Viscoelastic properties in polymers

Polymers are not ideal elastic bodies;

they are viscoelastic materials

viscoelasticity, which is a combination

of viscosity and elasticity in varying amounts
 - viscoelastic materials

Classical Extremes
Ideal Solid Ideal Fluid
STEEL WATER
Strong structure Weak structure
Rigidity Fluidity
Deform Flow
Retain/recover shape Lose shape
Store Energy Dissipate Energy
(purely Elastic – R. Hooke, 1678) [Energy] (purely Viscous – I. Newton, 1687)
ELASTICITY VISCOSITY
Storage Modulus Loss Modulus

Apparent Solid [Energy + time] Apparent Fluid

The solid stores all the energy which it obtains from
the external forces during the deformation, and this
energy is available to restore the original shape when
the forces are removed.

A viscous liquid has no definite shape and flows

irreversibly under the action of external forces.
 Viscoelastic Deformation
Amorphous/partially amorphous polymers may act like:
- Glass at low T (T < Tg Glass transition temperature)(100 % amorphous)
- Rubbery solid (Tm > T > Tg) (partially amorphous)
- Viscous liquid (T > Tm).
Viscoelasticity: mechanical characteristics exhibiting both viscous flow and elastic
deformation (rubbery solid).

Elastic Instantaneous response

with complete recovery.

Delayed response.
Viscoelastic Viscous
Not reversible.

Instantaneous and delayed response. Time-dependent

strain (an elastic). Depends on strain rates.
 Viscoelastic properties in polymers -
characteristics

A stress σ0 is applied at time t=0 A strain 0 is applied at t=0 and held

and held constant. The strain (t) constant. The stress σ(t) is followed
is followed over time. The creep over time. The stress relaxation
compliance J(t) is given by: modulus E(t) is given by:

(t) = σ0 J(t) σ(t)= 0E(t)

APPLICATIONS
 Stress Relaxation
The stress relaxation of a stressed polymeric material under constant
strain results in a decrease in the stress with time

Stress relaxation measurement:

s (t)

1. At a constant T, apply small stress (s) to achieve initial

strain (eo).
2. Adjust s to maintain eo as a function of time. (relax)
3. Repeat at different T.

s (t)
The modulus can be both time and temperature dependent.

For each T: Relaxation Modulus  (t )

E r (t ) 
o
The stress relaxation of a stressed polymeric material under constant
strain results in a decrease in the stress with time

Why?

The viscous flow in the polymeric material’s internal structure occurs by

the polymer chains slowly sliding each other by the breaking and reforming
of secondary bonds between the chains and by mechanical untangling and
recoiling of the chains.

Stress relaxation allows the material to attain a lower energy state

and the process depends on activation energy.

 Stress relaxation is temperature-dependent and associated with an

activation energy, Ea.
 The rate at which stress relaxation occurs depends on the
Relaxation time , which is a property of the material and which is
Defined as the time needed for the stress () to decrease to 0.37 (1/e)
Of the initial stress (0).
The decrease in stress with time t is given:

   0 e t / 
where  = stress after time t,
0 = initial stress and
 = relaxation time

The relaxation time  is the reciprocal of a rate, can relate it to the temperature
in kelvins by an Arrhenius-type rate equation:

1
 Ae  Ea / RT
 where A = rate constant independent of temp.
Ea = activation energy
T = temperature in kelvins
R= 8.314 J/mol.K
 Viscoelastic Creep
Polymeric materials subjected to a load may creep. They deform under a
constant load at a constant temperature continue to increase with time.

Time dependent deformation when stress is kept constant (as opposed to constant
strain for viscoelastic relaxation).

Creep modulus:

o
E c (t ) 
 (t )

Similar to relaxation modulus, creep modulus is dependent on T and structure.

In general: Ec(t) decreases with increasing T
Ec(t) increases with increasing crystallinity.
 Creep

At temperature below Tg, the creep rate is relatively low due to restricted
molecular chain mobility. Above their Tg thermoplastics deform, is referred to as
viscoelastic behaviour.

Reinforcing polymer and crosslinking greatly increase their creep modulus

and reduce their creep
Creep compliance:

 (t )
D(t ) 


Where  is the tensile stress applied to the specimen

And (t) is the tensile strain.
Five Regions of Viscoelastic Behavior

crystallinity
Five regions :
1. Glassy, Poly(methyl metacrylate), plastic
2. Glass Transition, Poly(vinyl acetate), paint
cross-linked 3. Rubbery Plateau, Cross-poly(butadiene-
stat-styrene), rubber bands
4. Rubbery Flow, Chicle, chewing gum
5. Liquid Flow, Poly(dimethyl siloxane)
Lubricant
Molecular Structure Effect

SemiCrystalline (isotactic PS)

Highly crosslinked

Amorphous
1. Glassy region
Young’s modulus is relatively constant across polymers
van der Waal’s interactions between chains are
fairly constant for hydrocarbons
2. Glass transition region
Modulus drops by 1000x over 25ºC
Tg is taken as maximum rate of decrease
More co-ordinated motion along chain.
3. Rubbery Plateau Region
Very elastic
Higher molecular weight, wider plateau
Natural rubber (unvulcanized) flows
4. Rubbery flow region
Increased molecular motion
Silly Putty
5. Liquid flow
DYNAMIC MECHANICAL PROPERTIES
• In dynamic mechanical analysis, DMA, a
sinusoidal strain or stress is applied to a
sample and the response is monitored as
a function of frequency.
• Polymers are not ideal energy elastic
bodies; they are viscoelastic materials.
In such cases the deformation (strain)
lags behind the applied stress.
 The complex modulus G*
If a sinusoidal strain is applied:  (t) =  0 sin (ωt)
the resulting stress is given by:

σ(t) = 0[G’ sin (ωt) + G’’ cos (ωt)]

The complex modulus, G*= G’ + G’’ is given by a Fourier

transform of G(t).

G’ gives elastic response, G’’ the viscous response

•DMA Viscoelastic Parameters:
•The Complex, Elastic, & Viscous Stress
The stress in a dynamic experiment is referred to as the
complex stress *
The complex stress can be separated into two components:
1) An elastic stress in phase with the strain. ' = *cosd
' is the degree to which material behaves like an elastic solid.
2) A viscous stress in phase with the strain rate. " = *sind
" is the degree to which material behaves like an ideal liquid.

Phase angle d
Complex Stress, * * = ' + i"

Strain, 
DMA Viscoelastic Parameters

The Complex Modulus: Measure of

materials overall resistance to G* = Stress*/Strain
deformation. G* = G’ + iG”
The Elastic (Storage) Modulus:
Measure of elasticity of material. The
ability of the material to store energy.
G' = (stress*/strain)cosd

The Viscous (loss) Modulus:

The ability of the material to dissipate G" = (stress*/strain)sind
energy. Energy lost as heat.

Tan Delta:
Measure of material damping - such
as vibration or sound damping. Tan d= G"/G'
•Dynamic Mechanical Testing

Purely Viscous
Purely Elastic Response Response
(Hookean Solid) (Newtonian Liquid)
d = 90°
d = 0°

Stress Stress

Strain Strain
 Dynamic Flow Testing

Deformation
 An oscillatory (sinusoidal)
deformation (stress or strain)
is applied to a sample.
Response
The material response
(strain or stress) is measured.

The phase angle d, or phase

shift, between the control and Phase angle d
the response is measured.
Dynamic Mechanical Testing Viscoelastic
Material Response

Phase angle 0° < d < 90°

Strain

Stress
•Definition of elastic and viscous materials under
shear.
•
• In analyzing the polymeric materials, G*,
the ratio of the peak stress to the peak
strain, reflects the total stiffness. The in-
phase component of IG*I, i. e. the shear
storage modulus G', represents the part of
the input energy which is not lost to heat
(the elastic portion).
• The out-of-phase component, i. e. the
shear loss modulus G" represents viscous
component of G*, viz., it reflects the loss
of useful mechanical energy through
dissipation as heat.
• The complex dynamic shear viscosity *
can be obtained from G* divided by the
frequency, while the dynamic viscosity is
•  = G"/ or  = G"/2f
•For purely elastic materials, the phase angle
will be zero,
•whereas for purely viscous materials, the
phase angle will be 90.

•Thus, the phase angle, expressed as tangent,

is an important parameter for describing the
viscoelastic properties of a material.
 The loss tangent is calculated simply as
the tangent of the phase angle, or alternatively,
as the ratio of the loss, to storage moduli:

tan d = G"/ G',

because G" = G*sind and G' = G*cosd.

The Viscoelastic Behavior are used to
study Rheology of polymer
The fundamental definition of rheology indicates that for a material to flow
its original structural composition must first exceed a critical limited
deformation.

Rheology, the science of deformation and flow of materials characterizes

materials through parameters such as;

• storage modulus (G’) loss modulus (G”)

• loss factor (Tan d) critical deformation c
• viscosity () yield point (y)
• characteristic times (l,z) flow index (n)
• ...
With exquisite presicion, rheology describes the behavior of materials as
viscoelastic fluids (G”>G’ and d -> 90°) to
viscoelastic solids (G’>G” and d -> 0°)

Information commonly used to improve formulations optimize processes,

select aplication conditiosn, evaluate product performance, determine
shelf life, evaluate product economy, and more.
Typical DMA curves. G is not shown in this plot

10

1.2
Log (G' / Pa )

9
G’ or E

0.9

Tan d
8
0.6
ED
ED10a-P
7 ED20a-P 0.3

0
6
140 160 180 200 220 240
Time / min
Note:
Tan d = G/G
Application of DMA for measuring molecular weight
between the crosslink, Mc of thermoset polymer.
 The rubber plateau and entanglements

we can explain the rubber plateau in a

qualitative way as a signature of
entanglements.

rubber plateau

It can be shown that in a rubber, a cross linked

polymer, the elastic modulus depends on the
RT
average molecular mass between crosslinks Mc, R T G
and the density ρ: MC
We can calculate an average mass of the molecular mass
between the entanglements (Mc).
 Rubber

Mc

Mc

Mc

Solid rubbery
Heat

RT
G
MC
Molecular mass/weight between cross-links Mc (g mol-1) is inversely
proportional to the crosslinked density, c

1
M c
c
(different crosslinked density may give little effect to the normal density)

High crosslinked density, c :

- the system is more rigid, low free volume,
- high Tg, high tensile, high modulus

So measurement of Mc is important because its related to

the mechanical and thermal properties.
PROBLEM

10
Table 1 Dynamic mechanical properties of
1.2 epoxy system systems.
9
Log (G' / Pa )

0.9 Sample G'R / MPa Mc

d
(Tg + 40 °C) g mol-1

Tan
8
0.6
ED
ED10a-P ED 11.8  0.4
7 ED20a-P 0.3

0 ED10a-P 11.2  0.6

6
140 160 180 200 220 240
Time / min ED20a-P 8.2  0.6

Calculate the average Molecular weight between crosslinks, Mc of

epoxy system. Where  is 1200 kgm-3, R is the universal gas
= 8.315 JK-1mol-1. The value of G can be obtained from Table1