Processing and Properties of Polymers (PPP)

3. Glass Transition
Martin van Drongelen, Leon Govaert
 Previous lectures

Structure of Thermoplastics
- Entanglements

- Chain length / mass distributions

- Chain configurations, dimensions, regularity

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 Molecular Weight
Example exam question 1 in lecture 2

PE has a molar mass of 140.000 g/mol, b0=0,154 nm and C∞ =6,7. r0

What is the average endpoint distance?

Molar mass PE = 28 g/mol

140.000/28 = 5000 units = 9999 segments (n)

9999*6,7*0.1542 = 1588 nm2

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 Molecular Weight
Example exam question 2 in lecture 2

Grade Molar mass Added mass

[g/mol] [g]
A 25000 50
B 40000 40
C 90000 30
D 180000 18
E 360000 12

For producing a certain type of PS coffee cups a number of monodisperse grades are
mixed, as indicated in the table above. What is the polydispersity of this blend?

A. 0,2 B. 2,0 C. 20 D. No clue, just give me the answer

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 Molecular Weight
Answer to Exam question

Total mass: 150 g.

Mw = (50/150)*25000 + (40/150)*40000 + (30/150)*90000 +
(18/150)*180000 + (12/150)*360000 = 87400 g/mol.
For Mn: number of mmol is 2 + 1 + 0.33 + 0.1 + 0.033 = 3.463.
Using molar fractions: Mn = (2/3.463)*25000 + (1/3.463)*40000 +
(0.33/3.463)*90000 + (0.1/3.463)*180000 + (0.033/3.463)*
360000 = 43269 g/mol.
Polydispersity D = Mw/Mn = 2.02

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 Molecular Weight
Example exam question 3 in lecture 2

Two polydisperse polymers are mixed in equal amounts of mass.

Calculate Mn and Mw of the mixture.

Poly Mn Mw
mer
1 15000 50000
2 10000 60000

Mw = 0,5*50000 + 0,5*60000 = 55000 1/Mn = 0,5/15000 + 0,5/10000.

Mn = 12000

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 Today’s lecture

 Phases and transitions in polymers

 Kinetics and influence of time

 Intramolecular interaction
 Intermolecular interaction

 The role of thermodynamics

 Tg of mixtures and co-polymers

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 Transition temperature

At high temperatures, all thermoplastic polymers are liquid and therefore amorphous.

Amorphous phase:
The viscosity & modulus increases strongly under the glass transition temperature Tg, but
the structure is retained - these polymers remain amorphous and able to ‘flow’

entanglement

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 Molecular background

With high mobility of the chains, segmental

mobility takes place on short time scales.

Entanglements remain!

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 Amorphous polymers
Elastic modulus

Log E chains
Tg : glass-rubber transition
“frozen in”
Tf : flow temperature

segmental
mobility

chain slip
low molecular
weight
T
Tg Tf
 Transition temperatures
For an amorphous polymer

T > glass-rubber transition temperature Tg

complete rotational freedom of the main chain
“main chain segmental motion”
entanglements still prevent chains from slipping

T > rubber-liquid transition temperature Tf:

chains can move completely past each other
“chain slip”
 ‘States’ of a polymer
For an amorphous polymer

Glass state
chains "frozen in";
modulus determined by secondary interaction forces
between chains: intermolecular interactions

Rubber state
segmental rotation freedom
chains move with load
coherence remains through entanglements

Liquid state
mobility allows chains
to slip past each other
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 Glass-rubber transition temperature
A matter of perspective

log E
PS
NBR

cross-linked

-40o 95o T [oC]

Tg is polymer-specific

how we perceive a polymer depends on the

distance of Tg to room temperature!
 Influence of Tg
Challenger O-ring

The disaster with the space shuttle Challenger was caused by failure of rubber O-rings that were
employed beneath their glass-rubber transition temperature on a peculiarly cold morning in Florida.
At this temperature the material was not flexible enough to adequately seal the sections between
the two solid-fuel rocket boosters.
 Today’s lecture

 Phases and transitions in polymers

 Kinetics and influence of time

 Intramolecular interaction
 Intermolecular interaction

 The role of thermodynamics

 Tg of mixtures and co-polymers

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D30 Company

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Smart armour application
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link
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 Molecular background

molecular mechanism: jump frequency:

∆U
−
segmental mobility Arrhenius: f= f0 ⋅ e kT

of the main chain

characteristic timescale:
energy

∆U
τ= A ⋅ e kT
ΔU

∆U
position lnτ= c +
1 2 kT

potential barrier equivalence of time

for changes in conformation and temperature
 Kinetics of the glass transition

characteristic timescale for the glass transition

∆U
τ c = Ae kT

the timescale on which considerable

conformation changes can occur

this timescale depends on temperature!

conformation changes also possible at lower temperatures

even beneath Tg!

 Kinetics of conformations
Time scale experiment vs time scale conformations

Rubbery behaviour requires very large conformational changes.

Not just the relaxation time of the molecules :

but also the experimental time scale (τexperiment) is of interest

Glass-like behaviour Rubbery behaviour

Deborah number

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 Kinetics of conformations
Influence of experimental timescale

In the Book of Judges, 5:5, the Prophetess Deborah proclaimed:

“The mountains flowed before the lord”

“Deborah knew two things. First, that

the mountains flow, as everything flows.
But, secondly, that they flowed before
the Lord, and not before man, for the
simple reason that man in his short
lifetime cannot see them flowing, while
the time of observation of God is
infinite.”

M Reiner (1964) “The Deborah number”.

Phys. Today. 17, pp62.]
Kinetics of conformations
Influence of experimental timescale

the shorter the

experimental timescale,
the higher Tg
 Kinetics of conformations
Influence of experimental timescale

In 1930 Professor Parnell started an experiment to visualize that pitch, a tar

derivative that feels at room temperature as a (brittle) solid (τc>τexperiment),
behaves like a viscous fluid in the long term (τc<τexperiment).

http://www.physics.uq.edu.au/pitchdrop/pitchdrop.shtml Link to timelapse video

Link to live stream of experiment

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Pitch drop experiment
One of the longest experiments
Date Event Years Months
1927 Hot pitch poured
Oct 1930 Stem cut
Dec 1938 1st drop fell 8,1 98
Feb 1947 2nd drop fell 8,2 99

Apr 1954 3rd drop fell 7,2 86

May 1962 4th drop fell 8,1 97
Aug 1970 5th drop fell 8,3 99
Apr 1979 6th drop fell 8,7 104
Jul 1988 7th drop fell 9,2 111
Nov 2000 8th drop fell 12,3 148
Jul 2013 9th drop 13,4 156
 Relation to the structure
Intra vs inter

Intramolecular:

Intermolecular:

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 Relation to the structure
Characteristic chain stiffness

Previously, we saw an application of the characteristic chain stiffness (C∞):

This parameter is dependent on the chain interaction

(especially the intramolecular interactions):
PE: 6,7
PVC: 6,8 Increasing steric hindrance

PMMA: 8,8
PVAc: 9,0
PS: 10,0

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 Relation to the structure
Intramolecular: steric hindrance

Steric hindrance from side groups ensures that the chains have less rotational freedom.

X=H : R = 0.09 nm, little hindrance

X=F : R = 0.14 nm, some hindrance
X = Cl : R = 0.18 nm, severe hindrance
X = CH3 : R = 0.20 nm, severe hindrance

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 Relation to the structure
Intramolecular interactions: size side groups

PE Tg=-120 °C [ CH2 CH2 ]n

PP Tg=-15 °C [ CH2 CH ]n
CH3

PS Tg=100 °C [ CH2 CH ]n

Side group prevents rotation and thus increases chain stiffness and thus Tg.

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 Relation to the structure
Example: PMA and PMMA

poly(methyl acrylate) poly(methyl methacrylate)

Tg=9 °C Tg=114 °C

Rubbery Glassy

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 Relation to the structure
Intramolecular: rigid bonds in the main chain

Not only the rotation barrier through side groups, but also freedom of rotation of
the main chain itself.

Decreasing flexibility
C O C POM

= increasing C∞
C N C PA

C C C BR

C PC

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 Relation to the structure
Intramolecular interactions

[ CH2 CH2 ]n PE Tg = -120 °C

[ CH2 CH2 O CO CO O ]n PETP Tg = 70 °C

CH3 O

[O C O C ]n PC Tg = 150 °C
CH3

The stiffer the main chain (or: the lower the chain flexibility), the higher Tg.
- more difficult to move segmentally.

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 Relation to the structure
Intramolecular: chain length

Each chain end is extra flexible, therefore probably the (number average) molecular
weight influences Tg.
An empirical relationship has been found:

Even if a polymer is strongly cross-linked (with crosslinks / entanglements), this has

an effect on chain stiffness and Tg is higher.

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 Relation to the structure
Intermolecular

Links in the main chain are much stronger than the bonds between the chains
themselves; the secondary bonds:

 Permanent dipoles
 Induced dipoles
 Dispersion forces
 Hydrogen bonds

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Relation to the structure
Intermolecular: permanent dipole

An electro-static attraction is created.

Polarity measure:
dipole moment.

Dipole moment

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 Relation to the structure
Intermolecular interactions: dipole interaction

PP Tg=-15 °C [ CH2 CH ]n
CH3

PVC Tg=85 °C [ CH2 CH ]n Dipole moment

Cl

PAN Tg=120 °C [ CH2 CH ]n

CN

Due to increasing dipole interaction, the Tg increases.

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 Relation to the structure
Intermolecular: dispersion forces (Vanderwaals)

Due to fluctuations within the electron cloud, the charge distribution fluctuates.
London-Vanderwaals forces are the most universal interacting forces.

Due to the length of the polymer chains and strong cross-linking, this force is very
important for polymers!

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 Relation to the structure
Intermolecular: hydrogen bonds

Hydrogen can form a relatively strong bond with O, N and F atoms: hydrogen bonds.
The charge of the hydrogen atom is distributed over two adjacent O, N and / or F
atoms. A hydrogen donor and –acceptor group must be present in the polymer.

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 Relation to the structure
Intermolecular: hydrogen bonds in polymers

There are a number of bonds that often return in polymers that can form a
hydrogen bridge:

The valency of the H-atom of these side groups are shared.

Well-known example: polyamides (nylons)

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 Relation to the structure
Intermolecular interactions: size side groups

[ CH2 CH ]n PP Tg=-15 °C
CH3

[ CH2 CH ]n
PB Tg=-25 °C
CH2

CH3

[ CH 2 CH ]n Polyhexene-1 Tg=-50 °C
CH 2
Chain interactions and therefore also Tg (often) decrease due to the
CH 2
increasing length of the side chain.
CH2 Note: the intramolecular interaction increases with the length of the
CH3
side chain, so the influence on Tg is not always immediately
predictable.
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 Relation to the structure
Summary of the factors that influence Tg

Intramolecular:
Chain flexibility
Size side groups
Chain length (Mn)
Intermoleculair
Dipole interaction side groups
VanderWaal's forces
Hydrogen bonds
Length side branches
Addition of plasticizers
Degree of cross-linking (more bonds between chains)

In addition, the value of Tg depends on the time scale of the experiment!

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 Secondary glass transition

In addition to the glass-rubber transition, some polymers also have a secondary

glass transition which is always at a lower temperature than Tg.

In the secondary glass transition, very local mobility develops (with respect to
segmental mobility at the glass-rubber transition).

example: cyclo-hexyl side group

two "states":

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 Secondary glass transition
Influence on modulus

In the secondary glass transition the

modulus decreases less than near the Tg.

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 Today’s lecture

 Phases and transitions in polymers

 Kinetics and influence of time

 Intramolecular interaction
 Intermolecular interaction

 The role of thermodynamics

 Tg of mixtures and co-polymers

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 Glass transition
The thermodynamic picture – influence of time

liquid

Volume
glass thermodynamic
metastable equilibrium

equilibrium
volume

Temperature
Tg

no thermodynamic equilibrium in the glass state!!

strive for equilibrium volume decreases in time

“physical ageing”
 Glass transition
The thermodynamic picture – influence of cooling rate

V
liquid
fast
glass

slow

Tg ?? T

At higher cooling rates the deviation from the equilibrium volume is larger
stronger time-dependent volume shrinkage
 Glass transition of mixtures
Molecular dissolved systems

log E
PPO
“Noryl” If the polymers are "compatible", a
PS molecular mixture is created

"Real mixtures"

100 160 220 T

The "mixture" behaves like a new material with one Tg,

the height of which depends on the mixing ratio.
There are few polymers that are fully compatible with each other!

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 Glass transition of mixtures
Incompatible polymers (dispersions)

log Ed
B

A+B
A If both polymers are “incompatible”,
a “dispersion” develops.

Tg, A Tg, B T

In this case individual Tg's remain visible and the modulus is determined by the composition

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 Glass transition of co-polymers
Random co-polymer; example. SBR = butadiene and styrene

log Ed -B-S-B-B-B-S- “random”

PS
SBR

BR

-100 100 T

With a random copolymer, the material response is similar to that of a molecular mixture.
We see one Tg !

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 Glass transition of co-polymers
Block co-polymer; example sbs

-(S-S-S)n-(B-B-B)m-(S-S....-S)-
log Ed
PS

SBS
BR

-100 100 T
If the "blocks" are long enough, PS domains develop that, below Tg,PS, form physical
crosslinks in the system. Above Tg,PS , the material can be processed in the melt.
"Thermoplastic rubbers" (thermoplastic elastomers)

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Summary

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 Study material

The study material of this lecture is:

• CH3

Next lecture, tomorrow 8:45: Crystallinity

Slides have been uploaded to Canvas

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