UNIT - 5

Glass transition temperature

When an amorphous polymer is heated, the temperature at which the polymer
structure turns ―viscous liquid or rubbery" is called the Glass Transition Temperature, Tg. If a
polymer is amorphous, the solid-to-liquid transition occurs very gradually, going through an
intermediate ―rubbery‖ state without a phase transformation. The transition from the hard and
brittle glass into a softer, rubbery state occurs over a narrow temperature range referred to as
the glass transition temperature.

It is also defined as a temperature at which amorphous polymer takes on

characteristic glassy-state properties like brittleness, stiffness and rigidity (upon cooling).
This temperature (measured in °C or °F) depends on the chemical structure of the polymer
and can therefore be used to identify polymers.

In the case of a partially crystalline polymer, the above transformation occurs only in
the amorphous regions. The crystalline zones remain unchanged and act as reinforcing
elements thus making the sample hard and tough. If heating is continued, a temperature is
reached at which the crystalline zones begin to melt. The equilibrium crystalline melting
point, Tm, for polymers corresponds to the temperature at which the last crystallite starts
melting. Again, in contrast to simple materials, the value of Tm depends on the degree of
crystallinity and size distribution of crystallites.

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 The thermal behavior of polymers is of considerable technological importance.
Knowledge of thermal transitions is important in the selection of proper processing and
fabrication conditions, the characterization of the physical and mechanical properties of a
material, and hence the determination of appropriate end uses. For example, the glass
transition temperature of rubber determines the lower limit of the use of rubber and the upper
limit of the use of an amorphous thermoplastic. In addition, there is a still more fundamental
difference between the thermal behavior of polymers and simple molecules which was shown
in Figure 4.1. The general changes in physical state due to changes in temperature and
molecular weight are shown in Figure 4.2 for amorphous and crystalline polymers.

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Characteristic of Tg

1. Amorphous polymers only exhibit a Tg.

2. Crystalline polymers exhibit a Tm (melt temperature) and typically a Tg since there is

usually an amorphous portion as well (―semi‖-crystalline).

3. The value of Tg depends on the mobility of the polymer chain, and for most synthetic
polymers lies between 170 K to 500 K.

4. The transition from the glass to the rubber-like state is an important feature of
polymer behavior, marking a region of dramatic changes in the physical properties,
such as hardness and elasticity.

5. At Tg, changes in hardness, volume, percent elongation to break and Young’s

modulus of solids are mainly seen.

6. Some polymers are used below their Tg (in glassy state) like
polystyrene, poly(methyl methacrylate) etc., which are hard and brittle. Their Tgs
are higher than room temperature.

7. Some polymers are used above their Tg (in rubbery state), for example, rubber
elastomers like polyisoprene, polyisobutylene. They are soft and flexible in nature;
their Tgs are less than room temperature.

Applications include
Identifying the Tg of polymers is often used for quality control and research and
development. Also, it is an important tool used to modify physical properties of polymer
molecules.

Further, improvement in handling characters, solubility and reproducibility in

dissolution of solids can be achieved by increasing the Tg of solids.

Factors Affecting Tg / Significance of Tg

1. Molecular Weight: In straight chain polymers, increase in MW leads to decrease in

chain end concentration resulting in decreases free volume at end group region – and
increase in Tg. Glass Transition Temperature is directly proportional to molecular
weight of polymer

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2. Molecular Structure : Insertion of bulky, inflexible side group increases Tg of
material due to decrease in mobility.

3. Chemical Cross-linking : Increase in cross-linking decreases mobility leads to

decrease in free volume and increase in Tg. By definition, cross-linking involves the
formation intermolecular connections through chemical bonds. This process
necessarily results in reduction in chain mobility. Consequently, Tg increases. Glass
Transition Temperature is directly proportional to degree of cross links.
For lightly cross-linked systems like vulcanized rubber, Tg shows a moderate
increase over the uncross-linked polymer. In this case, Tg and the degree of cross-
linking have a linear dependence, as shown by the following approximate empirical
equation.

Tg - TO = 3.9 x 105/Mn

Where, Tg = the glass transition temperature of the uncross-linked polymer having

the same chemical composition as the cross-linked polymer

Mc = the number-average molecular weight between cross-linked points

4. Polar groups: Presence of polar groups increases intermolecular forces; inter chain
attraction and cohesion leading to decrease in free volume resulting in increase in Tg.
intermolecular bonding in polymers is due to secondary attractive forces.
Consequently, it is to be expected that the presence of strong intermolecular bonds in
a polymer chain, i.e., a high value of cohesive energy density, will significantly
increase Tg . The effect of polarity, for example, can be seen from Table 4.6.

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5. Flexibility : Glass Transition Temperature is inversely proportional to flexibility.
Chain flexibility is determined by the ease with which rotation occurs about primary
valence bonds. Polymers with low hindrance to internal rotation have low Tg values.
Long-chain aliphatic groups —ether and ester linkages — enhance chain flexibility,
while rigid groups like cyclic structures stiffen the backbone. These effects are
illustrated in Table 4.1.

Bulky side groups that are stiff and close to the backbone cause steric hindrance,
decrease chain mobility, and hence raise Tg (Table 4.2.).

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6. Inter molecular force: Glass Transition Temperature is directly proportional to
intermolecular force.

7. Side groups : Glass Transition Temperature is directly proportional to number of side

groups. The influence of the side group in enhancing chain stiffness depends on the
flexibility of the group and not its size. Table 4.3.

8. Addition of Plasticizers: Addition of plasticizer increases the free volume in polymer

structure (Plasticizer gets in between the polymer chains and spaces them apart from
each other). Glass Transition Temperature is inversely proportional to plasticization.
Plasticizers are usually nonpolymeric, organic liquids of high boiling points.
Plasticizers are miscible with polymers and, in principle, should remain within the

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 polymer. Addition of plasticizers to a polymer, even in very small quantities,
drastically reduces the Tg of the polymer. This is exemplified by the versatility of
poly(vinyl chloride) which, if unmodified, is rigid, but can be altered into a flexible
material by the addition of plasticizers such as dioctylphthalate (DOP).

9. Crystallinity : In semicrystalline polymers, the crystallites may be regarded as

physical cross-links that tend to reinforce or stiffen the structure. Viewed this way, it
is easy to visualize that Tg will increase with increasing degree of crystallinity. This is
certainly not surprising since the cohesive energy factors operative in the amorphous
and crystalline regions are the same and exercise similar influence on transitions. It
has been found that the following empirical relationship exists between Tg and Tm.

Tg / Tm = 1/ 2 for symmetrical polymers ; 2 3 for unsymmetrical polymers

where Tg and Tm are in degrees Kelvin.

10. Water or moisture content: Increase in moisture content leads formation of

hydrogen bonds with polymeric chains increasing the distance between polymeric
chains. And, hence increases the free volume and decreases Tg.

11. Effect of entropy and enthalpy: The value of entropy for amorphous material is
higher and low for crystalline material. If value of entropy is high, then value of Tg is
also high.

12. Pressure and free volume: Increase in pressure of surrounding leads to decrease in
free volume and ultimately high Tg.

Glass Transition Temperature Vs Melting Temperature

At the molecular level, at Tg, the chains in amorphous (i.e., disordered) regions of the polymer
gain enough thermal energy to begin sliding past one another at a noticeable rate. The
temperature where entire chain movement occurs is called the melting point (Tm) and is greater
than the Tg

1. Glass Transition is a property of the amorphous region while melting is the property of
crystalline region
2. Below Tg, there exists disordered amorphous solid where chain motion is frozen and
molecules start wiggling around above Tg. The more immobile the chain, the higher the
value of Tg.

3. While, below Tm it is an ordered crystalline solid which becomes disordered melt above
Tm
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 GLASS TRANSITION TEMPERATURE OF SOME POLYMERS
Polymer Tg (K)a

Polypropylene (PP) 260 (239)

Polyethylene (HDPE) 148 (148)

Polymethylacrylate (PMA) 283 (285)

Polypropyleneglycol (PPG) 198 (205)

Polyvinylacetate (PVA) 303 (316)

Polystyrene (PS) 373 (363)

Polytetrafluoroethylene (PTFE) 390 (384)

Poly(Bisphenol A carbonate) (PC) 447 (435)

Poly(ethylene terephthalate) (PET) 345 (346)

Amorphous Polymers and Crystalline Polymers

As the amorphous polymer (line ABCD) is heated from the low-temperature region
(region D), the volume expands at a constant rate. At a characteristic temperature, Tg, the rate
of volume expansion increases suddenly to a higher constant level, i.e., there is a change in
the slope of the volume–temperature curve from a lower to a higher volume coefficient of
expansion. At the same time, there is an abrupt change in physical behaviour from a hard,
brittle, glassy solid below Tg (region D) to a soft, rubbery material above Tg (region C). On
further heating, the polymer changes gradually from the rubbery state to a viscous liquid
(region B) whose viscosity decreases with increasing temperature until decomposition sets in.

For a crystalline polymer, the changes at Tgare less drastic. This is because these
changes are restricted mainly to the amorphous domains while the crystalline zones remain
relatively unaffected. Between the glass transition (Tg) and the melting temperature (Tm)
(region E) the semicrystalline polymer is composed of rigid crystallites immersed (dispersed)
in a rubbery amorphous matrix. In terms of mechanical behaviour, the polymer remains rigid,
pliable, and tough. At the melting temperature, the crystallites melt, leading to a viscous state
(region B). Above Tm the crystalline polymer, like the amorphous polymer, exists as a
viscous liquid.

Polymers (plastics, elastomers or rubber) are made up of long chains of molecules

and may be amorphous or crystalline. The structure of a polymer is defined in terms of
crystallinity.
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 Amorphous polymers have a random molecular structure that does not have a sharp
melting point. Instead, amorphous material softens gradually as temperature rises.
Amorphous materials are more sensitive to stress failure due to the presence of hydrocarbons.
E.g. PC, GPPS, PMMA, PVC, ABS.

Crystalline or Semi-crystalline polymers have a highly ordered molecular

structure. These do not soften as the temperature rises, but rather have a defined and narrow
melting point. This melting point is generally above that of the upper range of amorphous
thermoplastics. E.g. Polyolefins, PEEK, PET, POM etc.

Measurement of Tg for copolymers

A copolymer system may be characterized either by the geometry of the resulting polymer —
that is, the arrangement of the different monomers (random, alternating, graft, or block) — or
by the compatibility (miscibility) of the two monomers.

If the glass transitions (Tg1 and Tg2) of the individual homopolymers (1 and 2) are known, it
is possible to estimate the Tg of the copolymer (or polyblend) using the relation

Tg = V1Tg1 + V2 Tg2

Where, V1 and V2 are the volume fractions of components 1 and 2, respectively

Example 1.
What is the Tg of butadiene–styrene copolymer containing 10 vol% styrene?
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Solution:
Butadiene and styrene form a completely compatible random copolymer. Therefore
the following relation is applicable: Tg = V1Tg1 + V2 Tg2

Example 2
Toluene behaves as a plasticizer for polystyrene. Estimate Tg of a polystyrene sample
containing 20 vol% toluene.

How to Measure Glass Transition Temperature

The most usual test method to determine Glass Transition Temperature of plastics

10
 is ASTM E1356. This test method covers the assignment of the glass transition temperatures
of materials using differential scanning calorimetry or differential thermal analysis.

This test method is applicable to amorphous materials or to partially crystalline

materials containing amorphous regions, that are stable and do not undergo decomposition or
sublimation in the glass transition region. Both methods, DTA and DSC, yield peaks relating
to endothermic and exothermic transitions with thermal input and show phase changes or
occurrence of reactions.

In DTA, the difference in temperature between the sample and a reference material is
monitored against time or temperature while the temperature rise/fall of the sample, in a
specified atmosphere, is programmed.

In DSC, the difference in heat flow to a sample and to a reference is monitored against
time or temperature while the temperature rise/fall of the sample, in a specified atmosphere,
is programmed.

Glass Transition Temp. Measurements of Different Polymers Using DSC

(Source: Mettler-Toledo Analytical)

Ofourse there exists several other methods as well to determine Tg, such as:

 Specific heat measurements

 Thermo mechanical analysis
 Thermal expansion measurement
 Micro-heat-transfer measurement
 Isothermal compressibility
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 Heat capacity

Experimental study to Determine Glass Transition Temperature (Tg) and

Melting Temperature(Tm)
Two types of DSC instruments are widely used: the heat flux DSC (eg. TA DSC and Mettler
DSC) and the power compensated DSC (Perkin-Elmer system).

Heat Flux DSC :

In a heat flux DSC system the sample and reference are heated at the same rate from a single
heating source as shown in Figure 6. The temperature difference between the pans is recorded
and converted to a power difference. This power difference gives the difference in heat flow.

Power Compensated DSC

The sample and reference are heated separately in power compensated DSC, as shown in
Figure. The pan temperatures are monitored using thermocouples attached to the disk
platforms. The thermocouples are connected in series and measure the dierential heat flow
using the thermal equivalent of Ohm's Law
dq/dt = ΔT/RD

where, dq/dt is the heat flow, ΔT is the temperature difference between the reference and
sample, and RD is the thermal resistance of the disk platform. The heat flow to each pan is
adjusted to keep their temperature difference close to zero while the furnance temperature is
increased linearly. It is used to obtain qualitative and quantitative information about the
physical and chemical changes that materials undergo during heating.

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DSC sample preparation procedures

DSC sample preparation procedures are as follows:

1. Weigh your sample to the nearest 0.1 mg with the analytical balance in Room 409. Record
the weight.

2. Use forceps to place sample in the bottom half of an aluminum DSC pan.

3. Use forceps to place the aluminum pan lid on top of your sample.

4. Use forceps to load the aluminum pan and sample into the sample encapsulating press
(Pope Jon…shown below). Align the sample pan in the encapsulating press, and press down
on the handle to seal the aluminum pan.

5. Crimp an empty aluminum pan and lid. You will use the empty pan as a reference sample.

Working Principle:

Differential scanning calorimetry (DSC) measures the energy absorbed (endotherm)

or produced (exotherm) as a function of time or temperature. It is used to characterize
melting, crystallization, resin curing, loss of solvents, and other processes involving an
energy change. Differential scanning calorimetry may also be applied to processes involving
a change in heat apacity, such as the glass transition. Similar to thermomechanical analysis,
one test can generally be used to measure most or all of these properties.

In DSC analysis, the sample is placed in an aluminum pan, and the sample pan and an
empty reference pan are placed on small platforms within the DSC chamber. Thermocouple
sensors lie below the pans. DSC measurements can be made in two ways: by measuring the
electrical energy provided to heaters below the pans necessary to maintain the two pans at the
same temperature (power compensation), or by measuring the heat flow (differential
temperature) as a function of sample temperature (heat flux).

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 The DSC ultimately outputs the differential heat flow (heat/time) between your
material and the empty reference pan. Heat capacity may be determined by taking the ratio of
heat flow to heating rate. Thus,

Cp= q /∆ T

where Cp is the material‘s heat capacity, q is the heat flow through the material over
a given time, and ∆T is the change in temperature over that same time.

A schematic of a DSC thermogram is shown in the following figure:

Notice that this graph labels four critical points: the glass transition temperature (Tg ), the
crystallization temperature (Tc ), the melting temperature (Tm), and the curing temperature.

The glass transition temperature (Tg) is also an important characteristic of noncrystalline

and semicrystalline materials, but Tg is a particularly significant property of many common
polymers. At temperature below Tg, amorphous and semicrystalline polymers tend to be hard
and brittle because he polymer chains are locked in a tangled, coiled position. Above Tg, the
polymeric chains are able to ore easily rotate and slip past each other, and the polymer
becomes softer and more ductile. Generally the glass transition point depends on the
processing of the material, as well as that material‘s natural characteristics such as structure,
14
bonding, and molecular weight. Since it takes energy to break these bonds, the glass
transition appears on a DSC curve as an endothermic process. In DSC, the Tg can be found
by a permanent decrease in baseline heat flow, and Tg is usually taken as the inflection point
in the curve.

Determination of Melting Temperature (Tm) Melting is a transition which occurs in

thermoplastic semi-crystalline polymers such as PEEK, polypropylene, polyvinyl chloride,
polystyrene, and polyphenylene sulphide used in composites. Melting happens when the
polymer chains fall out of their crystal structures and become a disordered liquid [8]. When a
crystalline polymer is heated, the temperature increases at a constant rate until it reaches its
melting point. The temperature will hold steady for a while until the polymer has completely
melted, even though the heating continues. All the energy added to the crystalline polymer at
its melting point goes into melting, and none of it goes towards raising the temperature. This
heat is called the latent heat of melting. Once the polymer has melted, the temperature begins
to rise again, but now it rises at a slower rate. The molten polymer has a higher heat capacity
than the solid crystalline polymer, so it can absorb more heat with a smaller increase in
temperature. So when a crystalline polymer melts, it absorbs a certain amount of heat (the
latent heat of melting) and it undergoes a change in its heat capacity. This is called a first-
order transition [7]. This extra heat flow during melting shows up as a large endothermic
melting peak in the DSC plot, as indicated in Figure

The heat of melting can be obtained by measuring the area of this peak. The temperature at
the apex of the peak is taken to be the point where the polymer is completely melted. Because
energy is added to the polymer to make it melt, this process is called as an endothermic
transition.

The crystallization temperature (Tc) is another important transition that occurs in some
polymeric materials. At the crystallization temperature, the polymer loses its random chain
arrangement, intermolecular bonds form, and the polymer molecules become more ordered.
Formation of bonds during crystallization is an exothermic process, so an increase in heat
flow (a peak on the DSC curve) accompanies the crystallization process. Generally, the Tc is

15
found by finding the onset point of the crystallization curve. Note that many amorphous
polymers never undergo crystallization.

Melting occurs when your material changes phase from a solid to a liquid. When a material
starts to melt, its intermolecular bonds absorb energy and begin to loosen and break. Since
melting involves absorption of energy, it is an endothermic process and appears on the DSC
curve as a large, temporary decrease in heat flow. Once the material has completely melted,
the heat flow returns to its original baseline value. The melting temperature is generally
measured at the onset point of the melting curve.

Curing of a polymer occurs when individual chains form strong bonds to other chains, a
process that is sometimes referred to as ―crosslinking.‖ Like crystallization, this process of
chain ordering and bond formation is exothermic. The curing temperature is generally given
as the onset of the curing peak on the DSC curve.

Interpretation and analysis of DSC data may be difficult for some samples. For example,
polymers containing moisture, fillers, or additives such as plasticizers may behave quite
differently than ―pure‖ polymers. In addition, some polymer properties determined by DSC
may depend on the processing methods used to create or shape the materials. The TA
Instruments Universal Analysis software is helpful for most baseline analyses.

The First and Second Order Transition

The glass transition temperature (Tg) is one of the most important thermophysical
properties of amorphous polymers. It is sometimes called the ―melting point of amorphous
materials‖. In the highly viscous region above the Tg, polymeric materials are soft and
rubbery, whereas below the Tg, polymers are hard and brittle. However, there is one
important difference between glass transition and melting; melting is a true first-order phase
transition, whereas glassification (vitrification) is only a pseudo-second-order transition, that
is, melting causes a discontinuity in the first derivative of the Gibbs free energy (volume,
entropy), whereas glassification causes a (pseudo) discontinuity in the second derivative of
the Gibbs free energy (e.g. heat capacity, expansion coefficient, etc.).

The glass transition is a complex process that is affected by a number of factors,

including heating rate, ageing history, morphology, molecular weight. In fact, the true nature
of the glass transition is not well understood. Several theories have been developed over the
years to explain the glass transition. The theories can be divided into kinetic and equilibrium
theories. The kinetic theories consider the glass transition as a dynamic process. Vitrification
or glassification is caused by "freezing" the movements of chain segments (kinetic units).
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Starting at very low temperatures, the first (solid-state) transition occurs when localized bond
movements (bending and stretching of bonds) and side chain movements can occur. This is
the so called gamma transition (Tγ). As the temperature increases, other localized motions
that involve whole side chain and localized group movements are activated and the material
starts to develop some toughness. This transition is called beta transition (Tβ). As heating
further continues, the Tg is reached. In this region, large scale coordinated motions of the
polymer chains occur and a dramatic change in properties is observed.

Another theory treats the glass transition as a true second-order thermodynamic

transition. The ideal equilibrium state can, of course, not be reached because it requires an
infinite time. The first equilibrium theory of the glass transition was developed by Gibbs and
DiMarzio (1955 - 1958). They estimated the changes in conformational entropy with
increasing temperature and postulated that the conformational entropy becomes zero when a
thermodynamic second-order transition is reached. Below this temperature, all conformations
are essentially "frozen".

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CRYSTALLINITY IN POLYMERS

When a metastable liquid of small molecules undergoes a phase transition into a crystal, the
mechanism of this ordering process [1] is recognized to be nucleation and growth. As
sketched in Figure 1.1(a), nuclei of crystalline phase with linear dimension larger than a
critical value rc are formed by thermal fluctuations that then offer surfaces for further growth
into full-fledged crystalline phase. The rate of nucleation of viable nuclei and the
systemdependent value of rc are determined by the extent of metastability [1]. Now, what
happens to the nucleation and growth process if the small molecules are tethered together to
form polymer chains, as sketched in Figure 1.1(b)? Clearly the ability of different portions of
a long polymer chain to participate in different initial nuclei inevitably prohibits a polymer
melt from forming a perfect polymer crystal. This results in a semicrystalline state. Starting
from the original declaration [2] by Storks in 1938 that chains must fold back and forth in the
formation of crystals, there has been a cultivation of rich phenomenology [3–9].

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The modern availability of sensitive experimental techniques using synchrotron radiation and
atomic force microscopy, and fast computers for molecular modeling, has spurred recent
intense interest in following the mechanism of polymer crystallization. In spite of the heroic
efforts by the polymer community since the early 1940s, the fundamental mechanism of
polymer crystallization is still not understood. From a conceptual point of view, polymer
crystallization requires an understanding of the free-energy landscape with many metastable
states frustrated by entropic barriers separating them. Among the numerous challenges faced
in understanding polymer crystallization, the present review focuses only on the following
issues, which are directly pertinent to the phenomenon of nucleation in polymer crystals.

A. Spontaneous Selection of Lamellar Thickness Independent of crystallization conditions,

whether from solutions or melt, the polymer molecules crystallize into thin lamellae. The
lamellar thickness is about 10 nm, about two orders of magnitude smaller than values allowed
by existing equilibrium considerations. This is in contrast to the case of crystallized short
alkanes, where the lamellar thickness is proportional to the length of the molecules. Clearly
the chains in the case of polymers should fold back and forth in the lamellae to support the
experimentally observed lamellar thickness. It is believed in the literature [3–9] that the
lamellar thickness is kinetically selected and that if enough time is permissible, the lamella
would thicken to extended chain crystal dimension. What determines the spontaneous
selection of lamellar thickness?

B. Nucleation in the Very Early Stage

There is considerable experimental evidence [9–15] for density fluctuations at very early
times of crystallization before the full crystallographic features can be detected. What are the
molecular origins of structural development in the primordial stage of polymer
crystallization?

C. Kinetics at Growth Front

The problem of how a sufficiently large lamella grows further has attracted most of the
theoretical effort [16–22] in the past and a vast amount of experimental data is available. In
the analytically tractable model [4,8,16] of Lauritzen and Hoffman (LH) and further
generalizations [17,19], the growth occurs via crossing another nucleation barrier associated
with the formation of one stem of the polymer (of contour length comparable to lamellar
thickness) followed by an essentially downhill process of lateral spreading by other stems.
What are the molecular details of the barrier for the attachment of a stem at the growth front
and what constitutes the stems?

D. Flow Effects

When polymers are crystallized under flow (stirring, extensional, etc.), the ubiquitous
morphology [23] is the ‗‗shish-kebab‘‘structure, consisting of central core (shish) surrounded
by lamellae (kebabs) attached along the shish. What is the underlying mechanism behind the
formation of ‗‗shish-kebab‘‘ structure? Before addressing these fundamental questions, we
present a brief review on phenomenology, classical thermodynamics, and kinetic models of

24
polymer crystallization. Advances made recently (as of 2003) using molecular modelling are
reviewed next.

Crystallization Kinetics

As an example, we consider crystallization of polyethylene from a melt. As mentioned above,

crystallization proceeds with the initial formation of isolated spherulites, which then grow
until their mutual impingement with further slow crystallization. Time (t)-dependent
measurements [26] of the density of the crystallizing melt at different temperatures are given
in Figure 1.3 as a plot of degree of crystallinity versus logarithm of time.

A decrease in the crystallization temperature results in a rapid increase in crystallization rate.

All curves have similar sigmoidal shape. There is an initial induction time required for the
formation of spherulitic nuclei, followed by a period of accelerated crystallization during
which spherulites grow in radius. When the spherulites begin to touch each other,
crystallization rates slow down again. Eventually, same degree of crystallinity is achieved,

25
essentially independent of crystallization temperature. Complete crystallinity is almost never
achieved, and the final degree of crystallinity is molecular-weightdependent.

During the growth stage of spherulites, radial growth rate is a constant. This growth rate
constant depends on temperature nonmonotonically, as illustrated in Figure 1.4 for
spherulites of isotactic polystyrene [27]. As the supercooling is increased, growth rate
increases first and then decreases after reaching a maximum value. As we will see below, the
increase in rate with supercooling is due to nucleation processes and the decrease in rate with
supercooling (i.e., decrease in temperature) is due to slowing down of diffusion of polymer
chains. At very early times of crystallization, there is considerable experimental evidence [9–
15] for density fluctuations before the full crystallographic features can be detected. The
major evidence is the appearance of a peak (at qmax) in intensity, Iðq; tÞ, of the small-angle
X-ray scattering versus scattering wavevector q at an early time t, before any signal in the
wide-angle X-ray scattering, for a wide variety of polymers. In the early stage, the integrated
intensity grows exponentially with time, and qmax is proportional to ðTÞ 1=2 (where T is the
supercooling). The rate (q) of growth of Iðq; tÞ divided by q2 decreases linearly with q2 for

26
intermediate values of q, as shown in Figure 1.5. These observations are analogous to those
of phase-separating mixtures by spinodal decomposition mechanism, leading several
researchers to invoke the idea that the early stage of polymer crystallization is spinodal
decomposition.

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RELATIONSHIP BETWEEN PROPERTIES AND CRYSTALLINE STRUCTURE
Why is a particular drug effective? Why is a certain chemical toxic? Why does a particular
pesticide not break down in the environment? Why does a bullet-proof vest work the way it
does? The answer to all of these questions is that the structure of the molecules comprising
these materials determines the properties that the materials have.
―Structure Determines Properties‖ is a powerful concept in chemistry and in all fields in
which chemistry is important including, but not limited to, environmental science, biology,
biochemistry, polymer science, medicine, engineering, and nutrition.
What is meant by structure? How does one describe the structure of a molecule? This can
be done at various levels of sophistication.
- The molecular formula, e.g., C12H17ClNO3 , tells us which elements are present and in what
ratio.
- The relative overall size and 3-dimensional shape, known as the steric properties, give
additional detail.
- Functional groups in the molecule indicate electrostatic properties (Polarity, Hydrogen
Bonding).
- A description of chirality is necessary to account for the spatial relationship of the atoms.
- A further piece of information at a still higher level of sophistication would be the heat of
formation.
- To be precise, a description of the exact structure would require defining the exact positions
of all atoms in the molecule.
30
Simple molecular model kits and molecular modeling software are very helpful in visualizing
the structure of a molecule. High-level calculations can accurately describe structures.
Experimental methods of studying structure include spectroscopy such as NMR spectroscopy
and X-ray crystallography, which can define the exact positions of the atoms in a molecule.
What is meant by properties?
These fall into three general categories.
- Chemical (e.g., reaction rates, position of equilibria). Why does an SN2 reaction occur well
on a primary center but not at all on a tertiary center? Answer: steric effects. Why is
trichloroacetic acid 10,000 times more acidic than acetic acid? Answer: electrostatic or polar
effects.
- Physical (e.g., melting points, boiling points, solubility, spectra) Compare dimethyl ether,
CH3-O-CH3 (BP –24°) and its isomer, ethanol, CH3CH2-O-H (BP 78°). Structure
determines the boiling points. The molecules of alcohol, having the ability to H-bond, attract
one another with stronger forces (H-bonds) than do the molecules of ether, which only have
normal dipole-dipole forces holding them together.
- Biological (e.g., odor, color, taste, drug action, toxicity) Why does vanilla taste so different
than chocolate? Why do we perceive the color of a banana as yellow and an orange as
orange? Different molecules, because of their structures fit differently into the biological
receptors present in living systems, consequently causing different neural responses.
(Note that biological properties are actually a subset of chemical properties, in which at least
one of the interacting chemicals is a biological chemical such as an enzyme.)
Why is chirality such an important structural characteristic? As an example, compare the
enantiomers of thalidomide. Thalidomide was used as a sedative for pregnant women in the
1950‘s in Europe. The drug was a mixture of the two enantiomers. Severe birth defects
resulted.
It turns out that one enantiomer is an effective antidepressant while the other is teratogenic
(causes birth defects). Why might this be? The biologically active sites in living systems are
chiral themselves. Thus enantiomers fit differently into those sites and consequently have
different biological effects.

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What factors affect the degree of crystallinity in polymers and why?

1.) Polymer structure and nature of functional groups: Crystallinity in polymers is governed
by the extent of chain ordering, or chain folding. If the side groups of the polymer backbone
are large and heavy, chain movement and folding is hindered, which reduces the probability
of forming crystalline domains.

2.) Arrangement (Tacticity): In continuation of the above, chains (or side groups) that are
arranged in an ordered manner can pack together more efficiently which leads to increased
crystallinity.

3.) Secondary bonding: Both inter- and intra-molecular Hydrogen bonding play important
roles in polymer crystallinity. With increased chain to chain secondary bonding, there is an
increase in crystallinity of the polymer, making the material stronger.

Effect of Crystallinity on Mechanical Properties

How does the % crystallinity affect the mechanical properties?

• In a semi-crystalline polymer, a higher level of crystallinity will provide:

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– Higher modulus of elasticity

– Higher yield strength

– Lower elongation

– lower toughness

• The chains in the crystalline region are closely packed and cannot slide past one another.

• This does not necessarily mean that a semi-crystalline material will be always …….. than
an amorphous material.

• It is more a matter of the individual material‘s ……………… and the ……… ……. in
relation to its …..

Crystallinity and polymer structure

A polymer's molecular structure strongly affects crystallinity. If it's regular and orderly,
highly symmetrical, it will pack into crystals more easily. In a way, the molecules want to get
next to each other in crystalline domains. If the molecular structure is not highly regular and
symmetrical, it won't. Let's take a look at polystyrene in it's various forms to help us
understand how this works.

As you can see in the lists above, there are two kinds of polystyrene. There
is atactic polystyrene, and there is syndiotactic polystyrene. The former is totally amorphous
and the later is very crystalline.

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Syndiotactic polystyrene has a very regular and orderly structure, with the phenyl groups
falling on alternating sides of the linear carbon backbone. This means it can pack very easily
into crystals because the backbones can come close together without the phenyl groups
getting in the way. In fact, the phenyl groups are able to also come very close to each other,
which they like to do very much. That interaction is called "pi-stacking," and occurs in lots of
polymers with aromatic rings in the backbone or pendent to the polymer chains.

But atactic styrene has no such order. The phenyl groups come on any which side of the chain
they please going down the backbone. With no order, the chains can't pack very well plus the
pi-stacking isn't there as much. So atactic polystyrene is very amorphous. Does that mean it
has lousy properties? Of course not! Atactic polystyrene is one of the most widely used
commercial polymers in products today. Take a look at the stores in level one and see how
many items contain this polymer.

Other atactic polymers like poly(methyl methacrylate) and poly(vinyl chloride) are also
amorphous. And as you might expect, stereoregular and symmetrical polymers like
isotactic polypropylene and polytetrafluoroethylene are highly crystalline. But of course, not
completely so. That's why these polymers have such incredible combinations of properties,
strong AND tough.

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Polyethylene is another good example. It can be crystalline or amorphous. Linear
polyethylene can be nearly 100% crystalline, depending on how it's processed and handled.
But the branched stuff just can't pack the way the linear stuff can, with the branch points
getting in the way, so it is more highly amorphous. It still has some crystalline domains,
though, and those act as physical crosslinking sites. Low density polyethylene (highly
branched version) is weaker than the other, more linear kinds, but still useful for sandwich
bags and food wrap.

Crystallinity and intermolecular forces

Intermolecular forces can be a big help for a polymer if it wants to form crystals. A good
example is nylon. You can see from the picture below that the polar amide groups in the
backbone chain of nylon 6,6 are strongly attracted to each other. They form strong
intermolecular hydrogen bonds. This strong binding holds chains together, and because those
chains are so symmetrical, they're also form crystals. This raises the melting point of the
crystals compared to polymers without such strong intermolecular interactions. That's why
nylons have much higher melting points than, say, polyethylene or polypropylene.

Polyesters are another example. Let's look at the polyester we call poly(ethylene
terephthalate) or PET.

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The polar ester groups make for strong interactions, just like the poles of a magnet pull
toward each other. In addition, the aromatic rings like to stack together in an orderly fashion
(remember pi-stackin?), making the crystal even stronger. These strong interaction again
raise the Tm of PET much higher than that of polyethylene.

And now you might be asking yourself, "If those intermolecular forces affect crystallinity and
Tm, don't they also affect Tg? Wouldn't stronger interactions causing a higher Tm also lead
to a higher Tg?"

Wow! You've come a long way already. Great questions and the answer to both is "Yes!" In
fact, for many polymers, there's a more-or-less linear relationship between Tg and Tm. Take
a look at the plot below for some of the more common polymers that are at least semi-
crystalline. And as you might have guessed, Tm is always greater than Tg.

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How Much Crystallinity?

Remember we said that many polymers contain lots of crystalline material and lots of
amorphous material. Almost no polymer is 100% crystalline and, in fact, most polymers are
only around 10-30% crystalline. There's a way we can find out how much of a polymer
sample is amorphous and how much is crystalline. This method has its own page, and it's
called differential scanning calorimetry. It uses an analytical instrument to actually measure
the glass transition and melting temperatures. More importantly, it can measure how much of
each is in a given sample. This kind of "quantitation" is very important in understanding how
well any polymer will behave and what it can be used for. Lesson here is: the more you
know, the more you understand.

There are other methods that can tell you something about what kind of crystallinity is
present, such as neutron and x-ray scattering. Solid state NMR has recently become an
important tool for looking at the types and amounts of crystalline and amorphous domains
present. We don't have time or space to tell you all about these powerful tools here, but if
you're interested, you can find tons of information on the web.

Using a combination of these techniques, it's even possible to differentiate amorphous

domains from what's called rigid amorphous areas. The former makes a polymer tougher and
more flexible while the latter makes it stronger.

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