Topics to be Covered

• Polymer Melt Rheology

• Introduction to Viscoelastic Behavior

• Time-Temperature Equivalence

Chapter 11 in CD (Polymer Science and Engineering)

Polymer Melt R h e o l o g y
 Newton’s Law
δ
τxy

The most convenient way to describe deformation

under shear is in terms of the angle θ through which
the material is deformed;
z
θ δ
tan θ = = γ xy
z
Then if you shear a fluid at a constant rate

δ˙ v
γ˙xy = = 0
z z
dv d dx 
γ˙xy = =  
v0 dz dt  dz 
Just as stress is proportional to strain in
y
Hooke‛s law for a solid, the shear stress is
proportional to the rate of strain for a fluid
τxy ∝ γ˙xy
τxy = ηγ˙xy
 Newtonian and Non - Newtonian
Fluids
. .
τxy = ηa (γ) γ Shear Newtonian Fluid
Thinning (η = slope)
Shear Slope = ηa
Stress

Shear Thickening

Strain Rate
When the chips are
down, what do you use?
 Variation of Melt Viscosity
with Strain Rate

Log ηa 5 Zero Shear Rate Viscosity

(Pa)
4

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

SHEAR RATES ENCOUNTERED IN PROCESSING

Compression Injection Spin
Molding Calendering Extrusion Molding Drawing

100 101 102 103 104 105

Strain Rate (sec-1)

 How Do Chains Move
- Reptation

D ~ 1/M2
η0 ~ M3
 Variation of Melt Viscosity
with Molecular Weight
Log ηm + constant

Poly(di-methylsiloxane)
Poly(iso-butylene)
Poly(ethylene)
Poly(butadiene)
Poly(tetra-methyl p-silphenyl siloxane)

ηm = KL(DP)1.0
Poly(methyl methacrylate)
Poly(ethylene glycol)
Poly(vinyl acetate)
Poly(styrene)

ηm = KH(DP)3.4

Redrawn from the data of G. C.

Berry and T. G. Fox, Adv. Polym.
Sci., 5, 261 (1968)
1 2 3 4 5
Log M + constant
 Entanglements

Short chains don‛t entangle but long ones do - think of

the difference between a nice linguini and spaghettios,
the little round things you can get out of a tin (we have
some value judgements concerning the relative merits of
these two forms of pasta, but on the advice of our
lawyers we shall refrain from comment).
 Entanglements
Viscosity - a measure of the frictional forces
acting on a molecule

ηm = KL(DP)1.0
Small molecules - the viscosity varies directly
with size

At a critical chain length chains start to become

tangled up with one another, however

Then
ηm = KH(DP)3.4
 Entanglements and the Elastic
Properties of Polymer Melts

d0 d

2.0
160°C
d/d0
180°C
1.8

Depending upon the rate at 1.6

which chains disentangle relative 200°C

to the rate at which they stretch 1.4

out, there is an elastic component

to the behavior of polymer melts. 1 .2

There are various consequences

as a result of this. 1.0
10-1 10-2 100 101 102 103
Strain Rate at Wall (sec-1)

Jet Swelling
Melt Fracture

Reproduced with permission from J. J. Benbow,

R. N. Browne and E. R. Howells, Coll. Intern.
Rheol., Paris, June-July 1960.
 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

Homer knew that the first

thing To do on getting your
chariot out in the morning
was to put the wheels back
in.
(Telemachus,in The Odyssey,
would tip his chariot against
a wall)

Robin hood knew never to

leave his bow strung
Experimental Observations

•Creep

•Stress Relaxation

•Dynamic Mechanical Analysis

 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
 Redrawn from the data of W. N. Findley, Modern
Plastics, 19, 71 (August 1942)

Creep and
50
2695psi

Recovery
2505 psi
Creep(%)

2305 psi 2008 psi

40

Strain
30
(c) VISCOELASTIC RESPONSE
Creep

Recovery
20 1690 psi Permanent
} deformation
Stress Stress Time
applied removed

10

1018 psi
1320 psi

0
0 2000 4000 6000 8000
Time (hours)
 S t r a i n v s. Time Plots - Creep

(a) PURELY ELASTIC RESPONSE

Strain (b) PURELY VISCOUS RESPONSE

Strain
Permanent
Deformation
Stress Stress Time
applied removed
Shear Shear Time
Stress Stress
applied removed

(c) VISCOELASTIC RESPONSE

Strain Creep

Recovery
Permanent
} deformation
Stress Stress Time
applied removed
 Redrawn from the data of J.R. McLoughlin and A.V.

Stress
Tobolsky. J. Colloid Sci., 7, 555 (1952).

400C

Relaxation 10
600C

Log E(t), (dynes/cm2)

The data are not usually reported as a 920C
800C
stress/time plot, but as a 9 1000C
modulus/time plot. This time
dependent modulus, called the
relaxation modulus, is simply the time 1100C
dependent stress divided by the Stress relaxation
(constant) strain
of PMMA
8 0
112 C
σ (t) 1200C 1150C
E(t ) = ε
0 1250C
7

1350C

0.001 0.01 0.1 1 10 100 1000

Time (hours)
Amorphous Polymers - Range
of V i s c o e l a s t i c B e h a v i o u r
Liquid
Vs Semi- Like
Solid
Rubbery

Leather
Soft Like
Hard Glass
Glass

T
Tg
 V i s c o e l a s t i c Properties 0f
Amorphous Polymers

Log E
(Pa) Glassy
10 Region

9 Measured over
8 Some arbitrary
Time period - say
7
Cross-linked 10 secs
6 Elastomers
Rubbery
5 Plateau
Low
4 Molecular Melt
Weight
3
Temperature
 V i s c o e l a s t i c Properties 0f
Amorphous Polymers

Glassy
Region
Glass

Log E(t) (dynes/cm2)

10
Stretch sample an Transition

arbitrary amount, 9
Rubbery
measure the stress 8 Plateau
required to maintain 7
this strain. Low
6
Then E(t) = σ(t)/ε Molecular High
Weight Molecular
5
Weight
4

3
- 10 -8 -6 -4 -2 0 +2
Log Time (Sec)
 Time
Log E Glassy
(Pa)10 Region

Temperature 9
8
Equivalence 7
Cross-linked
6 Elastomers
5 Rubbery
Plateau Low
Log E(t) (dynes/cm2)

Glassy 4 Molecular Melt

Region Weight
Glass 3
10 Transition Temperature
9
Rubbery
8 Plateau
7
6 Low
Molecular High
Weight Molecular
5 Weight
4
3
- 10 -8 -6 -4 -2 0 +2
Log Time (Sec)
 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,
How quickly can I do
gauche, etc) changes to accommodate
these things?
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 neighbors,
we say the chain RELAXES to the new
state and the relaxation is described
by a characteristic time τ.
 Amorphous Polymers - the Four
Regions of Viscoelastic B e h a v i o r

Log E
(Pa) GLASSY STATE - conformational
10 changes severely inhibited.
9
Tg REGION - cooperative motions
8
of segments now occur,but the
7 motions are sluggish ( a maximum in
6 tan δ curves are observed in DMA
experiments)
5
Low
4 Molecular Polymer
Melt
RUBBERY PLATEAU - τt becomes
Weight
3 shorter,but still longer than the
Temperature time scale for disentanglement

TERMINAL FLOW - the time scale for disentanglement becomes

shorter and the melt becomes more fluid like in its behavior
 S e m i c r y s t a l l i n e Polymers

•Motion in the amorphous domains

constrained by crystallites

•Motions above Tg are often more

0.30
complex,often involving coupled
α processes in the crystalline
and amorphous domains
0.25

0.20

•Less easy to generalize - polymers

LDPE
0.15
β LPE
0.10 often have to be considered individually
γ
0.05 - see DMA data opposite
0.00
-200 -150 -100 -50 0 50 100 150

Redrawn from the data of H. A. Flocke,

Kolloid–Z. Z. Polym., 180, 188 (1962).
 Topics to be Covered

• Simple models of Viscoelastic Behavior

• Time-Temperature Superposition Principle

Chapter 11 in CD (Polymer Science and Engineering)

Mechanical and TENSILE SHEAR
EXPERIMENT EXPERIMENT
Theoretical
Stress Relaxation
Models of
σ (t) τ (t)
Viscoelastic E(t ) = G(t) =
ε0 γ0
Behavior Creep

ε (t) γ (t)
GOAL - relate G(t) and J(t) to D(t) = J(t) =
relaxation behavior.
σ0 τ0
We will only consider LINEAR Linear Time Independent Behavior
MODELS. (i.e. if we double
1 1
G(t) [or σ(t)], then γ(t) [or
E= G=
ε(t)] also increases by a factor D J
of 2 (small loads and strains)). Time Dependent Behavior

1 1
E(t ) ≠ G(t) ≠
D(t) J(t)
 Simple Models of the Viscoelastic
Behavior of Amorphous Polymers

Keep in mind that simple

(c) VISCOELASTIC RESPONSE
creep and recovery data for
Strain Creep
viscoelastic materials looks
something like this Recovery
Permanent
} deformation
Stress Stress Time
applied removed
 Simple Models of the Viscoelastic
Behavior of Amorphous Polymers

While stress relaxation Glassy

Region
data look something like Glass

Log E(t) (dynes/cm2)

10 Transition
this;
9
Rubbery
8 Plateau

7
Low
6 Molecular High
Weight Molecular
5
Weight
4

3
- 10 -8 -6 -4 -2 0 +2
Log Time (Sec)
Simple Models of the Viscoelastic
Behavior of Amorphous Polymers

Extension

Hooke's law
l0
σ = Eε
∆l

I represent linear
elastic behavior
σ = Eε
 Simple Models of the Viscoelastic
Behavior of Amorphous Polymers

Viscous flow

v0

Newtonian fluid
y v .
τ xy= ηγ

dε
σ =η
dt
S t r a i n v s. T i m e f o r S i m p l e
Models
PURELY ELASTIC RESPONSE
PURELY VISCOUS RESPONSE
σ = Eε
dε
σ =η
Strain dt

Strain

Time
Permanent
Stress Stress Deformation
applied removed

Shear Shear Time

Stress Stress
applied removed
 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

Then allowed σ to vary with time _ = Εdε

dσ _
dt dt

Writing for a Newtonian fluid σ = η dε

_
dt

Then assuming that the rate of strain _ = σ

dε 1 dσ
_+ _ _
is simply a sum of these two contributions dt η Ε dt
 M A X W E L L M O D E L - Creep a n d R e c o v e r y

Strain

Creep and
recovery
_ = σ
dε _
dt η 0 t Time

Strain

Recall that real viscoelastic

behaviour looks something
like this

A picture representation
of Maxwell‛s equation 0 t Time
 Maxwell Model -S t r e s s R e l a x a t i o n

_ = σ
dε _ + 1_ dσ
_
dt η Ε dt Log (Er /E0 )
0
In a stress relaxation experiment
-1

dε
_ = 0 -2
dt -3

Hence dσ
_ = σ
_ dt -4
σ η -5

σ = σ 0 exp[-t/τ t ] -6
-2 -1 0 1
Log (t/τ )
Where

τt = η
_
Ε
Relaxation time
M a x w e l l M o d e l -S t r e s s R e l a x a t i o n
Log E(t)
(Pa) Real data looks like this
10
9
8 The Maxwell
7 model gives
curves like this,
6 OR like this

5
4

3
Time
MAXWELL MODEL
σ (t) σ 0  t
E(t ) = = exp − 
ε0 ε0  τ t 
 Voigt Model
Maxwell model essentially assumes a uniform distribution
Of stress.Now assume uniform distribution of strain -
VOIGT MODEL

Picture representation

Equation
σ1 σ2
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 σ = σ 1 + σ2
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, σ0

σ1 σ2 σ(t) = σ 0 = Eε(t) + η dε(t)

__
dt
dε(t)
__ + ε(t)
__ σ0
_ =
dt τ t‘ η
S train RETARDED ELASTIC RESPONSE
σ = σ 1 + σ2 Strain

σ
ε(t) = _ 0 [1- exp (-t/τ t‘ )]
Ε
τ t‘ - retardation time (η/E)
Time
t1 t2
 Summary

What do the strain/time plots look like?

Problems with Simple Models
I can’t do creep
•The maxwell model cannot account for
a retarded elastic response

And I can’t do stress relaxation •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
EM

Eg CREEP

ε = σ __0 t + _
_0 + σ σ0
ΕM ηM Ε M [1- exp (-t/τ t )] ηV
EV

Retarded or
Anelastic Response
Strain

Elastic
ηM
Response Permanent
} deformation
Stress Stress Time
applied removed
 Distributions of Relaxation and
Retardation Times

Stress Relaxation
We have mentioned that although the
Maxwell and Voigt models are seriously E(t ) = E0 exp (− t / τ t )
∞
flawed, the equations have the right
form. E(t ) = ∫ E(τ t )exp(− t / τ t )dτ t
0
What we mean by that is shown Creep
opposite, where equations describing the
Maxwell model for stress relaxation and D(t) = D0 [1 − exp(− t / τ ′t )]
the Voigt model for creep are compared ∞
to equations that account for a D(t) = ∫ D(τ t′)[ 1 − exp(− t / τ t′)] dτ ′t
continuous range of relaxation times.
0

These equations can be obtained by assuming that relaxation occurs at a rate that
is linearly proportional to the distance from equilibrium and use of the Boltzmann
superposition principle. We will show how the same equations are obtained from
models.
 The Maxwell - W i e c h e r t Model
_ = σ
dε 1 dσ
_1 + _ _1
dt η 1 Ε 1dt
σ 1 dσ
= _ 2 _
+ _2
η 2 Ε 2dt
σ 1 dσ
= _ 3 _
+ _3
η 3 Ε 3dt E1 E2 E3

Consider stress relaxation

dε
_ =0 η1 η2 η3
dt
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

σ(t) = σ 1 + σ 2 + σ 3

σ 01 σ 02 σ 03
E(t) = __
ε0 exp (-t/τ01 ) + __
ε0 exp (-t/τ02) + __
ε 0 exp (-t/τ03)
Or, in general
σ 0n
__
E(t) = Σ E n exp (-t/τtn ) where En = ε
0

Similarly, for creep compliance combine voigt elements to obtain

D(t) =ΣDn [1- exp (-t/τ tn‘ )]

 Distributions of Relaxation and
Retardation Times
Example - the Maxwell - Wiechert Model With
n = 2 10

Log E(t) (Pa)

Glassy 8
Region
Glass
Log E(t) (dynes/cm2)

10 Transition 6

9
Rubbery 4
8 Plateau
2
7
0
6 -2 -1 0 1 2 3 4
Log time (min)
5
Melt E(t) = Σ E n exp (-t/τtn )
4
n=2
3
- 10 -8 -6 -4 -2 0 +2
Log Time (Sec)
 Time - Temperature
Superposition Principle
Recall that we have seen that Log E Glassy
(Pa) Region
there is a time - temperature 10
equivalence in behavior 9
8
7
Log E(t) (dynes/cm2)

Glassy Cross-linked
Region 6 Elastomers
Glass Rubbery
10 Transition 5 Plateau Low
9 4 Molecular Melt
Rubbery
8 Plateau Weight
3
7 Temperature
6 Low
Molecular High
5 Weight Molecular
Weight This can be expressed
4 formally in terms of a
3 superposition principle
- 10 -8 -6 -4 -2 0 +2
Log Time (Sec)
 Time Temperature Superposition
Principle - C r e e p

T 3 > T2 > T1

G'
ε(t) T
σ0

T3 T2 T1

log t Master Curve at T0 0C

ε(t) T log a T
σ0

T0

[log t - log a T] T
 Time Temperature
Superposition

Log Shift Factor

SHIFT FACTOR vs
Principle - S t r e s s
+8
TEMPERATURE

Relaxation +4

Stress
Stress Relaxation Modulus

Relaxation 0
1011 Data
dynes/cm2

-80.8°C
1010 -4
-76.7°C -80 -40 0 40 80
109 Temperature 0C
-74.1°C
-70.6°C
108
-65.4°C
-58.8°C
107 -49.6°C
-40.1°C
-0.0°C
106
+25°C Master Curve at 250C
+50°C
105
-80° -60° -40° -20° -10° 0° 25°

10-2 100 102 10-14 10-12 10-10 10-8 10-6 10-4 10-2 10-0 10+2
Time (hours)
Relaxation Processes above T g
- the WLF Equation
From empirical observation

-C1 (T - Ts )
Log a T = _________ For Tg > T < ~(Tg + 1000C)
C2 + (T - Ts )

Originally thought that C1 and C2 were universal constants,

= 17.44 and 51.6, respectively,when Ts = Tg. Now known
that these vary from polymer to polymer.
Homework problem - show how the WLF equation can be
obtained from the relationship of viscosity to free
volume as expressed in the Doolittle equation
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