Glass Transition Temperature and Visco Elastic Creep Behaviour of Polymers
Glass Transition Temperature and Visco Elastic Creep Behaviour of Polymers
Glass Transition Temperature and Visco Elastic Creep Behaviour of Polymers
Submitted to
BATCHELOR OF TECHNOLOGY
IN
MECHANICAL ENGINEERING
Submitted by
Y.RAJASEKHAR REDDY
MR V.GIRISH CHANDRAN
(UGC-Autonomous)
STUDENT DECLARATION
In this paper, the peeling and spalling resistance of unidirectional fiber reinforced
polymer (FRP) sheets externally bonded to concrete surface are investigated
experimentally through a series of peeling tests. A peeling load is applied on the
FRP sheet by a circular rod placed into the central notch of the beam. The effects
of different FRP composites, adhesives, surface treatments and strength of concrete
on peeling behavior are investigated. Three different modes of debonding failure
are identified: debonding within concrete surface, debonding in concrete–adhesive
interface, and debonding in FRP composites–adhesive interface. It is observed that
the failure pattern debonding within concrete layer yields a higher peeling load
carrying capacity. Moreover, a typical failure due to the FRP rupture is also
observed experimentally. Based on the experimental results, a theoretical analysis
is conducted on specimens representing the peeling behavior and spalling
resistance. Load carrying capacity is expressed as the function of peel angle based
on geometrical analysis and equilibrium of forces between FRP sheets and the
circular rod. Interfacial fracture energy is calculated analytically using membrane-
peeling method. Finally, a close agreement between the predicted and the
experimental results is demonstrated by means of some numerical example
Contents:
Chapter-1 Introduction
Chapter-2 Glass Transition Temperature
1. Transition temperature Tg
1.1. Polymers
1.2. Silicates and other covalent network glasses
2. Kauzmann’s paradox
3. The glass transition in specific materials
3.1. Silica, SiO2
3.2. Polymers
4. Mechanics of vitrification
4.1. Electronic structure
Chapter-3 DMA for visco-creep behavior of polymer
1. Viscoelastic properties of materials
2. Applications
2.1. Measuring glass transition temperature
2.2. Polymer composition
3. Instrumentation
3.1. Types of analyzers
3.2. Test modes
3.2.1. Temperature sweep
3.2.2. Frequency sweep
3.2.3. Dynamic stress-strain studies
3.2.4. Combined sweep
Conclusion
References
Chapter-1 : Introduction
In this chapter, a discussion of the viscoelastic properties of selected polymeric
materials is performed. The basic concepts of viscoelasticity, dealing with the
fact that polymers above glass-transition temperature exhibit high entropic
elasticity, are described at beginner level. The analysis of stress-strain for some
polymeric materials is shortly described. Dielectric and dynamic mechanical
behavior of aliphatic, cyclic saturated and aromatic substituted
poly(methacrylate)s is well explained. An interesting approach of the relaxational
processes is presented under the experience of the authors in these polymeric
systems. The viscoelastic behavior of poly(itaconate)s with mono- and
disubstitutions and the effect of the substituents and the functional groups is
extensively discussed. The behavior of viscoelastic behavior of different
poly(thiocarbonate)s is also analyzed.
Viscoelastic materials are those which exhibit both viscous and elastic
characterists. Viscoelasticity is also known as anelasticity, which is present in
systems when undergoing deformation. Viscous materials, like honey, polymer
melt etc, resist shear flow (shear flow is in a solid body, the gradient of a shear
stress force through the body) and strain, i.e. the deformation of materials caused
by stress, is linearly with time when a stress is applied. Shear stress is a stress state
where the stress is parallel or tangencial to a face of the material, as opposed to
normal stress when the stress is perpendicular to the face. The variable used to
denote shear stress is τ which is defined as:
τ = VQ/ It
for shear stress in a beam where V is the shear force, Q is the first moment of area,
t, is the thickness in the material perpendicular to the shear and I is the second
moment of area of the cross section. When an elastic material is stressed, there is
an immediate strain response. The classical representation of stress strain response
in a perfectly elastic material is schematically represented . As can be observed
when the stress is removed the strain also returns to zero. In a perfectly elastic
material all the deformation is returned to the origin. If this energy is not stored
elastically then it would be dissipated as either heat or sound. Tyre suqueal and the
heat build-up in the sidewalls of care tyres are good examples of such dissipation.
Another example is when a plastic beaker struck, emits a dull note of short
duration, which is quite different from the ringing note emitted by a bell or a
crystal wine glass . This property of high mechanical damping is another
manifestation of viscoelasticity. It is a property that is frequently of value, for
instance in shock absorbers as McCrum et al pointed out . In plastic structures
subject to forced oscillation, mechanical vibrations at the natural frequencies of the
structure do not easily build up due to the high damping capacity of the plastic.
According to McCrum a good example of this is the application of plastic materials
in sailing craft, particularly in hull construction. Vibration of the hull stimulated by
elements are rapidly damped.the authors in these polymeric systems. The
viscoelastic behavior of poly(itaconate)s with mono- and disubstitutions and the
effect of the substituents and the functional groups is extensively discussed. The
behavior of viscoelastic behavior of different poly(thiocarbonate)s is also
analyzed
CHAPTER-2 : Glass Transition Temperature
Transition temperature Tg
Refer to the figure on the right plotting the heat capacity as a function of
temperature. In this context, Tg is the temperature corresponding to point A on the
curve. The linear sections below and above Tg are colored green. Tg is the
temperature at the intersection of the red regression lines.
Different operational definitions of the glass transition temperature Tg are in use,
and several of them are endorsed as accepted scientific standards. Nevertheless, all
definitions are arbitrary, and all yield different numeric results: at best, values
of Tg for a given substance agree within a few kelvins. One definition refers to
the viscosity, fixing Tg at a value of 1013 poise (or 1012 Pa·s). As evidenced
experimentally, this value is close to the annealing point of many glasses.
In contrast to viscosity, the thermal expansion, heat capacity, shear modulus, and
many other properties of inorganic glasses show a relatively sudden change at the
glass transition temperature. Any such step or kink can be used to define Tg. To
make this definition reproducible, the cooling or heating rate must be specified.
The most frequently used definition of Tg uses the energy release on heating
in differential scanning calorimetry (DSC, see figure). Typically, the sample is first
cooled with 10 K/min and then heated with that same speed.
Yet another definition of Tg uses the kink in dilatometry (a.k.a. thermal expansion).
Here, heating rates of 3–5 K/min (5.4–9.0 °F/min) are common. Summarized
below are Tg values characteristic of certain classes of materials
Polymers :
Dry nylon-6 has a glass transition temperature of 47 °C (117 °F). Nylon-6,6 in the
dry state has a glass transition temperature of about 70 °C
(158 °F). Whereas polyethene has a glass transition range of −130 – −80 °C
(−202 – −112 °F) The above are only mean values, as the glass transition
temperature depends on the cooling rate and molecular weight distribution and
could be influenced by additives. For a semi-crystalline material, such
as polyethene that is 60–80% crystalline at room temperature, the quoted glass
transition refers to what happens to the amorphous part of the material upon
cooling.
Kauzmann’s paradox:
As a liquid is supercooled, the difference in entropy between the liquid and solid
phase decreases. By extrapolating the heat capacity of the supercooled liquid
below its glass transition temperature, it is possible to calculate the temperature at
which the difference in entropies becomes zero. This temperature has been named
the Kauzmann temperature.
If a liquid could be supercooled below its Kauzmann temperature, and it did indeed
display a lower entropy than the crystal phase, the consequences would be
paradoxical. This Kauzmann paradox has been the subject of much debate and
many publications since it was first put forward by Walter Kauzmann in 1948.
One resolution of the Kauzmann paradox is to say that there must be a phase
transition before the entropy of the liquid decreases. In this scenario, the transition
temperature is known as the calorimetric ideal glass transition temperature T0c. In
this view, the glass transition is not merely a kinetic effect, i.e. merely the result of
fast cooling of a melt, but there is an underlying thermodynamic basis for glass
formation. The glass transition temperature:
There are at least three other possible resolutions to the Kauzmann paradox. It
could be that the heat capacity of the supercooled liquid near the Kauzmann
temperature smoothly decreases to a smaller value. It could also be that a first
order phase transition to another liquid state occurs before the Kauzmann
temperature with the heat capacity of this new state being less than that obtained
by extrapolation from higher temperature. Finally, Kauzmann himself resolved the
entropy paradox by postulating that all supercooled liquids must crystallize before
the Kauzmann temperature is reached.
The glass transition in specific materials
Silica SiO2:
Silica (the chemical compound SiO2) has a number of distinct crystalline forms in
addition to the quartz structure. Nearly all of the crystalline forms
involve tetrahedral SiO4 units linked together by shared vertices in different
arrangements. Si-O bond lengths vary between the different crystal forms. For
example, in α-quartz the bond length is 161 picometres (6.3×10−9 in), whereas in α-
tridymite it ranges from 154–171 pm (6.1×10−9–6.7×10−9 in). The Si-O-Si bond
angle also varies from 140° in α-tridymite to 144° in α-quartz to 180° in β-
tridymite. Any deviations from these standard parameters constitute
microstructural differences or variations that represent an approach to
an amorphous, vitreous or glassy solid. The transition temperature Tg in silicates is
related to the energy required to break and re-form covalent bonds in an
amorphous (or random network) lattice of covalent bonds. The Tg is clearly
influenced by the chemistry of the glass. For example, addition of elements such
as B, Na, K or Ca to a silica glass, which have a valency less than 4, helps in
breaking up the network structure, thus reducing the Tg. Alternatively, P, which has
a valency of 5, helps to reinforce an ordered lattice, and thus increases the Tg.[32]
Tg is directly proportional to bond strength, e.g. it depends on quasi-equilibrium
thermodynamic parameters of the bonds e.g. on the enthalpy Hd and entropy Sd of
configurons – broken bonds: Tg = Hd / [Sd + Rln[(1-fc)/ fc] where R is the gas
constant and fc is the percolation threshold. For strong melts such as SiO2 the
percolation threshold in the above equation is the universal Scher-Zallen critical
density in the 3-D space e.g. fc = 0.15, however for fragile materials the percolation
thresholds are material-dependent and fc <<1. The enthalpy Hd and the
entropy Sd of configurons – broken bonds can be found from available
experimental data on viscosity.
Polymers
In polymers the glass transition temperature, Tg, is often expressed as the
temperature at which the Gibbs free energy is such that the activation energy for
the cooperative movement of 50 or so elements of the polymer is exceeded[citation
needed]
. This allows molecular chains to slide past each other when a force is applied.
From this definition, we can see that the introduction of relatively stiff chemical
groups (such as benzene rings) will interfere with the flowing process and hence
increase Tg. The stiffness of thermoplastics decreases due to this effect (see figure.)
When the glass temperature has been reached, the stiffness stays the same for a
while, i.e., at or near E2, until the temperature exceeds Tm, and the material melts.
This region is called the rubber plateau.
In ironing, a fabric is heated through this transition so that the polymer chains
become mobile. The weight of the iron then imposes a preferred orientation. Tg can
be significantly decreased by addition of plasticizers into the polymer matrix.
Smaller molecules of plasticizer embed themselves between the polymer chains,
increasing the spacing and free volume, and allowing them to move past one
another even at lower temperatures. The "new-car smell" is due to the
initial outgassing of volatile small-molecule plasticizers[citation needed]
(most
commonly known as phthalates) used to modify interior plastics (e.g., dashboards)
to keep them from cracking in the cold of winter weather. The addition of
nonreactive side groupsto a polymer can also make the chains stand off from one
another, reducing Tg. If a plastic with some desirable properties has a Tg that is too
high, it can sometimes be combined with another in a copolymer or composite
material with a Tg below the temperature of intended use. Note that some plastics
are used at high temperatures, e.g., in automobile engines, and others at low
temperatures.
In viscoelastic materials, the presence of liquid-like behavior depends on the
properties of and so varies with rate of applied load, i.e., how quickly a force is
applied. The silicone toy Silly Putty behaves quite differently depending on the
time rate of applying a force: pull slowly and it flows, acting as a heavily viscous
liquid; hit it with a hammer and it shatters, acting as a glass.
On cooling, rubber undergoes a liquid-glass transition, which has also been called
a rubber-glass transition.
Mechanics of vitrification
Molecular motion in condensed matter can be represented by a Fourier
series whose physical interpretation consists of
a superposition of longitudinal and transverse waves of atomic displacement with
varying directions and wavelengths. In monatomic systems, these waves are
called density fluctuations. (In polyatomic systems, they may also
include compositional fluctuations.)
Thus, thermal motion in liquids can be decomposed into elementary longitudinal
vibrations (or acoustic phonons) while transverse vibrations (or shear waves) were
originally described only in elastic solids exhibiting the highly ordered crystalline
state of matter. In other words, simple liquids cannot support an applied force in
the form of a shearing stress, and will yield mechanically via macroscopic plastic
deformation (or viscous flow). Furthermore, the fact that a solid deforms locally
while retaining its rigidity – while a liquid yields to macroscopic viscous flow in
response to the application of an applied shearing force – is accepted by many as
the mechanical distinction between the two.
The inadequacies of this conclusion, however, were pointed out by Frenkel in his
revision of the kinetic theory of solids and the theory of elasticity in liquids. This
revision follows directly from the continuous characteristic of the structural
transition from the liquid state into the solid one when this transition is not
accompanied by crystallization—ergo the supercooled viscous liquid. Thus we see
the intimate correlation between transverse acoustic phonons (or shear waves) and
the onset of rigidity upon vitrification, as described by Bartenev in his mechanical
description of the vitrification process.
The velocities of longitudinal acoustic phonons in condensed matter are directly
responsible for the thermal conductivity that levels out temperature differentials
between compressedand expanded volume elements. Kittel proposed that the
behavior of glasses is interpreted in terms of an approximately constant "mean free
path" for lattice phonons, and that the value of the mean free path is of the order of
magnitude of the scale of disorder in the molecular structure of a liquid or solid.
The thermal phonon mean free paths or relaxation lengths of a number of glass
formers have been plotted versus the glass transition temperature, indicating a
linear relationship between the two. This has suggested a new criterion for glass
formation based on the value of the phonon mean free path.
It has often been suggested that heat transport in dielectric solids occurs through
elastic vibrations of the lattice, and that this transport is limited by
elastic scattering of acoustic phonons by lattice defects (e.g. randomly spaced
vacancies). These predictions were confirmed by experiments on
commercial glasses and glass ceramics, where mean free paths were apparently
limited by "internal boundary scattering" to length scales of 10–100 micrometres
(0.00039–0.00394 in). The relationship between these transverse waves and the
mechanism of vitrification has been described by several authors who proposed
that the onset of correlations between such phonons results in an orientational
ordering or "freezing" of local shear stresses in glass-forming liquids, thus yielding
the glass transition.
Electronic structure
The influence of thermal phonons and their interaction with electronic structure is
a topic that was appropriately introduced in a discussion of the resistance of liquid
metals. Lindemann's theory of melting is referenced, and it is suggested that the
drop in conductivity in going from the crystalline to the liquid state is due to the
increased scattering of conduction electrons as a result of the
increased amplitude of atomic vibration. Such theories of localization have been
applied to transport in metallic glasses, where the mean free path of the electrons is
very small (on the order of the interatomic spacing).
The formation of a non-crystalline form of a gold-silicon alloy by the method
of splat quenching from the melt led to further considerations of the influence of
electronic structure on glass forming ability, based on the properties of the metallic
bond.
Other work indicates that the mobility of localized electrons is enhanced by the
presence of dynamic phonon modes. One claim against such a model is that
if chemical bonds are important, the nearly free electron models should not be
applicable. However, if the model includes the buildup of a charge
distribution between all pairs of atoms just like a chemical bond (e.g., silicon,
when a band is just filled with electrons) then it should apply to solids.
Thus, if the electrical conductivity is low, the mean free path of the electrons is
very short. The electrons will only be sensitive to the short-range order in the glass
since they do not get a chance to scatter from atoms spaced at large distances.
Since the short-range order is similar in glasses and crystals, the electronic energies
should be similar in these two states. For alloys with lower resistivity and longer
electronic mean free paths, the electrons could begin to sense that there
is disorder in the glass, and this would raise their energies and destabilize the glass
with respect to crystallization. Thus, the glass formation tendencies of certain
alloys may therefore be due in part to the fact that the electron mean free paths are
very short, so that only the short-range order is ever important for the energy of the
electrons.
It has also been argued that glass formation in metallic systems is related to the
"softness" of the interaction potential between unlike atoms. Some authors,
emphasizing the strong similarities between the local structure of the glass and the
corresponding crystal, suggest that chemical bonding helps to stabilize the
amorphous structure.
Other authors have suggested that the electronic structure yields its influence on
glass formation through the directional properties of bonds. Non-crystallinity is
thus favored in elements with a large number of polymorphic forms and a high
degree of bonding anisotropy. Crystallization becomes more unlikely as bonding
anisotropy is increased
from isotropicmetallic to anisotropic metallic to covalent bonding, thus suggesting
a relationship between the group number in the periodic table and the glass
forming ability in elemental solids.
Chapter-3 DMA for visco-creep behavior of polymer
Applications
Measuring glass transition temperature
Polymer composition
Varying the composition of monomers and cross-linking can add or change the
functionality of a polymer that can alter the results obtained from DMA. An
example of such changes can be seen by blending ethylene-propylene-diene
monomer (EPDM) with styrene-butadiene rubber (SBR) and different cross-
linking or curing systems. Nair et al. abbreviate blends as E0S, E20S, etc., where
E0S equals the weight percent of EPDM in the blend and S denotes sulfur as the
curing agent.
Increasing the amount of SBR in the blend decreased the storage modulus due
to intermolecular and intramolecular interactions that can alter the physical state of
the polymer. Within the glassy region, EPDM shows the highest storage modulus
due to stronger intermolecular interactions (SBR has more steric hindrance that
makes it less crystalline). In the rubbery region, SBR shows the highest storage
modulus resulting from its ability to resist intermolecular slippage.
When compared to sulfur, the higher storage modulus occurred for blends cured
with dicumyl peroxide(DCP)because of the relative strengths of C-C and C-S
bonds.
Incorporation of reinforcing fillers into the polymer blends also increases the
storage modulus at an expense of limiting the loss tangent peak height.
DMA can also be used to effectively evaluate the miscibility of polymers. The E40S
blend had a much broader transition with a shoulder instead of a steep drop-off in a
storage modulus plot of varying blend ratios, indicating that there are areas that are
not homogeneous.
Instrumentation
The instrumentation of a DMA consists of a displacement sensor such as a linear
variable differential transformer, which measures a change in voltage as a result of
the instrument probe moving through a magnetic core, a temperature control
system or furnace, a drive motor (a linear motor for probe loading which provides
load for the applied force), a drive shaft support and guidance system to act as a
guide for the force from the motor to the sample, and sample clamps in order to
hold the sample being tested. Depending on what is being measured, samples will
be prepared and handled differently. A general schematic of the primary
components of a DMA instrument.
Types of Analyzers
There are two main types of DMA analyzers used currently: forced resonance
analyzers and free resonance analyzers. Free resonance analyzers measure the free
oscillations of damping of the sample being tested by suspending and swinging the
sample. A restriction to free resonance analyzers is that it is limited to rod or
rectangular shaped samples, but samples that can be woven/braided are also
applicable. Forced resonance analyzers are the more common type of analyzers
available in instrumentation today. These types of analyzers force the sample to
oscillate at a certain frequency and are reliable for performing a temperature
sweep.
Analyzers are made for both stress (force) and strain (displacement) control. In
strain control, the probe is displaced and the resulting stress of the sample is
measured by implementing a force balance transducer, which utilizes different
shafts. The advantages of strain control include a better short time response for
materials of low viscosity and experiments of stress relaxation are done with
relative ease. In stress control, a set force is applied to the same and several other
experimental conditions (temperature, frequency, or time) can be varied. Stress
control is typically less expensive than strain control because only one shaft is
needed, but this also makes it harder to use. Some advantages of stress control
include the fact that the structure of the sample is less likely to be destroyed and
longer relaxation times/ longer creep studies can be done with much more ease.
Characterizing low viscous materials come at a disadvantage of short time
responses that are limited by inertia. Stress and strain control analyzers give about
the same results as long as characterization is within the linear region of the
polymer in question. However, stress control lends a more realistic response
because polymers have a tendency to resist a load.
Stress and strain can be applied via torsional or axial analyzers. Torsional
analyzers are mainly used for liquids or melts but can also be implemented for
some solid samples since the force is applied in a twisting motion. The instrument
can do creep-recovery, stress-relaxation, and stress-strain experiments. Axial
analyzers are used for solid or semisolid materials. It can do flexure, tensile, and
compression testing (even shear and liquid specimens if desired). These analyzers
can test higher modulus materials than torsional analyzers. The instrument can
do thermomechanical analysis (TMA) studies in addition to the experiments that
torsional analyzers can do. Figure 4 shows the general difference between the two
applications of stress and strain.
Changing sample geometry and fixtures can make stress and strain analyzers
virtually indifferent of one another except at the extreme ends of sample phases,
i.e. really fluid or rigid materials. Common geometries and fixtures for axial
analyzers include three-point and four-point bending, dual and single cantilever,
parallel plate and variants, bulk, extension/tensile, and shear plates and
sandwiches. Geometries and fixtures for torsional analyzers consist of parallel
plates, cone-and-plate, couette, and torsional beam and braid. In order to utilize
DMA to characterize materials, the fact that small dimensional changes can also
lead to large inaccuracies in certain tests needs to be addressed. Inertia and shear
heating can affect the results of either forced or free resonance analyzers,
especially in fluid samples
Test modes
Two major kinds of test modes can be used to probe the viscoelastic properties of
polymers: temperature sweep and frequency sweep tests. A third, less commonly
studied test mode is dynamic stress-strain testing.
Temperature sweep
A common test method involves measuring the complex modulus at low constant
frequency while varying the sample temperature. A prominent peak in
appears at the glass transition temperature of the polymer. Secondary transitions
can also be observed, which can be attributed to the temperature-dependent
activation of a wide variety of chain motions. In semi-crystalline polymers,
separate transitions can be observed for the crystalline and amorphous sections.
Similarly, multiple transitions are often found in polymer blends.
For instance, blends of polycarbonate and poly(acrylonitrile-butadiene-styrene)
were studied with the intention of developing a polycarbonate-based material
without polycarbonate’s tendency towards brittle failure. Temperature-sweeping
DMA of the blends showed two strong transitions coincident with the glass
transition temperatures of PC and PABS, consistent with the finding that the two
polymers were immiscible
Dynamic stress-strain curves
Combined sweep
Because glass transitions and secondary transitions are seen in both frequency
studies and temperature studies, there is interest in multidimensional studies, where
temperature sweeps are conducted at a variety of frequencies or frequency sweeps
are conducted at a variety of temperatures. This sort of study provides a rich
characterization of the material, and can lend information about the nature of the
molecular motion responsible for the transition.
For instance, studies of polystyrene (Tg ~ 110 °C) have noted a secondary
transition near room temperature. Temperature-frequency studies showed that the
transition temperature is largely frequency-independent, suggesting that this
transition results from a motion of a small number of atoms; it has been suggested
that this is the result of the rotation of the phenyl group around the main chain.
Conclusion:
This work presents an extensive experimental programme performed on a
polyamide compound, in order to determine its non-linear behaviour when
subjected to various loading scenarios.
The first set of tests studied the strain-rate dependency of the material with
deformation speeds ranging from 0.00028 to 2.8 s -1. Tests were performed in
tension and highlighted the strong influence of this parameter on the material’s
strength and stiffness. Going further than the low-speed tests, creep tests were
performed in order to determine the material softening with time. The tensile
compliance increased drastically in the first few minutes of the tests and even
though it decreased significantly after 7 h, no plateau (saturation of the viscous
strain) was observed after 24 h.
Temperature-dependency tests were performed in order to determine the
mechanical properties of the polyamide in an envelope of temperatures that might
occur during service. A substantial difference in behaviour was observed between
the tests performed at low temperatures (−25 and 0°C) and the tests performed at
high temperatures (23 and 50 °C).
Regarding the dynamical properties and keeping in mind the deformation range
that products manufactured from this material might be subjected to, DMA tests at
high strains (up to ~4% deformation) were performed. The dynamic moduli vary
with strain as expected and the damping coefficient reaches a plateau when
deformations get close to the yield region.
Further insight about the long-term effects of loadings was obtained by performing
low-cycle fatigue tests. The experimental programme focused on the influence of
the number of cycles, frequency and strain on the mechanical properties of the
material. It was concluded that, considering the given test regimes, the magnitude
of the plastic deformation was reduced, viscous flow having the main influence on
the behaviour of the material.
References:
Getreport.in/report-air-brake-system
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