Overview of the lectures in polymer physics

Topics:
The amorphous state
The crystalline
cr stalline state
Thermal transitions and properties
Mechanical properties
Rubber elasticity
Polymer blends and IPNs
Polymer
y composites
p and nanocomposites
p
Polymer processing and rheology

Lecurer: Patric Jannasch

Institute of Chemistry, Division of Polymer & Materials Chemistry
patric.jannasch@polymat.lth.se

Solid-State Properties

Different chain
conformations in
different phases

Amorphous Semi-crystalline
Dissordered, Partly ordered, partly
entangled state folded state

Increasing crystallinity

PS PVC PE
PMMA PP

p. 153

1
 The Amorphous State

Randomly coiled interpenetrating chains

Entanglements at sufficiently high molecular
weight
Not all volume is occupied: free volume concept
Diffusion of small molecules
Segmental and chain mobility strongly dependent
on temperature and free volume
Amorphous
A h hi
high
h molar
l mass polymers
l can be
b in
i the
th
glassy state, rubbery state or melt state going from
low to high temperature
spaghetti analogy

p. 154

Chain Entanglements

Sufficiently long molecules

Critical molecular weight
Depend on chain flexibility
Restrict flow

Mc critical molecular weight for formation

of stable entanglements
Me molecular weight between
entanglements
Mc 2Me
Flexible chains give high Mc, aromatic main
chains give low Mc
The molecular weight of commercial
polymers significantly above Mc

p. 154

2
 Reptation model in the melt state

How do polymers move in the entangled state?

Theory of De Gennes

long range movements of chains

snakelike motion within a virtual tube
frictional
f l resistance b
by entanglements
l
successful in predicting viscous
properties of entangled polymer melts

p. 156

The Glass Transition

Different theories isoviscous state (1012 Pa s)

- isofree volume state
p state: conformational entropy
- isoentropic py goes
g to zero

Free volume Vf is the difference between actual volume V and

occupied volume V0.

Vf = V - V0

The glass transition depends on

- chain flexibility
- interaction

p. 156

3
 Secondary-Relaxation Processes

Small scale molecular motions that occur in the glassy state:

- Limited rotations in the main chains
- Movements of side groups
Important for glassy state properties (impact strength, gas permeation)

Example: crankshaft motion 5 bonds rotate around

the main chain

p. 158

Summary

low Temperature high

Mobility and free volume

Glassy state ---- Glass rubber transition ---- Rubbery state ----- Melt state

Small scale molecular motions - large scale segmental motions polymer chain reptation

4
 The Crystalline state

Many important polymers are partially crystalline

Polyethylene
Polypropylene
Polyamides; Nylon 6, Nylon 6.6, Nylon 4.6
Linear polyesters; PET, PBT

Crystallinity influences
stiffness and brittleness
fracture strength and elongation at break
solubility
permeability of gases and water sorption
many other properties
p. 158

Ordering of polymer chains

High thermal energy favours a large number of conformations

Lower-energy conformations are favoured during cooling

Eventually the polymers are able to attain their lowest-energy conformation,

often the extended chain or the planar zigzag (e.g., polyethylene, nylons)

polymer helix

folded p
polymer
y chain

The lowest-energy conformation of syndiotactic polymers,

and polymers with large substituents, is usually a helix
(e.g., polypropylene, polyisobutylene)

The packing of polymers in ordered structures is favoured

by stereo regular symmetrical chain structures and specific
interactions (tacticity, trans configuration, hydrogen bonding)

5
 Crystalline structures

Polymer crystallisation by chain folding

folded polymer chain

crystalline lamellae

p. 158

Chain folding in lamellae

Three idealized models for chain folding in lamellae

A. Nonadjacent reentry

B. Regular adjacent reentry

C. Irregular adjacent reentry

Lamellae thickness: 10-20 nm (in PE 40-80 repeating units)

p. 158

6
 Thermal Transitions

Hydrogen bonding between the

amide groups in nylon 6.6

For many polymers Tg is one-half to two thirds of the melting

temperature Tm ( in Kelvin )
p. 162

Crystalline-Melting Temperature

Free energy of fusion per repeating unit:

Gu = Hu TSu

Equilibrium melting temperature at Gu=0

(crystalline lamellae are destroyed as fast as they are formed)

Tm0 = Hu/Su Tm0 > Tm

p. 163

7
 Crystallization Kinetics

Linear growth rate of spherulites in PET

Tg = 69 oC, Tm = 265 oC
Thermodynamic
y driving
g force below Tm, and
necessary mobility above Tg
Crystallisation possible between Tg and Tm
Increasing viscosity at low temperatures
Possible to quench polymers with slow
crystallisation rates

Avrami equation: the

fractional crystallinity is

= 1 exp(-ktn)

k is a temperature dependent parameter p. 164

n varies between 1 and 4 depending on the nature of growth process

Techniques to Determine Crystallinity

Non-destructive

Density measurements: fractional crystallinity

= ( a)/(c - a) c from single crystals, a from quenched samples

X-Ray diffraction (WAXS): weight fraction of crystalline phase

HDPE
Wc = 1 Iam/ Iam0
Bragg peaks

From thermal transitions Amorphous halo

Differential Scanning Calorimetry
Dilatometry

p. 167

8
 Measurement Techniques - Dilatometry

Principle:
capillary

bulb

increasing T

mercury
polymer sample

Specific volume as a
function of temperature
of a semicrystalline
polymer

Change in thermal expansion coefficient at Tg:

= l - g
p. 173

Measurement Techniques - Differential Scanning

Calorimetry (DSC)

Principle S is sample and R is reference pan

Individual heaters to keep T=0
during a temperature scan.
scan
Difference in the required heat
flow is measured.

DSC thermogram of PET

glass transition near 75 oC
recrystallization above 143 oC
melting endotherm around 250 oC
crystallinity = Q/Hf with Q
the heat of fusion measured and Hf
the heat of fusion at 100%
crystallinity
p. 175

9
 Other Measurement Techniques

Many properties change drastically at the glass transition

temperature and can be used to determine Tg such as:
Mechanical properties
Dielectric properties
Optical properties

load pressure

Temperature at 0.25 mm
deflection = HDT

p. 177

Structure-Property Relationships

Influence of flexibility of the polymer chain on the melting

temperature for an analogous series of polyesters

Tm0 governed by Su. Flexible polymers have higher Su

Tm0 = Hu/Su
p. 178

10
 Structure-Property Relationships

Influence of hindered chain rotation of the polymer chain on the

glass-transition temperatures of selected vinyl polymers

O O
O O
flexible polymer

inceased
polarity

rod polymer

R R

R' R'
ladder polymer

p. 179

Structure-Property Relationships

Effect of increasing size of the substituent groups on the glass-transition

temperature of polymethacrylates

Increasing flexibility
of the side chain

i-PMMA, Tg = 45 oC
Influence by tacticity a-PMMA, Tg = 105 oC
s-PMMA, Tg = 115 oC
p. 179

11
 Effect of molecular weight on Tg

The glass transition temperature is dependent on the number

average molecular weight
The effect levels off at high Mn

Fox-Flory equation:

Tg = Tg K/Mn in Kelvin

The constant K is polymer-specific

The effect can be related to the free volume contribution of
chain ends.

p. 180

Effect of composition on Tg

The glass transition temperature of a homogeneous mixture is

dependent on the amount of each component present, and their
respective Tg.

Rule of mixtures: Tg = W1 Tg,1 + W2 Tg,2

Fox equation
equation: 1/Tg = W1 / Tg,1
g 1 + W2 / Tg,2
g2

p. 181

12
 Mechanical Properties

How are polymers deformed? - mechanisms of deformation

At small elastic, viscous, viscoelastic

deformations: time dependent, frequency dependent

crazing
At large
large
deformations: shear banding
fracture

p. 183

Crazing

Crazes consist of polymer microfibrils (0.6-30 nm in diameter) bridging

two surfaces of a crack.
Crazes develop
d l at a certain criticall strain
True cracks appear after degradation of crazes

direction of
deformation

craze
propagation

p. 184

13
 Crazing

Crazes in a polycarbonate dogbone

Crazes in poly(phenylene oxide)

p. 184

Shear banding

Shear banding:
g
- occurs in some glassy
amorphous polymers instead of,
or together with, crazing.
- is the dominant mode of
deformation of ductile
polymers during tensile testing
- provides larger energy
dissipation in, e.g.,
polycarbonate and SAN

p. 185

14
 Stiffness and Strength

Methods of testing

In tension, shear or hydrostatic

static: deformation rate is constant

transient: creep and stress relaxation
impact: Izod and Charpy
cyclic: fatigue

p. 186

Static tensile testing

Dogbone sample

engineering (nominal) stress = F/A0

engineering (nominal) strain = L / L0

Alternatively: true stress and true strain

true stress T = F/A actual cross section A
true strain T = ln (L/L0)

p. 187

15
 Static tensile testing

During uniaxial tensile deformation, glassy amorphous polymers increase in

volume V.

V = V V0 = ( 1-2 V0

V0 is the initial (unstrained) volume

is the true strain
is Poissons ratio, defined as the ratio of true strain in
transvers direction and true strain in longitudinal direction.

= - trans / axial = - x / y

p. 187

Poissons Ratio

Molecular origin: strain

contacted

extended
relaxed

= - trans / axial

For the majority of polymers 0.4

Incompressible polymers have = 0.5

p. 188

16
 Static testing

Determination of materials properties in tension

Hookes law = Elinear elastic behaviour

= stress,
stress E = tensile modulus,
modulus = strain
Alternatively: = D D = 1/E = tensile compliance

In reality:
effects of
time, rate and
temperature

p. 189

Modulus as a function of temperature

Glassy modulus typically 1 GPa

Rubbery plateau modulus typically
1 MPa
Entanglements responsible for
rubbery plateau (physical crosslinks)
Chemical crosslinks have the same
effect
The rubbery plateau modulus Ep is
inversely proportional to the
molecular
l l mass between
b t
entanglements Me

Ep proportional to RT/Me

p. 190

17
 Materials properties in shear

Engineering (nominal) shear

stress,
= F/A0

Shear strain,
= tan = X/C

Hookes law: = GG = shear modulus

= JJ = 1/G = shear compliance

p. 191

Stress-strain as a function of temperature

1. Brittle low temperature

x marks the stress and strain at failure
behaviour
2. Ductile behaviour with yield
stress
3. Ductile behaviour with yield
stress, necking, cold
drawing and orientation
y hardening
4. Rubbery behaviour with
strain-induced
crystallisation

p. 193

18
 Necking of ductile polymers

Simulation of the development of a neck via shear banding

Effective plastic strain

A polyethylene
sample with a
stable neck

Mechanism for the deformation of a semicrystalline polymer

(e) Orientation of the block

(a) Two adjacent segments and tie chains with
chain folded the tensile axis in the final
lamellae and deformation stage
interlamellar
amorphous
h
material before
deformation (d) Separation of the
crystalline block
segments during the
third stage

(b) Elongation of (c) Tilting of lamellar

amorphous tie chains chain folds during the
during the first stage of second stage
deformation

19
 Mechanical properties of representative polymers

Tensile response depends on: - polymer structure and architecture

- MW and MW distribution
- sample preparation
- crystallinity
- temperature
- rate of deformation
p. 194

Time dependent behaviour: creep

Creep : constant stress 0 and measuring the time dependent strain (t)

Result: compliance D(t) = (t)/0

I
Important
t tf for polymers
l th
thatt mustt sustain
t i lloads
d ffor llong periods
i d

t
(0) (t)

F0
F0

= D0

p. 196

20
 Time dependent behaviour: stress relaxation

Stress relaxation : constant strain 0 and measuring the time dependent

relaxing stress (t)

Result: modulus E(t) = (t) / 0

t
0 0

(0) (t)

(0)

0
0 t

p. 196

Stress and strain

F(t)

Static tensile testing: constant strain rate d

= const.
dt
Ob
Observe h
how the
h stress varies
i with
i h the
h strain
i

Creep testing: constant stress

Observe how the strain varies with time (t)

F0

Stress relaxation: constant strain

Observe how the stress varies with time 0 (t)

21
 Relations between moduli and compliances

Modulus in tension E
Compliance in tension D
Modulus in shear G
Compliance in shear J
Bulk modulus in compression K

For isotropic materials two independent material properties

E = 2(1+)G J = 2(1+)D K = E/3(1-2)

With Poissons ratio = 0.5

E = 3G J =3D K =infinite (incompressible)

p. 192

Impact and fatigue testing

Measures energy expended up to

failure under conditions of
rapid loading

Impact strength critical in

many applications

Fatigue testing

Oscillative stress

p. 200

22
 Rubber elasticity

p. 249

Chain conformations and entropy

Which dynamic chain has the highest (conformational) entropy, S?

a)

b)

c) S = k lnW

d)

23
 Rubber elasticity the Gough-Joule effect

elongation

Unloaded coiled chains in an Stretched chains in a less

entropically favoured entropically favoured state
dissordered state

heating
A rubber band acts
like an entropy spring

Stretched chains with a more

entropically favoured state

Rubber elasticity - models

Elastic force = f = G0(-

= L/L0 = 1 +
G0 = shear modulus
modulus, proportional to T and
the crosslink density
- Good fit at low
- Overestimation at moderate because
of deviation from Gaussian distribution
- Underestimation at high because of
strain-induced crystallisation

Fillers in rubbers:
Guth-Smallwood equation
Ef/E0 =1 + 2.5f + 14.1f2
p. 254

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