1

Overview of the lectures in polymer physics

Topics:
The amorphous state
The cr stalline state The crystalline state
Thermal transitions and properties
Mechanical properties
Rubber elasticity
Polymer blends and IPNs
Polymer composites and nanocomposites y p 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
Dissordered,
entangled state
Semi-crystalline
Partly ordered, partly
folded state
p. 153
PS PVC PE
PMMA PP
Increasing crystallinity
2
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
A h hi h l l b i th
p. 154
Amorphous high molar mass polymers can be in the
glassy state, rubbery state or melt state going from
low to high temperature
spaghetti analogy
Chain Entanglements
Sufficiently long molecules
Critical molecular weight
Depend on chain flexibility Depend on chain flexibility
Restrict flow
M
c
critical molecular weight for formation
of stable entanglements
M
e
molecular weight between
entanglements
M 2M
p. 154
M
c
2M
e
Flexible chains give high M
c
, aromatic main
chains give low M
c
The molecular weight of commercial
polymers significantly above M
c
3
Reptation model in the melt state
How do polymers move in the entangled state?
long range movements of chains
snakelike motion within a virtual tube
f l b l
Theory of De Gennes
p. 156
frictional resistance by entanglements
successful in predicting viscous
properties of entangled polymer melts
The Glass Transition
Different theories isoviscous state (10
12
Pa s)
- isofree volume state
- isoentropic state: conformational entropy goes to zero p py g
Free volume V
f
is the difference between actual volume V and
occupied volume V
0.
V
f
= V - V
0
p. 156
The glass transition depends on
- chain flexibility
- interaction
4
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)
5 bonds rotate around
the main chain
Example: crankshaft motion
p. 158
Summary
Temperature
low high
Temperature
Mobility and free volume
Glassy state ---- Glass rubber transition ---- Rubbery state ----- Melt state
low high
Small scale molecular motions - large scale segmental motions polymer chain reptation
5
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
p. 158
stiffness and brittleness
fracture strength and elongation at break
solubility
permeability of gases and water sorption
many other properties
High thermal energy favours a large number of conformations
Lower-energy conformations are favoured during cooling
Ordering of polymer chains
Eventually the polymers are able to attain their lowest-energy conformation,
often the extended chain or the planar zigzag (e.g., polyethylene, nylons)
folded polymer chain
polymer helix
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)
p y
6
Crystalline structures
Polymer crystallisation by chain folding
crystalline lamellae
folded polymer chain
p. 158
Chain folding in lamellae
Three idealized models for chain folding in lamellae
A. Nonadjacent reentry
B. Regular adjacent reentry
p. 158
C. Irregular adjacent reentry
Lamellae thickness: 10-20 nm (in PE 40-80 repeating units)
7
Thermal Transitions
Hydrogen bonding between the
amide groups in nylon 6.6
p. 162
For many polymers T
g
is one-half to two thirds of the melting
temperature T
m
( in Kelvin )
Crystalline-Melting Temperature
Free energy of fusion per repeating unit:
AG
u
= AH
u
TAS
u
T
m
0
= AH
u
/AS
u
Equilibrium melting temperature at AG
u
=0
(crystalline lamellae are destroyed as fast as they are formed)
T
m
0
> T
m
p. 163
8
Crystallization Kinetics
Linear growth rate of spherulites in PET
Thermodynamic driving force below T
m
, and
T
g
= 69
o
C, T
m
= 265
o
C
y g
m
,
necessary mobility above T
g
Crystallisation possible between T
g
and T
m
Increasing viscosity at low temperatures
Possible to quench polymers with slow
crystallisation rates
Avrami equation: the
p. 164
Avrami equation: the
fractional crystallinity is
u = 1 exp(-kt
n
)
k is a temperature dependent parameter
n varies between 1 and 4 depending on the nature of growth process
Techniques to Determine Crystallinity
Non-destructive
Density measurements: fractional crystallinity
u = (
a
)/(
c
-
a
)
c
from single crystals,
a
from quenched samples
X-Ray diffraction (WAXS): weight fraction of crystalline phase
W
c
= 1 I
am
/ I
am
0
HDPE
p. 167
From thermal transitions
Differential Scanning Calorimetry
Dilatometry
Bragg peaks
Amorphous halo
9
Measurement Techniques - Dilatometry
bulb
capillary
Principle:
Specific volume as a
function of temperature
increasing T
bulb
polymer sample
mercury
p. 173
function of temperature
of a semicrystalline
polymer
Change in thermal expansion coefficient at T
g
:
Ao = o
l
- o
g
Measurement Techniques - Differential Scanning
Calorimetry (DSC)
S is sample and R is reference pan
Individual heaters to keep AT=0
during a temperature scan
Principle
during a temperature scan.
Difference in the required heat
flow is measured.
DSC thermogram of PET
glass transition near 75
o
C
recrystallization above 143
o
C
p. 175
recrystallization above 143 C
melting endotherm around 250
o
C
crystallinity | = AQ/AH
f
with AQ
the heat of fusion measured and AH
f
the heat of fusion at 100%
crystallinity
10
Other Measurement Techniques
Many properties change drastically at the glass transition
temperature and can be used to determine T
g
such as:
Mechanical properties
Dielectric properties
Optical properties
load pressure
p. 177
Temperature at 0.25 mm
deflection = HDT
Structure-Property Relationships
Influence of flexibility of the polymer chain on the melting
temperature for an analogous series of polyesters
p. 178
T
m
0
= AH
u
/AS
u
T
m
0
governed by AS
u
. Flexible polymers have higher AS
u
11
Structure-Property Relationships
Influence of hindered chain rotation of the polymer chain on the
glass-transition temperatures of selected vinyl polymers
inceased
polarity
O
O
O
O
rod polymer
flexible polymer
p. 179
R
R'
R
R'
rod polymer
ladder polymer
Structure-Property Relationships
Effect of increasing size of the substituent groups on the glass-transition
temperature of polymethacrylates
Increasing flexibility
of the side chain
p. 179
i-PMMA, Tg = 45
o
C
a-PMMA, Tg = 105
o
C
s-PMMA, Tg = 115
o
C
Influence by tacticity
12
Effect of molecular weight on T
g
The glass transition temperature is dependent on the number
average molecular weight average molecular weight
The effect levels off at high M
n
Fox-Flory equation:
T
g
= T
g

K/M
n
in Kelvin
p. 180
The constant K is polymer-specific
The effect can be related to the free volume contribution of
chain ends.
Effect of composition on T
g
The glass transition temperature of a homogeneous mixture is
dependent on the amount of each component present, and their
respective T respective T
g
.
Rule of mixtures: T
g
= W
1
T
g,1
+ W
2
T
g,2
Fox equation: 1/T
g
= W
1
/ T
g 1
+ W
2
/ T
g 2
p. 181
Fox equation 1/T
g
W
1
/ T
g,1
W
2
/ T
g,2
13
Mechanical Properties
How are polymers deformed? - mechanisms of deformation
elastic, viscous, viscoelastic
time dependent, frequency dependent
At small
deformations:
At large
crazing
p. 183
At large
deformations:
shear banding
fracture
Crazing
Crazes consist of polymer microfibrils (0.6-30 nm in diameter) bridging
two surfaces of a crack.
d l l Crazes develop at a certain critical strain
True cracks appear after degradation of crazes
direction of
deformation
craze
propagation
p. 184
propagation
14
Crazing
p. 184
Crazes in a polycarbonate dogbone
Crazes in poly(phenylene oxide)
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
p. 185
provides larger energy
dissipation in, e.g.,
polycarbonate and SAN
15
Stiffness and Strength
Methods of testing Methods of testing
In tension, shear or hydrostatic
static: deformation rate is constant
p. 186
transient: creep and stress relaxation
impact: Izod and Charpy
cyclic: fatigue
Static tensile testing
Dogbone sample
engineering (nominal) stress o = F/A
0
engineering (nominal) strain c = AL / L
0
p. 187
Alternatively: true stress and true strain
true stress o
T
= F/A actual cross section A
true strain c
T
= ln (L/L
0
)
16
Static tensile testing
During uniaxial tensile deformation, glassy amorphous polymers increase in
volume AV.
AV = V V = ( 1-2v ) c V AV = V V
0
= ( 1-2v ) c V
0
V
0
is the initial (unstrained) volume
c is the true strain
v is Poissons ratio, defined as the ratio of true strain in
transvers direction and true strain in longitudinal direction.
p. 187
v = - c
trans
/ c
axial
= - c
x
/ c
y
Poissons Ratio
Molecular origin:
contacted
strain
v = - c
trans
/ c
axial
relaxed
extended
p. 188
For the majority of polymers v 0.4
Incompressible polymers have v = 0.5
17
Static testing
Determination of materials properties in tension
Hookes law o = Ec linear elastic behaviour
o = stress E = tensile modulus c = strain o = stress, E = tensile modulus, c = strain
Alternatively: c = Do D = 1/E = tensile compliance
In reality:
effects of
p. 189
time, rate and
temperature
Modulus as a function of temperature
Glassy modulus typically 1 GPa
Rubbery plateau modulus typically
1 MPa 1 MPa
Entanglements responsible for
rubbery plateau (physical crosslinks)
Chemical crosslinks have the same
effect
The rubbery plateau modulus E
p
is
inversely proportional to the
l l b t
p. 190
molecular mass between
entanglements M
e
E
p
proportional to RT/M
e
18
Materials properties in shear
Engineering (nominal) shear
stress, t
t = F/A
0
Shear strain,
= tan u = AX/C
p. 191
Hookes law: t = G G = shear modulus
= Jt , J = 1/G = shear compliance
Stress-strain as a function of temperature
1. Brittle low temperature
behaviour
2. Ductile behaviour with yield
stress
x marks the stress and strain at failure
stress
3. Ductile behaviour with yield
stress, necking, cold
drawing and orientation
hardening
4. Rubbery behaviour with
strain-induced
crystallisation
o
y
p. 193
crystallisation
19
Simulation of the development of a neck via shear banding
Effective plastic strain
Necking of ductile polymers
A polyethylene
sample with a
stable neck
Mechanism for the deformation of a semicrystalline polymer
(a) Two adjacent
chain folded
lamellae and
interlamellar
h
(e) Orientation of the block
segments and tie chains with
the tensile axis in the final
deformation stage
amorphous
material before
deformation
(d) Separation of the
crystalline block
segments during the
third stage
(b) Elongation of
amorphous tie chains
during the first stage of
deformation
(c) Tilting of lamellar
chain folds during the
second stage
20
Mechanical properties of representative polymers
p. 194
Tensile response depends on: - polymer structure and architecture
- MW and MW distribution
- sample preparation
- crystallinity
- temperature
- rate of deformation
Time dependent behaviour: creep
Creep : constant stress o
0
and measuring the time dependent strain c(t)
Result: compliance D(t) = c(t)/o
0
I t t f l th t t t i l d f l i d Important for polymers that must sustain loads for long periods
F
0
F
0
t
c(0) c(t)
p. 196
c
0
= Do
0
21
Time dependent behaviour: stress relaxation
Stress relaxation : constant strain c
0
and measuring the time dependent
relaxing stress o(t)
Result: modulus E(t) = o(t) / c
0
t
c
0
o(t)
c
0
o(0)
o(0)
o
p. 196
0
t
0
Stress and strain
Static tensile testing: constant strain rate
Ob h h i i h h i
dc
dt
= const.
F(t)
Observe how the stress varies with the strain
Creep testing: constant stress
Observe how the strain varies with time
F
0
c(t)
Stress relaxation: constant strain
Observe how the stress varies with time o(t) c
0
22
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+v)G J = 2(1+v)D K = E/3(1-2v)
p. 192
With Poissons ratio v = 0.5
E = 3G J =3D K =infinite (incompressible)
Impact and fatigue testing
Measures energy expended up to
failure under conditions of
rapid loading
Fatigue testing
Impact strength critical in
many applications
Oscillative stress
p. 200
23
Rubber elasticity
p. 249
Chain conformations and entropy
Which dynamic chain has the highest (conformational) entropy, S?
a)
b)
c)
S = k lnW
d)
24
Rubber elasticity the Gough-Joule effect
elongation
Unloaded coiled chains in an
entropically favoured
dissordered state
Stretched chains in a less
entropically favoured state
heating
A rubber band acts
Stretched chains with a more
entropically favoured state
like an entropy spring
Rubber elasticity - models
Elastic force = f = G
0
(-
2
)
= L/L
0
= 1 + c
G = shear modulus proportional to T and G
0
= shear 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
p. 254
Fillers in rubbers:
Guth-Smallwood equation
E
f
/E
0
=1 + 2.5|
f
+ 14.1|
f
2