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A – liquid region
B – viscous liquid w/ some elastic
response
C – rubbery region
D – glassy region
E – crystallites in a rubbery matrix
F – crystallites in a glassy matrix
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
Tg = V1Tg1 + V2Tg 2
Tg = V1Tg1 + V2Tg 2
Random or alternating
(nonisomorphous systems)
1 W1 W2
= +
Tg Tg1 Tg 2
Wi – weight fraction of
component i
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
separation
• 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
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
Example
• What is the Tg of polystyrene at Mn = 3000?
K
Tg = Tg ,∞ −
Mn
5
2 × 10 0
= 100 − = 33 C
3000
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:
1 W1 W2
Tg = V1Tg1 + V2Tg 2 = +
Tg Tg1 Tg 2
Effect of Plasticization on Tg
Solution:
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
tendency
- 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
Tm
1) MPs approach that of PE as the
spacing between polar groups
increases
2) For the same number of chain
atoms in the repeat unit,
polyureas, PAs, and PUs have
high MPs than PE; polyesters
have lower
Tm = 390 K = 117 0 C