganic solutes in stem tracheal (xylem) sap and fruit tip [39] sap
of legume Lupinus albus is about a thousand times higher than elements content in the
same plants [41]. Sucrose and specific proteins are the main compounds of plants,
which are synthesised during an acclimation procedure toward cold.
Sugars are commonly used as cryoprotectants. Their concentrations and the indi-
vidual types of sugars must be optimized toward the developing cryopreservation
methods [34], those based on glass involvement. The cryobiologists tested various
carbohydrates in an attempt to improve the percentage of explants surviving with their

regeneration. Unlike sugar alcohols such as sorbitol and manitol, which are not readily
metabolised in the cells of many plant species, sucrose is readily metabolized and is
thought to have several protective functions during dehydration and subsequent
freezing and thawing. Most of these sugar alcohols are not as effective cryoprotectants
as sucrose is. Sucrose has been found to be the most effective cryoprotectant in many
other studies [34, 42].
Carbohydrate activities are an important intermediary for cryopreservation:
l Can decrease water content by osmotic dehydration;
l After influx of carbohydrate into the cells, the osmotic potential of plant tissues
often decreased;
l Osmoprotectants (sugars like sucrose) are thought to contribute maintaining the
membrane integrity during the dehydration and freezing processes. It is inter-
mediated by the formation of hydrogen bonds between sugars and the hydro-
philic components of cellular membranes [43];
l Act as a glue sticking for shoot tips to the carrier (for example aluminum foil)
after dehydration;
l Accomplish the first aid during the energy starvation throughout the plant
regeneration after warming.
Sugars are seen as the most usable cryoprotectants involved in plants as a reaction
to abiotic stress (mainly in drought and cold conditions). The sucrose is used also as
the most acceptable cryoprotectant added to the plant during their cryopreservation
at ultra-low temperatures. Using sugar as a cryoprotective example, it can be shown
how difficult it is to interpret a more complex behaviour even for such a relatively
simple substance and how difficult it can become to define its mixtures in the plant
tissue (Fig. 18.4). None explicit expression derived from theoretical models is able
to predict the behaviour satisfactorily enough.
The glass transition temperature for a binary mixture of water and sucrose
seems to follow the semi-empirical Couchman and Karasz expression [35], which
is only partially profitable in the description of aqueous solutions. Although
empirical, this equation [35] seems to be the best model to describe varying Tg
along with the composition. Modified Gordon–Taylor equation (MGT, Eq. 18.1)
can be used to estimate the Tg values of single-phase sucrose solutions (when no
ice is present). Glass transition temperature data for sucrose with various water
contents were collected from the literature (Fig. 18.4) and then fitted by the
following Eq. 18.1

Tg ¼ kTg2 Cw kTg2 Tg1 = Cw 1 kTg þ kTg
þ a1 Cw ð1 Cw Þ þ a2 C2 ð1 Cw Þ; (18.1)
where Cw is the concentration of water at Tg (weight fraction), Tg1 and Tg2 are the
mid-points of the glass transitions for pure water and sucrose, while k, a1 and
a2 are constants. Here we use 348.2 K for Tg2, the glass transition temperature of
120 s - I sucrose
100
80 40 % 63 %
60
40
20 s - I water
0
T, °C
–20 1
–40 T'g T'g
–60 2 TH1
–80
–100 Tg
–120
–140 Fox eq. heterogeneous nucleation
–160
0 10 20 30 40 50 60 70 80 90 100
Wsuc
Fig. 18.4 Schematic state diagram of aqueous solution of sucrose [30], an example of 40%
concentrated sucrose. Curve 1 is for equilibrium freezing, curve 2 is for thawing of 63% frozen
solution. Glass transitions corresponding to the nominal composition of the initial solution of
sucrose Tg, glass transition of maximum freeze concentrated phase Tg1, glass transition domains
around sucrose crystals Tg´. Solid curves are for water solid–liquid boundary (s–l water) and
sucrose solid–liquid boundary (s–l sucrose)
pure sucrose, and Tg1 for water is taken as 135 K. The “best fit values” for the
parameters are k ¼ 0.092, a1 ¼ 481 and a2 ¼ 1,225 [31].
No attempts are made to apply this equation to multi-component plant samples,
but it could become feasible under further credentials. However, the equation
allows considering a mixture of several components as one component and water
as another one having chiefly some practical values only. The problem still remains
because it does not recognize the definite DCp even for pure water, which the
Couchman-Karasz equation uses for predicting the Tg data of multi-component
systems. Nevertheless, both equations were satisfactorily used for description of
water content and glass transition for such multi-component biological material as
the fruit powders are [44].
From the above mentioned results, it follows that diluted and semi-concentrated
aqueous solutions of sucrose (wsuc weight fraction of sucrose in Fig. 5.4, Table 5.1)
freeze under a non-equilibrium state. The system is heterogeneous and contains
crystals of ice and sucrose. These exhibit two types of domains of amorphous solids
[4], which composition corresponds to that of maximum freeze concentrated phase
(MFCP) characterised by glass transition temperature T´g. The solution inside the
domains around sucrose crystals is characterised by glass transition temperature Tg1.
At very low temperatures, the resulting structure of the solution is heterogeneous
containing ice, sucrose crystals, and two glasses formed from the freeze-concen-
trated phase and the solution lying in the neighbourhood of sucrose crystals. During
plant freezing and drying, sucrose works as an explicit and inherent protecting agent,
but a mere accumulation of sucrose alone is not a sufficient precondition for all plant
species toward a successful survival at the ultra-low temperatures.
18.2.3 Proteins
The formation of intracellular glass is proposed to be relevant to protein stabiliza-

tion and survival of anhydrobiotic organisms in the dry state. The stability of
proteins in the amorphous carbohydrate matrix and its relevance to seed survival
has been investigated [45]. Thermal stability of seed proteins exhibited a strong
dependence on the Tg of intracellular glass. These results indicate an important role
of the glassy state in protein stabilization. This data suggest an association
between protein stability in intracellular glass and seed and pollen survival during
storage [45–48].
18.3 Artificial State of Biological Glasses Contributing Plants’

Survival at Ultra-Low Temperature
A new approach how to store plant samples at ultra-low temperature is called the
‘ice free cryogenic storage’ [1, 50], which is based on the instigated formation of
biological glasses. Such a strategy how to reach the glass transition in plant samples
for their long-term storage by cryopreservation methods is prospective in the three
following ways of an external control of:
l The rate of cooling and warming;
l Dehydration removing excess of water from the tissue, safeguarding enough
water volume in the tissue to keep the plants alive. The dehydration can be done
often by three ways (see below);
l Infiltration of plant samples with substances shielding the unwanted crystalliza-
tion, so-called ‘cryoprotective’ fixatives or cryoprotectants, which are usually
efficacious glass formers.
18.3.1 Cooling and Warming Rate
An important factor is the rate of freezing, which is crucial for the ice growth and
sizing. The ice formation in plants meets a certain temperature stress. By
application of a well guarded rate of cooling/warming, the cryopreservation method

subsists as the oldest method, which was ever used [51, 52]. For the first time, it was
demonstrated that the willow twigs collected during very strong winter, addition-
ally prefrozen at 30 C, were successfully cryopreserved in liquid nitrogen for
1 year with subsequent plant regeneration [51]. The principle of this method is to
give enough time to precede the extracellular freezing of water by slow cooling to
30 C. In principle, it is like the natural freezing occurring in wildlife.
The two-step freezing method based on extracellular freezing was successfully
applied to hardy tree buds, which were recovered by grafting [53, 54]. Controlled
rate of cooling is efficient for storing suspension and callus cultures, embryogenic
cultures and in vitro shoot tips from temperate and subtropical plants. In addition,
cryopreservation of cultured cells and meristems was achieved by controlled slow
pre-freezing to about 40 C in the presence of a relevant cryoprotectant [55] where
single chemicals or their combination in various ratios (mixed in a suitable cryo-
protective cocktails) can be employed. These cryoprotectants help the plant sam-
ples to stabilize their membranes and proteins after deep dehydration, alternatively
acting as an energy pool during the recovery of plants. For a common use,
dimethylsulfoxide (DMSO) is utilized as a representative cryoprotectant of colliga-
tive group capable of penetrating inside the cells. The polysaccharides
(mainly sucrose and polyethylene glycols) are representative of non-penetrating
cryoprotectants [56]. The volume of water inside the cell is decreasing while the
concentration of solutes increases until the equilibrium of water activity outside and
inside the cells is reached.
A control of glass formation in the tissue during this researching method was
invented by authors [52, 57] but not proved yet. After freeze dehydration it is
speculated that plants can adapt to survival due to inherent glass transition ongoing
inside the plant’s cells. It is anticipated by following facts. The intracellular matrix
occurs highly concentrated owing to extracellular freezing so the intracellular ice
nucleation cannot take place during the slow cooling and, therefore, the plants turn
out to be capable to survive even at ultra-low temperatures. When the intracellular
(‘freezable’) water is reduced to that level, which is not dangerous for the plants
plunging into liquid nitrogen, its remaining amount probably caught in the glass is,
however, still high enough to keep viable function of cellular compartments inside
the cells. Usually, after the dehydration the cells are able to recover and/or repair
their full function indispensable for living.
Warming rates are rather critical for the plant survival when taken from liquid
nitrogen. The controlled rate of warming is mainly important for the two-step
freezing method. In controlled rate of cooling taking place in the presence of
cryoprotectant, the consequent higher warming rates are frequently applied. The
highest rate of warming can be reached by quench-immersing cryovials into the hot
water held at about 40 C. Upon such a higher rate of warming it is believed that the
recrystallization becomes avoidable. However, immediately after warming, the
potentially toxic cryoprotectant must be washed out from the plants. The high
rates of warming minimize cold crystallization often proceeding after the glass
transition.
In the course of a slow cooling, ice crystals start to grow inside the cells, which
is mostly lethal. Extracellular artificially-induced ice nucleation can, however,
avoid the random intracellular nucleation. Moreover, slow cooling rate may result
in colligative concentration of the solution inside the cell where the ions in the
highly concentrated solution can interact with the main components of membranes
[58], causing thus non-reversible injury.
When the rate of cooling is too rapid (>3 C min1), cells will not likely remain
in an equilibrium with extracellular ice, and the intracellular solution would
become supercooled. Such a supercooled state of the intracellular solution is
lacking ice crystal formation and bears alongside a sensitive state of plant called
metastable state, which could be dangerous, likewise. When the ice formation
occurs in a supercooled state at ultra-low temperatures, it usually leads to intracel-
lular ice formation from either intracellular ice nucleation [59] or through seeding
via extracellular ice [28, 60]. Mostly, this metastable state becomes noxious for
plants. At ultra-high cooling rates (applied down to ultralow temperatures taking
place during rapid quenching under ~500 C s1) [52], the supercooled water
solution is often transited into an amorphous/glassy state. Plant cells exploit such
a non-extensible glassy state and its diminishable possibility of ice crystal forma-
tion.
The survival of seeds exposed to liquid nitrogen temperatures is also influenced
by an interaction between cooling rate and moisture content. Rapid cooling of
seeds with higher moisture contents (where ‘freezable’ water is clearly displayed)
has beneficial effects, while rapid cooling of dry seeds with high lipid contents is
detrimental. It is suggested that glass transitions are associated with the two effects
of the water and lipid components of the seed [61].
18.3.2 Dehydration
Plant cells and tissues that are supposed to survive impact of liquid nitrogen need to
be dehydrated to a certain level ahead of their immersion into liquid nitrogen. The
aim of all following dehydration approaches is to increase cell-inner viscosity to the
level at which the ice crystallization is inhibited and the intracellular matter
becomes present in glassy state.
Three main methods for dehydration of plant tissue used in cryopreservation of
plants are the following:
l Evaporative dehydration in the air – the driving force for dehydration is a lower
vapour tension than that over the plant sample.
l Osmotic dehydration – the driving force for dehydration is a lower osmotic
potential in solution than that of the plant sample.
l Freezing dehydration – the driving force for dehydration is a difference in water
vapour over the supercooled state of water in plants and over the ice in the
surrounding space.
During dehydration, the viscosity of plant protoplast increases to a level required

for glass formation, avoiding accordingly the dangerous voluminosity of ice crystal
formation.
18.3.3 Desiccation
It is worth reminding that the water activity depends on the inherent temperature,
water content and on the associated glass transition. If we know them we can
assume a certain critical water activity corresponding to the relation Tg ¼ T. The
relationship between water activity and the state diagram was described by Slade
and Levine [65]. Water remains fairly mobile within glassy plant parts and the
water activity in glassy state can thus be determined.
The relationship between glass transition temperature, Tg, and the water content,
can be measured. This relationship is useful for finding at what a low level we need
to dry/desiccate the plants to incorporate the glass transition inside plant tissues.
The subsequent importance for such a desiccation is the threshold of water content
up to which the plant is able to fully regenerate its recovering to original, new plant.
Between these two limits of water content the cryopreservation of plants is feasible
for enough long time. A high probability of plant liveability and associated plant
crucial recovery is reaching after warming them from the conservation state at
ultra-low temperatures.
Glass transition temperature must be determined under the number of gradually
changed water contents. This must be accomplished in such a way as to become sure
that the transition measured is really a glass transition relevant to the water and not, for
example, an associated glass transition for lipids and other substances. Since the plant
matrix is complex, a phase separation often occurs. The local water content in sub-
localities (micro-regions, micro-domains) may become very important. The driving
force for desiccation of the plants in the air is related to the difference between water
vapour in the tissue and the surrounding air (Table 18.1). The greater the difference in
water vapour the greater the strength for removing water from plant tissue.
Osmotic dehydration is one of the most common ways how to remove water from
plant samples not only providing less water but also a possible incorporation of some
osmotic compounds for a direct protection. In principle, during the osmotic dehy-
dration a plant part is factually bathed in solution, which has a higher concentration
of solutes than that inside the cells. The driving force for the osmotic dehydration is
the difference in water potential between cells and the osmotic potential of surround-
ing solution (Table 18.1).
Fully turgid1 plant cells have water potential close to zero like a very low
concentrated solution. The highly concentrated solution inside the cells (representing
low osmotic potential) is compensated by turgor potential with opposite signs. For an
Table 18.1 Temperature and dehydration conditions for glass transition involvement as a basis
for plant cryopreservation methods
Dehydration Cryopreservation Dehydration Dehydration at Glass transition
method method driving force temperature temperature
Air dehydration Encapsulation- Dp ¼ pp pa T>0 Tg<T
dehydration
Osmotic Plant vitrification Dc ¼ c ps T>Tm Tg <T
dehydration solution (PVSx, (c pp + c T)
MPVS)
Freezing Two-step freezing, Dp ¼ psw pi ~ 40<T<0 Tg < Tm
dehydration Controlled rate
cooling
Note: Dp – difference in water vapour tension; pp – water vapour tension in plants; pa – water
vapour tension in air; D c – difference in water potential; c ps – osmotic potential of plant
vitrification solution; c pp – osmotic potential in plants; c T -turgor potential (turgor potential at
plasmolysis is zero); psw -water vapour tension of suppercooled solution in plant cells; pi – water
vapour tension over ice; T – ambient temperature; Tg – glass transition temperature; Tm – temper-
ature of freezing point depression. PVSx Plant Vitrification Solution (PVS2 [62], PVS3 [63],
MPVS [64])
involved glass transition, the osmotic dehydration must be very deep. In the case of an
excessive volume of osmotic solution, the changes in osmotic potential of the
surrounding solution can be constant, taking in account rather low volume of water
removed from the tissue. The samples are gradually dehydrated by water removal
until equilibrium with the surrounding osmotic solution is reached.
18.4 Distinctiveness of Measurements of Biological

Glass – DTA/DSC
Different types of methods are commonly used to determine the temperature span
of glass transition, preferably based on:
l Thermodynamics, that is, using conventional differential scanning calorimeter
(DSC) or differential thermal analysis (DTA) technique
l Other dynamic measurements of properties such as mechanical spectroscopy
l Characteristic times can then be associated with enthalpy and mechanical
relaxations, which may be different because of certain “decoupling” between
different relaxation modes. It should be considered there are differences induced
by the given method of experimental data analysis
l Definition of Tg on the DSC, DTA curves
l Characterization of relaxation times
l Mechanical measurements often determined in terms of modulus, such as
dielectric measurements in terms of compliance
One of the main advantages of DSC, DTA is that the measurements can be
performed in sealed pans. The size of plant samples is usually small enough to fit to
the hermetic pan. One to three pieces of Allium shoot tips weight 3–5 mg and one to
three 3–8 mg vegetative apple buds weight of 1–3, as an example.
Although DSC is not the most sensitive method to measure Tg the main
advantage of DSC is that it allows repeated and relatively reproducible measure-
ments easy to carry out along a wide temperature range.
Glassy state and associated phase appraisal during cryopreservation can be
determined by DSC, which is a sensitive method for the determination of various
crossing phenomena occurring towards the vitrification (Fig. 18.5, as an example).
Second consequent DSC run with the same biological sample could, however, be
substantially different from the first run, because the plant samples could be injured
or completely destroyed after the first run completion. Starting temperature is
important to hold plant samples in equilibrium allied with the starting temperature.
Room temperature as a starting temperature for plant investigation is often for their
non-acclimated state.
Starting temperature for cold-hardened plants should be at least close to 0 C and
should be accepted after a long-time equilibrium. At extremely slow cooling rates,
degrading biological samples could occur frequently. The maximum temperature of
warming cannot cause a change of substances, e.g., protein denaturation, sugar
caramelization and starch gelatinization. The temperature condition of samples in
an autosampler is important for long-running measurement.
A new technique, called dynamic cooling protocols, is using a conventional DSC
and has been developed to obtain chart of dynamic and quantitative water transport
data in cell suspensions during freezing [66].
18.5 Stability of Biological Glasses
The quality of glass is possible to classify. In simplicity it is possible to express

as the distance of glass transition and freezing onset of melting. The greater
difference between glass transition and freezing onset of melting the higher stability
of glass is [27].
Glassy status as a common solid, rigid state occurring in biological samples
habitually results from a suitable circumvention of crystallization. The quality of
glassy state is possible to classify simply by ratio (Tg, Tm) – the lower ratio reveals
the higher difference of Tg and Tm, thus showing a greater stability of glassy state.
A more sensitive interrelation to the glass formation peculiarities can be found
based on Hruby coefficient Kg1:

Kg1 ¼ Tc Tg = Tm Tg ; (18.2)
where Tc, Tg, Tm are temperatures of crystallization, glass transition and melting
temperature, respectively, the values of which, however, can be found only by
Allium sativum
cv. Dzambul
Reversing Cp [J/g°C]
Full saturated
Partly dehydrated
Dry matter
1 J/g°C
melting
glass transition
– 70 –60 –50 –40 –30 –20 – 10 0 10 20

Temperature (°C)
Fig. 18.5 An example of the glass transition (middle curve) in Allium shoot tips measured by
quasi-isothermal modulated differential scanning calorimetry (Zámečnı́k et al. submitted)
suitable experiment using the ready-to measure sample (pre-prepared glasses) [15].
It is clear that the greater the value of Kgl the better is the glass-forming. The best
utilization of Kgl is in the comparison of glass-forming ability and glassy state
stability of different biological materials under different conditions and thermal
treatments. Hruby coefficient (Kgl) indicates the glass stability against crystalliza-
tion on heating and could be used to estimate the vitrification ability of glass
forming liquids. These both characteristics (Tg,Tm) are easily measured by conven-
tional DTA, by DSC samples in glassy state. The correlation between glass stability
characterized by Hruby parameter and the glass forming tendency characterized by
critical rate of cooling for glass formation was confirmed [67].
The kinetic property of biological objects in glassy state is poorly understood
yet. Dynamic processes including the membrane fusion and solute leakage of
frozen and dry liposomes in carbohydrate glasses, and ice formation haemolysis
of frozen human red blood cells, were recently studied [68]. The kinetic stability of
biological glasses is clearly Tg-dependent. The reaction rate constants deviated
notably from the traditional Arrhenius behaviours can be well fitted to the Wil-
liams-Landel-Ferry (WLF) [26, 69] equation

loga ðTÞ ¼ C1 T Tg = C2 þ T Tg ; (18.3)
where C1 and C2 are universal WLF constants. It was found that different polymers
exhibit similar WLF constants. The universal values of constants in the WLF equation,
used for abroad spectrum of amorphous materials (C1 ¼ 17.44, C2 ¼ 52.1) do not
match, however, to the dynamic processes of biological material. The derived C1 and
C2 constants of the WLF equation for seed survival of three species at T>Tg are: for
Glycine ~ 37.5 and 269.8, for Pisum sativum 22.3 and 179.2, and for Phaseolus
vulgaris 22.1 and 183.1, respectively [26]
Angell [70] defined fragility via the diagrams of log (Z) vs. Tg/T, where Z is
viscosity. When the temperature dependency of viscosity is high, such glass is
called fragile. At temperatures higher than the glass transition temperature, a
different behaviour of glasses can be commonly distinguished according to the
ratio of the crystalline melting point [30] and glass transition temperature [26].
Consequently according to Slade and Levine [65], it is possible to define three
classes of amorphous systems:
l The ratio Tm/Tg 1.5 is characteristic for the first-class. The amorphous system
in this class of biologic-like materials is represented by glucose, for example,
where the viscosity decrease is moderate. Description is typical to comply with
some ‘well-behaved’ polymers or ‘fragile’ liquid [35]. The universal constants
in WFL equation are 17.44 for C1 and 51.6 for C2.
l The ratio Tm/Tg >> 1.5 is often categorized for the second-class. The viscosity
decrease is very small. Such glasses are typical products of ‘poorly behaved’
polymers or strong liquids. This ‘typical but not well-behaved’ class is a readily
crystallisable matter (e.g., water) and the WLF constants are about 20 and 155
for C1 and C2, respectively.
l The ratio Tm/Tg <<1.5 (when the temperature of glass transition is close to the
temperature of the melting) is distinguished for the third-class. The WLF con-
stants of C1 ¼ 12.3 and C2 ¼ 22.3 apply [7] and the glass-forming systems are
described as ‘a typical and poorly behaved’ class represented by, e.g., native
starch, gelatine, fructose or galactose and/or other very fragile liquids.
The kinetics of ice formation also deviates from the Arrhenius relationship, follow-
ing the WLF kinetics. The WLF constants for the process of ice formation were
calculated to be 2.1 and 11.2 for C1 and C2, respectively. Therefore, the ice
formation in frozen cells may be distinguished by WFL constants from glass
transition in the above mentioned three classes.
For some supercooled liquids, typically water, a fragile-strong transition exists
[71]. The simple model system has been reported by Angel et al. [72]. For electrolyte
solutions that are very fragile, and become stronger as concentration increases due to
the replacement of weaker hydrogen bonding with stronger ion-dipole interaction. In
contrast, any sugar solution becomes more fragile as concentration increases. High
molecular weight proteins such as gluten are relatively strong.
The prediction of the stability of biological materials preserved in the amorphous
matrix is of a very particular interest. From the WLF Eq. 18.3, one can easily derive
that the stability of biological materials in the amorphous matrix will decrease at a
rate proportional to (10TTg) if held in the rubbery state at temperatures T > Tg.
However, more accurate estimation is needed in practice. A conceptual illustra-
tion has been provided by Slade and Levine, who used the constants of WLF
equation to characterize the three classes of amorphous systems (see previous
discussion). For the systems of the first class with the ratio Tm/Tg 1.5, a change
by factor 10 for every 3 C is recognizable. However, for both, for the second ratio
Tm/Tg >> 1.5 [73] and for the third class with the ratio Tm/Tg <<1.5, this stability
can show the decrease by a factor of 10 for any increase of every 6 C [25]. Sun [26]
has done a similar calculation using the derived WLF constants knowing that the
rate of ice formation in frozen blood cells (prepared during the devitrification)
increases approximately by the factor 10(TTg)/6 (this is a 10-fold increase over a
6 C interval above the Tg). This value matches wonderfully to the second-class of
amorphous systems, which includes water [7]. However, the stability of frozen and
dehydrated biological cells and membranes, as measured by haemolysis and solute
leakage, turns up to decrease much slower than expected, roughly at a rate of
10(TTg)/15 at temperatures T > Tg, (i.e., a 10-fold decrease over 15 C above the
Tg).
18.6 Biodiversity Long-Term Storage Based on Glassy

State Involvement
Detrimental influence of man-affected environment bears, however, an injurious

impact on plant growth and endurance. In some cases, the hostile environmental
conditions may even lead to a serious depression, and in limit, extinction of the
population density of certain plant specimens on our planet. On the other hand,
there are also many plant species close to the edge of their disappearance under the
current deterioration effect of changing environment or even under a routine fatality
of species vanishing. There is a supplementary call for the urgent need to store
plants with their entire genetic information, using preferably the cultural varieties,
land-races and original wild-plant genetic resources. Fortunately, it is not necessary
to store a whole plant but it is enough to have its buds, even just protoplast, because
the plant cells are totipotent. Therefore it is possible to store only a small part of
plants, mostly a part of meristematic tissues of vegetatively propagated plants [33]
or a seed axis (mostly of recalcitrant seeds) of generatively propagated plants [49].
The plant storage at low or even at ultra low temperatures (cryopreservation) is one
of the appropriate ways how to keep their viability in a long term prospect.
From the view of cryopreservation, the glassy state, which possesses the same
volume as liquid, occurs as the most suitable state for a long-term biological storage
of germplasm. This strategy of ’being in the glassy state’, is repeatedly exploited by
plants in the nature in order to withstand unfavourable freezing conditions of
surrounding environment, which can be seen as a sort of miracle. For example,
plant pollen flying in the air has a potential to be in glassy state, keeping its viability
after stigma pollination. Dormant poplar twigs can survive the low temperatures
being in the glassy state in midwinter. It is possible to add other examples of glassy
state occurrence in plant species in the nature. However, the conditions at which the
glassy state is induced are not fully understood. Through the glass formation in
plants can be of help to control the ‘cryogenic status’ in which the optimal cooling
conditions achieve a suitable cryopreservation of plant germplasm.
Acknowledgments This work was supported by MSMT grant 0002700604

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Chapter 19
Thermophysical Properties of Natural Glasses
at the Extremes of the Thermal History Profile
Paul Thomas, Jaroslav Šesták, Klaus Heide, Ekkehard F€

uglein,
and Peter Šimon
19.1 Introduction
Natural amorphous glassy silicates are widely distributed and are found in quantities
that range from micrograms to kilo tonnes and, hence, their occurrence is from
microscopic glassy inclusions to “glassy mountains” [1]. These natural glasses have
two generic origins which may be generalised as vitreous glasses, formed from the
melt state by relatively rapid cooling at cooling rates that inhibit crystal formation, or
diagenetic glasses, formed by a dissolution-precipitation mechanism where
P. Thomas (*)
Department of Chemistry and Forensic Science, University of Technology,
Sydney, PO Box 123, Broadway NSW 2007, Australia
J. Šesták
Academy of Sciences, Institute of Physics, v.v.i., Solid-State Physics Section,
Cukrovarnická 10, CZ-162 00 Praha 6, Czech Republic
K. Heide
Chemisch-Geowissenschaftliche Fakultat, Universitat Jena, Burgweg 11, 07749 Jena,
Germany
E. F€uglein,
Netzsch-Ger€atebau GmbH, Wittelsbacherstraß e 42, 95100 Selb, Germany
P. Šimon
Faculty of Chemical and Food Technology,
Department of Physical Chemistry, Slovak University of Technology,
Radlinského 9, SK-812 37 Bratislava, Slovak Republic

312 P. Thomas et al.
3000
Tektites (Moldavites)
2500
2000
Temperature/°C
1500 Industrial Glasses
Obsidian
1000
500
Hyalite
Opal
0
0.001 0.1 10 1000
Time/hr
Fig. 19.1 Schematic T–t plot of glass-forming processes in nature and industry (Adapted from Ref. [3])
crystallisation is inhibited by the Ostwald’s rule of stepwise petrogenesis [2]. The

thermal histories of a range of natural glasses are depicted in the schematic of Fig. 19.1
and vary significantly from the typical conditions used in the glass industry which
are optimised between processing speed and energy conservation. In the extremes,
tektites like moldavites are formed by extremely fast heating and melting at very high
temperatures (> 3,000 K) followed by quenching at extreme cooling rates (10 K/s).
By contrast the formation of amorphous glasses from mineral diagenesis or biotic
processes occurs at much lower temperatures and over longer time periods; the
formation of sedimentary opal, for example, occurs at ambient temperatures, it is
essentially isothermal, and takes place over long periods of time of the order of months
to years.
The chemical composition of natural glasses also differs significantly from the
industrial glasses. The composition of industrial glasses is tailored to the optimisation
of the thermo-rheological properties for processing and durability during application;
as a consequence, industrial glasses tend to have low alumina contents and their
softening temperatures are reduced by the addition of alkali oxides which reduces
the proportion of network forming ions. The majority of natural vitreous glasses,
on the other hand, are network forming ion rich (>70% SiO2, S S(SiO2 + Al2O3)
> 80%) and per aluminous (i.e. Al2O3 S(Na2O + K2O + CaO)) and are princi-
pally characterised by a rhyolitic composition reflecting the elemental compositions of
their origins (Table 19.1). The diagenetic or biotic glasses tend to have even higher
silica contents which can approach 99% of the anhydrous composition and are also
peraluminous.
The influence of the chemical composition is reflected in the significant durability
of the natural glasses. The glassy state is a frozen in metastable and, hence, there is a
19 Thermophysical Properties of Natural Glasses 313
Table 19.1 Typical chemical compositions of natural and industrial glasses (%)
Soda-lime
Coober Pedy Obsidians industrial
Oxide Moldavites [4] sedimentary opal [5] utah [6] Pitchstone [7] glass
SiO2 79.0 90.8 75.0 70.3 70–75
TiO2 0.3 – 0.11 0.1 0.01
Al2O3 10.3 0.8 12.5 13.3 0–1
Fe2O3 – 0.05 – 1.28 0–0.1
FeO 1.7 – 1.0 – –
MgO 2.1 0.02 0.03 0.1 0–4
CaO 2.5 0.3 0.6 1.2 8–10
Na2O 0.4 0.1 2.9 4.4 10–15
K2O 3.4 0.1 5.1 2.1 0–0.3
P2O5 0.06a – 0.1 – –
H2O <0.02b 7.8 0.3 7.9 0.2
a
[8], b[9]
tendency towards crystallisation or devitrification as well as the potential

for weathering. Industrial glasses are relatively susceptible to weathering and
degradation at relatively short periods of time (<1,000 years) due to the high alkali
content. Specimens of natural vitreous or diagenetic glasses, however, are known to
have significant durability. For example, in relatively inert environments, such as on
the surface of the moon, vitreous solids have existed for more than a billion years.
This inherent stability may be attributed to the low alkali and high network forming
ion (S(Si + Al)) content of natural glasses (Table 19.1).
The water contents of the natural glasses also vary significantly and ranges from
<0.01% in tektites to between 3% and 13% (or greater) in opaline glasses which
compares with 0.2% in typical soda-lime industrial glasses. An example of the effect
of the water content is given in the thermal mechanical analysis (TMA) data shown
in Fig. 19.2 which is a comparison of the expansion properties of a series of siliceous-
aluminous glasses which are discussed in more detail below. The expansion curves for
the as received opal and pitchstone, which contain significant proportions of water
(Table 19.1), are complex, compared to the natural silica glasses of low water content,
and expansion and contraction segments attributable to the water removal are
observed. Once dehydration has been completed, the thermal expansion behaviour
reverts to that typical of amorphous siliceous-aluminous glasses.
Although a variety of natural glasses exist, this Chapter limits its scope to a
discussion of the thermophysical properties of tektites and opal as examples of
vitreous and digenetic natural glasses formed at the extremes of the thermal
histories shown in Fig. 19.1. Both tektites and opal are rare non-crystalline rocks
which are prized for their aesthetic value and both have an important role to play in
the understanding of the environments in which they are found. Reference is,
however, made to industrial and rhyolitic glasses formed by magmatic processes
in order to provide a context for the discussion.
1
0.7 a
0 b
i
–1
0.5 c
Dimension Change / %
–2 j
0.3 –3 d
0 500 1000 e
gf
0.1 h
–0.1
–0.3 j
i
–0.5
0 200 400 600 800 1000
Temperature / °C
Fig. 19.2 Thermal expansion curves of (a) soda-lime glass, (b) obsidian, (c) pitchstone – second
heating, (d) Bohemian moldavite – second heating, (e) Bohemian moldavite – first heating, (f)
Mahren moldavite, (g) Coober Pedy white play-of-colour opal – second heating, (h) fused silica,
(i) Coober Pedy white play-of-colour opal – first heating and (j) pitchstone – first heating. Inset
shows and expanded scale for curves of (i) and (j) (Adapted from the data in Refs. [3, 10])
19.2 Tektites – Moldavites
Tektites are centimetre to decimetre-sized bottle green to blackish glassy “bodies”

found in gravels ranging in age from upper tertiary to alluvial in four main strewn
fields; the European strewn field associated with the Nördlinger Ries (which includes
the moldavites), and Australasian strewn field (no associated crater), the North
American strewn field associated with the Chesapeake Bay crater and the Ivory
Coast strewn field associated with the Lake Bosumtwi crater. Tektites are also
known originate in east Asia and microtektites (vitreous spherules <500 mm in
diameter) have been found in deep-sea deposits in the Gulf of Mexico and north-
western Atlantic Ocean [11].
The origin of tektites was intensively studied in the latter decades of the
twentieth century, particularly, with respect to the mass extinction during the
short time event known as the Cretaceous – Tertiary boundary. The discussion
was dominated by two mechanisms for the formation of tektite material: the
Terrestrial Impact Theory (TIT) and the Lunar Volcanic Theory (LVT) [12, 13].
As Izokh [12] noted the TIT “won a complete victory over O’Keefe’s Lunar
Volcanic Theory ([13])” as, based on trace element ratios of geochemically well
known pairs which show a clear distinction of origin between different bodies of the
solar system (e.g. K/Sc; Ba/Zr, La/Yb), the chemical evidence demonstrated that
tektites were chemically indistinguishable from terrestrial rocks and soils and,
hence, tektites were attributed a terrestrial origin [14–17].
According to the TIT, tektites were formed during the significant energy transfer
from asteroids impacting with the earth’s surface where high pressures and tem-
peratures in the impact zone resulted in the fusion and vaporisation of the terrestrial
rocks. The energy of these impacts was such that the fused and vaporised material
was catapulted out to near space. As this material returned to earth, it rapidly cooled
and solidified with an absence of gaseous inclusions (although vacuous inclusions
are observed). During the quenching process the solidifying phase was generally
shaped aerodynamically and, as the molten droplets were spinning, a range of
bizarre shapes; plate, spheroid, rod, dumbbell, teardrop, star, curly, winkled and
bubble, were produced (Fig. 19.3). As these particles were returned to earth, the
particles were distributed by aerodynamic transport over large areas of the Earth-
surface in strewn fields and, as such, tektites from a particular strewn field have
a high degree of compositional homogeneity [4].
Tektites have a similar composition to the terrestrial rhyolitic volcanic glasses, in
particular, to the obsidians (Table 19.1). Despite the similar elemental composition, a
remarkable difference in the water content (tektites < 0.01 wt%, obsidians > 0.1 wt%)
and in the redox state (in tektites Fe2+ >> > Fe3+, in obsidians Fe2+ Fe3+) exists
between tektites and obsidians. These differences are a direct consequence of the
formation history; the high temperature and vacuous formation environment of the
tektites removed the volatile content, including water, and the shifted the redox equilib-
rium from Fe3+ to Fe2+.
The rhyolitic composition of the tektites is also responsible for the significant
durability with ages determined to be between 700,000 years (australites) and 34
million years (bediasites, North American tektites). In the more inert lunar envi-
ronment, durability of these metamorphic glasses has been demonstrated by glass
spherules which have been aged at more than 2 billion years. In general, recovered
specimens of tektite have been observed to be resistant to hydration or
Fig. 19.3 Images of typical Moldavites specimens conforming to the aerodynamic shapes
expected from the quenching of the molten glass at high velocities. The characteristic surface
topography of the moldavites is a modification and a result of a ‘characteristic corrosion’ of the
surface (see text)
devitrification of the bulk [15]. Only a characteristic corrosion of the surface is

observed in the Bohemian tektites – the moldavites (Fig. 19.3) [18].
19.3 Thermophysical Properties of Tektites
As the volatile contents of the tektites are very low (<0.02 wt%), the thermal
properties of tektites are most easily characterised by the thermal expansion
(Fig. 19.2). The thermal expansion coefficient, a, for moldavite (3.7 106 K1)
is greater than that of fused silica (0.5 106 K1), but less than that of obsidian
(6.3 106 K1) and soda lime glass (7.5 106 K1) [3, 15]. The comparison
with obsidian is apt as both glasses have a similar rhyolitic composition
(Table 19.1). The difference in the expansion coefficient is most likely due to the
relative proportions of sodium and potassium with respect to calcium and magne-
sium within the silica network. The higher CaO and MgO and lower Na2O content
of moldavites results in a more tightly bound structure and a lower expansion
coefficient. This difference is also reflected in the glass transition temperature
(Tg ~ 780 C) and is approximately 100 K higher for moldavite than obsidian.
The fictive temperature, which is indicative of the frozen in temperature and the
rate of quenching, tends to be higher for moldavites as the high melting temperature
produces a lower density melt which is rapidly cooled producing a lower density or
higher fictive temperature glass. Relaxation of this thermal history is observed
at ~600 C as the moldavite is heated (Fig. 19.2). The differences in the fictive
temperature have their origins in the relative cooling rates which have been
estimated from expansion coefficient measurements [19] and, more recently, by
the geospeedometric double-density technique developed by Klöss [20]. The geos-
peedometric method is based on the difference in density between a quenched and
thermally annealed glass specimen. A linear relationship is produced that can be
extrapolated by regression of the experimental cooling rates to an unknown natural
cooling rate (Fig. 19.4). Based on this model, the cooling rates of magmatic glasses
such as obsidian have been determined to be of the order of K/annum while for
tektite glasses cooling rates of the order of 10 K/s have been estimated.
Further evidence of the extreme thermal history of the tektites may be gleaned
from the characteristic intermediate rage order which, in glasses, may be defined by
the magnitudes of two parameters a and f [21]. The “a-value” is a measure of the
average diameter of the typical space-filling polyhedra, which in tektites are
composed of SiO4 and AlO4 tetrahedra. This parameter results from the bond
length and the ring size; for low-quartz a ¼ 0.436 nm and for high-cristobalite a
¼ 0.497 nm. Moldavite has a cristobalite-like intermediate structure with a ~ 0.485
nm; for industrial silica glass a ~ 0.510 nm; this high value may be attributed to the
more open structure resulting from a higher alkali and lower network forming ion
(S(Si + Al)) content. The “f-value” characterises the fluctuations of the intermedi-
ate range order. It monitors the “quality” of glass structure and can be calculated
from the ratio of the “a-value” to the “correlation length”. In a homogenous and
0.6
Obsidian
0.4
Moldavite
δD / D / % 0.2
–0.2
–0.4
–0.6
–0.8
0.0001 0.01 1 100
Cooling Rate / K / min
Fig. 19.4 Density changes as a function of the cooling rates for known thermal histories are
plotted to allow estimation of the cooling rates of the natural glasses during formation (Adapted
from Ref. [3])
relaxed silicate glass f is ~ 0.35. Short fusion processes and fast cooling increase
the “f-value”. For moldavites f ~ 0.46 and is greater than that of a relaxed glass. The
value of a tending toward that of cristobalite correlates with the quenching of the
glass from high temperature. The high value of the “f-value” correlates with a rapid
cooling regime. The values of these parameters for moldavite suggest a short fusion
process leading to high degree of structural disorder. Annealing of moldavites by
heating up to 1,000 C reduces the fluctuations and especially the mechanical stress.
The origins of tektites as rapidly quenched glasses from high temperature melts
is further supported by the low degree of dissolved gasses found in tektites. Mass
loss measurements at atmospheric pressure show little mass loss up to 1,600 C for
Bohemian moldavites [10]. Additionally, due to the high alumina content, the glass
is inhibited from devitrifying and, hence, no crystallisation takes place. The degas-
sing under vacuum (using a special high-vacuum-hot-extraction method DEGAS
combined with a quadrupol mass spectrometer) shows even lower gas content and
water content of the order of few ppm (0.0004 wt%) [10, 22–24]. The low volatile
content of the moldavites correlates with the micrograph shown in Fig. 19.5 where a
number of bubbles and striations are observed as a consequence of rapid gas release
during solidification.
19.4 Precious Opal
Precious or noble opal is a post depositional mineral formed in voids in the host rock
by the diagenesis and transport of inorganic silica and is prized for its play-of-colour,
the origins of which are based on the diffraction of visible light off ordered arrays of
monodispersed silica spheres [25, 26]. Precious opal is composed of amorphous
hydrous silica with the general formula SiO2.nH2O and is precipitated as
Fig. 19.5 Micrograph of a moldavite specimen “thick-section” (ca. 3 mm) in transmitted light
showing bubbles and striations resulting from rapid gas release [3]
Fig. 19.6 SEM micrographs of hydrofluoric acid vapour etched fracture surface of a Coober Pedy
white play-of-colour (POC) opal (width of field 25.4 mm). Note the ‘grain boundary’ in the top left
to bottom right diagonal. Random orientation of the ordered arrays provides the play-of-colour
monodispersed colloidal particles from 150 to 400 nm in diameter which are concen-
trated by sedimentation, evaporation or by filtration under pressure to form the ordered
arrays of that are responsible for the diffraction of light observed (Fig. 19.6).
A likely source of the monodispersed silica colloid is the weathering of silicates
such as feldspars [2, 26]. In the weathering model, the source of the silica is the
sandstones associated with the GAB where the chemical weathering of relatively
soluble silicates such as the feldspars contained in these sediments results in the
formation of an alkaline silica solution. An example of such a mineral is potassium
feldspar which weathers through the idealised stoichiometry:
2KAlSi3 O8 þ 3H2 O ! Al2 Si2 O5 ðOHÞ4 þ 2KOH þ 4SiO2 (19.1)
by the permeation of ground water through the sediments resulting in kaolinite,

dissolved silica and an increase in pH through the release of potassium hydroxide.
Reported trace element distributions in opal from a wide variety of sources are
consistent with such a weathering model [5, 27, 28]. Once the silica is in solution,
enrichment of the solution by evaporation or filtration can occur. Increasing the
concentration of the silica solution coupled with a lowering of the pH through alkali
ion exchange with the surrounding clays allows the nucleation of primary silica
spheres and, subsequent, sphere growth as more silica is supplied to the system. The
supply of silica appears to be a cyclic process as generations of growth rings are
commonly observed in the silica spheres [25, 29]. The monodispersed silica colloid
is then concentrated and in certain cases, ‘crystallisation’ occurs to form the ordered
arrays which result in the prized play-of-colour. The interstices are subsequently in-
filled with a silica cement completing the formation of the opal producing a hard
material which, despite the gel-like structure, has a Berkovich hardness of 5.7–6.2
GPa which is similar to that of soda-lime glass (6.4 GPa), but, as might be expected
for a gel like material, is significantly less than that of fused silica (10.8 GPa) [30].
Although the weathering model is important in aiding the understanding of the
formation of opal, a number of other models have been proposed to account for
specific observations in specimens acquired by the authors of these models. Examples
of such models are the microbial model where microbes have been observed
in Lightning Ridge matrix specimens suggesting that microbial action is responsible
for the source of the silica [31], the syntechtonic fluid model where high pressure,
warm hydraulic silica rich fluids are the silica source [32] and the mound spring model
where the silica rich waters derived from the artesian basin well up through the mound
springs supplying the silica rich solutions required for opal formation [33]. Although
these models source the silica from different origins, the formation of the monodis-
persed colloid must occur by homogenous precipitation followed by a concentration
mechanism such as evaporation, filtration or sedimentation [5, 34]. This ‘sol-gel’
mechanism for the formation of opal is responsible for the high water contents (6–10%
for Australian sedimentary opal) and the high proportion of molecular
water; in Australian sedimentary opal as much as 90% has been reported to be
molecular, trapped in silica cages in the bulk of the opal, with the remainder as silanol
water [35–39].
The environment in which opal is formed is important as can be discerned from

the differences in physical properties of opal derived from the volcanic and sedi-
mentary environments [38–42]. In general, hydrous opaline silica has been found to
occur with a range of morphologies which, based on x-ray diffraction (XRD)
measurements [43], were originally divided into three categories; crystalline opal
predominantly composed of cristobalite, opal-C, partially crystalline opal contain-
ing XRD characteristics of cristobalite and tridymite, opal-CT, and amorphous opal,
opal-A. Subsequent analysis by Langer and Flörke [36] resulted in a sub-division of
opal-A into two further categories, amorphous network silica, opal-AN (e.g. hya-
lite), and an amorphous gel silica, opal-AG (e.g. precious opal displaying play-of-
colour), based on their relative proportions of water and appearance. These forms of
silica are related by their relative solubility in water and their thermodynamic
stability resulting in an Ostwald like succession of formation [2, 44, 45]:
Opal - A ! Opal - CT ! Opal - C ! microcrystalline quartz (19.2)
Australian sedimentary opal, opal-AG, may be considered as a first generation of

silica formed by these low temperature aqueous processes as it is the first of the
‘pure’ silica phases that are produced from the weathering of basic aluminosilicates.
Opal derived from volcanic environments is generally found to have the opal-CT
morphology. This significant difference in morphology demonstrates the significance
of the environment on the formation of opal. Although volcanic opal may be cate-
gorised as opal-CT based on the XRD data, the designation of volcanic opal as a
second generation silica polymorph is contentious. As volcanic opal displays play-of-
colour, it contains a monodispersed ordered array of silica spheres. This fact suggests
that a monodispersed colloid is the precursor of the opal which suggests homogeneous
precipitation and, hence, a first generation silica [38, 39]. The first generation silica in
Eq. 19.2, Opal-A, should, therefore, be extended to include precious play-of-colour
volcanic opal-CT, being formed by homogeneous precipitation, as later generations
are formed through a heterogeneous nucleation and growth mechanism.
19.5 Thermophysical Properties of Precious Opal
Opal is a hydrous silica containing circa 8% water (depending on the origin) [46] and
due to the formation mechanism, 90% of the water in sedimentary opal is molecular
water trapped in silica cages [35–39]. The thermophysical properties of opal are,
therefore, dominated by the irreversible process of removing the water. An example of
the effect of the water content is given in the TMA data shown in Fig 19.2 [10]. The
opal initially has a high rate of expansion (7.4 106 K1) as it contains 7.5% water
(based on the TG mass loss in Fig. 19.7) and compares well with the expansion of
pitchstone (8.5 106 K1) which contains a similar proportion of water. After a
period of dehydration a peak in the expansion curve is observed (210 C, circa 200 C
for pitchstone). Contraction of the specimen is then observed until the remaining
106 1
303°C
217°C DSC 1st Heating 1166°C
104
102
DSC 2nd Heating
0
Heat Flow / W / g
100
Mass / %
98 TG 2nd Heating
–1
96
TG 1st Heating
94
exo
Residual Mass: 92.5 %
92 –2
0 500 1000 1500
Temperature/°C
Fig. 19.7 TG data of the CP white play-of-colour opal heated to 1,640 C at 20 K/min in an air
atmosphere. The second heating run shows the ab cristobalite transition at 217 C suggesting
crystallisation has occurred corresponding to the exotherm observed above 1,166 C in the first
heating run [10]
trapped water exerts such a high hydrostatic pressure that expansion is once again
observed above 540 C. This type of behaviour is relatively common for opal as well
as other natural glasses which contain a significant proportion of water such as
the pitchstone specimen shown in Fig. 19.2 where contraction occurs at similar
temperature although, for this pitchstone specimen, no significant secondary expan-
sion is observed under the heating rates used (1 C/min). Once all the water has been
removed from the opal, the expansion coefficient on reheating the sample is low
(1.4 106 K1) and much closer to that of a fused silica (0.5 106 K1) due to
the high silica content. As the pitchstone has a rhyolitic composition, the expansion
coefficient for the dehydrated material (4.3 106 K1) is much closer to that of
moldavite (3.7 106 K1) and obsidian (6.3 106 K1).
Although opal has been observed to be relatively stable to thermal treatment, the
amorphous character, as, indeed, the play-of-colour, of the opal has been observed
to be retained even after prolonged heating up to 1,000 C, crystallisation of this
metastable silica polymorph may be achieved at higher temperatures and is
observed in the exothermic behaviour above 1,166 C and is confirmed in the
second heating run, where a sharp endothermic peak is observed at 217 C
corresponding to the a b cristobalite transition (Fig. 19.7). Crystallisation of
the amorphous opal is facilitated by the high silica and low alumina content which
is in contrast to the rhyolitic composition glasses such as the moldavite which are
observed to be resistant crystallisation even at high temperature due to the high
aluminium content.
2.0 × 10–8
200°C
1.5 × 10–8
Ion Current m / z 18
1.0 × 10–8
456°C
689°C
0.5 × 10–8 1219°C
1024°C
0
0 200 400 600 800 1000 1200 1400
Temperature / °C
Fig. 19.8 Water release from Coober Pedy white play-of-colour opal under high vacuum heated
to 1,440 C at a heating rate of 10 K/min. The water loss corresponds to 99.63 wt% of the total mass
loss. The spiky release of water between 456 C and 689 C is 0.29 wt% and between 1,024 C and
1,219 C is 0.08 wt% is as a result of the sudden release of water from enclosed pores or fluid
inclusions [10]
Characterisation of the water evolution under high vacuum using the DEGAS
technique has also yielded further understanding of the character of the water and
the morphology of opal (Fig. 19.8) [10]. The typical water loss is observed around
200 C which corresponds to the TG data [38, 47]. A shoulder peak between 400 C
and 700 C and continued water mass loss up to and beyond 1,000 C is also
observed. It is also interesting that spikes in the data in Fig. 19.8 are observed
and correspond to sudden losses and may be ascribed to the sudden release of water
from inclusions or entrapped micropores in which the pressure escalates beyond
the breaking stress of the opal. In addition to water, hydrogen and methane have
also been observed to be released. The hydrogen released around 880 C is likely to
be derived from micellar decomposition of silanols [48], but the methane evolved
around 100 C is a little more difficult to explain as the temperatures are too low for
the micellar reactions. It is possible that very small proportions of molecular
methane are trapped in the gel structure as the opal network is formed giving a
further indication of the nature of the waters in which precious opal is formed.
19.6 Final Remarks
An analysis of the thermophysical properties of tektites, as an extreme example of

the vitreous glasses, and precious opal, as an extreme example of the diagenetic
glasses, yields the formational and chemical characteristics expected of these
precious natural glasses. The high silica and alumina content of the tektites results
in significant durability and thermal stability and the high concentrations of trace
elements results in the higher expansion coefficients observed. The high water
content of opal, by contrast, is the dominant characteristic controlling its thermo-
physical properties. The thermophysical properties observed for the tektites and the
opal are typical of their origins and, as these observed properties are the properties
of the natural glasses at the extremes of the thermal history profiles, the glasses with
intermediate thermal histories and compositions will exhibit intermediate combina-
tions of these properties, as was briefly noted for obsidian and pitchstone.
Although tektites and sedimentary opal are rare natural non crystalline solids,
whose primary value is aesthetic, these natural glasses that are formed at the
extremes of the thermal history profiles are also important as a record of the
environments in which they are found. Both of these material types are important
in their as found shapes, in the case of moldavite – the aerodynamic forms and in the
case of opal – the infilling of voids, seams and cracks in the host rock and, in
particular, in fossil replacement (opalised fossils). Both of these natural minerals
have an important part to play in the understanding of geological processes as their
formation is a record of change in the natural environment [2, 49]. The tektites,
based on their models of formation have given an insight into the impact processes
that have remodelled the Earth’s fauna and flora. The opal is the first step to
understanding the diagenesis of silica and its mobility. The characteristics of
these rare gems are exemplified by their thermal properties and, even though both
of these non-crystalline solids are formed at the extremes of forming processes,
both tektites and opals, as forms of silica, help to enrich our lives.
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Abbreviations
DEGAS High vacuum hot extraction gas analysis by mass spectroscopy

GAB Great Artesian (Australian) Basin
LVT Lunar volcanic theory
Opal-A Amorphous opal
Opal-CT Cristobalite-tridimite ordered opal
Opal-C Cristobalite ordered opal
Opal-AG Amorphous gel-like opal
Opal-AN Amorphous network-like opal
TIT Terrestrial impact theory
TMA Thermomechanical analysis
XRD X-ray diffraction
Chapter 20
Hotness Manifold, Phenomenological
Temperature and Other Related Concepts
of Thermal Physics
Jiřı́ J. Mareš
20.1 Introduction
Although the operative methods of temperature measurement are well-known and

described in detail in various practical instructions [1, 2] and discussed in many
textbooks [3–10], the systematic treatment of the central concept of thermal
physics, the temperature itself, is paradoxically almost lacking in the current
literature. The temperature, namely, is there at present defined mostly from the
theoretical positions of statistical physics and not as a phenomenological quantity.
Nevertheless, the predominant majority of practical measurements in physics,
chemistry and technology or in thermal analysis and calorimetry particularly are
performed by means of macroscopic devices (thermometers) yielding as a result the
phenomenological temperature, and not by means of statistical analysis of proper-
ties of ensembles of particles and excitations. It is thus evident that prior to the
identification of the temperature defined in the frame of statistical theory with the
phenomenological temperature, the latter has to be satisfactorily defined first.
The purpose of this contribution is thus to re-examine a fundamental concept of
thermal physics, phenomenological temperature, from the logical, epistemological
and partially also from historical points of view. The mathematical structure of the
precursor of temperature, hotness manifold, is, as far as we know, for the first time
discussed here in terms of elementary set theory. In the exposition of the subject the
emphasis is put on experiment, elucidation of allied concepts and on generalization
of empiric data while the reader must confer with special references already given
on mathematical proofs of some statements.
J.J. Mareš (*)

Institute of Physics ASCR, v.v.i., Cukrovarnická 10, 162 00 Praha 6, Czech Republic

328 J.J. Mareš
20.2 Early Thermal Measurements, Thermoscope
The first devices known as thermoscopes appeared during the later Renaissance in
connection with the first edition of Latin translation of Hero’s “Pneumatica” by
F. Commandino Urbinate (1575) [11]. The influence of this book dealing with
various unexplained natural phenomena and curious contrivances worked by air,
water or steam was so general that it is almost impossible to tell whether a particular
device was directly derived from Hero’s descriptions or whether it is an original
invention. Therefore one can find in the literature a long series of “inventors of
thermometer”, e.g. Cardano, Galileo, Sanctorius, Besson, de la Porta, Drebbel,
Fludd, Leurechon, Ens, Harsdoerfer, Kirchner etc. [12, 13], but to decide about the
priority of any one of them is a very difficult task. Quite early it was recognized that
these devices, having various forms of fluid or air dilatometers, enabled the objecti-
fication of the subjective feelings of hot and cold. Almost simultaneously appeared
an idea that the thermal states of bodies which were in common terms described by
means of ordered series of terms cold, cool, tepid, warm, hot, could be characterized
by the ordered series of thermoscope readings as well. The substitution of thermo-
scope for human sensations in experiments leads finally to the conviction that the
thermal state of bodies or of environment can be characterized by thermoscope
readings incomparably better than by means of sensation in itself. The thermoscope
typically a glass tube provided with an arbitrary scale and bottom opened vessel
filled with wine, the upper bulb of which contained a mixture of air with water and
alcohol vapours, was thus promoted to the device apt to indicate with certain
“absolute exactness” the thermal state of vicinal bodies. Such a (of course, very
optimistic!) belief reflects also famous Fludd’s quotation [14] “Weather-glass (i.e.
thermoscope) became a mighty weapon in the Herculean fight between Truth and
Falsehood”. However, the principles behind the operation of thermoscope remain
for a long time unclear and the conditions for its proper application were discovered
only step-by-step by means of painful experimental work. Let us now summarize the
fundamental concepts of thermometry in terms of modern language.
20.3 Introduction of Phenomenological Conjugate

Variables and Thermal Equilibrium
The basic task of any mathematical theory of material systems is to establish

general rules for the further treatment of empirical constitutive relations describing
the state of a body in terms of suitably chosen parameters. We do not mean here the
parameters specific for the description of thermal effects but just the parameters
already introduced in other branches of physics and generally known as the
phenomenological variables [15]. The existence of such variables, playing the
roles of macroscopic conditions which are compatible with a huge number of
parameters describing each microscopic component of the body, is clearly a matter
20 Hotness Manifold, Phenomenological Temperature 329
of experience. Usually, there is an appreciable number of various phenomenological

variables determining the state of the body but fixing a chosen one by external
means, this number can ever be diminished by one. Continuing such a procedure, the
number of significant phenomenological variables can be finally reduced to two. It is
a fact worth to noticing that the two-parameter system is the simplest model of a real
system because it enables one to construct a meaningful constitutive relation and,
simultaneously, it is apt for straightforward generalization, e.g. by adding another
pair of independent variables. In order to ensure easy perceptibility of mathematical
description of two-parameter systems a special form of phenomenological variables
was found to be desirable. It is a well known fact that the terms entering the energy
balance equations in mechanics and electrodynamics have a canonical form which
may be characterized by means of the following dimensional relation,
½Energy¼½X ½Y; (20.1)
where square brackets mean the physical dimension of the quantities enclosed.
As the energy is an extensive quantity, it is favourable to choose for the first
phenomenological variable also an extensive quantity, say X. In such a case,
however, the second parameter has to be inevitably an intensive quantity, Y [16].
Such a couple of quantities obeying relation 20.1 is then called a couple of conjugate
variables. For example, extensive quantities are volume V, momentum G, electrical
charge Q, mass M, and paired, conjugate, intensive quantities are pressure p,
velocity v, electrical potential j, and gravitational potential g. The existence of
the intensive and extensive “aspects” of heat which was already recognized by J.
Black [17] is thus in this context the discovery of primary importance for the
formalization of theory of heat and its compatibility with other branches of physics.
His “intensity of heat” and “matter of heat” can be, namely, quite naturally assigned
to a certain couple of conjugate variables, which may be tentatively called “temper-
ature” and “heat”. Formal compatibility of these two quantities with the system of
quantities already introduced in other branches of physics is thus only a matter of
proper choice of suitable operative definitions and units.
The idea to treat a real system in terms of conjugate variables enables one to
introduce some fundamental concepts of thermal physics in a quite systematic way
and, somewhat astonishingly, without a priori reference to the thermal phenomena
per se, particularly to the quantities of temperature and heat [18]. The important
role plays here the so called correlation test. It is the procedure frequently used in the
practical thermometry which enables one to check whether the thermometer is in
proper thermal contact with the measured body. Simultaneously, it provides the
basis for the following operational definition of diathermic and adiabatic partitions
(walls), viz: Let us have two systems characterized by couples of conjugate variables
(X,Y) and (X‘,Y‘), respectively, and separated by a macroscopically firm material
partition (wall) defining their common boundary. Such a partition is called diather-
mic if the changes of the variables (X,Y) induce the changes of the variables (X‘, Y‘)
and vice versa, i.e. if the changes of both otherwise separated systems are correlated
(“diathermic” originates from Greek diά ¼ through, yermóB ¼ warm). A concept
330 J.J. Mareš
complementary to that of diathermic partition is the adiabatic partition (from Greek

a ¼ negation, diά ¼ through, baıńein ¼ to go) which prevents the thermal contact of
neighbouring bodies, i.e. ensures their thermal insulation. Obviously this concept is
a limiting one, depending to an appreciable extent on the accuracy of the correlation
test. The adiabatic partition is, namely, any partition for which the experimental
proof of its ability to realize the diathermic contact by the said test failed.
Using then the language of the two-parameter description, the general definition
of the equilibrium state as known from other branches of physics can be extra-
polated also to the region of thermal phenomena. Let us recall first what the
equilibrium state means e.g. in mechanics. Standard formulation for the two-
parameter system reads: Any state of a body in which the conjugate coordinates
X and Y remain constant in time so long as the external conditions are unchanged is
called equilibrium state [19]. Combining then this definition with that of the
diathermic partition, we can immediately define the concept of thermal equilibrium,
which already belongs to the scope of thermal physics, namely:
If two bodies being in diathermic contact are both in equilibrium state, they
are in thermal equilibrium.
Let us then call thermoscope any two-parameter system in which one of the
conjugate parameters, say Y, can be fixed, Y¼Y0. It is further assumed that
thermoscope can be brought into a diathermic contact with other bodies and that
it is sufficiently “small” in comparison with these bodies in order to not appreciably
disturb their thermal equilibrium. The second conjugate real parameter X, which is
called in this connection thermoscopic variable, is generally of quite a diverse
physical nature and dimension. It may be length, volume, resistance, voltage,
frequency and many others. In order to distinguish formally among various thermo-
scopic variables, differently constructed thermoscopes and physical conditions
under which they operate, a small Latin index is used. Applying this convention,
reading Xk(P) of the k-th thermoscope which is in diathermic contact with a body
under investigation defines the thermoscopic state P of the body. The corresponding
set of the thermoscopic states which can be observed in this way is then marked as
Hk. Notice that the readings Xk are related to the thermoscope while the indicated
thermoscopic state such as P ∈ Hk, already relates to the body. It is a matter of fact
that the phenomenological parameters were introduced into classical mechanics
and electrodynamics as continuous quantities covering certain closed intervals of
real axis. Therefore, according to our definitions, such a property is transferred also
to the thermoscopic variables Xk. We will thus assume that the numerical values of
quantity Xk also continuously cover a certain closed interval Ik, operation range of
the k-th thermoscope, which is a proper part of the set of real numbers, E1. In usual
symbols we can thus write: Xk ∈ Ik E1. If it is further for every couple P, Q ∈ Hk,
P 6¼ Q, , Xk(P) 6¼ Xk(Q), the set Hk can be ordered in accordance with the intrinsic
order already existing in real interval Ik E1.
This provides basis for the construction of a primitive temperature scale. Indeed,
unambiguous assignment of a certain value Xk(P) to every state P ∈ Hk is nothing
but realisation of a local empirical temperature scale in terms of thermoscopic

variable Xk. It is, however, an important fact belonging rather to the scope of
epistemology that although the empirical scales enable one to characterize the
thermal states of bodies, for the revealing of the very nature of the physical quantity
called temperature are almost useless and further development of more involved
concepts is thus necessary.
There is another requirement ensuring the objectivity of the above conception. It
is so called Principle of indifference [20] according to which different thermo-
scopes k, j operating in the common range of thermoscopic states should distinguish
any two different states P 6¼ Q, P, Q ∈ (Hk\Hj), regardless of their construction,
thermometric substances, variables X and other physical conditions used. A proce-
dure worked out by Dulong and Petit [21] is used in practical thermometry for the
comparison of different empirical temperature scales. So called Dulong-Petit plot is
a locus of readings Xk of one thermoscope versus readings Xj of another thermo-
scope both being in thermal contact with the same body (thermal bath). Evidently,
in terms of such a plot the Principle of indifference may be formulated simply as
follows: Two empirical temperature scales agree with the Principle of indifference
just if their Dulong-Petit plot is monotonic. Interestingly, very similar method was
used much earlier by savants of Accademia del Cimento who discovered in this
way, just above the freezing point of water its anomaly, i.e. non-monotonic Dulong-
Petit plot with respect to the other at that time known thermoscopes [14, 22], which
excludes water from being in this range a suitable thermometric substance.
20.4 Fixed Thermometric Points, Mach’s Postulates
A serious obstacle for the development of non-peripatetic thermal physics was an

appreciable irreproducibility of early thermoscopes used. There were attempts to
improve the situation by making exact copies of a standard instrument and by
sending them to the various laboratories where they were intended to serve as
secondary standards [23]. This, theoretically correct approach had nevertheless lot
of practical limitations. It required a really high reproducibility of glass-blowing
and preparation of glass and thermometric substances. Consequently, standard
“thermometers” were very expensive and the transport of such delicate instruments
over the long distances was quite risky. Therefore an important qualitative step
toward the scientific thermometry was done when the so called fixed thermometric
points were discovered and came into general use.
The fixed point is called a body prepared by a definite prescription revealing

by some observable qualitative property its physical state (e.g. boiling point
of helium, melting point of water, melting point of platinum – all at normal
atmospheric pressure) and which being in thermal equilibrium with other
bodies defines unambiguously their thermoscopic state.
332 J.J. Mareš
Fixed points thus may serve as a mean for the realization of fiducial points on
empirical temperature scales corresponding to the different thermoscopes. Decisive
steps in this direction were made by Danish astronomer O. Rømer, and especially by
his immediate follower, German instrument maker G. D. Fahrenheit who used large
deal of Rømer’s know-how [24]. He devoted an enormous care to the purification of
thermometric substance, improvements of glass-blowing procedure and exact spec-
ification of conditions for realization of fixed points. As a result, Fahrenheit’s
thermometers were much admired throughout the scientific community for their
accuracy and extraordinary reproducibility and became thus for a long time a
thermometric standard.
As was recognized very early the fixed points are of crucial significance for
sewing together local thermometric scales. In order to cover much larger range of
thermoscopic states it is, namely, necessary to combine the thermoscopes of
different construction and sometimes of different physical nature of thermoscopic
variables. It is then obvious that just the existence of a common fixed point incident
with two different local empirical scales ensures that these scales really overlap and
that they can be sewn at this point together.
Importance of fixed points for thermometry is, however, not confined only to the
calibration of thermoscopes but as was recognized not before the end of the
nineteenth century their theoretical significance is much more general. Quite inter-
estingly, it has been originally taken for a self-evident empirical fact that it is always
possible to find, in an operation range of any thermoscope, a sufficient number of
fixed points enabling calibration of a local empirical scale. The very fact that such a
liberty of choice can only be a consequence of the existence of enormous (if not
infinite) number of fixed points falling into any interval of thermoscopic states
remained for a long time quite unnoticed. Similar fate, i.e., being effectively
undiscovered, has also the fact that the fixed points can be always found out of
any interval of thermoscopic states.
These and other experimentally observed properties of fixed points have been
generalized by means of the method of incomplete induction, the reasoning accord-
ing to which the conclusion related even to the infinite number of cases is drawn
from the knowledge of a finite number of cases provided that they, without
exception, imply the same conclusion. Such a type of generalization of experience
resulting into certain verities or postulates is quite analogous to that made e.g. prior
to the axiomatic construction of Euclidean geometry. As the propositions given
below received their first explicit formulation in the hands of E. Mach [21], we
suggest calling them tacitly Mach’s postulates (M1–M5).
First of all, as every fixed point defines unambiguously a certain thermoscopic
state and because the set of thermoscopic states Hk is ordered by means of relation
(≺, ), the set of fixed points F (F¼[Fk, where Fk are sets of fixed points related to
Hk) can be also ordered just according to the same relation. Giving a physical
meaning to such an idea, we can say that calibration of empirical scales by means of
fixed points can be interpreted as an ordering of fixed points. This fact then enables
one to postulate:
(M1) The set of fixed points F is ordered by means of binary relation (≺, ).
The generalizations of experience with experimental establishment of new fixed

points and of making their inventory list lead then to the following three postulates1:
(M2) To every fixed point P ∈ F there exists at least one fixed point Q such
that QP.
(M3) To every fixed point R ∈ F there exists at least one fixed point S such
that S≺R.
(M4) For every couple of fixed points P≺R there exists at least one interlay-
ing point Q such that the relations P≺Q and Q≺R are simultaneously
valid.
There is another remarkable empirical property of the set of thermoscopic states

closely related to that of fixed points which can be formulated as follows:
(M5) Let A and B be two different fixed points such that A≺B. Then if the body
changes its thermoscopic state from the state corresponding to a fixed
point A to that represented by a fixed point B, it must inevitably pass
through all the interlaying thermoscopic states P, for which A≺P≺B.
20.5 Hotness Manifold and Definition of Temperature
It is a matter of historical fact that formulation of Mach’ postulates (1896, [21])

and establishment of Cantor’s set theory (1895, [25]) were practically contempora-
neous events. That is probably why the mathematical structure of hotness manifold
has not been fully appreciated and, as far as we know, has never been systematically
analyzed from the point of view of the set theory. In terms of this theory (e.g.
[26, 27]) Mach’s postulates may be interpreted in the following way.
Taking first into account the fact that the realizations of fixed points are real
bodies, their number must be either finite or equivalent to the set of natural
1
Speaking for a while in terms of Kelvin’s temperature which will be specified later, the
temperatures observed range from ~1010 K (Low Temperature Lab, Helsinki University of
Technology) up to ~109 K (supernova explosion) without any traces that the ultimate limits
were actually reached. Speculative upper limit provides only the so called Planck temperature
TP¼√(ħ/G)(c2/k)1.4171032 K, hypothetically corresponding to the first instant of Big Bang
and depending on the assumption that the constants c, G and k involved are really universal.
Therefore the conjecture referred to as Mach’s postulates M2 and M3, i.e. that the hotness
manifold has no upper or lower bound, is obviously operating at least for all phenomena already
known.
334 J.J. Mareš
numbers, i.e. F must be countable. In the 4th Mach’s postulate one can easily
recognize the definition of dense sets belonging to Cantor’s theory; from this we
can immediately conclude that F is also dense. Postulates 2 and 3 then mean that the
set F has no upper or lower bound. Any ordered countable dense set is, however,
called rational series or a set of rational numbers. We can thus summarize, the set of
fixed points F is equivalent to an unbounded set of rational numbers.
The mathematical structure of hotness manifold H, which is a union of all sets of
thermoscopic states Hk, H ¼ [ Hk, is not as simple as the structure of F. It is
necessary first to make clear the operational method (i.e. a method related to the
experimental procedures which can be really performed) enabling sewing-up the
overlapping sets of thermal states and matching of corresponding empirical tem-
perature scales. Let us assume that two sets of thermal states, Hk, Hk+1, overlap, i.e.
that Hk \ Hk+1 6¼ 1. In order to realize this fact in experiment one has to find a
fixed point R ∈ F belonging to both these sets, i.e. R ∈ Hk, R ∈ Hk+1. Theoretically
the possibility of such an operation is ensured by 4th Mach’s postulate M4. For the
sake of definiteness and without loss of generality we can further construct the
0 0 0
subsets H k Hk, and H k+1 Hk+1 in such a way that Q ≺ R for every Q ∈ H k and
0
PR for every P ∈ H k+1. Evidently, the empirical temperature scale for thermal
0 0
states from Hk [ Hk+1¼H k [ H k+1 below R corresponds to the empirical scale in
Hk and above R to that in Hk+1. Moreover, in order to assign the same value of
empirical temperature to the common point R, it is necessary to make formal
changes at least in one of the empirical scales. Applying the procedure just
described and simultaneously looking for new fixed points and for new physical
effects enabling the construction of new kinds of thermoscopes, we can build a
chain of Hk’s more and more extending the region of accessible thermal states. We
are obliged to Professor Mach for belief that such a procedure is limited only by our
skills. Taking now into account the fact that every Hk is equivalent to a real interval
Ik E1, it is obvious that Hk is a continuous set. Furthermore, fixed points, such as
R, are then nothing but rational cuts in sets Hk and Hk+1 [27]. Analyzing these
circumstances, we can conclude that the properties of the hotness manifold H ¼ [
Hk discussed above can be put in the form of two axioms already well-known from
the set theory, namely
Dedekind’s axiom: If H1 and H2 are any two non-empty parts of H, such that
every element of H belongs either to H1 or to H2 and every element of H1
precedes every element of H2, then there is at least one element R ∈ H such
that:
1. any element that precedes R belongs to H1,
2. any element that follows R belongs to H2.
Axiom of linearity: The hotness manifold H contains countable subset F H
in such a way that between any two points P ≺ Q ∈ H there is a point R ∈ F
such that P ≺ R and Q R.
As the second axiom ensures that the requirements of 5th Mach’s postulate are
automatically satisfied, the couple of Dedekind’s axiom and axiom of linearity may
be regarded as a concise reformulation of Mach’s postulates. The simultaneous
validity of both these axioms, however, defines in set theory the class of sets which
are equivalent to the set of real numbers E1. The mathematical structure of hotness
manifold may thus be summarized as follows:
Hotness manifold (a set of all accessible thermoscopic states) H is a set

topologically equivalent to the set of all real numbers (real axis) E1. It
contains a countable, dense and unbounded subset of all fixed points F
H, realizing the skeleton of H.
As we have seen above, the construction of this manifold is based on well-

defined operational methods specifying conditions and procedures necessary for
determination or reestablishment of a particular thermoscopic state. Manifold H is
just the experimentally accessible entity enabling one to judge how hot or cold the
bodies are. Therefore, it is this entity which is right to be regarded as an entity
objectively existing in the Nature and representing the universal Platonic idea
behind the usual concept of temperature, in philosophical jargon, the temperature
“an sich”. Of course, as the set H has no intrinsic metric properties, it yields directly
no physical quantity [16, 28]. Introduction of corresponding physical quantity,
tacitly called temperature, thus requires special definition which obviously has to
involve all the properties of hotness manifold.
As has been shown in previous paragraphs, the temperature and even the hotness
manifold cannot be taken for primary concepts of thermal physics but are in fact the
subjects of somewhat convoluted constructions. In the hierarchy of conceptual basis
of thermal physics, however, the concept of temperature plays the role subordinate
to that of hotness manifold H, which is characterized just only by its topological
properties. On the other hand, it is quite clear that hotness manifold alone is not
sufficient for the development of quantitative theory of thermal effects. For such a
purpose, namely, a regular physical quantity [16] preserving simultaneously all
essentials of hotness manifold, is necessary. Keeping the sufficient generality, such
requirements may be satisfied by the following definition:
Temperature is any continuous one-to-one order preserving mapping of

hotness manifold on a simple connected subset of real numbers.
20.6 Kelvin’s Temperature Scale
It is quite obvious that the definition of temperature given in the preceding paragraph
offers an enormous liberty for the construction of temperature scale. It is thus necessary
336 J.J. Mareš
to rationally choose the limitations which will be decisive for intelligibility of the future
theory of thermal effects. Traditionally the safest guide for the introduction of new
concepts into science is the so called anthropomorphic principle respecting the com-
monly accepted patterns of thinking and involving also practical and cultural aspects.
The special mapping of the hotness manifold on an ordered subset of real numbers
defining the operating temperature scale T was thus chosen on the more-or-less
historical and practical grounds, in other words, on the basis of fully arbitrary anthro-
pomorphic criteria. One of such restrictions having in fact no physical reason but which
significantly simplifies the mathematical operations with temperature concerns the
class of absolute temperature scales defined as follows [29]:
Any temperature scale which is chosen in such a way that their functional
values have the highest lower bound equal to zero (i.e. T is always positive) is
called absolute temperature scale and the corresponding temperatures are
called absolute temperatures2.
Notice that the possible value T ¼ 0 (equal to the highest lower bound) is already
excluded by our definition of temperature because due to the absence of the lowest
hotness level in the hotness manifold any continuous one-to-one order-preserving
transformation on the set with lower bound ¼ 0 has inevitably to map its improper
point (e.g. –1) just on the point corresponding to absolute zero. Nernst’s law of
unattainability of absolute zero of temperature (the “Third Law of Thermodynam-
ics”) [30] is thus together with its consequences intrinsically involved in these
definitions of temperature and absolute temperature and as such needs no addi-
tional, sometimes very curious, justifications or “proofs” [31].
It is a result of rather a complicated historical development that the present
temperature scale (Kelvin’s international temperature scale ITS [1]) is based on two
independent anthropomorphic idealizations, namely, idealized substance, ideal
(perfect) gas and idealized process, Carnot’s reversible cycle. It is an important
provable fact with large practical impact that both approaches define the identical
scales which can thus be in particular cases used alternatively.
The first approach is based on the idealization of the most salient common
features of the constitutive relations of real gases. The behaviour of majority of
real gases is, namely, almost the same in cases where the gases have sufficiently low
density. This fact was used for the definition of the perfect gas and later for the
construction of the ideal (perfect) gas temperature scale T. The equation
controlling the behaviour of the ideal gas, which is a hypothetical substance or
concept rather than a real thing, reads:
T ¼ pV=nR; (20.2)
2
Notice that this definition of absolute temperature scale differs from that due to Lord Kelvin who
related the adjective “absolute” rather to the independence of temperature scale of thermometric
substance than to the existence of lower bound of temperature values.
where p and V are respectively the pressure and the volume of the ideal gas which
may both alternatively play the role of thermoscopic variables. As the hypothetical
thermoscope a conventional gas thermometer [2] filled with n moles, n > 0, of ideal
gas is considered. The constant R on the right side, has then a form of product R ¼ k N
where k and N are Boltzmann’s and Avogadro’s constants, respectively (in SI system
of units k ¼ 1.38 1023 J/K, N ¼ 6.02 1023 mol1). The scale defined by means of
Eq. 20.2 has some other remarkable properties. For example, as both quantities p and
V have a natural lower bound ¼ 0 (this very fact was already recognized by Amon-
tons [21] and formulated as the hypothesis of l’extreˆme froid), the temperature T has
also this lower bound and thus automatically belongs to the class of absolute
temperatures. Moreover constitutive relation 20.2 reveals remarkable symmetry
with respect to quantities p and V. We can thus exploit anyone of these two quantities
as a thermoscopic variable keeping the other one constant. Comparing these two
cases it must be inevitably:
Tp ¼ TV ¼ T; (20.3)
where Tp and TV are temperatures of a body (e.g. corresponding to temperature of a

certain fixed point) determined by means of constant pressure and constant volume
method, respectively. The exact realization of condition 20.3 in experiments with
real gases and with prescribed high accuracy (typically of the order of 0.1%) is very
difficult if not impossible. However, Berthelot [32] devised a simple graphical
method based on plausible assumptions which enables one to extrapolate experi-
mental data obtained on real gases at finite pressures to the case corresponding to
the ideal gas and finally determine also the value of T satisfying conditions 20.3.
From these facts it is thus apparent that the ideal gas temperature scale can be in
principle realized in the range where the gaseous phase of real gases and, of course,
also the gas thermometer itself, can exist.
20.7 Carnot’s Theorem and Kelvin’s Proposition
Reasonably chosen temperature function which maps the hotness manifold on a

subset of real numbers E1 should be, as was already mentioned, conformal with
other terms entering the energy balance equation. In such a case temperature
(intensive quantity T) and heat (extensive quantity B) will make up a couple of
conjugate variables obeying dimensional equation 20.1, i.e.
½Energy ¼ ½T ½B : (20.4)
The principal possibility to write down the thermal energy term just in this form
was confirmed by early experiments on the development of mechanical work by
338 J.J. Mareš
means of heat engines. In spite of the fact that these experiments were backed by a
rather primitive technique (e.g. temperatures were measured by roughly calibrated
mercury thermometers and heat by the weight of burned coal), being thus of
doubtful accuracy, their analysis enabled S. Carnot to introduce some new theoreti-
cal concepts and to draw out definite conclusions. In the present context among new
Carnot’s concepts the most important roles play two idealizations of real thermal
process taking place in the heat engine, namely, the cyclic process and reversible
process. By cyclic process (cycle) is meant any thermal process in which initial and
final physical state of the heat engine are the same. The reversible process is then a
thermal process in which the heat engine works without wastes of heat. For the heat
engines utilizing the cyclic reversible process (so called ideal heat engines) Carnot
was able to formulate a theorem which in its archaic version reads3[33]:
The motive power of heat is independent of the agents set at work to realize it;
its quantity is fixed solely by the temperatures of the bodies between which, in
the final result, the transfer of caloric is done. (S. Carnot, 1824)
Of course, from the modern point of view Carnot’s theorem is rather a desideratum
than piece of scientific knowledge. (Remarkable is also a somewhat inconsequent use
of heat and caloric as synonyms.) On the other hand, it has a form of the energy balance
postulate we are searching for. Indeed, if we, namely, transform the theorem into
mathematical symbols we can write it in terms of finite differences [34]
DL ¼ B F0 ðtÞ Dt, (20.5)
where B means the quantity of heat regardless of the method of its measurement, DL
is the motive power (i.e. useful work done by heat engine) and Dt is the difference
between empirical temperatures of heater and cooler. The unknown function F0 (t)
called Carnot’s function should be for a concrete empirical scale determined by
experiment [36, 37]. As the gained work DL has a dimension of energy and as this
energy must be for reversible cycle equal per definition to the thermal energy of
heat B supplied to the ideal heat engine, we can conclude that the terms suitable for
insertion into the energy balance equation have to have a form of products
BDt properly modified by Carnot’s function.
A revolutionary step toward the definition of the temperature scale independent
of particular type of thermometer and thermometric substance was made in 1848 by
Lord Kelvin [38]. He proposed to treat Carnot’s theorem not as a heuristic statement
3
It should be stressed here that there exist in the literature a lot of various arbitrarily changed forms
of “Carnot’s theorem” or “principle” which are not equivalent one to each other and which
essentially differ in their very content from the original formulation. As was thus quite correctly
pointed out by H. L. Callendar [35] distinguished researcher into the vapour turbines and president
of Royal Society, the original oldest Carnot’s formulation of his principle is at the same time the
best one.
deduced from experiments of rather a limited accuracy but as a fundamental

postulate of absolute validity. He further pointed out that the very purpose of
Carnot’s function is to modify or correct the difference of temperatures measured
in a particular empirical temperature scale in such a way that it could serve as an
exact proportionality factor between work, DL, and heat, B. As this factor has to be
according to Carnot’s postulate the same for all substances and reversible cycles,
Kelvin, inverting the logics of reasoning, suggested to define a universal (in his
terminology “absolute”, see footnote 2) temperature scale just by prescribing a
proper analytical form of Carnot’s function. For example, giving to Carnot’s
function the simplest permissible analytical form, namely, F0 (*T) ¼ 1 (so called
“caloric gauge”), we are in fact defining a new temperature scale *T in terms of
which Eq. 20.5 reads:
DL ¼ B ð T2 T1 Þ: (20.6)
It is immediately seen that using such a definition of the temperature scale the energy
terms have the desired form of a product of two conjugate variables B and *T.
Interestingly enough, Eq. 20.6 is simultaneously a fundamental relation of the
caloric theory of heat (cf. [34, 39]). Accordingly, from the phenomenological
point of view the heat is a kind of substance or fluid, caloric (calorique, W€armestoff,
mеnлopo∂Ъ, teplı´k), which being dissolved in all bodies is responsible for their
thermal state. It is treated as an indestructible fluid (recall that the only method of
how to get rid of heat is to convey it away), which is created in every irreversible
processes such as rubbing, chemical reactions, burning, absorption of radiation and
eating during which “something” simultaneously disappears for ever. The properties
of so defined quantity are thus very near to the concept of heat in a common sense
[40]. Taking further into account the structure of Eq. 20.6, we can also conclude that
the development of moving force in an ideal heat engine is not connected with some
actual consumption of heat as is claimed in thermodynamics but rather with its
transfer from hotter body to a colder one (water-mill analogy [33]). At the same time,
Eq. 20.6 defines an entropy-like unit of heat fully compatible with the SI system
which may be, according to Callendar’s suggestion, appropriately called “Carnot”
(Abbreviation “Ct”) [35]. One Carnot is then that quantity of heat which is in a
reversible process capable of producing 1 J of work per 1 K temperature fall.
Nevertheless, in the present context another aspect of Eq. 20.6 is far more
important. Accordingly, namely, the temperature difference *T2 *T1 between
two bodies used e.g. as “heater” and “cooler” of an ideal heat engine, is identical
with the ratio DL/B where both of these quantities are measurable in principle; DL by
means of standard methods well-known from mechanics and B e.g. by the amount of
fuel consumed by heating the heater or, if the cooler is kept at freezing point of water,
by amount of ice melted during the cycle. It is quite obvious that such a technique of
temperature measurement, although possible in principle, is rather a curiosity which
would be very difficult to realize with sufficiently high accuracy in practice. The idea
of this method is, however, of primary importance for theory. Obviously, due to
Carnot’s postulate, Eq. 20.6 has to be valid for any ideal heat engine regardless of its
340 J.J. Mareš
construction and working substance used. Analyzing thus one particular representa-
tive case of the ideal heat engine, general conclusions can be made. For example, if
we imagine an ideal heat engine driven by perfect gas and working in cycles which
consist of two isothermal and two isochoric reversible processes, the useful work can
be easily computed, provided that the temperatures are measured in terms of perfect
gas scale. The result of such a computation reads
DL ¼ nR lnðV2 =V1 ÞðT2 T1 Þ; (20.7)
where V1 and V2 are the limits of volume between which the engine operates. It is
apparent at first glance that the last equation is fully congruent with Eq. 20.6 with the
proviso that the heat (measured in entropy units, e.g. Ct) transferred from heater to
cooler per cycle is given by B ¼ nR ln(V2/V1). The congruence of these equations
means that the system of units can be always chosen in such a way that scales *T and
T will be identical [16]. Expressing this fact more physically, we can say:
The measurement of temperature by means of ideal gas thermometer is

equivalent to the measurement of temperature by means of ideal heat engine.
The theoretical significance of this theorem is enormous because it enables one

to relate without ambiguity the ideal gas (Kelvin) temperature scale to the tem-
peratures defined by other types of ideal heat engines, e.g. “gedanken” reversible
cycles, in systems controlled by electric, magnetic or electrochemical forces.
Besides, it should be stressed that this theorem, although based on arbitrary
assumptions, is by no means accidental. The idealization of the constitutive relation
of real gases and the idealization involved in Carnot’s postulate have the same
anthropomorphic roots, namely, the feeling that the thermal dilation of bodies must
be linearly dependent on their thermal state. Incidentally, in the range between 0 C
and 100 C the air scale and the mercury temperature scale, prevailingly used in
experiments related to establishment of Carnot’s theorem, are almost identical.
For the sake of completeness we have to mention here also the so called
thermodynamic gauge of Carnot’s function. The general acceptance of this gauge
in classical thermodynamics was, however, not a result of a free choice but a direct
consequence of admittance of Joule-Mayer’s Principle of equivalence of work
(energy) and heat. This Principle which is till now in practically all modern text-
books on thermodynamics treated as an experimentally proved “truth” was, how-
ever, quite correctly from the very beginning criticized by M. Faraday [41] as an
absolutely wrong “strange conclusion” which was “deduced most illogically” on
the basis of fatal misinterpretation of Joule’s paddle-wheel experiment. Accord-
ingly, namely, the existence of exchange rate between two different quantities,
mechanical work and heat, called mechanical equivalent of heat, J 4.2 J/cal, is
confused with the experimental proof of identity of these two entities. Thus in such
a context Joule-Mayer’s Principle has rather a character of arbitrary redundant
postulate than that of experimental result [42]. Nevertheless, once this Principle is
accepted, Carnot’s function, in terms of ideal gas temperature scale T, has to have
inevitably the form F0 (T) ¼ J/T (thermodynamic gauge) [36], cf. also [43]. Such a
gauge, however, enormously complicates the formalism of classical thermodynam-
ics, because it requires introducing into the thermal term (4) of balance equation,
instead of “quantity of heat” already associated with the energy, another somewhat
artificial physical quantity, entropy, which has no clear phenomenological interpre-
tation [40]. Typical claims which can thus be found in the current literature on
thermodynamics sound “Joule’s experiment conclusively established that heat is a
form of energy...” It is, however, worth mentioning here some remarkable facts
which undermine the credibility of such statements. For example, practically all
measurements (i.e. more than about 30 serious extensive works Joule’s works
including from the second half of the nineteenth to the end of the twentieth
centuries) of mechanical equivalent of heat were made at only single temperature.
It is thus quite evident that the experimentalists tacitly assumed, prior making the
experiment, the validity of Joule-Mayer’s Principle, being convinced that the
measured equivalent is nothing but a conversion factor between two different
energy units, which has to be inevitably temperature independent. “Derivation”
of Joule-Mayer’s Principle from such an experimental data is obviously nothing but
a case of circular reasoning. Moreover, the mechanical equivalent of heat was (with
much smaller accuracy but in the correct way) determined by Carnot [33] more than
20 years before Joule within the frame of caloric theory, i.e. without any possible
reference to Joule-Mayer’s Principle.
Interestingly enough, the choice of particular gauge does not directly influence
the properties of Kelvin’s temperature scale itself but it is quite decisive for
the mathematical behaviour and physical interpretation of corresponding conjugate
extensive quantity.
20.8 Problem of Distant Measurements of Temperature
Under the term “distant measurements” in a restricted sense we mean the determi-
nation of a physical quantity belonging to a certain moving inertial frame by means
of measurements made in the rest system. The operational methods for distant
measurements of e.g. length, time, frequency and intensity of fields are generally
known from the Special Theory of Relativity. In the case of temperature, however,
due to its peculiar physical nature, we encounter serious difficulties which result
into quite controversial solutions of the problem [44]. At first glance it may seem
that the problem of distant measurement of temperature belongs to the scope of
practical calorimetry and thermal analysis performed in laboratories only margin-
ally, being of primary importance only for thermo-physical processes taking place
on remote objects like stars or spacecrafts. It should be stressed, however, that the
342 J.J. Mareš
considerations dealing with relativistic transformations of thermal quantities reveal

their physical structure and are thus quite crucial for a consistent interpretation of
these quantities even under the terrestrial conditions.
The main difficulty in distant measurement of temperature is the principal
impossibility of realization of correlation test and establishment of thermal equilib-
rium between two relatively moving inertial systems. Indeed, the relative move-
ment of systems A and B prevents one from answering without ambiguity, on the
basis of correlation test, the question of whether the common boundary is diather-
mic or not, which makes any judgment on the thermal equilibrium between A and B
quite questionable. It is further clear that the boundary between two relatively
moving systems has to move at least with respect to one of them. In such a case,
however, the interaction between these systems can exist even if the boundary is
non-diathermic (adiabatic). For example, the moving boundary can exert a pressure
on one of the systems without changing the state of the other and/or a charged
system A surrounded by a metallic envelope, regardless of the fact whether it is
diathermic or adiabatic, can induce dissipative equalization currents in system B
without affecting the charge distribution inside system A. In order to exclude such
cases, the temperature of any body must be measured only by means of a thermom-
eter which is in the rest with respect to the body, and this operation cannot be, in
principle, performed by a relatively moving observer (cf. also [45]). Hence the
temperature cannot be the subject of a direct distant measurement in principle. It
can only be the result of local measurement and subsequent data transfer into
another inertial system. (If possible, the digital mailing of the data would be the
best choice.) The operational rules for distant measurement of temperature
may then be formulated as follows:
1. Bring the body under investigation into diathermic contact with the ther-
mometer placed in the same inertial frame
2. Reconstruct in another (e.g. rest) inertial system the reading of the ther-
mometer applying transformation rules relevant to the thermoscopic
variable used
Having already at our disposal the prescription defining the temperature in mathe-
matical terms, it is in principle possible to perform the Lorentz transformation of
the left-hand side of Eq. 20.2 and to obtain in this way the formula for the
relativistic transformation of temperature T. However, in order to be able to analyze
also other temperature measuring methods (using e.g. platinum resistance, black-
body radiation, thermoelectric voltage) in a sufficient generality a methodical
approach is more relevant.
Fortunately, the properties of hotness manifold enable one to make the following
fairly general considerations. First of all, it is evident that in order not to violate
the Principle of Relativity the behaviour of bodies realizing fixed thermometric
points has to be the same in all inertial frames (cf. [46]). For example, it would be
absurd to admit an idea that the water violently boiling in its rest system can
simultaneously4 look calm if observed from another relatively moving inertial

system. In other words, any fixed point has to correspond to the same hotness level
regardless of the inertial frame used for the observation. Assigning, by means of
some convention, to each body realizing the fixed point a certain “inventory entry”,
the resulting, by pure convention established list of numbers cannot be changed by a
mere transfer from one inertial system to another.
For example, using thus as an operative rule for stocktaking of fixed points
formula 20.2 (in SI units with R ¼ 8.3145 J/K mol) and assigning to the triple point
of water an inventory entry 273.16 K, we obtain an ordered table of fiducial points
of ideal gas scale (similar to the ITS [1]) which must be valid in all inertial frames.
As the set of fixed points provides a dense subset (skeleton) in continuous hotness
manifold, such a Lorentz-invariant table can be extended and made finer as we like
and consequently, any hotness level can be, by means of this table, approximated
with arbitrary accuracy. Due to the continuity of prescription 20.2 the whole ideal
gas (Kelvin) scale T is then inevitably Lorentz invariant.
The invariance of Kelvin scale has, however, a very interesting and far reaching
consequence. Let us make the following thought experiment with two identically
arranged gas thermometers both filled with one mole of ideal gas which are in two
relatively moving inertial systems in diathermic contact with the same fixed point
bath (for definiteness, with triple point of water) placed in their own frames. As the
pressure in both devices is Lorentz invariant [47, 48], we can write:
p ¼ p0 ; (20.8)
T ¼ T0 ; (20.9)
where index 0 is related, as above, to the quantities measured in the a-priori chosen
rest system. Taking now the well-known Lorentz transformation of volume into
account, we obtain from 20.8 and 20.9 the following series of equations
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
pV ¼ p0 V0 ð1 v2 =c2 Þ ¼ RT ¼ R0 T0 ð1 v2 =c2 Þ; (20.10)
from which a somewhat astonishing relation immediately follows:

pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
R ¼ R0 ð1 v2 =c2 Þ: (20.11)
The physical meaning of this formula is really far reaching. Taking into account,
namely, that R is an entropy unit, Eq. 20.11 must simultaneously enter the transfor-
mation formulae for entropy in general. This is, however, in severe contradiction
with Planck’s Ansatz claiming that the entropy is Lorentz invariant. We have to
4
Notice that we have to do here with the essentially time-independent stationary process where the
Lorentz transformation of time plays no role. Let us also recall that the pressure, controlling e.g.
boiling point of water, may be proved independently to be Lorentz invariant [47, 48]
344 J.J. Mareš
recall here that this Ansatz, serving as a starting point of numerous considerations in
relativistic thermodynamics, has never been proved with sufficient exactness but
from the beginning it was mere an intuitive conjecture [49]. It was namely argued
that the entropy has to be invariant, because it is the logarithm of a discrete number
of states which is “naturally” Lorentz invariant. Nevertheless, such a seemingly
transparent argument cannot be true in general as can be shown by means of the
following consideration. Let us imagine first that a sample of paramagnetic salt is
submerged in a bath of boiling helium kept at normal atmospheric pressure realiz-
ing the Lorentz invariant fixed point corresponding to the temperature of 4.2 K [8].
At zero magnetic fields certain entropy can be ascribed to such a state of paramag-
netic salt independently of the fact in what inertial system the experiment is
performed. Let us further assume that there is distributed static electric charge in
the rest system not affecting the entropy of paramagnetic salt. As is well known
from the special theory of relativity, however, the magnetic field is nothing but the
electrostatic field observed from the relatively moving inertial system [50]. There-
fore, the observer in the relatively moving inertial frame has to detect magnetic
field, and the entropy of the said paramagnetic sample kept at 4.2 K must be smaller
than that in the rest system. In other words, because the entropy in this particular
case depends on the choice of inertial system of observation, it cannot be generally
Lorentz invariant. If we thus once admit the relativistic invariance of temperature,
we have to reject Planck’s conjecture as unsound and particularly, we can also no
more treat various entropy pre-factors, e.g. gas constant R and Boltzmann’s con-
stant k, as universal constants.
20.9 Summary
In conclusion, the central concept of thermal physics, temperature, is defined in

terms of the set theory as an arbitrary one-to-one order preserving continuous
mapping of the so-called hotness manifold (set) H on a certain simple connected
open subset of real numbers. It has been shown that the hotness manifold represent-
ing all in the Nature existing thermoscopic (thermal) states is the only entity
accessible to direct physical observation. This set which was further proved to be
topologically equivalent to the set of all real numbers (real axis) E1, contains a
countable, dense and unbounded subset of all fixed points F H. Any fixed point is
realized by means of a specially prepared body which defines just one thermal state.
The properties of the set F and its relation to the manifold H are specified by means
of Mach’s postulates which are generalizations of empirical facts. As was further
shown, the special mapping of H on the set of all positive real numbers known as
the International Kelvin Temperature Scale T was chosen on the grounds of two
essentially anthropomorphic idealizations providing a concordant result, namely,
on ideal substance, perfect gas and on ideal process in heat engine, reversible cycle.
Finally, on the basis of simple physical arguments taking into account the mathe-
matical structure of the hotness manifold the Lorentz invariance of the temperature
was proved. Consequently, the variable conjugate to temperature, i.e. entropy-like

heat, cannot be Lorentz invariant in severe contradiction to Plank’s Ansatz claiming
the Lorentz invariance of entropy in general.
Acknowledgments This work was supported by Institutional Research Plan of Institute of

Physics No AV0Z10100521.
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Chapter 21
Historical Roots and Development of Thermal
Analysis and Calorimetry
Jaroslav Šesták, Pavel Hubı́k and Jiřı́ J. Mareš
21.1 Historical Aspects of Thermal Studies,

Origins of Caloric
Apparently, the first person which used a thought experiment of continuous heating
and cooling of an illustrative body was curiously the Czech thinker and Bohemian
educator [1], latter refugee Johann Amos Comenius (Jan Amos Komenský,
1592–1670) when trying to envisage the properties of substances. In his “Physicae
Synopsis”, which he finished in 1629 and published first in Leipzig in 1633, he showed
the importance of hotness and coldness in all natural processes. Heat (or better fire) is
considered as the cause of all motions of things. The expansion of substances and the
increasing the space they occupy is caused by their dilution with heat. By the influence
of cold the substance gains in density and shrinks: the condensation of vapor to liquid
water is given as an example. Comenius also determined, though very inaccurately, the
volume increase in the gas phase caused by the evaporation of a unit volume of liquid
water. In Amsterdam in 1659 he published a focal but rather unfamiliar treatise on the
principles of heat and cold [2], which was probably inspired by the works of the Italian
philosopher Bernardino Telesius. The third chapter of this Comenius’ book was
devoted to the description of the influence of temperature changes on the properties
of substances. The aim and principles of thermal analysis were literally given in the
first paragraph of this chapter: citing the English translation [3–5]:
In order to observe clearly the effects of heat and cold, we must take a visible object and
observe its changes occurring during its heating and subsequent cooling so that the effects
of heat and cold become apparent to our senses.
J. Šesták (*)
New Technologies Research Centre, University of West Bohemia,
Univerzitnı́ 8, CZ-30614, Plzeň, Czech Republic
P. Hubı́k and J.J. Mareš
Cukrovarnická 10, 162 00, Praha 6, Czech Republic

In the following 19 paragraphs of this chapter Comenius gave a rather systematic

description (and also a partially correct interpretation) of the effects of continuous
heating and cooling of water and air, and also stressed the reversibility of processes
such as, for example, evaporation and condensation, etc., anticipating somehow the
concept of latent heat. Comenius concludes this chapter as follows: All shows
therefore that both heat and cold are a motion, which had to be proved. In the
following chapter Comenius described and almost correctly explained the function
of a thermoscope (‘vitrum caldarium’) and introduced his own qualitative scale
with three degrees of heat above and three degrees of cold below the ambient
temperature launching thus a concept of “caloric”.
Nonetheless, it is difficult to trace [1, 3–6] and thus hard to say if it was possible
(though likely) to disseminate the Comenius idea of caloric from Amsterdam (when
he mostly lived and also died) to Scotland where a century later a new substance, or
better a matter of fire, likewise called caloric (or caloricum), was thoroughly
introduced by Joseph Black (1728–1799) [7] and his student Irvine. Unfortunately,
Black published almost nothing in his own lifetime [5, 8] and his attitude was
mostly reconstructed from contemporary comments and essays published after his
death.
Caloric [1, 7, 9–11] was originally seen as an imponderable element with its own
properties. It was assumed, e.g., that caloric creeps between the constituent parts of
a substance causing its expansion. Black also supposed that heat (caloric) was
absorbed by a body during melting or vaporization, simply because at the melting
or boiling points sudden changes took place in the ability of the body to accumulate
heat (~1761). In this connection, he introduced the term ‘latent heat’ which meant
the absorption of heat as the consequence of the change of state. Irvine accounted
that the relative quantities of heat contained in equal weights of different substances
at any given temperature (i.e., their ‘absolute heats’) were proportional to their
‘capacities’ at that temperature and it is worth noting that the term ‘capacity’ was
used by both Black and later also Irvine to indicate specific heats [7, 9–11].
Black’s elegant explanation of latent heat to the young James Watts
(1736–1819) became the source of the invention of the businesslike steam engine
as well as the inspiration for the first research in theory related to the novel domain
of thermochemistry, which searched for general laws that linked heat, with changes
of state. In 1822, Jean-Baptiste Joseph Fourier (1768–1830) published an influen-
tial book on the analytical theory of heat [12], in which he developed methods for
integration of partial differential equations, describing diffusion of the heat sub-
stance. Based on the yet inconsistent law of conservation of caloric, Simeón D.
Poisson (1823) derived a correct and experimentally verifiable equation describing
the relationship between the pressure and volume of an ideal gas undergoing
adiabatic changes. Benjamin Thompson (Count Rumford, 1753–1814) presented
qualitative arguments for such a fluid theory of heat with which he succeeded to
evaluate the mechanical equivalent of heat [11, 13]. This theory, however, was not
accepted until the later approval by Julius Robert Mayer (1814–1878) and, in
particular, by James Prescott Joule (1818–1889), who also applied Rumford’s
theory to the transformation of electrical work.
21 Historical Roots and Development of Thermal Analysis and Calorimetry 349
In the year 1826 Nicolas Clement (1779–1842) [11] coined the unit of heat as
amount of caloric, necessary for heating 1 g of liquid water by 1 C. Though the
expected temperature changes due to “thickened caloric” did not experimentally
occur (cf. measurements in “Torricelli’s vacuum” over mercury by Gay-Lussac)
and in spite of that Thompson (1798) showed that the heat could be produced by
friction ad infinitum, the caloric theory survived many defeats and its mathematical
scheme is in fact applied for the description of heat flow until today. The above
customary unit was called ‘calorie’ (cal) or ‘small calorie’, whereas a ‘large
calorie’ corresponded to the later ‘kilocalorie’ (kcal). The word “calorie” was
more widely introduced into the vocabulary of academic physicists and chemists
by Favre and Silbermann [14] in 1852. The expression of 1 kcal as 427 kg m was
given by Mayer in the year 1845.
We should add that caloric differed from the foregoing concept of phlogiston
because, beside else, it could be measured with an apparatus called a calorimeter,
however, it is not clear who was the first using such an instrument. If we follow the
studies of Brush [8], Mackenzie [15] and Thenard [16] they assigned it to Wilcke. It,
however, contradicts to the opinion presented in the study by McKie and Heathcote
[17] who consider it just a legend and assume that the priority of familiarity of ice
calorimeter belongs to Laplace who was most likely the acknowledged inventor
and first true user of this instrument (likely as early as in 1782). In fact, Lavoisier
and Laplace entitled the first chapter of their famous “Me´moire sur la Chaleur”
(Paris 1783) as “Presentation of a new means for measuring heat” (without
referring Black because of his poor paper evidence). Report of Black’s employment
of the calorimeter seems to appear firstly almost a century later in the Jamin’s
Course of Physics [1].
21.2 Underlying Features of Thermal Physics Interpreted

Within the Caloric Theory
In the light of work of senior Lazare Carnot (1753–1823) on mechanical engines [11],
Sadi Carnot (1796–1832) co-opted his ideas of equilibrium, infinitesimal changes
and imaginatively replicated them for caloric (in the illustrative the case of water fall
from a higher level to a lower one in a water mill). He was thinking about writing a
book about the properties of heat engines applying caloric hypothesis generally
accepted in that time within broad scientific circles [18–20]. Instead, he wrote a slim
book of mere 118 pages, published in 200 copies only, which he entitled as the
“Reflections on the motive power of fire and on machines fitted to develop that
power” (1824) [21], which was based on his earlier outline dealing with the derivation
of an equation suitable for the calculation of motive power performed by a water steam
[11]. He discussed comprehensively under what conditions it is possible to obtain
useful work (“motive power”) from a heat reservoir and how it is possible to realize a
reversible process accompanied with heat transfer. Sadi also explained that a
reversibly working heat engine furnished with two different working agents had to
have the same efficiency related to the temperature difference, only. Among other
notable achievements [14, 22–27] there was the determination of the difference
between the specific heats of gases measured at constant pressure and volume. He
found that the difference was the same for all gases, anticipating thus the Mayer’s
relation for ideal gas: cp – cv ¼ R. Sadi also introduced the “Carnot’s function” the
inverse of which was later (1850) identified by Rudolph Clausius (1822–1888) [28],
within the classical thermodynamics, with the absolute temperature T. Finally, Sadi
adjusted, on the basis of rather poor experimental data that for the production of 2.7
mechanical units of “motive power” it was necessary to destruct 1 cal unit of heat,
which was in a fair correspondence with the later mechanical equivalent of heat: (4.1 J/
cal). It is worth noting that already when writing his book he started to doubt the
validity of caloric theory [11, 27] because several of experimental facts seemed to him
almost inexplicable. Similarly to his father, Sadi’s work remained unnoticed by
contemporary physicists and permanently unjustly criticized for his principle of the
conservation of caloric, which is, however, quite correct for any cyclic reversible
thermal process.
Adhering to the way of Carnot’s intuitive thinking [26, 27], the small amount of
work done dL (motive power in Carnot’s terms) is performed by caloric B literarly
falling over an infinitesimal temperature difference dT [11, 16, 26], dL ¼ B F(T) dT.
The function F(T) here is the Carnot’s function, which has to be determined experi-
mentally, certainly, with respect to the operative definitions of quantities B and T.
Carnot assumed that caloric is not consumed (produced) by performing work but only
loses (gains) its temperature (by dT). Therefore, the caloric has there an extensive
character of some special substance while the intensive quantity of temperature plays
the role of its (thermal) potential; the thermal energy may be thus defined as the
product B T, in parallel with other potentials such pressure (choric potential) for
volume, gravitational potential for mass and electrostatic potential for charge.
Taking into account that caloric is conserved during reversible operations, the
quantity B must be independent of temperature and, consequently, Carnot’s function
F(T) has to be also constant. Putting the function equal identically 1 the unit of
caloric fully compatible with the SI system is defined. Such a unit (Callendar [23]),
can be appropriately called “Carnot” (abbreviated as “Cn” or “Ct”). One “Ct” unit
is then such a quantity of caloric, which is during a reversible process capable of
producing 1 J of work per 1 K temperature fall. Simultaneously, if such a system of
units is used [26, 27], the relation dL ¼ B dT retains.
The caloric theory can be extended for irreversible processes by adding an idea
of wasted (dissipated) motive power which reappears in the form of newly created
caloric [26]. Analyzing Joule’s paddle-wheel experiment from view of both this
extended caloric theory and classical thermodynamics, it can be shown that the
relation between caloric and heat in the form dB ¼ J dQ/T takes place, which, at
first glance, resembles the famous formula for entropy, certainly if we measure the
heat in energy units. This correspondence between entropy and caloric, may serve
as a very effective heuristic tool for finding the properties of caloric by exploitation
the results known hitherto from classical thermodynamics. From this point of
view it is clear that the caloric theory is not at any odds with experimental facts,
which are only anew explained ([26]). The factor J historically determined by Joule
(J ~ 4.185 J/cal) should have been rather related with the establishment of
a particular system of units then with a general proof of the equivalence between
heat and energy.
One of the central questions of the Carnot’s theory of heat engines is the evalua-
tion of engine efficiency. The amount of caloric B which is entering the completely
reversible and continuously working heat engine at temperature T1 and leaving it at
temperature T2 will produce a motive power of amount L. Carnot’s efficiency C
defined as a ratio L/B is then given by a plain temperature drop DT ¼ (T1 T2)
(as measured in the ideal gas temperature scale). Transforming the incoming caloric
into thermal energy T1B, we obtain immediately Kelvin’s dimensionless efficiency
K of the ideal reversible heat engine, K ¼ {1 (T2/T1)}, which is well-known
from textbooks of thermodynamics [3, 29].
However, K is of little significance for the practical evaluation of the perfor-
mance of real heat engines, which are optimized not with respect to their efficiency
but rather with respect to their available output power. As a convenient model for
such a case it may be taken an ideal heat engine impeded by a thermal resistance
[26]. The effect of thermal resistance can be understood within the caloric theory in
such a way that the original quantity of caloric B, taken from the boiler kept at
temperature T1, increases, by passing across a thermal resistance, to the new
quantity equal to B + DB, entering than the ideal heat engine at temperature
T < T1, and leaving it temperature T2. If we relate the quantities L and B to an
arbitrary time unit (we conveniently use for this purpose a superscript u), it follows
Lu ¼ l(T1 T)(T T2)/T, where for the evaluation of temperature drop across the
thermal resistance we can apply the Fourier law [12] Bu T1 ¼ l (T1 T), where l
is a constant representing the inverse of thermal resistance. The condition for the
optimum of the output powerpwith respect to temperature T then reads dLu/dT ¼ 0,
from which we obtain T ¼ (T1 T2) [26]. Consequently, the Carnot’s true effi-
ciency of suchpa system with optimized output power is thus given by a formula,
C ¼ T1 {1– (T2/T1)}. Such a square root dependence, which is the direct
consequence of linearity of Fourier’s law, is also obviously repeated for the
above mentioned dimensionless Kelvin’s efficiency, K. Because of enormous
effort of engineers to optimize the real output power of concrete heat engines, the
above formula describes the actual efficiencies quite well as interestingly shown for
authentic industrial cases by Curzon and Ahlborn [30].
21.3 Early Scientific and Societal Parentage of Thermal

Analysis
Standard reference books [16, 19, 21, 29, 31] are rather coy about the history of
thermometry and thermal analysis being the subject of specified papers and book
chapters [1, 4–11, 15, 32–35], which goes back to historic times of Isaac Newton
(1642–1727) who published his temperature scale in 1701 the significance of which
lies both in its range of temperature and in its instrumentation presenting also the
famous Newton’s Law of Cooling [36]. First cornerstone of the theory of warmth
propagation was provided by J.-B. J. Fourier who initiated the investigation of
Fourier series and their application to problems of heat transfer [12]. The very roots
of thermal analysis appear in the nineteenth century where temperature became an
observable and experimentally decisive quantity, which thus turned into an experi-
mentally monitorable parameter associated with an consequent underpinning of the
field of thermodynamics [29, 34, 35]. The first characterization of thermometric
measurements is identified in Uppsala in 1829 through the earliest documented
experiment which nearly meets current criteria. It was Fredrik Rudberg
(1800–1839) [15, 22] who recorded the inverse cooling-rate data for lead, tin,
zinc and various alloys which were placed in a smaller vessel surrounded by a
large double-walled iron vessel where the spaces between its two walls, as well as
the top lid, were filled with snow to ensure that the inner walls were always kept at
zero temperature. Once the experimental condition was set up, Rudberg noted and
tabulated the times taken by the mercury in thermometer to fall through each 10
interval. The longest interval then included the freezing point.
One of important impacts came with the discovery of thermoelectric effect [37]
by Thomas J. Seebeck (1770–1831) occurring in a circuit made from two dissimilar
metals and the consequent development of a device called thermocouple [37, 38],
suitable as a more accurate temperature-measuring tool, in which gas volume or
pressure changes were replaced by a change of electric voltage (Augustin G.A.
Charpy (1865–1945) [39]). Henry L. Le Chatelier (1850–1936) [38] was the first
who deduced that varying thermocouple output could result from contamination of
one wire by diffusion from the other one or from the non-uniformity of wires
themselves. The better homogeneity of platinum-rhodium alloy led him to the
standard platinum – platinum/rhodium couple so that almost 70 years after the
observation of thermoelectricity, its use in thermometry was finally vindicated,
which rapidly got a wider use. Floris Osmond (1849–1912) [15, 40] investigated the
heating and cooling behavior of iron with a goal to elucidate the effects of carbon so
that he factually introduced thermometric measurements to then most important
field: metallurgy [40].
In 1891, Sir William C. Roberts-Austen (1843–1902) [41] was accredited to
construct a device to give a continuous record of the output from thermocouple and
he termed it as ‘thermoelectric pyrometer’ (see Fig. 21.1) and in 1899, Stanfield
published heating curves for gold and almost stumbled upon the nowadays idea of
differential thermal analysis (DTA) when maintaining the thermocouple ‘cold’
junction at a constant elevated temperature measuring thus the entire differences
between two high temperatures. Such an innovative system of measuring the
temperature difference between the sample and a suitable reference material placed
side-by-side in the same thermal environment, in fact initiated the consequent
development of DTA instruments [42–44].
a D
b –
Thermo-Electric Pyrometer. +
–
M
F b
A a
B E c
H
C X
+ T
Fig. 21.1 Upper: Thermo-electric pyrometer of Roberts-Austen (1881) showing the instrument
(left) and its cooling arrangement (right) with particularity of the sample holder. Middle: Historical
photo of the early set-up of Hungarian “Derivatograph” (designed by brothers Paulik), which was
one of the most frequent instruments in the former Eastern bloc. Below: photo of one time very
popular and widespread instruments for high-temperature DTA produced by the Netzsch
Ger€atebau GmbH (Selb, Germany) from its early version (left) presented to the market on 1950
up to the latest third-generation rendering new STA 449 F1 Jupiter (right). The middle type (yet
based on then fashionable analogous temperature control) was particularly sold during 1970s and
survived in many laboratories for a long period (being gradually subjected to enduring computeri-
zation and digital data processing)
In 1909 there was elaborated another reliable procedure of preserving the high-
temperature state of samples down to laboratory temperature, in-fact freezing-in the
high-temperature equilibrium as a suitably ‘quenched’ state for further investiga-
tion [34]. It helped in the consistent construction of phase diagrams when used in
combination with other complementary analytical procedures, such as the early
structural microanalysis (introduced by Max von Laue (1879–1960) and Sir William
L. Bragg (1890–1971) when they detected the X-rays diffraction on crystals) along
with the traditional metallographic observations. Another important step toward the
modern solid state physics was induction of the notion of diffusion by Adolf E. Fick
(1829–1901) and its improved understanding by Ernest Kirkendall (1914–2005) as
well as the introduction of the concept of disorder by Jakob I. Frenkel (1894–1952)
[45] and models of glasses by Tammann [46].
By 1908, knowledge of the heating or cooling curves, along with their rate
derivatives and inverse curves were sufficient enough to warrant a first review and
more detailed theoretical inspection given by George K. Burgess (1874–1932) [47].
Not less important was the development of heat sources where coal and gas were
almost completely replaced by electricity as the only source of controllable heat.
Already in 1895, Charpy described in detail the construction of wire-wound,
electrical-resistance based, tube furnaces that virtually revolutionized heating and
temperature regulation [39]. Control of heating rate had to be active to avoid
possibility of irregularities; however, little attention was paid to it as long as the
heat source delivered a smooth temperature-time curve. All early users mention
temperature control by altering the current and many descriptions indicate that this
was done by manual or clockwork based operation of a rheostat in series with the
furnace winding, the system still in practical use up to late 1950s.
However, the first automatic control was published by Carl Friedrich in 1912,
which used a resistance box with a specially shaped, clock-driven stepped cam-
plate on top. As the cam rotated it displaced a pawl outwards at each step and this in
turn caused the brush to move on to the next contact, thus reducing the resistance of
furnace winding. Suitable choice of resistance and profiling of the cam achieved the
desired heating profile. There came also the reduction of sample size from 25 g
down to 2.5 g, which lowered the ambiguity in melting point determination from
about >2 C down to ~0.5 C. Rates of about 20 K/min were fairly common during
the early period later decreased to about quarter. Early in 1908, it was Burgess [47]
who considered the significance of various experimental curves in detail concluding
that the area of the inverse-rate curve is proportional to the quantity of heat
generated divided by the rate of cooling.
The few papers published in the period up to 1920 gave, nonetheless, little
experimental details so that White [48] was first to show more theoretically the
desirability of smaller samples providing a more exhaustive study of the effect of
experimental variables on the shape of heating curves as well as the influence of
temperature gradients and heat fluxes taking place within both the furnace and the
sample. It is obvious that DTA was initially more a qualitative empirical technique,
though the experimentalists were generally aware of its quantitative potentialities.
The early quantitative studies were treated semiempirically and based more on
instinctive reasoning. Andrews (1925) was first to use Newton’s law while Berg
gave the early bases of DTA theory [49, 50], which was independently simplified by
Speil. In 1939 Norton published his classical paper on differential thermal techni-
ques where he made rather excessive claims for their value both in the identification
and quantitative analysis exemplifying clay mixtures [51]. Vold (1948) [52] and
Smyth (1951) [53] proposed a more advanced DTA theory, but the first detailed
theories and applicability fashions, free from restrictions, became accessible by
followers in 1950s [3, 50, 54–58], e.g., Keer, Kulp, Evans, Blumberg, Erikson,
Soule, Boersma, Borchard, Damiels, Deeg, Nagasawa, Tsuzuki, Barshad, Strum,
Lukaszewski, etc.
In general, the thermoanalytical methods gained theoretical description
early 1960s [59–61]. The resulting thermal effects, explicitly temperature disparity
(DT), can be analyzed at four different but gradually escalating levels [3, 34, 62,
63]: fingerprinting (identity), quality, quantity (peak areas) and kinetics (peak
shape) which were extensively applied to assessments of phase diagrams, transition
temperatures, and chemical reactions, as well as to the qualitative analysis of
metals, oxides, salts, ceramics, glasses, minerals, soils, and foods. Because of its
easy accessibility DTA was used to study behavior of the constrain states of glasses
[64–68], inherent processes conventionally viewed as a diagram of temperature (T)
versus enthalpy (H) [66], which derivative resembles the entire DTA curve
(informative for the analysis of glassforming processes [34]).
21.4 Theoretical Basis, Quantitative Thermometric

and Calorimetric Measurements
In the beginning, DTA could not be classified as a calorimetric method since no

heat was measured quantitatively [59–62]. Only the temperature was determined
with the precision of the thermocouple. The quantitative heat effects were tradi-
tionally measured by calorimetry. Beside the above quoted ice-calorimeter pio-
neered by Laplace the early instrumentation for the determination of heat capacity
was based on the classical adiabatic calorimeter and designed by Walther H. Nernst
(1864–1941) [69, 70] for low temperature measurements [71] (in Germany 1911).
Its original experimental arrangement involved the introduction of helium gas as a
thermally conducting medium by which the specimen would rapidly reach the
temperature required for the next measurement.
Although the measurements of heat changes is common to all calorimeters, they
differ in how heat exchanges are actually detected, how the temperature changes
during the process of making a measurement are determined, how the changes that
cause heat effects to occur are initiated, what materials of construction are used,
what temperature and pressure ranges of operation are employed, and so on. If the
heat, Q, is liberated in the sample, a part of this heat accumulates in the calorimetric
sample-block system and causes a quantifiable increase in the temperature. The
remaining heat is conducted through the surrounding jacket into the thermostat. The
two parts of the thermal energy are closely related. A mathematical description is
given by the basic calorimetric equation, often called the Tian equation [72].
The calorimetry classification came independently from various sources, e.g. [3,
73–75]. The principal characteristics of a calorimeter are the calorimeter capacity,
effective thermal conductivity, and the inherent heat flux, occurring at the interface
between the sample-block, B, and the surrounding jacket, J. The temperature
difference [3], TB – TJ, is used to classify calorimeters, i.e., diathermal (TB ¼ 6 TJ),
isodiathermal (TB – TJ) ¼ const. and d(TB – TJ) ! 0, adiabatic (TB ¼ TJ), isother-
mal (TB ¼ TJ ¼ const.) and isoperibolic (TB – TJ) ! 0. The most common version of
the instrument is the diathermal arrangement where the thermal changes in the sample
are determined from the temperature difference between the sample-block and jacket.
The chief condition is, however, the precise enough determination of temperatures.
With an isodiathermal calorimeter, a constant difference of the block and jacket
temperatures is maintained during the measurement, thus also ensuring a constant
heat loss by introducing extra heat flux to the sample from an internally attached
source (often called ‘microheater’). The energy changes are then determined from the
energy supplied to the source. For low values of heat, the heat loss can be decreased to
minimum by a suitable instrumental set-ups and this version is called as adiathermal
calorimeter. An adiabatic calorimeter suppresses heat losses by maintaining the block
and jacket temperatures at the same temperature. Adiabatic conditions are more
difficult to assure at both higher temperatures and faster heat exchanges so that it is
preferably employed at low temperatures.
Eliminating the thermal gradients between the block and the jacket by using an
electronic regulation requires, however, sophisticated circuits and more complex
set-ups. For this reason, the calorimeters have become experimentally very multi-
faceted instruments. With compensation “quasiadiabatic” calorimeter, the block
and jacket temperatures are kept identical and constant during the measurement as
the thermal changes in the sample are suitably compensated, so that the block
temperature remains the same. If the heat is compensated by phase transitions in the
reseivoir in which the calorimetric block is contained, the instrument are often
termed transformation calorimeter. Quasi-isothermal calorimeters are, in turn,
instruments with thermal compensation provided by electric microheating and
heat removal is accomplished by forced flow of a fluid, or by the well-established
conduction through a system of thermocouple wires or even supplemented by
Peltier cooling effect. The method in which the heat is transferred through a
thermocouple system is often called Tian-Calvet calorimetry [76, 77]. A specific
group is formed by isoperibolic calorimeters, which essentially operate adiabati-
cally with an isothermal jacket.
Even in the 1950s, it was a doubtful prediction that classical DTA and adiabatic
calorimetry would merge, producing a differential scanning calorimeter (DSC).
The name DSC was first mentioned by O’Neil [78] for a differential calorimeter that
possessed continuous power compensation (close-to-complete) between sample
and reference. This development came about because the key concern of calorime-
try is the reduction of, and certainly also correction for, heat losses and/or gains due
to inadvertent temperature distribution in the surroundings of the calorimeter. The
heat to be measured can never be perfectly insulated; even in a true adiabatic
calorimeter certain heat-loss corrections have to be made and resulting adiabatic
deviation must then be corrected through extensive calibration experiments. In
order to cancel the heat losses between two symmetric calorimeters were used
(e.g., twin calorimetry – one cell with the sample and the other identical, but empty
or filled with a reference material), however presented control problems were not
easy to handle [3].
True DSC is monitoring the difference between the counterweighing heat fluxes
by two extra micro-heaters respectively attached to both the sample and reference in
order to keep their temperature difference minimal, while the samples are main-
tained in the pre-selected temperature program. This technique was originally
introduced by Eyraund in 1950s [84]. Such an experimental regime bears a quite
different measuring principle when comparing with DTA because the temperature
difference is not used for the observation itself but is exclusively employed for the
regulation only. Certainly, it is the way for accomplishing the most precise measure-
ments of heat capacity (close to adiabatic calorimetry) but technically restricted, to
the temperature range up to about 700 C, where heat radiation become decisive
making consequently the regulation and particularly compensation complicated.
Three major types of DSCs emerged that all are classified as scanning [79],
isoperibolic twin-calorimeters. One type makes use of approximate power com-
pensation between two separately heated calorimeters, and the other two merely
rely on heat exchange of 2 calorimeters placed symmetrically inside a single heater,
but differing in the positions of the controlling thermometers. Even the majority
commercial DTA instruments can be classified as a double non-stationary resem-
bling calorimeter in which the thermal behaviors of sample are compared with a
correspondingly mounted, inert reference [3]. It implies control of heat flux from
surroundings and heat itself is a kind of physico-chemical reagent, which, however,
could not be directly measured but calculated on the basis of the measurable
temperature gradients. We should remark that heat flow is mediated by massless
phonons so that the inherent flux does not exhibit inertia as is the case for the flow of
electrons. The thermal inertia of apparatus (as observed in DTA experiments) is
thus caused by heating a real body and is affected by the entire properties of
materials, which structure the sample under study.
The decisive theoretical analysis of a quantitative DTA was based on the
calculation of heat flux balances introduced by Factor and Hanks [80], detailed in
1975 by Grey [81], which premises were completed in 1982 by the consistent
theory made up by Holba and Šesták [3, 82, 83]. It was embedded within a ‘caloric-
like’ framework centered on macroscopic heat flows encountered between large
bodies (DTA cells, thermostats). Present DTA/DSC instruments marched to high
sophistication, computerization and miniaturization, see, e.g., Fig. 21.1
All the equations derived to the description of theoretical basis of DTA/DSC
methods can be summarized within the following schema [3, 34], which uses a
general summation of inherent terms (each being responsible for the subsequent
distinct function): Enthalpy + Heating + Inertia + Transient ¼ Measured Quan-
tity. It implies that the respective effects of enthalpy change, heating rate and heat
transfer are reflected in the value of the measured quantity for all set-ups of the
thermal methods commonly exercised. Worth noting is the inertia term, which is a
particularity for DTA (as well as for heat-flux DSC) expressing a specific correction
due to the sample mass thermal inertia owing to the inherent heat capacity of real
materials. It can be visualized as the sample hindrance against immediate ‘pouring’
heat into its heat capacity ‘reservoir’ and it is apparent similarity to the definite
time-period necessary for filling a bottle by liquid. Keep in mind, that the conse-
quential compensation DSC calorimetry is of a different nature because it evalu-
ates, instead of temperature difference (DT ) 0), compensating heat fluxes and
thus the heat inertia term is absent [3, 34, 82]. The practice and basis of DSC has
been treated numerously [85, 86].
In order to meet an experimental pre-requisition of the transient term (involving the
instrumental constant characteristic of a particular DTA apparatus), the routine pro-
cedure of calibration is indispensable for a quantitative use of DTA. It is commonly
guaranteed by a practice of an adequate incorporation of defined amounts of enthalpy
changes by means of the selected test compounds (which widespread standardization,
however, failed so that no ICTAC recommendation was issued). Nevertheless, in the
laboratory scale, certain compounds (and their tabulated data) can be employed, but
the results are questionable due to the various levels of the tabulated data accuracy.
Thus it seems be recommendable to use the sets of solid solutions because they are
likely to exhibit comparable degree of uncertainty (such as Na2CO3–CaCO3 or
BaCO3–SrCO3 or various sesquioxides mixtures like manganese spinels) [3]. How-
ever, the use of the Joule heat effect from a resistance element on passage of electric
charge is a preferable method for achieving a more ‘absolute’ calorimetric calibration.
It certainly requires special set-ups of the measuring head enabling the attachment of
the micro-heater either on the crucible surface (similarly to DSC) and/or by direct
immersing it into the mass of (often powdered) sample. By combination of both
experimental methods (i.e., substance’s enthalpies and electric pulses) rather benefi-
cial results [87] may be obtained, particularly, when a pre-selected amount of Joule
heat is electronically adjustable (e.g., simple selection of input voltage and current
pairs) [3, 34]. It was only a pity that no commercial producer, neither an ICTAC
committee, have ever became active in their wider application.
21.5 Modulated Temperature, Exploration of Constrained

and Nano-Crystalline States, Perspectives
Yet another type of thermal measurement that had an early beginning, but initially did
not see wide application, is the alternating current (AC) calorimetry [79, 88]. Advan-
tage of this type of measurement lies in the application of a modulation to the sample
temperature, followed by an analysis of responses. By eliminating any signal that does
not correspond to the chosen operating frequency, many of the heat-loss effects can be
abolished. Furthermore, it may be possible to probe reversibility and potential fre-
quency-dependence of changes of the studied sample. The heat capacity Cs of the
sample can be determined from the ratio of the heat-flow response of the sample,
represented by its amplitude AHF, to the product of the amplitude of the sinusoidal
sample-temperature modulation ATt and the modulation frequency o ¼ 2p/p (p being
the period). The next advancement in calorimetry occurred in 1992 with the amal-
gamation of DSC and temperature modulation to the temperature-modulated DSC
(TMDSC) [79, 89–91]. In this quasi-isothermal operation, sample temperature TS

oscillates about the underlying temperature T0 (constant/increasing) similarly as in an
AC calorimeter (which bears an analogy modulus of a familiar isothermal dynamic
mechanical analysis – DMA). The ensuing phase lag, e, is taken relative to a reference
oscillation, TS ¼ T0 + ATt sin (ot – e), and by deconvolution of the two signals; an
average signal, practically identical to the standard DSC output and a reversing signal,
related to the AC calorimetry. There, however, are additional factors necessary for
consideration because of the peculiarity of twin calorimeter configuration, such as
there is no thermal conductance between the sample and reference calorimeters, zero
temperature gradients from the temperature sensors to the sample and the reference
pans, and, also, zero temperature gradients within the contents of the pans. In other
words, an infinite thermal conductance between temperature sensors and the
corresponding calorimeters should be assumed. In summary, three directions of
calorimetry were, thus, combined in the twentieth century, which dramatically
changed the capabilities of thermal analysis of materials [79]: The high precision of
adiabatic calorimetry, the speed of operation and small sample size of DSC, and the
possibility to measure frequency dependence of thermal behavior in AC calorimetry.
Another reason for both the modulation mode and the high-resolution of temper-
ature derivatives is the fight against ‘noise’ in the heat flow signal in temperature
swinging modifications. Instead of applying a standard way of eliminating such
noise (and other unwanted signal fluctuations) by a more appropriate tuning of an
instrument, or by intermediary measurements of the signal in a preselected distinct
window, the fluctuations can be forcefully incorporated in a controlled and regulated
way of oscillation. Thus the temperature oscillations (often sinusoidal) are located to
superimpose over the heating curve and thus incorporated in the entire experimen-
tation (temperature-modulated DTA/DSC) [89]. This was, in fact, preceded by the
method of so-called periodic thermal analysis introduced by Proks as early as in
1969 [92], which aimed at removing the kinetic problem of ‘undercooling’ by
cycling temperature. Practically the temperature was alternated over its narrow
range and the sample investigated was placed directly onto a thermocouple junction
until the equilibrium temperature for the coexistence of two phases was attained.
Another way of a more clear-cut investigation was introduction of micro-analysis
methods using very small samples and millisecond time scales [93, 94]. It involved
another peculiarity of truthful temperature measurements of nano-scale crystalline
samples [95] in the particle micro range with radius r. The measurement becomes
size affected due to increasing role of the surface energy usually described by an
universal equation: Tr/T1 ffi (1 – C/r) p where 1 portrays standard state and C and
p are empirical constants (0.15 nm < C < 0.45 nm and p ¼ 1 or ½) [96–98].
Measurement in such extreme conditions brings extra difficulties such as mea-
suring micro-porosity [99], quenching [94] and associated phenomena of the sample
constrained states [64–68], variability of polymeric macromolecules [100, 101]
together with non-equilibrating side effect or competition between the properties
of the sample bulk and its entire surface [97] exposed to the contact with the cell
holder [34]. Increasing instrumental sophistication and sensitivity provided possi-
bility to look at the sample micro-locally [93, 101–103] giving a better chance to
search more thoroughly toward the significance of baselines, which contains addi-
tional but hidden information on material structure and properties (inhomogeneities,
local nonstoichiometry, interfaces between order–disorder zones [104]). Popular
computer built-in smoothing of the noised experimental traces (chiefly baselines)
can, however, become counterproductive.
In the future, we may expect certain refining trends possible returning to the
original single-sample set-ups with recording mere heating/cooling curves. How-
ever, it will happen at the level of fully computerized thermal evidence involving
self-evaluation of ‘calibration’ behavior of the sample thermal inertia and its
subtraction from the entire thermal record in order to proliferate thermal effects
possibly computing the DTA-like records. In addition, it may even incorporate the
application of an arbitrary temperature variation enabling the use of self-heating
course by simple placing the sample into the preheated thermostat and consequent
computer evaluation of standardized effects or hitherto making possible to intro-
duce fast temperature changes by shifting the sample within the temperature
gradient of a furnace [3, 34], etc. Worth noting are special trends [105] particularly
based on the modified thermophysical procedure of the rate controlled scope of
thermal analysis (RCTA) [106] and/or on the diffusion structural diagnostics as a
result of suitably labeled samples [107].
Upcoming prospect of thermal analysis scheme may go down to the quantum
world [108] as well as may extend to the global dimension [109] touching even the
remote aspects of temperature relativity [110], which, however, would become a
special dimension of traditional understanding yet to come.
21.6 Some Issues of Socially Shared Activity, Thermoanalytical

and Calorimetric Journals and Societies
The historical development and practical use of DTA in the middle European
territory of former Czechoslovakia [33] was linked with the names Otto Kallauner
(1886–1972) and Joseph Matějka (1892–1960) who introduced thermal analysis as
the novel technique during the period of the so called “rational analysis” of ceramic
raw materials [111] replacing the process of decomposition of clay minerals by
digestion with sulphuric acid, which factually played in that time the role of
the contemporary X-ray diffraction. They were strongly affected by the work of
H. Le Chatelier [38] and their visits at the Royal Technical University of Wroclaw
(K. Friedrich, B. Wohlin) where the thermal behavior of soils (bauxite) was
investigated during heating and related thermal instrumentation was elaborated.
Calorimetric proficiency was consequently gained from Polish Wojciech Świe˛to-
sławski (1881–1968). Much credit for further development of modern thermal
analysis was attributed with Rudolf Bárta (1897–1985) who stimulated thermal
analysis activity at his coworkers (Vladimı´r Šatava, Svante Procházka or Ivo Proks)
and his students (Jaroslav Šesták) at the Institute of Chemical Technology (domes-
tic abbreviation VŠChT) in Prague.
In this aspect a special notice should be paid to the lengthy efforts, long journey
and fruitful service of International Confederation of Thermal Analysis (ICTA and
Calorimetry – ICTAC, instituted later in the year 1992 and facilitated by G. Della
Gatta) as an important forerunner and developer in the field of thermal analysis, cf.
Fig. 21.2. It has an important preceding history [6, 112, 113] connected with the
former Czechoslovakia and thermoanalytical meetings organized by R. Bárta just
mentioning the earliest first Conference on DTA, (Prague 1956), the Second (Prague
1958) and the Third Conference on Thermography (Prague 1961) and the Forth
Conference on DTA (Bratislava 1966). Robert C. Mackenzie (1920–2000) from
Scotland was an invited guest at the 1961 meeting and upon the previous communi-
cation with Russian L.G. Berg and US P.D. Garn as well as Hungarian L. Erdey an
idea for the creation an international society was cultivated aiming to enable easier
contacts between national sciences, particularly across the separating ‘iron curtain’,
which in that time divided the East and West Europe [6]. The first international
conference on thermal analysis was then held in the Northern Polytechnic in
London, April 1965 and was organized by British scientists namely B.R. Currell,
D.A. Smith, J.P. Redfern, W. Gerrard, C.J. Keattch and D. Dollimore with a help of
R.C. Mackenzie, B. Stone and US professors P.D. Garn and W.W. Wendlant,
Canadien H.G. McAdie, French M. Harmelin, Hungarian L. Erdey, Japanese
T. Sudo, Swedish G. Berggrenn and Italian G. Lombardi. Some invited speakers
from the East Europe were particularly asked to come to bridge then existing tough
political control on physical, freedom and civil frontiers strongly restricting the
human rights of the Easterners (dominated by Soviet Union until the late 1980s),
such as F. Paulik (Hungary) and J. Šesták (Czechoslovakia). The consequent ICTA
foundation in Aberdeen, September 1965, was thus established by these great
progenitors of thermal analysis, Russian Lev G. Berg being the first ICTA presidents
(with the councilors J.P. Redfern, R.C. Mackenzie, R. Bárta, S.K. Bhattacharrya,
C. Duval, L. Erdey, T. Sudo, D.J. Swaine, C.B. Murphy, and H.G. McAdie).
The progress of thermal analysis was effectively supported by the allied founda-
tion of international journal, which editorial board was recruited from the key-
speaker of both 1965 TA conferences as well as from the renowned participants at
the second ICTA in Worcester (USA 1968). In particular it was Journal of Thermal
Analysis, which was brought into being by Judit Simon (1937-, who has been serving
as the editor-in-chief until today) and launched under the supervision Hungarian
Academy of Sciences (Akadémiai Kiadó) in Budapest 1969 (L. Erdey, E. Buzagh,
F. and J. Paulik brothers, G. Liptay, J.P. Redfern, R. Bárta, L.G. Berg, G. Lombardi,
R.C. Mackenzie, C. Duval, P.D. Garn, S.K. Bhattacharyya, A.V. Nikolaev, T. Sudo,
D.J. Swaine, C.B. Murphy, J.F. Johanson, etc.) to aid preferably the worthwhile East
European science suffering then under the egregious political and economic condi-
tions. Secondly it came to pass Thermochimica Acta that appeared in the year 1970
by help of Elsevier [114] and, for a long time, edited by Wesley W. Wendlandt
(1920–1997) assisted by wide-ranging international board (such as B. R. Currell,
T. Ozawa, L. Reich, J. Šesták, A. P. Gray, R. M. Izatt, M. Harmelin, H. G. McAdie,
H. G. Wiedemann, E. M. Barrall, T. R. Ingraham, R. N. Rogers, J. Chiu, H. Dichtl,
P. O. Lumme, R. C. Wilhoit, etc.).
The field growth lead, naturally, to continuous series of the US Calorimetry

Conferences (CalCon) [115–117], which supposedly evolved from a loosely knit
group operating in the 1940s to a recent highly organized assembly working after the
1990s. Worth mentioning are Hugh M. Huffman (1899–1950) and James
J. Christensen (1931–1987), whose names were recently used to shield the CalCon
Awards presented annually for achievements in calorimetry. There is a number of
other respectable cofounders, (let us point out D.R. Stull, G. Waddington, G.S.
Parks, S. Sunner, F.G. Brickwedde, E.F. Westrum, J.P. McCullough, D.W. Osborne,
W.D. Good, P.A.G. O’Hare, P.R. Brown, W.N. Hubbart, R. Hultgren, R.M. Izatt, D.
J. Eatough, J. Boerio-Goates, J.B. Ott). It provided a good example how the
democracy-respecting society changing their chairmanships every year, which,
however, did not find a place in the statutes of later formed ICTA (with its 4-years
period and its unfortunate consequence of the 15 years of personality cult having
been in effect at the turn of twenty-first century). Consequentially, the Journal of
Chemical Thermodynamics began publication in the year 1969 firstly edited by
L.M. McGlasham, E.F. Westrum, H.A. Skinner and followed by others. More details
about the history and state-of-art of thermal science and the associated field of
thermal analysis were published elsewhere [3–6, 32–35, 79, 112, 113, 115–117].
A specific domain of thermal analysis worth of attention (but laying beyond this
file) is the weight measurement under various thermal regimes, pioneered by Czech
Stanislav Škramovský (1901–1983) who coined the term ‘statmograph’ (from Greek
stathmos ¼ weight) [1, 6, 35], which, however, was overcome by the generalized
ä
Fig. 21.2 Portraits show some influential personalities on the international scene, which are
noteworthy for their contributions to the progress of the fields of thermal analysis (TA) and
calorimetry including the founders of ICTA/ICTAC (around the inserted emblem), living persons
limited to age above 75. Upper from left: Cornelius B. Murphy (1918–1994), USA (TA theory);
Robert C. Mackenzie (1920–2000), Scotland (DTA, clay minerals, history); Sir William C.
Roberts-Austen (1843–1902), England (thermoelectric pyrometer); Gustav H.J. Tammann
(1861–1938), Germany (inventing the term thermal analysis) and Nikolaj S. Kurnakov
(1860–1941), Russia (contriving the first usable DTA); below: Lev G. Berg (1896–1974), Russia
(TA theory); Rudolf Bárta (1897–1985), Czechoslovakia (ceramics, cements); Walther H. Nernst
(1864–1941), Germany (originating low-temperature calorimetry); Edouard Calvet (1895–1966),
France (heat-flow caolrimetry) and Henry L. Le Chatelier (1850––1936), France (devising
thermocouple); yet below: David J. Dollimore (1927–2000), England (later USA – theory,
kinetics); Hugh M. Huffman (1899–1950), USA, founder of CalCon; James J. Christensen
(1931–1987), USA (calorimtery); Wojciech Świe˛tosławski (1881–1968), Poland (calorimetry);
Čenk Strouhal (1850–1922), Czechoslovakia (thermics, Strouhal numbers); yet below: Hans-
Joachim Seifert (1930–), Germany (phase diagrams); Takeo Ozawa (1932–), Japan (energetic
materials, kinetics); Eugene Segal (1933–), Romania (kinetics); Hiroshi Suga (1930–), Japan
(calorimetry) and Giuseppe Della Gatta (1935–), Italy (calorimetry); yet below: Wesley W.
Wendlandt (1920–1997), USA (TA theory, instrumentation); Bernhard Wunderlich (1931–),
USA (macromolecules, modulated TA); Paul D. Garn (1920–1999), USA (TA theory, kinetics);
Jean-Pierre E. Grolier (1936-), France (calorimetry) and Ole Toft Sørensen (1933-), Denmark
(CRTA, non-stoichiometry); Bottom: Cyril J. Keattch (1928–1999), England (thermogravimetry);
Hans G. Wiedemann (1920–), Switzerland (TG apparatuses, instrumentation); Shmuel Yariv
(1934–), Israel (earth minerals); Joseph H. Flynn (1922–), USA (DSC, kinetics) and Patrick K.
Gallagher (1931–), USA (inorganic materials)
Fig. 21.3 Recognized pioneers of thermal analysis, of Hungarian origin, who were accountable for
the development of instruments (popular East-European TA apparatus “derivatograph”) – Ferenc
Paulik (1922–2005), right, and for initiation of fingerprint methodology (multivolume atlas of TA
curves by Akademia Kiado) – Geörge Liptay (1931–), left
Fig. 21.4 The photo from 28th conference of the Japanese Society on Calorimetry and Thermal
Analysis (JSCTA) in Tokyo (Waseda University, 1992) shows (from left) M. Taniguchi (Japan),
late C.J. Keattch (GB), late R. Otsuka (Japan), S. St. J. Warne (Australia, former ICTA president),
H. Suga (Japan), J. Šesták (Czechoslovakia) and H. Tanaka (Japan). The regular JSCTA confer-
ences started in Osaka 1964 under the organization of S. Seki who became the first president when
the JSCTA was officially established in 1973. Since then, the JSCTA journal NETSU SOKUTEI
has been published periodically
expression ‘thermogravimetry’ as early introduced by French Cle´ment Duval

(1902–1976) or Japanese Kotaro Honda (1870–1954) [33–35, 118–121]. Conse-
quently, it yielded a very popular topic of simultaneous weight-to-caloric
measurements under so called quasi-isothermal and quasi-isobaric conditions [35,

122] making use of the apparatus ‘derivatograph’, see Fig. 21.1, originated in
Hungary in late 1950s [122], see Fig. 21.3. It apparently lunched an extended field
of microbalance exploitation and their presentation in regular conferences [123].
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Index
A stability
Absolute temperature scales, 336 fragile, 305
Adiabatic calorimeter, 97 Hruby coefficient, 303
Amorphates, 137–138 kinetic property, 304
Amorphous chalcogenides Block copolymers, 124–125
dynamic viscosity, 171–173 Borate glasses, 189
kinematic viscosity, 174–175 Brittle point. See Glass transitions
Anhydrates and hydrates, 133–134 Brownian motion, 239–242
Apparent activation energy, 217–221
Applications
emanation thermal analysis C
brannerite, thermal behaviour, Capillary method (C), 166–167
266–269 Carnot’s theorem and Kelvin’s proposition
thermal stability, 263 caloric gauge, 339
zircon, thermal behaviour, 264–265 cyclic and reversible process, 338
scanning transitiometry energy balance equation., 337
food science, 286 Joule–Mayer’s Principle, 340–341
petroleum industry, 276–278 thermodynamic gauge, 340
polymer science, 279–285 Chalcogenide glass-forming systems, viscosity
Arrhenius behaviour, 9 measurements
Artificial state, biological glasses amorphous
cooling and warming rate, 298–300 dynamic viscosity, 171–173
dehydration, 300–301 kinematic viscosity, 174–175
desiccation definition, 165
glass transition temperature, 301 measuring methods
temperature and dehydration beam-bending method (BB), 170
conditions, 301–302 capillary method (C), 166–167
Atkinson-normal-growth (ANG)-type Eisenberg method (EM), 170
crystallization, 69 falling sphere method (FS), 167
low-temperature torsion viscometer
(LV), 170
B magnetic bearing torsional creep
BB method. See Beam-bending method method (TC), 170
Beam-bending method (BB), 170 parallel-plate method (PP), 169
Biodiversity long-term storage, 306 penetration method (P), 169
Biological glasses rod elongation (RE), 168
glass transition, 303, 304 rotating cylinder method (RC),
methods, 302 167–168
371
372 Index
torsion oscillating cup method (TOC), dynamic DSC (DDSC), 144

168 of Jeffamine ED2003, 121–122
Chalcogenide glasses of nanophase separated polyurethane
differential scanning calorimetry (DSC), networks, 125, 126
142–143 of poly(vinylmethylether), 120–121
glass transition of polyethylenes, 280
conventional DSC, 143 polystyrene and PMMA blends, 123–124
description of, 153–159 StepScan DSC, 145, 146
dynamic DSC (DDSC), 144 temperature modulated DSC (MDSC), 144,
enthalpic relaxation, 146–153 145
heat rate dependencies, 145, 146 Diffusion and stochastic quantum mechanics,
modelling, 159–162 234–236
StepScan DSC, 145, 146 DIL. See Dilatometry
temperature modulated DSC (MDSC), Dilatometry (DIL), 84
144, 145 Disordered states, 61
optical properties, 141 DMTA. See Dynamic mechanical thermal
Cocrystals, 135–137 analysis
Constrained states, plants Double non-stationary resembling calorimeter,
artificial state, biological glasses 357
cooling and warming rate, Drug formulation, 133–134
298–300 DSC. See Differential scanning calorimetry
dehydration, 300–301 Dynamic DSC (DDSC), 144
desiccation, 301–302 Dynamic mechanical thermal analysis
biodiversity long-term storage, 306 (DMTA), 84
biological glasses
measurements, 302–303
stability, 303–306 E
glass forming components Ehrenfest first order transitions, 107
carbohydrates, 295–298 Eisenberg method (EM), 170
proteins, 298 Emanation rate, 262
supercooled water, 294–295 Emanation thermal analysis, diffusion
water properties structural diagnostics
excessive dehydration, protoplast, application
292–293 brannerite, thermal behaviour,
extra-organ freezing, 293 266–270
fractal dimension, 291 thermal stability, 263
freezing process, 292 zircon, thermal behaviour, 264–265
vitrification, 293 quasi-permanent source, 261
Continuous belt-running method, 72 radon atoms implantation, a-decay recoil
Conventional DSC, 143 energy, 261–262
CRS. See Crystalline reference state radon release mechanisms, 262–263
Cryo-preservation, 17 Enthalpy relaxation
Crystalline reference state (CRS), 180 DSC curves, 149
Curie-Weiss behaviour, 212, 213 equilibrium enthalpy, 151, 152
Cyclohexanol, 11, 12 glass transition, 146–148
model, 148–149
multiphase structure, 123
D non-exponentiality parameter b, 150, 151,
Darcy’s law, 229–230 153
Deborah number, 15 Perkin–Elmer Pyris 1 DSC calorimeter, 149
Differential scanning calorimetry (DSC), polymers, 117
142–143 qualitative concept, 150, 151, 153
conventional DSC, 143 relaxation temperature, 149, 150, 153
Index 373
structure-breaking/structure-forming conventional DSC cooling scan, 157,

process, 9 158
Equilibrium enthalpy, 151, 152 fictive-thermodynamic temperature
Equilibrium viscosity, 217, 218 relation, 156, 157
Ethanol, 11, 13 heating rate dependence, 155
kinetic heat flow, 158, 159
StepScan DSC, 154
F dynamic DSC (DDSC), 144
Falling sphere method (FS), 167 enthalpic relaxation
Fick’s law, 232–234 DSC curves, 149
Fourier’s law, heat transfer, 227–229 equilibrium enthalpy, 151, 152
Fragile liquids, 22, 30, 36 glass transition, 146–148
Frozen-in disordered states, 2, 3, 10, 15, 17 model, 148–149
FTMT-EC treatment, 246, 247, 256 non-exponentiality parameter b, 150,
151, 153
Perkin–Elmer Pyris 1 DSC calorimeter,
G 149
Gibbs free energy, 118–120 qualitative concept, 150, 151, 153
Glass forming components relaxation temperature, 149, 150, 153
carbohydrates entropy contributions
cryopreservation, 296 molecular polarizability, 48
glass transition temperature, 296 Vogel’s temperature, 47
MFCP, 297 glassy crystals
schematic state diagram, sucrose anisotropic liquids, 11–12
solution, 296–297 CO and H2O crystals, 14–15
proteins, 298 cyclohexanol crystal, 11, 12
supercooled water Deborah number, 15
heat capacity, 294 dielectric and enthalpy relaxations,
homogeneous freezing point, 295 10–11
Glass transition temperature, 43 ethanol, 11, 13
elastomers, high pressure temperature, 13
amplitude, 281 heat capacity, 108
scanning transitiometry technique, heat capacity and entropy functions,
281–282 33–35
thermomechanical coeffcients, 280 heat rate dependencies, 145, 146
polystyrene, high pressure methane, 282 Kauzman paradox, 109
shift, high pressure gases linear cooperative phenomena
blowing effect, 283 alpha and beta slow processes,
mass fraction, 284 52–54
plasticization, 283 block time characteristic, 48–49
variation with pressure, 284, 285 molecular polarizability, critical
Glass transitions volume, 52
conventional DSC, 143 N-element estimation, built-in blocks,
critical temperature 49–51
crossover temperature, 43 local heterogeneity, 47
Debye-Waller factor, 45 modelling
glassy state formation, 46 normalized reversible parts, 160, 161
MCT, 41 steepness parameter, 161, 162
medium range structure, 41–42 rigid-amorphous fraction (RAF), 110
non-linear oscillators, 46 StepScan DSC, 145, 146
voids, definition, 41 temperature (see Glass transition
description of temperature)
374 Index
Glass transitions (cont.) states of aggregation of molecules,

temperature modulated DSC (MDSC), 144, 17–18
145 Glykosylated derivatives, 137
Glass viscosity
Angell’s steepness and fragility parameter
relation, 221, 223 H
apparent activation energy, 217–221 Heat capacity
equilibrium viscosity, 217, 218 cyclohexanol, 11, 12
mean jump frequency, 219–223 ethanol, 11, 13
non-equilibrium viscosity, 221–223 of isopropylbenzene, 6, 7
preexponential constant, 223–224 Heat capacity and entropy functions
Glassforming liquids, heat capacity of, 21–22 changeover of, above glass transition,
excess entropy and heat capacity, 29–30 35–37
SiO2, 28–29 CoFe alloy vs.silicate glass, 33
thermodynamic fragility plot, 30–31 glassforming liquids, 21–22
water in normal, supercooled liquid and excess entropy and heat capacity,
glassy states, 31–32 29–30
Glassy solids SiO2, 28–29
amorphous ice, 16–17 thermodynamic fragility plot, 30–31
character of water in normal, supercooled liquid and
ergodicity, 2 glassy states, 31–32
exotic formation of, 2 ionic conductivity in potassium iodide, 23, 24
glass products, 1 of 1-pentene, 21, 22
glass transition measurement, 1–2 of C60, order-disorder transition, 26
molecular assembly, 2–3 of Jagla model, 34
characterization of plastic crystal properties, 27, 28
enthalpy relaxation, 9 relaxation times, ionic crystal rotator
fragility, 9 phases, 23, 25
glass transition temperature, 5–6 two-state excitations model, 23
heat capacity and entropy, Heat treatment
isopropylbenzene, 6–7 electrical resistivity, 251–253
Kohlrausch–Williams–Watts equation, experiment and method, 247–248
7 in-situ X-ray diffraction results
non-exponential relaxation, 7 integrated intensity, 253, 254
thermal analysis, 5 peak position evolution, 254, 255
vibrational heat capacity, 9–10 Heavily cold drawn nanocrystalline Ni-Ti
viscosity, 8 wires
Vogel–Tammann–Fulcher (VTF) B2-R transformation, 258
equation, 8–9 electrical resistivity, 251–253
cryo-preservation of biological substances, electron diffraction patterns, 245, 246
17 experiment and method
glass transitions heat treatment, 247–248
anisotropic liquids, 11–12 synchrotron X-ray diffraction, 248–251
CO and H2O crystals, 14–15 FTMT-EC treatment, 246, 247, 256
cyclohexanol crystal, 11, 12 in-situ X-ray diffraction results, 253–255
Deborah number, 15 lattice recovery processes, 256, 257
dielectric and enthalpy relaxations, microstructures, 245, 246, 255–256
10–11 shape memory alloys (SMA), 245–246
ethanol, 11, 13 tensile stress, 258
temperature, 13 tensile stress-strain response, 245, 246
preparation High-density amorphous (HDA) ice, 16
chemical methods, 5 Hotness manifold and temperature, 333–335.
methods of, 3–5 See also Thermal physics concepts
Index 375
I Medium range order (MRO), 199

Ideal gas temperature scale, 336 MFCP. See Maximum freeze concentrated
Ionic conductivity, 23, 24 phase
Islands-of-mobility, 53 Mode coupling theory (MCT), 41
Isoperibolic twin-calorimeters, 357 Modulated structure, 62
J N
Jeffamine ED2003, 121–122 Nano-crystalline splat-quenched (Fe,
Johnson–Mehl–Avrami–Yerofeev– Mn)2O3–B2O3
Kolmogorov (JMAYK)-type of borate glasses, 206–207
nucleation growth, 69 DTA curves, 209, 210
DTA data, 211
extrapolated temperature, 209
K glass-forming abilities, 209–210
Kohlrausch–Williams–Watts equation, 7 magnetic interactions strength, 211–212
moment-related properties, 208
unconventional glasses properties, 207
L Nanocrystallinity
LCST. See Lower critical solution temperature artificial and natural disordered materials
Lechatelierite, 60 melt-cooling processes, 60
Liesegang’s rings, 236, 237 methods, 61
Linear cooperative phenomena quenching, 59
alpha and beta slow processes freeze-in process
diffusion displacements, 52 continuous belt-running method, 72
relaxation time, 53 fast-quenching device, 71
standard Arrhenius relation, 54 heat transfer coefficient, 70
N-element estimation, built-in blocks surface laser glazing, 71
crossover temperature, 51 twin roll technique, 72
shear elasticity, 50 noncrystalline chalcogenide materials,
shear viscosity, 49 63–64
Liquid-cooling method, 3 pressure and temperature-induced
Liquids amorphization
definition, 93 compressive amorphization, 64
glass transitions, 94 superstrong liquid, 65
Low-density amorphous (LDA) ice, 16 thermobaric amorphization, 64
Low-temperature torsion viscometer (LV), 170 Vogel–Fulcher–Tammann–Hesse
Lower critical solution temperature (LCST), (VFTH) parameter viscosity
120, 121 relation, 65
LV. See Low-temperature torsion viscometer structural features
diffusional-driven ordering process, 63
glass-formation, 61
M medium-range order, 62
Magnetic bearing torsional creep method (TC), short-range order, 63
170 vitrification vs. crystallization
Maximum freeze concentrated phase (MFCP), ANG-type, 69
297 enthalpy vs. temperature, 67–68
Maximum in the loss tangent. See Glass JMAYK-type, 69
transitions Nanophase separation, polymers, 125–126
MCT. See Mode coupling theory Nernst–Brunner kinetics, 236
Mean jump frequency, 219–223 Non-bridging oxygen (NBO)
Mechanical alloying, 4 continuous random network model (CRN),
Mechanical milling, 4 200
376 Index
Non-bridging oxygen (NBO) (cont.) NBO concept, 205

medium range order (MRO), 199 properties, 203
short range order (SRO), 199 structural unit concentration, 203–204
ternary system, 202 speromagnetic behaviour, (Fe,Mn)2O3–(B,
zero interconnected web state, 201 Bi)2O3, 212–214
Non-crystalline solids, amorphous stoichiometry
aggregation of molecules, 17–18 borate glasses, 189
character of, 1–3 silicate glasses, 187–189
cryogenic storage, 17 structure of, 185–187
glass transitions, glassy crystals, 10–15 thermodynamic glass models, 189–192
ice, 16–17 thermodynamic modelling, 192–195
preparation and characterization of, 3–10
Non-crystalline splat-quenching. See Nano-
crystalline splat-quenched (Fe, P
Mn)2O3–B2O3 PALS. See Positron annihilation lifetime
Non-equilibrium viscosity, 221–223 spectroscopy
Parallel-plate method (PP), 169
PASCA, 47
O Peltier cooling effect, 356
Ohm’s law, 230–232 Penetration method (P), 169
Oxide glasses Periodic reactions, 236–237
Curie-Weiss behaviour, 212, 213 Periodic thermal analysi, 359
glass formation, thermodynamics Perkin–Elmer Pyris 1 DSC calorimeter, 149
crystalline reference state (CRS), 180 Pharmaceutical molecules, solid forms
definition, 179–180 amorphates, 137–138
linear depandence slopes, 180, 181 anhydrates and hydrates, 133–134
thermal expansion coefficient, chemical and physical types, 129, 130
182–183 cocrystals, 135–137
thermodilatometric cooling curve, drug formulation, 133–134
181, 182 future of, 139
thumb rules, 184–185 glykosylated derivatives, 137
magnetic properties, (Fe,Mn)2O3–B2O3 parameters, 129, 130
borate glasses, 206–207 polymorphous transitions, 131, 132
DTA curves, 209, 210 polymorphs, 130–132
DTA data, 211 ROY molecule, 131
extrapolated temperature, 209 salts, 134–135
glass-forming abilities, 209–210 Phases of amorphous, crystalline and
magnetic interactions strength, intermediate order
211–212 amorphous defects, 95
moment-related properties, 208 glass transitions
unconventional glasses properties, 207 heat capacity, 108
non-bridging oxygen (NBO) Kauzman paradox, 109
continuous random network model rigid-amorphous fraction (RAF), 110
(CRN), 200 heat capacity, solids
medium range order (MRO), 199 bovine a-chymotrypsinogen type II
short range order (SRO), 199 protein, 103–104
ternary system, 202 skeletal vibrations, 102
zero interconnected web state, 201 vibrational spectrum, 101
quantitative Raman spectroscopy, 192–195 large amplitude motion
silicate glasses, ionic sites volume hole model, 105
alkali borate glasses compositions, 206 intramolecular conformational rotation,
field strength, 204 105
magnetic cations, 206 translational degrees of freedom, 104
Index 377
mesophases, 97 supermolecular structures, 81

microphase formation, 95 Polymers
nanophase vs. microphase, 96 block copolymers, 124–125
ordering phase transitions nanophase separation in, 125–126
Ehrenfest first order transitions, 107 polymer chain and random walk, analogy
free enthalpy, 106, 108 of, 116
integral calorimetric functions, 105–106 solutions and blends
nonequilibrium thermodynamics, 107 binodal and spinodal lines, 118
solid equilibrium crystal, 108 DSC scans, poly(vinylmethylether),
solids and liquids 120–121
definition, 93 Gibbs free energy, 118–120
glass transitions, 94 Jeffamine ED2003, phase diagram of,
thermal properties 121, 122
differential calorimeter, 98 thermal behaviour, PS and PMMA,
DSC vs. TMDSC, 100 123–124
heat capacity, 97 thermograms, Jeffamine ED2003, 121,
reversing temperature, 99 122
Phenomenological conjugate variables and upper critical solution temperature
thermal equilibrium (UCST), 117–118
adiabatic partition, 330 thermal analysis, 115
correlation test, 329 thermal properties of amorphous,
diathermic partition, 329–330 116–117
empirical constitutive relations, 328 Polymorphous transitions, 131, 132
energy balance equations, 329 Polymorphs, 130–132
equilibrium state, 330 Polystyrene (PS), 123–124
local empirical temperature scale, 331 Positron annihilation lifetime spectroscopy
principle of indifference, 331 (PALS), 84
PMMA. See Poly(methylmetacrylate) PP method. See Parallel-plate method
Poly(butadiene) diol (PBD), 125, 126 Precious opal
Poly(methylmetacrylate) (PMMA), 123–124 Coober Pedy white play-of-colour,
Poly(oxypropylene) triol (POPT), 125, 126 317–318
Polymer networks, 125–126 origin, 317
Polymer physics, thermal analysis sol-gel mechanism, 319
calorimetry thermophysical properties
definition, 78 a– b cristobalite transition, 321
DSC traces, 79–80 thermal expansion, 314, 320
heat capacity, 81 water characterisation, 320–321
morphology, 80 volcanic opal, 319
types of, 78 weathering model, 319
DIL and PALS Preexponential constant, 223–224
local relaxations, 84 Principle of indifference, 331
volume relationship, 82–83 Proteins, 17
DMTA, 84 Pumice, 60
structural relaxations and glass transition
temperatures, 88–89
supermolecular structure Q
crystallites formation, 85–86 Quantitative phase analysis, 250, 251
phase situation, 85–86 Quantitative Raman spectroscopy, 192–195
SAXS, 84 Quantum diffusion, 236–237
three-phase model, 87 Quantum resemblance, 239–242
WAXS, 84
thermogravimetry
membranes, 81–82 R
378 Index
Radon atoms implantation, a-decay recoil Stoichiometry, oxide glasses

energy, 261–262 borate glasses, 189
Radon release mechanisms, 262–263 silicate glasses, 187–189
Rate controlled scope of thermal analysis Strong liquids, 29, 36
(RCTA), 360 Synchrotron X-ray diffraction
RC method. See Rotating cylinder method electric power pulse and X-ray
RCTA. See Rate controlled scope of thermal measurements, 249, 250
analysis quantitative phase analysis, 250, 251
RE. See Rod elongation treatment setup, 248, 249
Relaxation temperature, 149, 150, 153
Rod elongation (RE), 168
Rotating cylinder method (RC), 167–168 T
ROY molecule, 131 TC method. See Magnetic bearing torsional
creep method
Tektites
S characteristic surface corrosion, 315
Salts, 134–135 origin, 314–315
SAXS. See Small angle X-ray scattering thermophysical properties
Scanning transitiometry cooling rates, 316–317
applications fictive temperature, 316
food science, 286 micrograph, moldavite, 317, 318
petroleum industry, 276–278 thermal expansion coefficient, 316
polymer science, 278–285 Temperature-modulated DSC (MDSC),
bulk properties, 272 144, 145
calorimetry, 273 Temperature-modulated differential scanning
cooking extrusion, 272 calorimeter (TMDSC), 97
starch, 272 Ternary system, NBO, 202
thermodynamic scheme, 273 Theory of capillarity, 95
thermophysical properties, 275 Thermal analysis
transitiometer, 273–275 aim and principles, 347
Shape memory alloys (SMA), 245–246 caloric theory
Short range order (SRO), 199 Fourier law, 351
Silicate glasses, 187–189 motive power, 349–350
Silicate glasses, ionic sites volume thermal energy, 350
alkali borate glasses compositions, 206 thermal resistance, 351
field strength, 204 constrained and nano-crystalline states
magnetic cations, 206 alternating current (AC) calorimetry,
NBO concept, 205 358
properties, 203 RCTA, 360
structural units concentration, early scientific and societal parentage
203–204 freezing-in, 353
Small angle X-ray scattering (SAXS), 84 Newton’s law, 354
Softening point. See Glass transitions thermocouple, 352
Solids thermoelectric pyrometer, 352–353
definition, 93 latent heat, 348
glass transitions, 94 polymer physics (see Polymer physics,
heat capacity thermal analysis)
bovine a-chymotrypsinogen type II quantitative thermometric and calorimetric
protein, 103–104 measurement.
skeletal vibrations, 102 diathermal arrangement, 356
vibrational spectrum, 101 inertia term, 357
Speed of diffusion, 237–239 Joule heat effect, 358
StepScan DSC, 145, 146 microheater, 356
Index 379
quasi-isothermal calorimeters, 356 sol-gel mechanism, 319

rational analysis, 360 thermal expansion, 314, 320
thermogravimetry, 364 volcanic opal, 319
thermoscope, 348 water characterisation, 320–321
Thermal physics concepts weathering model, 319
Carnot’s theorem and Kelvin’s proposition T-t plot, glass-forming processes, 312
caloric gauge, 339 tektites
cyclic and reversible process, 338 characteristic surface corrosion, 315
energy balance equation., 337 cooling rates, 316–317
Joule–Mayer’s principle, 340–341 fictive temperature, 316
thermodynamic gauge, 340 micrograph, moldavite, 317, 318
distant measurement problem, temperature origin, 314–315
Lorentz invariant, 343–344 thermal expansion coefficient, 316
operational rules, 342 thermal expansion curves, 313–314
elementary set theory, 327 Thread-pull temperature. See Glass transitions
fixed thermometric points, Mach’s Tian-Calvet calorimetry, 356
postulates, 331–333 Time-resolved small-angle X-ray scattering
hotness manifold and temperature, 333–335 (SAXS), 125, 126
Kelvin’s temperature scale TOC method. See Torsion oscillating cup
anthropomorphic principle, 335 method
Nernst law, 336 Torsion oscillating cup method (TOC), 168
phenomenological conjugate variables and Transitiometric traces, starch-water
thermal equilibrium suspension, 286–287
adiabatic partition, 330 Transport constitutive relations
correlation test, 329 Darcy’s law, 229–230
diathermic partition, 329–330 Fick’s law, 232–234
empirical constitutive relations, 328 Fourier’s law, heat transfer, 227–229
energy balance equations, 329 Ohm’s law, 230–232
equilibrium state, 330 Twin roll technique, 72
local empirical temperature scale, 331
principle of indifference, 331
thermoscope, 328 U
Thermodynamics UCST. See Upper critical solution temperature
glass formation, oxide glasses Upper critical solution temperature (UCST),
crystalline reference state (CRS), 180 117–118
definition, 179–180
linear depandence slopes, 180, 181
thermal expansion coefficient, 182–183 V
thermodilatometric cooling curve, 181, Vapour deposition, 3–4
182 Very high-density amorphous (VHDA) ice, 17
thumb rules, 184–185 Vibration forms. See Glass transitions
glass models, 189–192 Viscosity, chalcogenide glass-forming systems
modelling, 192–195 amorphous
Thermophysical properties dynamic viscosity, 171–173
chemical compositions, natural and kinematic viscosity, 174–175
industrial glasses, 312–313 measuring methods
dissolution-precipitation mechanism, 311 beam-bending method (BB), 170
precious opal capillary method (C), 166–167
a–b cristobalite transition, 321 Eisenberg method (EM), 170
Coober Pedy white play-of-colour, falling sphere method (FS), 167
317–318 low-temperature torsion viscometer
origin, 317 (LV), 170
380 Index
magnetic bearing torsional creep Vogel–Tammann–Fulcher (VTF) equation,

method (TC), 170 8–9
parallel-plate method (PP), 169 Void creation. See Glass transitions
penetration method (P), 169
Viscosity
rod elongation (RE), 168 W
rotating cylinder method (RC), 167–168 Wanderers, 41
torsion oscillating cup method (TOC), WAXS. See Wide angle X-ray scattering
168 Wide angle X-ray scattering (WAXS), 84
Vitrification, 32

Glassy, Amorphous and Nano-Crystalline Materials

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What is the book about?

What is the book about?

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What topics are discussed in the book?

Glassy, Amorphous

and Nano-Crystalline Materials

For other titles published in this series, go to

ISBN 978-90-481-2881-5 e-ISBN 978-90-481-2882-2

# Springer Science+Business Media B.V. 2011

Printed on acid-free paper

Springer is part of Springer ScienceþBusiness Media (www.springer.com)

Early Research into Amorphous Semiconductors

Numerous aspects of physics and chemistry of non-crystalline solids and glassy

the research into amorphous semiconductors stimulated development of qualita-

May 2010 Jiřı́ J. Mareš

Prof. Jaroslav Šesták, MEng., Ph.D., DSc.

Dr. Jiřı́ J. Mareš, Ph.D.

Dr. Pavel Hubı́k, Ph.D.

Prepared under the support of the following projects:

1 Introduction: Some Essential Attributes of Glassiness

2 Heat Capacity and Entropy Functions in Strong and

3 Vibration Forms in the Vicinity of Glass Transition,

4 Some Aspects of Vitrification, Amorphisation and

5 Basic Role of Thermal Analysis in Polymer Physics. . . . . . . . . . . . . . . . . . . . 77

6 Phases of Amorphous, Crystalline, and Intermediate

7 Thermal Portrayal of Phase Separation in

8 Solid Forms of Pharmaceutical Molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129

9 Chalcogenide Glasses Selected as a Model System

10 Viscosity Measurements Applied to Chalcogenide

11 Thermal Properties and Related Structural Study

12 Oxide Glass Structure, Non-bridging Oxygen and Feasible

13 New Approach to Viscosity of Glasses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217

14 Transport Constitutive Relations, Quantum Diffusion

15 In-Situ Investigation of the Fast Lattice Recovery during

16 Emanation Thermal Analysis as a Method for Diffusion

17 Scanning Transitiometry and Its Application in Petroleum

18 Constrained States Occurring in Plants Cryo-Processing

19 Thermophysical Properties of Natural Glasses

20 Hotness Manifold, Phenomenological Temperature

21 Historical Roots and Development of Thermal

1.1 Character of the Amorphous Solids

J. Šesták et al. (eds.), Glassy, Amorphous and Nano-Crystalline Materials, 1

One method to answer this question is to detect in amorphous solids possible

1.2 Preparation and Characterizations of Amorphous Solids

A wide variety of amorphous solids can be prepared by physical and chemical

Fig. 1.1 Various methods of preparation of amorphous solids

Table 1.1 Glass transition temperature Tg of various amorphous solids

Fig. 1.2 Heat capacity and en-

DHc ðtÞ ¼ DHc ð0Þ exp½ðt=tÞb ; (1.1)

where Hc is the part of enthalpy related to the structure or configuration of the

dDHc ðtÞ=dt ¼ ½dHvib ðtÞ=dT ½dT=dt ¼ Cvib ½dT=dt: (1.2)

Obviously the temperature T means the vibrational temperature. The structural

TðtÞ ¼ a þ bt þ c exp½ðt=tÞb : (1.3)

where G1 is the instantaneous shear modulus. Numerical evaluation of this equa-

¼ 0 exp ½A=ðT T0 Þ; (1.5)

t ¼ Aexp½z Dm=kT ¼ Aexp½NA Dmsc =kTScðTÞ: (1.7)

Here Sc(T) is the macroscopic configurational entropy of liquid, Dm the chemical

z ðT1 Þ=z ðT2 Þ ¼ ScðT2 Þ=ScðT1 Þ (1.8)

1.3 Glass Transitions in Crystals: Glassy Crystals

temperature at which the dielectric relaxation time td becomes (2pf)1, indicating a

Xc 500–625) where the polymer melt is characterized by constant and gradient-