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Thermal Transition in Polymers

Essentials of Polymer Science and

ChE 297
So far, we have covered the
following topics
• Introduction; Classification of Polymers
• Polymerization mechanisms (chain-reaction,
ionic, coordination, step-growth, ring-
• Chemical bonding and polymer structure
(primary: monomer, secondary: polymer
molecule, and tertiary: aggregate)
• Thermal transition in polymers
Thermal transition in polymers is different
compared w/ simple compounds
• Do not exist in gaseous state
• Decompose rather than boil
• Since a polymer is a mixture of molecules of
different chain lengths, transition from solid to
liquid is “diffuse”; occurs at a temperature
• On melting, they become very viscous
(viscoelastic); not freely flowing
Figures show relative thermal responses of
simple molecules and polymers

Simple molecules: Polymers:

transition at specific T transition at T range; MWD
There is still fundamental difference between
simple compounds and polymer in T transition
• Molecular motion = thermal energy
• Opposition to molecular motion = cohesive
forces (structural segments along the chain +
between neighboring chains)
• Cohesive forces  thermal transition 
polymer structure
• Glass transition temperature Tg
• Crystalline melting point Tm
What is the difference between Tg
and Tm?
• Solid to liquid transition is gradual in amorphous polymers
(intermediate rubbery state; no phase transition)
• Tg – a narrow T range; hard, brittle glass to softer, rubbery
• Partially crystalline polymer – glass transition only on the
amorphous phase; crystalline zones unchanged; act as
• If you continue heating  Tm – temperature at w/c the last
crystallite starts melting
• Tm – depends on crystallinity; size distribution of crystallites
Amorphous  solid-to-liquid
transition occurs very gradually, going
through an intermediate
“rubbery” state w/o phase
- glass transition (a T range;
hard/brittle to soft/rubbery)

Semicrystalline  only amorphous

regions undergo transition at Tg;
crystalline zones melt at Tm;
What is glass transition?

A – liquid region
B – viscous liquid w/ some elastic
C – rubbery region

D – glassy region
E – crystallites in a rubbery matrix
F – crystallites in a glassy matrix

Specific volume-temperature curves

for a semi-crystalline polymer
What is glass transition?
Amorphous – ABCD line
Crystalline – ABEF line

D – constant rate of V expansion

At Tg – sudden increase of rate (low to
high coefficient of V expansion)
DCBA = glass  rubber  viscous liquid

Less drastic glass transition in crystalline

polymer (FE); only amorphous domains
are in glass transition

A E range – rubber matrix + rigid

crystallites domains; polymer still rigid,
pliable, tough
Specific volume-temperature curves Similar behavior bet. amorphous and
for a semi-crystalline polymer crystalline polymers after Tm
What is the relationship between
molecular motion and glass transition?
• Intramolecular bonds – covalent bonds (primary
valence bonds)
• Intermolecular attraction – secondary bonding
forces; opposed by thermal agitation (vibration,
translation, rotation)
• Thermal degradation – energy of vibration > primary
bonding between atoms
• Glass transition, crystalline melting, deformation 
rotation & vibration of molecular chains
What is the relationship between
molecular motion and glass transition?
• Glassy state of amorphous polymer – frozen
chain segments in fixed positions; low-
amplitude vibratory motion
• Increase T  greater vibrations; reduction in
secondary bonding forces
• At Tg  rotational/translational motion of
chain ends and some segments
• Tg – onset of large-scale cooperative motion
of chain segments
What is the relationship between
molecular motion and glass transition?
• T < Tg – only atoms/small groups of atoms
move against local restraints of intermolecular
• Other transitions – α, β, γ, etc below Tg
• Conformation at low temperature – fully
extended chain (min. energy)
• Fully extended chain – low free volume 
difficult flow, hard, brittle, glassy
Theories of glass transition and
measurement of Tg
• Kinetic approach – considers relaxation
phenomena associated with glass transition
• Thermodynamic approach – considers entropy
of the glassy state
• Free volume theory
Theories of glass transition and
measurement of Tg
• Kinetic theory – glass transition as dynamic
phenomenon; Tg depends on heating/cooling
• Predicts Tg as dependent on time scale of
• Kinetic models that relate molecular motion
w/ macroscopic properties observed during
Theories of glass transition and
measurement of Tg
• One kinetic approach – vitrification is a
reaction of moving chain segments between
energy states; needs a “critical hole” or
“space” when moving bet. energy states
• Creating this hole – needs energy to overcome
cohesive forces (bet. mols) and potential
energy barrier (bet. rearrangements)
• Tg – temperature at w/c number of these
holes of sufficient size permits flow
Theories of glass transition and
measurement of Tg
• Equilibrium theory – glass transition as a true 2nd
order thermodynamic transition
• Consequence of the changes in conformational
entropy w/ changes in T
• At T < Tg – reduced number of available
• At T = Tg – equilibrium conformational energy = 0;
conformational changes become infinite
• T of experiment approaches Tg as time scale of
experiment becomes longer
Free Volume Theory of Glass Transition
and Measurement of Tg
Free volume of a substance (Vf) = V f = V − V0
specific volume – actual space occupied by molecules

V’ – extrapolated volume of glass at 0 K

αg – thermal expansion coeff. of the glass
V0 = V '+α gT

f – free volume fraction at T f = V f V = f g + α f (T − Tg )

fg – free volume fraction at Tg
αl – thermal expansion coeff. above Tg df 1 dV f
αg – thermal expansion coeff. below Tg
α f = αl − α g = =
dT V f dT
fg – usually 0.025 for most amorphous polymers
When amorphous polymers are cooled, they become glassy when f  fg

Tg measurement – dilatometry (sp. vol w/ T); refractometry; calorimetry (DSC, DTA);

mechanical energy absorption (DMA)
What are the factors that affect the
glass transition temperature?
• When T = Tg – large scale cooperative movement of
chain segments
• Structural factors/external variables that affect chain
mobility  also affect Tg
• Structural factors: chain flexibility, stiffness (steric
hindrance, polarity, inter-chain attractive forces),
geometric factors, copolymerization, MW, branching,
cross-linking, crystallinity
• External variables: plasticization, pressure, rate of
Effect of Chain Flexibility on Tg

 Chain flexibility – ease of rotation around primary valence bonds

 Low hindrance to rotation = low Tg
 Long-chain aliphatic groups — ether and ester linkages — enhance chain flexibility
(lowers Tg), while rigid groups like cyclic structures stiffen the backbone (enhances Tg).
Effect of Chain Flexibility on Tg

Bulky side groups that are stiff and close to the

backbone cause steric hindrance, decrease chain
mobility, and raise Tg
Effect of Chain Flexibility on Tg

Decrease of Tg with Increasing Flexibility of Side Chains for

Polymethacrylate Series

Longer R  more flexible chain  longer distance bet.

chains  higher f  lower Tg (accdg. to free V theory)
Effect of Geometric Factors on Tg
 Geometric factors = backbone symmetry and double bonds on the main chain

 Tg (asymmetrical) > Tg (symmetrical)

 Discrepancy – one expects

additional groups near the backbone
of a symmetrical polymer would
cause steric hindrance  raise Tg

 Discrepancy due to
conformational requirements;
additional groups are accommodated
in a conformation w/ a loose
structure  raises Vf  lowers Tg
Effect of Geometric Factors on Tg
Relative effects of cis-trans configuration on Tg

Double bonds in the cis form reduce the energy barrier for rotation of adjacent bonds;
“soften” the chain; reduces Tg
Effect of Interchain Attractive
Forces on Tg
Effect of Polarity on Tg

Steric effects due to pendant groups are similar, but polarity increases
Tg increases with polarity
Effect of Interchain Attractive
Forces on Tg

Effect of Polarity on the Tg

on some acrylic polymers

Tg increases with increasing CED

Effect of Copolymerization on Tg
• Difficult but desirable to control either Tg or
Tm independent of each other
• Polymer modification – copolymerization
and/or polyblending (polymer alloys)
• How to characterize a copolymer system? –
geometry (random, alternating, graft, or
block); compatibility (miscibility) of two
Effect of Copolymerization on Tg
• Isomorphous systems – homogeneous copolymers
and compatible polyblends
• Component monomers occupy similar volumes;
capable of replacing each other in the crystal system
• Resulting polymer is homogeneous;
polyblends/copolymers have similar transition
• Copolymerization merely shifts the Tg to the position
intermediate between those of the two
Effect of Copolymerization on Tg
Estimation of Tg for
isomorphous systems

Tg = V1Tg1 + V2Tg 2

Vi, Tgi – volume fraction

and pure glass
temperature of
component i

Modulus – temperature curves of

polybutadiene (100/0) and polystyrene
(0/100) & for various compositions
Effect of Copolymerization on Tg

Tg = V1Tg1 + V2Tg 2

Variation in Tg with copolymer

Effect of Copolymerization on Tg
• Nonisomorphous systems – specific volumes of
monomers are different; Tg dependent on resulting
polymer geometry
• Random or alternating – homogeneous; Tg between
those of the two homopolymers
• Increased disorder (from random or alternating
distribution of monomers) – increases free volume;
lower Tg predicted by linear mixing rule
Effect of Copolymerization on Tg

Random or alternating
(nonisomorphous systems)
1 W1 W2
= +
Tg Tg1 Tg 2
Wi – weight fraction of
component i

e.g. methyl methacrylate–acrylonitrile,

styrene–methyl methacrylate, and
acrylonitrile–acrylamide copolymers
Effect of Copolymerization on Tg

Random or alternating
(nonisomorphous systems)
e.g. methylacylate methylmethacrylate;
vinylidene chloride–methylacrylate
 Monomers introduce significant
interaction between chains
Effect of Copolymerization on Tg
• Nonisomorphous systems – specific volumes of
monomers are different; Tg dependent on resulting
polymer geometry
• Block and graft copolymers – incompatible; phase
• One phase will be dispersed in a continuous matrix
of the other
• Two separate glass transition values; corresponding
to Tg of each homopolymer
Effect of Copolymerization on Tg

Modulus vs. temperature for polyblends of polystyrene and a 30/70 butadiene–

styrene copolymer. Numbers on the curves are the weight percent of polystyrene
in the blend
• What is the Tg of butadiene–styrene
copolymer containing 10 vol% styrene?

Answer: Butadiene and styrene form a completely

compatible random copolymer.

Tg = V1Tg1 + V2Tg 2
= (0.90 )(− 80 ) + (0.10 )(100)
= −620 C
Effect of Molecular Weight on Tg
• Chain end segments restricted only at one end –
higher mobility than internal segments
• At given T – chain ends provide higher free volume
for molecular motion
• Increase in chain ends  decrease in MW; increase
in free volume; decrease in Tg
• As MW increases, Tg approaches asymptotic value

K Tg ,∞ = 1000 C
Tg = Tg ,∞ − For PS:
Mn K = 2 x 105
• What is the Tg of polystyrene at Mn = 3000?
Tg = Tg ,∞ −
2 × 10 0
= 100 − = 33 C
Effect of Cross-Linking and
Branching on Tg
• Cross-linking reduces chain mobility  increase in Tg
• For lightly cross-linked systems (e.g. vulcanized
rubber), we have the following empirical relation:

T0 - the glass transition temperature of

4 the uncross-linked polymer having the
3 .9 x 10 same chemical composition as the cross-
Tg − T 0 = linked polymer
Mc Mc – number-average molecular weight
between cross-link points

Branching increases the separation between chains,

enhances the free volume, and therefore decreases Tg
Effect of Cross-Linking and
Branching on Tg
• Highly cross-linked systems (phenolics; epoxy
systems) – glass transition virtually infinite
• Molecular chain length between cross-links
becomes smaller than that required for
cooperative segmental motion
Effect of Crystallinity on Tg
• In semicrystalline polymers, the crystallites may be
regarded as physical cross-links that tend to reinforce
or stiffen the structure
• Tg will increase with increasing degree of crystallinity
• Empirical relationship bet. Tg and Tm:
Effect of Plasticization on Tg
• Plasticity - ability of a material to undergo plastic or permanent
• Plasticization - process of inducing plastic flow in a material;
addition of low-molecular-weight organic compounds (plasticizers)
• Usually nonpolymeric, organic liquids of high boiling points;
miscible and remains w/ polymer
• Plasticizers reduce Tg (e.g. PVC and dioctylphthalate (DOP))
• Plasticized system may act as homogeneous polyblend (in
calculations, assume MP of plasticizer as its Tg)

1 W1 W2
Tg = V1Tg1 + V2Tg 2 = +
Tg Tg1 Tg 2
Effect of Plasticization on Tg

Shear modulus G vs. temperature, measured for a time scale of approximately 1

s, poly(vinylchloride) plasticized with diethylhexyl succinate. I, 100% monomer; II,
91%; III, 79%; IV, 70.5%; V, 60.7%; VI, 51.8%; VII, 40.8%.

 Observed broadening of the transition region in plasticized PVC

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

What is the crystalline melting
point Tm?
• Melting (simple materials) – change from
crystalline solid state to liquid form; true first-
order thermodynamic transition;
discontinuities in primary thermodynamic
variables (Cp, ρ, n, transparency, etc)
• Free energy of the process is zero
What is the crystalline melting
point Tm?
• Macromolecular nature of polymers and the
existence of molecular weight distribution
(polydispersity) lead to a broadening of Tm
• Crystallization involves chain folding 
inherent defects  actual Tm < ideal
thermodynamic MP
• Melting in polymer is more rate sensitive than
that in simple molecules
• No polymer is 100% crystalline
 Any property whose values are different for the crystalline and amorphous
states provides a convenient method for measuring the crystalline melting
point (dilatometry, calorimetry, thermal analysis, dynamic techniques, creep)
What is the crystalline melting
point Tm?
• Factors that determine crystallization
- structural regularity  for close alignment of
polymer molecules to form crystals
- chain flexibility  susceptibility to thermal
agitation; less tendency to crystallize
- intermolecular bonding  specific groups
that promote enhanced intermolecular
interaction; structural features that lead to
identity periods
What are factors that affect Tm?
• Tm = ∆Hm/∆Sm
• ∆Hm - difference in cohesive energies between
chains in the crystalline and liquid states
• ∆Sm - difference in the degree of order between
polymer molecules in the two states
• ∆Hm – independent of MW; affected by polar groups
• ∆Sm – dependent on MW; structural factors (e.g.
chain stiffness)
Effect of Intermolecular Bonding on
1) MPs approach that of PE as the
spacing between polar groups
2) For the same number of chain
atoms in the repeat unit,
polyureas, PAs, and PUs have
high MPs than PE; polyesters
have lower

 decrease in the CED associated

w/ the decrease in the density of
sites for intermolecular bonding
(increased space between polar
Trend of crystalline melting points in groups) leads to a reduction in the
homologous series of aliphatic polymers MPs
Effect of Intermolecular Bonding on

 same number of chain backbone atoms,

chain flexibility (∆Sm) will not be
significantly different for the various
 Similar in trend w/ previous figure

 Tm of Polyester < PE: presence of O

atoms in chain offsets weak polar bonding
from ester linkages

Group contributions to the melting point

Effect of Intermolecular Bonding on

 MPs of the nylons reflect the density of the hydrogen-bond-forming amide

 Amide units are more polar than the ester units
 Nylon 6 > polycaprolactone
Effect of Structure on Tm
 Unlike Tg, Tm is affected by
structural regularity

 Ratio of Tg/Tm (K) ranges from 0.5

– 0.75
 0.5 in symmetrical polymers (e.g.
PE and polybutadiene)

 0.75 in unsymmetrical polymers

(PS and polychloroprene)

Relation between Tm and Tg for

various polymers
Effect of Chain Flexibility on Tm
• Polymers w/ rigid chains have high Tm than w/
flexible chains
• Stiff backbone  low conformational entropy
• Chain flexibility  -O- and –(COO)-; increase
chain length of CH2 units in main chain
• Polar groups and rings restricts rotation of the
backbone  increases Tm
Effect of Chain Flexibility on Tm
Effect of Chain Flexibility on Tm
Effect of Copolymerization on Tm
• If comonomers have similar specific volumes, they can replace
each other in the crystal lattice (i.e., isomorphous systems),
and the MP will vary smoothly over the entire composition
• If the copolymer is made from monomers each of w/c forms a
crystalline homopolymer, the degree of crystallinity and the
crystalline MP decrease as the second constituent is added to
either of the homopolymers

Tm – MP of copolymer; Tm0 – MP of homopolymer/crystallizing component;

∆Hm – heat of fusion of the homopolymer/crystallizing component
X – mole fraction of homopolymer/crystallizing component
Effect of Copolymerization on Tm
• Impossible to attempt to raise the Tm of a
polymer by copolymerizing with small
amounts of a monomer with a high melting
point (except isomorphous systems; rare in
vinyl polymers)
• Block & graft copolymers w/ long
homopolymer chain sequences – crystallize;
exhibit properties of both polymers; have 2
• What is the melting point of a copolymer of ethylene
and propylene with 90 mol% ethylene?
1 1 R
= 0− ln x
Tm Tm ∆H m

Tm0 = 1350 C = 408 K (MP of PE)

∆H m of PE = 66.5 cal/g = 7.80 x 103 J/mol
R = 8.314
x = 0.9

Tm = 390 K = 117 0 C