MECHANICAL AND RHEOLOGICAL PROPERTIES

MECHANICAL PROPERTIES OF SOLIDS

Extension Shear

τxy
l0

θ
∆l l0

Hooke's law σ = Eε Hooke's law τ xy= G γ xy

MECHANICAL AND RHEOLOGICAL PROPERTIES

RHEOLOGICAL PROPERTIES OF FLUIDS

v0
Newtonian fluid
v .
y τ xy= ηγ
 OVERVIEW

Strength
POLYMERS TREATED AS SOLIDS Stiffness
Toughness

POLYMERS TREATED AS FLUIDS Viscosity of polymer melts

Elastic properties of polymer
melts !!!

VISCOELASTIC PROPERTIES Creep

Stress relaxation

STRESSES AND STRAINS

(or why you don’t fall through the floor)

HOW DOES AN INANIMATE OBJECT SUPPORT A LOAD ?

 HOOKE'S LAW
In 1676 Hooke published
"the true theory of elasticity or springiness"

Force = K * Extension

So the force relates to the extension by:

Force Force

Extension Extension
Questions : slope depends upon shape as well as the material being
stretched - can we obtain a material property -stiffness ?

how linear is the response of real materials ?

THERMODYNAMICS REVISTED
F = U - TS

 ∂F   ∂U   ∂S 
f = = −T
 ∂l  V ,T  ∂l  V ,T  ∂l  V ,T
Change in
internal Change in
energy entropy

For crystalline and For elastomer

glassy solids networks

 ∂U   ∂S 
f ~ f ~ −T
 ∂l V, T  ∂l V,T
 MOLECULAR ORIGIN OF HOOKE'S LAW
 dF   dU   dS 
  =  −T 
 dl V ,T  dl V ,T  dl V ,T

ONE DIMENSIONAL CRYSTALLINE SINGLE POLMER CHAIN

SOLID
σ
3 σ
2

σ σ
1
Potential energy for For 3 atoms the potential field 1
a pair of atoms experienced by the middle atom is: σ
2
σ
3

PE Unstrained state Strained state

+ y
(x0, y0, z0)

r
which can be
(x, y, z)
summed to give
the approximate form:
x
0
z
PE

f = K’∆l + K’’∆l 2+ --- r f = kTβ2 R

COMPARISON TO EXPERIMENT
POLYDIACETYLENE SINGLE
CRYSTAL
Hooke's law obeyed up to deformations ~ 2%
Deviations beyond this could be due to defects
as well as non linear terms in the force /
extension equation
Reproduced with permission from C. Galiotis and
R. J. Young, Polymer, 24, 1023 (1983).

ELASTOMER NETWORK
Rubber networks obey Hooke's law at low
extensions,but not,perhaps surprisingly,at
high strains (considering that deformation
is reversible).The simplest theory of rubber
elasticity gives:

f = NkT (λ -1/λ2 )
but this is not that good.the semi - empirical
Mooney - Rivlin equation provides a better
fit

2
Reproduced with permission from L. R. G. Treloar,
σ = 2 (C1 + C 2 /λ ) (λ -1/λ )
The Physics of Rubber Elasticity, Clarendon Press, Oxford, 1975
COMPARISON TO EXPERIMENT -POLYMERS
Once strains ~ 1% - 2% are reached,various types of deviations
From ideal behavior are observed;

Glassy polymer or
semi-crystalline polymer
x below Tg
Semi-crystalline polymer
x above Tg

Stress
x
(σ)
Rubber

Strain (ε)

More on these later!

HOW STRONG SHOULD MATERIALS BE?

GRIFFITHS; CALCULATED THE THEORETICAL
STRENGTH OF GLASS TO BE ~ 1 x 10 6 p.s.i
MEASURED VALUES ~ 25,000 p.s.i.

MATERIAL THEORETICAL MEASURED

STRENGTH STRENGTH

STEEL ~5 x 106 p.s.i ~ 400,000 p.s.i

(BEST)

POLYETHYLENE ~ 25 GPa ~ 0.35 GPa

FIBERS (TENSILE DRAWING)

~ 4 GPa
(GEL SPUN)
WHY ARE THEY WEAK? - BRITTLE SOLIDS

Reproduced with permission from J. E. Gordon,

The New Science of Strong Materials, Second Edition,
Penguin Books (1976). Reproduced with permission from C. Galiotis and
R. J. Young, Polymer, 24, 1023 (1983).

STRENGTH AND MODULUS OF VARIOUS MATERIALS

Specific tensile strength (104 m)

Specific tensile modulus (106 m)

Reproduced with permission from S. J. Krause, et al., Polymer, 29, 1354 (1988).
TOUGHNESS - OR HOW TO STOP CRACKS
PLINY - TO DETERMINE IF A DIAMOND IS
GENUINE,IT SHOULD BE PUT ON AN ANVIL
AND HIT VERY HARD WITH A HAMMER
- NOT A RELIABLE TEST !!!

CONFUSES BRITTLENESS AND HARDNESS

BRITTLENESS - LACK OF RESISTANCE TO THE

PROPOGATION OF CRACKS

TOUGHNESS - OR HOW TO STOP CRACKS

NOW CONSIDER TWO BRITTLE MATERIALS;
WINDOW GLASS (IN THE FORM OF FIBERS)
AND A THERMOSETTING POLYESTER RESIN
(HIGH Tg). DISPERSE ONE IN THE OTHER,BUT
KEEP THE INTERFACE WEAK

NOTE: CRACK STOPPING IS NOT THE ONLY

"TOUGHENING" OR ENERGY ABSORPTION
MECHANISM.YOU SHOULD KNOW WHAT
CRAZING AND YIELDING ARE
 CRAZING

Reproduced with permission from P. Beahan et al.,

Proc. Roy. Soc. London, A343, 525 (1975). Reproduced with permission from R. P. Kambour
and D. R. Russell, Polymer, 12, 237 (1971).

YIELDING

Reproduced with permission from P. B. Bowdon, Philos. Mag., 22, 455 (1970).
 STRESS / STRAIN CHARACTERISTICS
OF POLYMERS
Stress to break Glassy polymer or
semi-crystalline polymer
below Tg
x Semi-crystalline polymer
x above Tg
Energy to break
Stress
(σ) x
Stress (σ) Rubber

E
Strain (ε)
Strain (ε)

Many of the mechanical characteristics of polymers

that we have just discussed (Eg strength,stiffness, Real stress/strain diagrams are
toughness,yield behaviour) can be determined from much more complicated
Stress/strain measurements.

On the left is shown a stress/strain diagram for a

hypothetical material that obeys Hooke's law all
the way to failure

YIELDING IN SEMI-CRYSTALLINE
POLYMERS

Stress

Yield
Point

Strain

Reproduced with permiss-ion from J. Schultz,

Polymer Material Science, Prentice-Hall,
New Jersey, 1974.
 THE EFFECT OF HEAT AND PLASTICIZERS
ON THE MECHANICAL PROPERTIES OF
GLASSY POLYMERS

PMMA

QUESTIONS ;
Reproduced with permission from T. S. Carswell WHICH CURVE WOULD BEST REPRESENT
and H. K. Nason, Symposium on Plastics, THE BEHAVIOUR OF PURE PVC AT ROOM
American Society for Testing Materials,
Philadelphia, 1944. TEMPERATURE?
WHAT WOULD HAPPEN IF THE PVC WAS
NOW MIXED WITH A PLASTICIZER?

POLYMER MELT RHEOLOGY

HOW DO CHAINS MOVE - REPTATION

chain

obstacles

THEORY PREDICTS
D ∝ 12 (11.78)
M
3
η0 ∝ M (11.79)

NEWTONIAN AND NON - NEWTONIAN

FLUIDS
NEWTONIAN BEHAVIOUR: .
τ = ηa(γ) γ
.
Shear Newtonian fluid
. thinning (η = slope)
τ xy= ηγ slope = ηa

Shear
MOST POLMER MELTS ARE stress

SHEAR THINNING Shear

thickening

Strain
rate
 VARIATION OF MELT VISCOSITY
WITH STRAIN RATE
ZERO SHEAR RATE VISCOSITY

4
log ηa
(Pa) 3

0
-3 -2 -1 0 1 2 3 4
. -1
log γ (sec )

SHEAR RATES ENCOUNTERED IN PROCESSING

Compression Injection Spin
moulding Calendering Extrusion moulding drawing

0 1 2 3 4 5
10 10 10 10 10 10

-1
Shear rate (sec )

VARIATION OF MELT VISCOSITY

WITH MOLECULAR WEIGHT

1 .0
η m = K L ( DP ) w
3. 4
η m = K H (DP ) w

Reproduced with permission from G. C. Berry and T. G. Fox, Adv. Polym. Sci., 5, 261 (1968)
 ENTANGLEMENTS
VISCOSITY - A MEASURE OF THE FRICTIONAL
FORCES ACTING ON A MOLECULE
1.0
ηm = K L (DP) w (11. 18)
SMALL MOLECULES - THE VISCOSITY VARIES
DIRECTLY WITH SIZE

AT A CRITICAL CHAIN LENGTH CHAINS

START TO BECOME TANGLED UP WITH
ONE ANOTHER,HOWEVER

3.4
THEN ηm = KH (DP)w (11.19)

VISCOELASTICITY

If we stretch a crystalline solid, If we apply a shear stress to

The energy is stored in the A fluid,energy is dissipated
Chemical bonds In flow

VISCOELASTIC

Ideally elastic Ideally viscous

behaviour behaviour
 VISCOELASTICITY

ACHILES KNEW THAT THE FIRST

THING TO DO ON GETTING YOUR
CHARIOT OUT IN THE MORNING
WAS TO PUT THE WHEELS BACK
ON.

ULYSSES KNEW NEVER TO

LEAVE HIS BOW STRUNG

CREEP AND STRESS RELAXATION

CREEP - DEFORMATION
UNDER A CONSTANT LOAD
AS A FUNCTION OF TIME
5lb
5lb
5lb
5lb

TIME
STRESS RELAXATION -
CONSTANT DEFORMATION
EXPERIMENT
5lb 4lb 3lb 2lb

TIME
 CREEP AND RECOVERY
Creep ( % )

Time (hours)

STRESS RELAXATION

Data;
More on
Master curves
Later !
 (a) PURELY ELASTIC RESPONSE
Strain
STRAIN vs. TIME
PLOTS
Stress Stress Time
applied removed

(b) PURELY VISCOUS RESPONSE

Strain

Permanent
deformation

Shear Shear Time

Stress Stress
applied removed

(c) VISCOELASTIC RESPONSE

Strain Creep

Recovery

Permanent
} deformation
Stress Stress Time
applied removed

DYNAMIC MECHANICAL ANALYSIS

Apply an oscillating tensile
Or shear stress.
Assume we get an oscillating
Strain of the form

γ = γ sin 2πft = γ sin ωt

0 0

Using Hooke’s law

τ(t) =G γ sin ωt
0

ie. FOR A PERFECT ELASTIC SOLID STRESS

AND STRAIN ARE EXACTLY IN PHASE
 FLUIDS

.
τ(t) = ηγ(t)

=ηd
_
dt {γ0 sin ωt}

τ(t) =ηγ ω cos ωt

0
ie 90 0 out - of - phase

Viscoelastic solid - in-between !

ie a phase angle between 0 0and 90 0

VISCOELASTIC MATERIALS

Define a phase angle δ such that

τ(t) =τ 0 sin(ωt + δ)
γ = γ sin ωt
0
Then obtain
τ(t) =(τ0 cos δ)sin ωt + (τ0 sin δ)cos ωt
Hence
τ(t) = γ [G’(ω))sin ωt + G’’(ω)cos ωt]
0
Where
STORAGE
G’(ω) = τ_0 {cos δ} G’’(ω)
γ0 tan δ = __
MODULUS
and
LOSS
G’’(ω) = _
τ 0 {sin δ} G’(ω)
MODULUS
γ0
 VISCOELASTIC MATERIALS - DMA

G’(ω) = τ_0 {cos δ}

G'
STORAGE
MODULUS γ0
tan δ

G’’(ω) = τ_0 {sin δ}

log G
LOSS
MODULUS
γ0 (Pa)
G"

G’’(ω)
tan δ = __
G’(ω) log ω

TIME TEMPERATURE EQUIVALENCE

G'

tan δ

MEASURE AT CONSTANT T
log G

(Pa)
G"

log ω

G'

tan δ
MEASURE AT CONSTANT ω log G

(Pa)
G"

TEMPERATURE
 SUMMARY - DMA
•In Dynamic Mechanical Analysis experiments two moduli
Are measured,storage (G’(ω)) and loss (G’’(ω)).

•We defined a factor G’’(ω)

__
tan δ =
G’(ω)
•This shows a maximum when the storage modulus changes
From a value charecteristic of rubbers to one charecteristic
Of the glassy state

•There is apparently a TIME - TEMPERATURE EQUIVALENCE

The results appear simlar if we vary ω at constant T or if
We vary T at constant ω

AMORPHOUS POLYMERS - RANGE

OF VISCOELASTIV BEHAVIOUR

Liquid
Semi like
Vs -solid
Rubber

Leather
Soft like
glass
Hard
glass

Tg T
 VISCOELASTIC PROPERTIES OF
AMORPHOUS POLYMERS
Log E
(Pa) Glassy
region
10

9 Measured over
8 Some arbitrary
7
Time period - say
Cross-linked 10 secs
6 elastomers
Rubbery
5 plateau

4 Low
molecular Melt
weight
3
Temperature

TIME TEMPERATURE EQUIVALENCE

Log E
(Pa) Glassy

10
region 10 sec modulus
9

8
Glassy
7 region
Cross-linked
6 elastomers
10 Transition
Rubbery
5 plateau
Log E (t) (dynes cm- )
2

Rubbery
Low 8 plateau
4
molecular Melt
weight
3
Temperature 6

Low High
Stretch sample an arbitrary 4
molecular
weight
molecular
weight
Amount, then measure the
Stress required to maintain - 10 -8 -6 -4 -2 0 +2
Log time (sec)
This strain .Then E(t) = σ(t)/ε
0
 RELAXATION IN POLYMERS

First consider a hypothetical isolated

chain in space,then imagine stretching
this chain instantaneously so that there
is a new end - to - end distance.The
distribution of bond angles (trans,
gauche,etc) changes to accomodate
the conformations that are allowed
by the new constraints on the ends.
Because it takes time for bond rotations
to occur,particularly when we also add in the viscous forces due to
neighbours, we say the chain RELAXES to the new state and the
relaxation is described by a characteristic time τt

AMORPHOUS POLYMERS - THE FOUR

REGIONS OF VISCOELASTIC BEHAVIOUR
Log E GLASSY STATE - conformational
(Pa) Glassy
region
changes severely inhibited.
10

9
Tg REGION - cooperative motions
of segments now occur,but the
8 motions are sluggish ( a maximumin
7
tan δ curves are observed in DMA
experiments)
Cross-linked
6 elastomers
Rubbery
plateau
RUBBERY PLATEAU - becomes
5
shorter,but still longer than the
4 Low τt
time scale for disentanglement
molecular Melt
weight
3
Temperature

TERMINAL FLOW - the time scale for disentanglement becomes

Shorter and the melt becomes more fluid like in its behaviour
 SEMI - CRYSTALLINE POLYMERS

•Motion in the amorphous domains

constrained by crystallites

•Motions above Tg are often more

complex,often involving coupled
processes in the crystalline
and amorphous domains

•Less easy to generalize - polymers

often have to be considered individually
- see DMA data opposite

Reproduced with permission from H. A. Flocke,

Kolloid–Z. Z. Polym., 180, 188 (1962).

MECHANICAL AND THEORETICAL

MODELS OF VISCOELASTIC
BEHAVIOUR
DEFINITIONS

τ(t)
Relaxation modulus G(t) = _
γ0
γ(t) G(t) = _
1
J(t)
Creep compliance J(t) = _
τ0

GOAL - relate G(t) and J(t) to relaxation behaviour.

We will only consider LINEAR MODELS
ie if we double G(t) [or σ(t)],then γ(t) [or ε(t)] also
increases by a factor of 2 (small loads and strains).
SIMPLE MODELS OF THE VISCOELASTIC
BEHAVIOUR OF AMORPHOUS POLYMERS
Keep in mind that simple
creep and recovery data for
viscoelastic materials looks
something like this

Strain

Retarded
elastic
response

Elastic
response Permanent
deformation
t1 t2 Time (t)
applied removed

SIMPLE MODELS OF THE VISCOELASTIC

BEHAVIOUR OF AMORPHOUS POLYMERS
While stress relaxation data
look something like this
Glassy
region

10 Transition
Log E (t) (dynes cm- )
2

Rubbery
8 plateau

Low High
molecular molecular
4 weight weight

- 10 -8 -6 -4 -2 0 +2
Log time (sec)
SIMPLE MODELS OF THE VISCOELASTIC
BEHAVIOUR OF AMORPHOUS POLYMERS

Extension

Hooke's law
l0
σ = Eε
∆l
Spring

Model
σ

SIMPLE MODELS OF THE VISCOELASTIC

BEHAVIOUR OF AMORPHOUS POLYMERS
Viscous flow
Newtonian fluid
.
τ xy= ηγ
v0
v
y

Dashpot

Model
 STRAIN VS. TIME FOR SIMPLE
MODELS

E
MODELS
η

Spring Dashpot

Strain
RESPONSE

t1 t2 t1 t2

MAXWELL MODEL
Maxwell was interested in creep and stress relaxation and
developed a differential equation to describe these properties

Maxwell started with Hooke’s law

σ = Eε

dσ
_ dε
_
dt = Ε dt
Then allowed σ to vary with time

dε
_
Writing for a Newtonian fluid σ = η dt

Then assuming that the rate of strain dε

_ _
σ+ _
1 dσ
_
is simply a sum of these two contributions dt = η Ε dt
MAXWELL MODEL - creep and recovery
A picture representation
of Maxwell’s equation
Strain

Creep and
recovery
E
_ε _
σ
dt = η
d

0 t Time

η
Strain

Recall that real viscoelastic

behaviour looks something
like this

0 t Time

MAXWELL MODEL -stress relaxation

dε
_ σ 1_ dσ
_ _
dt = η + Ε dt
In a stress relaxation experiment
dε
_
dt =
0

dσ
_ = _
σ dt 0

σ η -1

Hence Er
( )
-2
log

σ = σ 0 exp[-t/τ t ]
E0
-3
Where
-4

τt = _
η -5
Ε
Relaxation time -6
-2 -1 0 1
log τt
 MAXWELL MODEL -stress relaxation
0

Maxwell model -1

Er
(E )
-2
log
0
-3

-4
Glassy
region -5

10 Transition -6
-2 -1 0 1
log τt
Log E (t) (dynes cm- )
2

Rubbery
8 plateau

6
Real data looks
Low
molecular
High
molecular something like
4
this
weight weight

- 10 -8 -6 -4 -2 0 +2
Log time (sec)

VOIGT MODEL
Maxwell mdel essentially assumes a uniform distribution
Of stress.Now assume uniform distribution of strain -
VOIGT MODEL

Picture representation

Equation

σ(t) = Eε( t ) + η dε(t)

__
dt
(Strain in both elements of the
model is the same and the total
stress is the sum of the two
contributions)
VOIGT MODEL - creep and stress relaxation
Gives a retarded elastic response
but does not allow for “ideal” stress
relaxation,in that the model cannot
be “instantaneously” deformed to
a given strain.
But in CREEP σ = constant, σ
0

σ(t) = σ 0 = Eε(t) + η dε(t)

__
dt
Strain dε(t)
__ + ε(t)
__ = _
σ0
dt τ t‘ η
_ 0 [1- exp (-t/τ ‘ )]
ε(t) = σ
t
1
t2 t Ε t

τ t‘ - retardation time (η/E)

SUMMARY

E
η

E
η
η

Maxwell Voigt
Spring Dashpot element element

Strain Spring Dashpot Maxwell Voigt

model model

t1 t2 t1 t2 t1 t2 t1 t2 t
 PROBLEMS WITH SIMPLE MODELS
•The maxwell model cannot account for
a retarded elastic response

•The voigt model does not describe stress

relaxation

•Both models are characterized by single

relaxation times - a spectrum of relaxation
times would provide a better description

NEXT - CONSIDER THE FIRST TWO PROBLEMS

THEN -THE PROBLEM OF A SPECTRUM OF
RELAXATION TIMES

FOUR - PARAMETER MODEL

ELASTIC + VISCOUS FLOW + RETARDED ELASTIC

eg CREEP
E
M

_ __ t _ 0 [1- exp (-t/τ )]

ε = σ0 + σ 0 + σ
ΕM η M ΕM t EV η
V

η
M

Strain

Retarded
elastic
response

Elastic
response Permanent
deformation
t1 t2 Time (t)
applied removed
 DISTRIBUTIONS OF RELAXATION AND
RETARDATION TIMES
The Maxwell - Wiechert Model

dε
_ σ1 _
_ 1 dσ
_1
dt = η 1 + Ε 1dt
σ2+ _
E1 E2 E3

= _ 1 dσ
_2
η 2 Ε 2dt η1 η2 η3
σ3+ _
= _ 1 dσ
_3
η 3 Ε 3dt
dε
_
dt =
Consider stress relaxation 0

σ 1 = σ 0 exp[-t/τ t1 ]
σ 2 = σ 0 exp[-t/τ t2]
σ 3 = σ 0 exp[-t/τ t3]

DISTRIBUTIONS OF RELAXATION AND

RETARDATION TIMES
Stress relaxation modulus
E(t) = σ(t)/ε 0 E1 E2 E3

η1
σ(t) = σ 1 + σ 2 + σ 3
η2 η3

E(t) = __
σ 01exp (-t/τ ) + __
σ 02 exp (-t/τ ) + __
σ 03 exp (-t/τ )
ε0 01
ε0 02
ε0 03
Or, in general

E(t) = Σ E n exp (-t/τtn ) where En = __

σ 0n
ε0

SIMILARLY, FOR CREEP COMPLIANCE COMBINE VOIGT ELEMENTS

TO OBTAIN
[1- exp (-t/τ tn‘ )]
D(t) =ΣDn
 DISTRIBUTIONS OF RELAXATION AND
RETARDATION TIMES
Example - The Maxwell - Wiechert Model with n = 2
E(t) = Σ E n exp (-t/τtn ) 10

n=2 8

Log E(t) (Pa)

Glassy 6
region

Transition 4
10
Log E (t) (dynes cm- )
2

Rubbery 2
8 plateau

0
-2 -1 0 1 2 3 4
6
Log time (min)
Low High
molecular molecular
4 weight weight

- 10 -8 -6 -4 -2 0 +2
Log time (sec)

TIME - TEMPERATURE
SUPERPOSITION PRINCIPLE
Recall that we have seen that there is a time - temperature
equivalence in behaviour
Glassy
region
Log E
(Pa) Glassy
region Transition
10 10
Log E (t) (dynes cm- )
2

9 Rubbery
8 plateau
8

7 6
Cross-linked
6 elastomers Low High
Rubbery molecular molecular
4 weight weight
5 plateau

4 Low - 10 -8 -6 -4 -2 0 +2
molecular Melt
weight Log time (sec)
3
Temperature

This can be expressed formally in terms of a superposition principle

 TIME TEMPERATURE SUPERPOSITION
PRINCIPLE - creep

T3 > T2 > T 1

ε(t) T
σ0 T T T
3 2 1

Log t

ε(t) T log aT
σ0

T0
log t - log aT T

SIGNIFICANCE OF SHIFT FACTOR

What is the significance of the log scale for a T,and what does
this tell us about the temperature dependence of relaxation
behaviour in amorphous polymers ?
Consider stress relaxation:

E(t) = Σ E n exp (-t/τ tn)

Let a particular mode of relaxation have a characteristic time
τ at T , and a characteristic time τ at T . Then DEFINE
t0 0 t1 1

τ t1 t t
aT = __ So that the exponential __ = a___
term can be written
τ t0 τ t1 T τ t0

Hence, taking logs

log (t/τ t1) = log (t/τt0 ) + log a T

 SIGNIFICANCE OF SHIFT FACTOR

log (t/τ t1) = log (t/τt0 ) + log a T

•ie relaxation behaviour at one temperature can be

superimposed on that at another by shifting an
amount a along a log scale.
T

•BUT ,real behaviour is characterized by a distribution

of relaxation times and relaxation mechanisms vary
and have different length scales as a function of
temperature

•This implies that all the relaxation processes involved

have (more or less) the same temperature dependence

RELAXATION PROCESSES ABOVE Tg

- The WLF equation

From empirical observation

-C 1 (T - Ts )
Log a T = _________ For Tg < T < ~Tg + 100 0 C
C2 + (T - Ts)
Originally thought that C 1and C 2 were universal constants,
= 17.44 and 51.6, respectively,when Ts = Tg . Now known
that these vary from polymer to polymer.
- Arrhenius temperature dependance

∆H 1 1 Where ∆H is the activation

aT = exp ___ (___ _ ___) enthalpy of the relaxation
R T T0 and R is the gas constant
 DYNAMICS OF POLYMER CHAINS
An advanced topic that we will not discuss in detail

Rouse - Bouche model

A chain as a string of
Beads linked by springs

chain

Reptation,scaling concepts
And other advanced theories

obstacles

NON - LINEA R BEHAVIOUR

LINEAR BEHAVIOUR - asumes small strains and strain rates
SOLIDS - Hooke’s law

FLUIDS - Newton’s law

VISCOELASTICITY - non linear response as a function of time

modeled by assuming a linear relationship
between stress and strain.Simple mechanical
models were constructed by combining linear
elastic and viscous elements

NON - LINEAR BEHAVIOUR - larger strains and strain rates

SOLIDS - will only consider rubber elasticity

FLUIDS AND VISCOELASTIC MATERIALS - some qualitative

obsevations
 RUBBER ELASTICITY
THERMODYNAMICS REVISTED
F = E - TS

f= ∂F ] = [ __
[ __ ∂E ] -T [ ∂__
S]
∂l V,T ∂l V,T ∂l V,T
Change in Change in
internal entropy
energy

For crystalline and For elastomer

glassy solids networks

f~ [ __
∂E
∂l
] V,T
__
f ~ -T[ ∂S ] V,T
∂l

STRETCHING OF A SINGLE CHAIN

Stretch along z direction

2 3/2
__
Ω = P(R) = P(x,y,z) = [ ]
β
π
exp (-β R )
2 2

Probability distribution
Is a Gaussian function
3
__ 3
__ For large N
β = 2Nl 2 = 2< R2 >
2
z
0
2 3/2
__
Ω = P(R) = P(x,y,z) = [ ]
β
π
2 2
exp (-β {x + y + z } )
2 2

S = k lnΩ
Ω = P(R) = P(x,y,z) = P(0,0,z)

S = constant - kβ 2 z 2
2 Hooke’s law !
f = 2kTβ z Modulus ~ T!
 NETWORKS

We need to consider the Loop

stretching of a cross - Dangling chain end

linked network. real
networks have defects.We
will consider the stretching
of a model network where
the functionality of all the
cross link points is identical, Elastically active chain

there are no dangling ends,

and the number of segments between all the junction points is the same

RUBBER ELASTICITY THEORY

σ
Define extension ratio 3 σ
2

λ = l/l0 σ
1 σ
1

σ
Assume no change in
2
σ
3

Volume upon stretching Unstrained state Strained state

y
λ1 λ 2 λ 3 = 1
(x0, y0, z0)

In the unstrained state (x, y, z)

2
R = x2+ y2 + z2 x
0 0 0 0 0
z

2 2 2 2
Hence s = constant -kβ ( x + y + z )
0 0 0 0
 RUBBER ELASTICITY THEORY
Affine assumption - chaindeforms in exact proportion to
Sample as a whole (parent cube on previous overhead)
x=λ x , y=λ y , z=λ z
1 0 2 0 3 0

s = constant -kβ 2 ( x2 + y 2 + z 2)

= constant -kβ2 (x2 λ2 + y 2 λ2 + z 2 λ2 )

0 1 0 2 0 3

∆s = constant -kβ 2 ((λ21 -1)x 20 + (λ22-1)y 2+ (λ23-1)z2 )

0 0

Σ R 0 = Σ x 0 + Σ y0 + Σ x 0
2 2 2 2

Using S = Σ ∆s And (1/3)Σ R 2 = Σ x 2 = Σ y 2 = Σ x2

0 0 0 0
2 2
ΣR = N< R >
0 0

Obtain ∆S = -(1/2)Nk(λ 21 + λ22 + λ 23 -3)

RUBBER ELASTICITY THEORY

∆S = -(1/2)Nk(λ 21 + λ22 + λ 23 -3)
Constant volume assumption
σ
λ1 λ 2 λ 3 = 1 3 σ
2

For simple extension in the σ σ

x direction the affine
1
1

σ
Assumption gives 2
σ
3

λ2 = λ 3 Unstrained state Strained state

1
λ = __
y
(x0, y0, z0)
1
Substituting λ 3 λ2
(x, y, z)
∆S = -(1/2)Nk(λ 21 + 2/λ 21 -3)
Hence 0
x

f = NkT(λ21 -1/λ 21 ) or f = E(λ21 -1/λ21 ) where E = NkT

Question - what would happen to a stretched rubber sample upon heating ?

 RUBBER ELASTICITY THEORY
- comparison to experiment

f = NkT(λ1 -1/λ 21 )

Agreement not bad at strains up

to ~ 300%,but the semi - empirical
Mooney - Rivlin equation provides a
better fit

σ = 2 (C1 + C 2/λ 1) (λ1 -1/λ 21 )

More advanced theories (eg Flory
Constrained Junction Model) does
a better job,but this is beyond
the scope of this course

SEMI - CRYSTALLINE POLYMERS

NON - LINEAR RESPONSE TO STRESS.SIMPLE
MODELS AND THE TIME - TEMPERATURE
SUPERPOSITION PRINCIPLE DO NOT APPLY

Temperature

Amorphous melt
Tm
Rigid crystalline domains
Rubbery amorphous domains
Tg
Rigid crystalline domains
Glassy amorphous domains