PHASE TRANSFORMATIONS,

GLASS TRANSFORMATION &

GLASS CERAMICS
Dr. Ir. Sotya Astutiningsih, M.Eng
PHASE TRANSFORMATIONS
… Spinoidal decomposition
… Nucleation and growth
Spinoidal
p decomposition
p

Refers to a continuous
type of ph transf in
which the change
begins as compositional
waves that are small in
amplitude and large in
spatial extent
In a ph diagram containing
miscibility gap, the free energu
vs composition relations for
several temps (see fig)

The free energy vs comp

relations for temp below the
consolute temp are
characterized by regions of neg
curvature

The inflections point

are termed the spinoides, and

their locus as a function of temp
defines the spinoidal curve
… The spinoidal represents the limit of chemical stability.
… For comp outside the spinoidal, the chemical potential of the given
component increases with the density of the comp, and a
homogeneous solution is stable or metastable, depending on whether
the give comp lies inside or outside the miscibility gap
… Within the gap but outside the spinoidal, a homogeneous solution is
stable against infinitesimal fluctuations in comp but can separate into
an equil
q two-phase
p system
y byy nucleation and growth
g process
p
… In contrast, for comps within the spinoidal, a hom solutions is unstable
against an infinitesimal fluctuations in density or comp, and there is
no thefrmodynamic barrier to the growth of a new phase
nucleation
… When a new phase is formed by a nucleation and
growth proces, it must start as a very small region and
the increase in size.
… Initially it has high surface-t0-volume ratio, which tends
to make it unstable because of its high surface energy
… Nucl fro a hom phase = hom nucl
… Het nucl = is when surfaces, grain boundaries, second
phase particles, and other discontinuities in the structure
serves as favorable sites. Het nucl is more commonly
observed
Homogeneous
g nucleation
… The formation of nuclei
requires
i theh fformation
i off an
interface between the two
phae (s/l) Æ
… The formation of very small
particles requires an inrease
in free energy
… Once the p particle has
reached a sufficiently large
size, the interfcial energy is
small compared to the vol
energy decrease
decrease, so that the
overall change in free energy
is neg
… Experiments shows that hom nucl for most liquids
occur at relative undercooling between 0.15 –
0.25
… From these values, the magnitude of the s/l
interface energy
gy is
… Where is the c/l interfc energy and is the heat of
fusion per atom
… for metals ~ ½
… For non metals ~1/31/3
Heterogeneous
g nucleation
… The nucl of most pphase transf take p place heterogeneously
g y
on container walls, impurity particles or structural
imperfection
… Wh a nucll is
When i fformedd on a substrate,
b in
i addition
ddi i off the
h
creation of nucl-matrix interfc, some high energy substrate
– matrix surface is replaced by a lower energy substrate-
nucl surface, resulting in a smaller overal surface energu
contribution
Crystal
y g
growth
… After a stable nuclei has been formed,, it g
grows at a
rate fixed by conditions of temp and the degree of
supersaturation
… The nature of the interface related to
thermodynamics:
† For
F crystallization
t lli ti process iinvolving
l i SSmallll entropy
t
change: even the most closely packed interface plane
should be rough on an atomic scale. The growth rate
anisotropy ( different in growth rate for diferent
orientation) should be small
†
† Crystallz involving
large entropy change,
the most closely
packed planes should
be smooth, the less
closely packed should
be rough, and the
growth rate anisotropy
is large
… Large entropy change
Ægrowth from vapor or
from dilute solution, in
most organic and
inorganic compounds
including most silicates
and borates from the
melt.
… characterized by
faceted interface
morphology
… Growth is affected
significantly by defects
… Small entropy change
Æ
Æmetals,l SiO2 and d GeO
G O
from the melt
… (under similar condition)
characterized by non-faceted
morph which are nearly
isotropic
… The fraction of ggrowth sites on
the interface is expected to
be in the order of unity (1),
and althought depend on the
orientation it should not vary
orientation,
strongly with undercoling
Glass formation
… Structural conditions necessary for forming an oxide
liquid with an energy similar to that of the
corresponding crystal.
… Glass former are found in every category of material
and that any glass former crystallizes if held for a
sufficiently
ffi i l llong time
i iin the
h temp range b below
l theh
melting temp
… It is more fruitful to consider how fast must a given liq
be cooled in order that detectable crystllzation be
avoided than whether a g given liq
q is a g
glass former
Cooling
g rate
… The estimation of a necessary cooling rate:
† How small a vol fraction of crystals embedded in a
glassy matrix can be detected and identified
† How can the vol fraction of crystals be related to the
kinetics constant describing the nucl and growth process
… The cooling rate necessary
to avoid
id a given
i voll
fraction crystallzd can be
estimated Æ T-T-T curve
(time – temp – transf)
… The nose in a T-T-T curve
correspond to the least
time for the given vol
fraction crystallized ---
results from a competition
between the driving force
for crystallization, which
increases with decreasing
temp and the atomic
mobility, which decreases
with decreasing g temp p
… The cooling rate required to avoid a given fraction
crystallzd may be roughly estimated :
… The material characteristics most conductive to glass
g
formation are a high viscosity at the melting pt and a
viscosity which increase strongly with falling temp below
melting pt.
pt
… For materials with similar viscosity – temp relations,
glass formation is then favored byy low Tm or liquidus
g q
temp
… The observed ease of glass formation in regions of
composition
iti near many eutectics
t ti can b be related
l t d to
t the
th
comp redistribution required for crystallzt to proceed as
well as the lower liquidus temp
… Emphasizing the importance of the crystallz rate
and viscosity in glass formation Æcharacteristics of
materials which determine their flow behaviour and
the nature of their cryst – liq interfc. In this view,
various correllation which have been suggested
between glass trans temp and liq temp is of limited
generality (eg. Ztg ~ 2/3 Tm)
… Materials such as Al2O3, H2O and Na2O.SiO2
which are quite fluid over a range of temp below
their Tm,, can only
y be obtained as g
glasses by
y veryy
rapid cooling
Glass ceramics materials
… Are produced by the comtrolled crystallization of
appropriate glasses.
… Consist of a large proportion, typically 95
95-98
98 vol%
of very small crystals, gnerally smaller than 1
micron, with a small amount of residual g glass phase
p
making up a porefree composite.
Fabrication of g
glass ceramics
… Bodies of desired shape are formed with
conventional glass-forming techniques.
… The conventional crystallization of glasses is almost
invariably observed to initiate at the external
surfaces, followed byy the crystals
y g
growingg into the
amorphous phase and producing a nonuniform
body of large grain size.
… For a variety of reasons, it is desirable that crystals
be small (less than 1 micron) and uniform in size
… To obtain such small crytals
y
occupying a large vol
fraction of material, a
uniform density of nuclei of
the order of 1012 to 1015
per cubic cm is required
… Æ this is produced by
adding nucl agent to the
batch during melting and
controlled heat treatment.
Important
p glass
g ceramic systems
y
… Li2O Al2O3 SiO2
Li2O-Al2O3-SiO2
… MgO-Al2O3-SiO2
… Na2O BaO Al2O3 SiO2
Na2O-BaO-Al2O3-SiO2
Phase separation
p in glasses
g
… Is a widespread
phenomenon in glass
forming system
… Has been the origin of
the interconnected
structures observed in
many systems in which
both phases occupy
large vol fraction.
… Cahn – spinoidal
decomposition –
interconnected structure
– phase separation
example
p
… Two phase lechable submicrostructure in alkali
Two-phase
borosilicates: the continuous second phase was
assumed to arise from a highg concentration of
second phase droplets which grew rapidly and
linked with one another to form a continuous
network
Thermal history effect on phase
separation
ti
… Borosilicate glasses 67.4SiO2,
25 7B2O3 6.9Na2O
25.7B2O3, 6 9Na2O wt%
… (a) the glass has been cooled to
ambient and heat treated for 3 hr at
750C exhibit a pronounced
interconnectivity
… (b) cooled directly to 750C and held
for 3 hr exhibited much smaller
degree of connectivity
… P b bl reflects
Probably fl a difference
diff iin the
h
density of second phase particles
forme at 750C and at various temp
during cooling to ambient, as well as
the increased likelihood of
coalescence for the case of small
particles occupying a large vol
fraction and, different mchanism of
initial separation at diff temp