UNIT: 4

❖ GLASS TRANSITION TEMPERATURE

❖ TRANSITIONS
❖ SIGNIFICANCE AND FACTORS INFLUENCING THE Tg
❖ EFFECTS OF PLASTICIZERS ON Tg
❖ GLASS TRANSITION OF COPOLYMERS
❖ MORPHOLOGY AND ORDER OF POLYMERS
❖ CRYSTALLINITY IN POLYMERS
❖ DEGREE OF CRYSTALLINITY AND POLYMER
CRYSTALLIZATION
❖ EFFECT OF CRYSTALLINITY ON PROPERTIES OF
POLYMERS
Amorphous and Crystalline Polymer
❖ 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.
❖ 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 (Polycarbonates), GPPS (General
Purpose Poly Styrene ), PMMA (Polymethyl Methacrylate), PVC, ABS
(Acrylonitrile Butadiene Styrene).
❖ 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
(Polyether Etherketone),PET (Polyethylene Terephthalate), POM (Polyoxy
Methylene) etc.
Glass Transition Temperature (Tg)
❖ 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. It is also defined as a temperature at which Amorphous
polymer takes on characteristic glassy-state properties like brittleness, stiffness
(rigid and difficult to bend) 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.
❖ Amorphous polymers only exhibit a Tg. Crystalline polymers exhibit a Tm
(melt temperature) and typically a Tg since there is usually an amorphous
portion as well (“semi”-crystalline).
❖ The value of Tg depends on the mobility of the polymer chain, and for most
synthetic polymers lies between 170 K to 500 K.
Glass Transition Temperature
❖ 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 & elasticity.
❖ Some polymers are used below their Tg
(in glassy state) like polystyrene, PMMA,
etc., which are hard and brittle. Their Tg’s
are higher than room temperature.
❖ 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 Tg’s are less than
room temperature.
Glass Transition Temperature
❖ At Tg, changes in hardness, volume, percent elongation to break of solids are
mainly seen.
❖ Tg is an important tool used to modify physical properties of polymer
molecules.
❖ Further, improvement in handling characters, solubility and reproduce ability
in dissolution of solids can be achieved by increasing the Tg of solids.
❖ The glass-transition temperature Tg of a material characterizes the range of
temperatures over which this glass transition occurs. It is always lower than
the melting temperature Tm, of the crystalline state of the material, if one exists.
❖ Hard plastics like PS and PMMA are used well below their glass transition
temperatures, i.e., when they are in their glassy state. Their Tg values are well
above room temperature, both at around 100 °C. Rubber elastomers
like polyisoprene & polyisobutylene are used above their Tg, that is, in the
rubbery state, where they are soft and flexible.
Glass transition curve
 Curve shows that specific vol. as a function of temperature in the transition region.
 When a liquid polymer is cooled, the transition from highly viscous super cooled
melt to the rigid glass begins at temperature T1.
 At T2 the solidification process is terminated. The process called ‘Glass transition’
because amorphous polymers exhibit a change from soft, elastic above Tg to glass
like below Tg.
 Tg is a point at which the tangents of the 2 curves intersect. Slope indicates the
transition/intermediate state, where liquid/rubbery/glassy state are co-exist in
equilibrium.
How to measure Tg
 The most usual test methods to
determine Glass Transition
Temperature of plastics is (DSC)
Differential Scanning Calorimetry &
Differential Thermal Analysis (DTA).
 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.
Factors influencing the Tg
 There are several factors affecting the value of Tg ---
1- chemical structure – i) molecular weight ii) molecular structure
iii) polarity iv) chemical cross linking
2- plasticizers
3- water or moisture content
4- enthalpy & entropy
5- pressure & free volume
6- chain flexibility
7- steric hinderance
8 -copolymerization
Factors influencing the Tg
 Chemical Structure
• Molecular Weight – Mole wt is directly proportional to Tg.
Increase in mole wt up to 20,000, value of Tg also increases but
after this value Tg unaffected because Tg reaches a limiting value.
• Relation between Tg & mole wt given by Flory and Fox -----
Tg = Tg ∞ - K/M (K = constant, M = mole wt)
• 1/Tg = 1/Tg ∞ + A/M (A =constant, M = mole wt)
• Molecular Structure - Insertion of bulky, inflexible side group
increases Tg of material due to decrease in mobility.
• Chemical cross-linking - Increase in cross-linking decreases
mobility leads to decrease in free volume and increase in Tg.
• 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.
Factors influencing the Tg
 Addition of Plasticizers
• Plasticizers are low molecular weight non volatile substances like – Dibutyl Phthalate (DP),
Dioctyl Sebacate (DS), Methyl Salicylate (MS) & Methyl Acetate (MA).
• Addition of plasticizer increases the free volume in polymer structure (Plasticizer gets in between
the polymer chains and spaces them apart from each other). This results in polymer chains sliding
more easily. As a result, the polymer chains can move around at lower temperatures resulting in
decrease in Tg of a polymer.

 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.

 Effect of entropy
• The value of entropy for amorphous material is higher and low for crystalline material. If value of
entropy is high, free volume increases then value of Tg decreases.
 Pressure and free volume
• Increase in pressure of surrounding leads to decrease in free volume and ultimately high Tg.
Factors influencing the Tg
 Chain flexibility
• It is defined as degree of freedom of rotation of different chain segments around
the covalent bonds of the polymer backbone chain.
• Polymers with linear chain mainly contains C-C, C-O, or C-N and possess high
chain flexibility thus show low Tg value (-125 °C for polythene).
• Presence of aromatic/cyclic ring in backbone chain reduces the flexibility and
increases Tg value (+100 °C for polystyrene).

 Stearic hinderance
• Presence of larger and bulky group on polymeric long chain restricts the degree of
freedom for free rotation hence Tg values increases.
• Ortho position restricts rotation (due to stearic hinderance) more than para & meta
position thus Tg value higher for ortho polymers than para or meta polymers.
Factors influencing the Tg
 Copolymerization
• The Tg value of many homopolymers could be lowered by
copolymerizing it with another suitable monomer. Like polythene and
polypropylene are crystalline polymer form by homo-polymerization
separately.
• Copolymerization of ethene & propylene form rubbery polymer.
• The magnitude of Tg of a copolymer expressed as ----
1/Tg = W1/Tg1 + W2/Tg2
(Tg = Tg of copolymer)
(Tg1 , Tg2 = Tg of homopolymer 1 & 2)
(W1 & W2 = Weight fraction of monomer 1 & 2 in copolymer)
Tg and Tm (Melting temperature)
 There are two types of temperature parameters that come under
transition temperatures namely, glass transition temperature (Tg) and
melting temperature (Tm).
 In polymer industry, these temperatures are used for the identification
of materials and their quality parameters.
 Glass transition temperature, a reversible change in phase from viscous
to glassy or vice versa occurs in the Amorphous regions of the polymer
due to a change in temperature, whereas at melting temperature,
the crystalline or semi-crystalline regions of a polymer change to a
solid amorphous phase.
 Melting temperature (Tm) is the temperature at which a phase transition
occurs; for example, solid to liquid or liquid to vapour.
 The melting temperature (Tm) is a temperature at which a transition
from a crystalline or semi-crystalline phase to a solid amorphous phase
takes place.
Tg and Tm
 The curve plotted between specific
volume & temperature.
 For crystalline polymer a
discontinuous change in specific
volume at Tm.
 For amorphous polymer the change is
continuous, no Tm is observed but
there is increase in slope at Tg.
 For semi-crystalline polymer,
intermediate to crystalline and
amorphous and shows Tm & Tg.
 Relationship between Tg & Tm:
Tg = Tm/2 (for symmetrical polymer)
Tg = 2 Tm/3 (for unsymmetrical
polymer)
Crystallinity in polymers

 Polymer crystallinity is one of the

most important property of all
polymers. polymers exists both in
amorphous and crystalline form.
 Crystallinity is indication of
amount of crystalline region in
polymer with respect to amorphous
region.
 It can be seen that part of molecules
are arranged in regular order, these
regions are called crystalline
regions.
Crystallinity in polymers
 No polymer is completely crystalline. If you're making plastics,
this is a good thing. Crystallinity makes a material strong, but it
also makes it brittle.
 A completely crystalline polymer would be too brittle to be used
as plastic. The amorphous regions give a polymer toughness, that
is, the ability to bend without breaking.
 Most crystalline polymers are not entirely crystalline. The chains,
or parts of chains, that aren't in the crystals have no order to the
arrangement of their chains. They are in the amorphous state.
 A crystalline polymer really has two components: the crystalline
portion and the amorphous portion. The crystalline portion is in
the lamellae, and the amorphous potion is outside the lamellae.
Degree of Crystallinity
 The degree of crystallinity is defined as the fractional amount of polymer that is
crystalline and it is expressed in the terms of mass fraction or the volume fraction.
 For semi-crystalline polymers, the degree of crystallinity is one of its most important
physical parameter since it reflects the sample’s morphology and determines various
mechanical properties of polymers.
 The degree of crystallinity has a significant influence on hardness, density, transparency
and diffusion.
 DSC is used to determine degree of crystallinity. The other methods are x-rays
diffraction, density measurement, NMR and IR (InfraRed) spectroscopy.
 The degree of crystallinity ranges from 5 to 95% and expressed by following equation –
XV = (ds - da)/ (dc - da)
where XV = degree of crystallinity, dc = density of crystalline sample
da = density of amorphous sample , ds = density of semi crystalline sample
Degree of Crystallinity
 The percentage of crystallinity expressed as –
% of crystallinity = [dc (ds - da)/ ds (dc - da)] X 100
 The % of crystallinity depends on basically 3 factors ---
❖ Rate of cooling of polymer, if it is high, the crystallinity will be less.
❖ Polymer structure, if structure have simple unit & high degree of molecular
ordering, they will be more crystalline. In copolymers crystallinity is less.
❖ Chain length, branching & interchain bonding, also affected the
crystallinity of polymers. HDPE have long unbranched hydrocarbon chain and
form crystalline with amorphous segment material while LDPE having small
but highly branched chain, not form crystalline structure easily. They are soft,
weaker, less dense and easily deformed polymers.
Crystallisability
 Crystallisability is the maximum crystallinity that a polymer can achieve at a
particular temperature, regardless of the other conditions of crystallization.
 Crystallisability at a particular temperature depends on-----
❖ The chemical nature of macromolecular chain, harder the polymer, greater the
crystallinity. Higher the intermolecular forces greater the crystallinity.
❖ Geometrical structure of polymer, crystallinity of linear polythene is 90% while
branched polythene is 40% only. The trans isomer (gutta percha) is more crystalline
than cis isomer(natural rubber).homopolymers are more crystalline than copolymers.
❖ Molecular weight of the polymeric chain, high molecular weight favors the crystallinity.
❖ Molecular weight distribution in the polymer. Narrow and high molecular weight
increases the crystallinity.
❖ Rate of cooling
❖ Temperature of molten polymer
❖ Rate of crystal growth
Crystallization
 Crystallization of polymers is a process associated with partial alignment of their
molecular chains.
 These chains fold together and form ordered regions called Lamellae, which
compose larger spheroidal structures named spherulites (spherical semi
crystalline region inside non branched linear polymer). In a sample of a
crystalline polymer weighing only a few grams there are many billions of
spherulites.
 Polymers can crystallize upon cooling from melting, mechanical stretching or solvent
evaporation. Crystallization affects optical, mechanical, thermal and chemical
properties of the polymer.
Crystallization
Properties affected by crystallinity
 Hardness: the more crystalline polymer, the more regularly aligned its chains.
Increasing the degree of crystallinity increases hardness and density.
 Tensile strength: as crystallinity of polymer increases, tensile strength also increases.
 Permeability: crystallinity decreases the rate of penetration of liquid/vapour through the
polymer matrix (permeability) crystalline polymers are far less permeable than the
amorphous variety. It means as the polymer crystallinity increases with decrease in
permeability.
 Strain & rigidity: crystallinity is directly proportional to strain n rigidity of polymers.
 Density: crystallinity increases the close packing of polymeric chain thus density of
polymer also increases.
 Transparency: crystallinity decreases the transparency of polymers.
 Molecular weight: as crystallinity increases mole. wt of polymer sample also increases
and vice versa.
Morphology & order of polymers
 Polymer morphology generally describes the arrangement and microscale
ordering of polymer chains in space.
 The macroscopic physical properties of a polymer are related to the interactions
between the polymer chain.
 Disordered polymers:
❖ In the solid state, atactic polymers, polymers with a high degree of branching and
random copolymers form amorphous (i.e. glassy structures). Atactic PP is a gummy
solid while its isotactic form is highly crystalline.
❖ In melt and solution, polymers tend to form a constantly changing "statistical
cluster“.
❖ In the solid state, the respective conformations of the molecules are frozen. Hooking
and entanglement of chain molecules lead to a "mechanical bond" between the
chains. Hence crystallinity increases.
❖ Intermolecular and intramolecular attractive forces only occur at sites where
molecule segments are close enough to each other. The irregular structures of the
molecules prevent an ordered arrangement.
Morphology & order of polymers
 Linear polymers
❖ Linear polymers with periodic structure, low branching and stereoregularity
(molecules arranged in an ordered/regular pattern. e.g. not atactic) have
a semi-crystalline structure in the solid state.
❖ In simple polymers (such as polyethylene), the chains are present in the crystal
in zigzag conformation. Several zigzag conformations form dense chain
packs, called crystallites or lamellae.
❖ The lamellae and are much thinner than the polymers are long (often about
10 nm). They are formed by more or less regular folding of one or more
molecular chains.
❖ Amorphous structures exist between the lamellae. Individual molecules can
lead to entanglements between the lamellae and can also be involved in the
formation of two (or more) lamellae (chains than called tie molecules).
❖ Several lamellae form a superstructure, a spherulite, often with a diameter in
the range of 0.05 to 1 mm.
Morphology & order of polymers
 The type and arrangement of (functional) residues of the repeat units effects or
determines the crystallinity and strength of the secondary valence bonds.
 In isotactic polypropylene ( functional groups are on same side of polymeric
chain), the molecules form a helix. Like the zigzag conformation, such helices
allow a dense chain packing.
 Particularly strong intermolecular interactions occur when the residues of the
repeating units allow the formation of H-bonds, as in the case of p-Aramid
[Aramid fibers are a class (aromatic polyamide) of heat-resistant and
strong synthetic fibers .They are used in aerospace and military applications].
 Crystallinity and superstructure are always depend on the conditions/mode of
their formation.
 Compared to amorphous structures, semi-crystalline structures lead to a higher
stiffness, density, melting temperature and higher resistance of a polymer.
Morphology & order of polymers

1)interlocking of polymers 2) lamella with tie molecules

3) p-aramid with H-bond 4) polypropylene helix
Morphology & order of polymers
 Cross-linked polymers:
❖ Wide-meshed cross-linked polymers are elastomers and cannot be molten
(unlike thermoplastics); heating cross-linked polymers only leads to decomposition.
❖ Thermoplastic elastomers, on the other hand, are reversibly "physically crosslinked"
and can be molten.
❖ Block copolymers in which a hard segment of the polymer has a tendency to
crystallize and a soft segment has an amorphous structure are one type of thermoplastic
elastomers. the hard segments shows interlocking of polymers/ crosslinking.
 Chain conformation
❖ The space occupied by a polymer molecule is generally expressed in terms of radius of
gyration, which is an average distance from the center of mass of the chain to the chain
itself.
❖ Alternatively, it may be expressed in terms of pervaded volume, which is the volume
spanned by the polymer chain and scales with the cube of the radius of gyration.The
simplest theoretical models for polymers in the molten, amorphous state are deal
chains.
THANKS