Viscoelastic Properties

Introduction
A distinctive feature of the mechanical behavior of polymers is that their

responses to an applied stress or strain depends on the deformation rate or

temperature.

At low temperatures and high rates of strain,

strain they display elastic solid behavior,
behavior

whereas at high temperatures and low rates of strain, they behave in a viscous

liquid manner.

Polymers are therefore characterized by viscoelastic,

viscoelastic as they display aspects of

both viscous and elastic behavior.

Thus, the mechanical behavior of most polymers can be thought of as being

somewhere between that of elastic solids and viscous liquids.

liquids
 Dynamic--Mechanical Analysis
Dynamic
Viscoelastic behavior can be characterized by a variety of techniques that

record the time dependent response of a polymer material to a periodic

perturbation such as the application of a sinusoidal strain or an electrical

voltage.

The most common method to measure viscoelastic properties is dynamic-

dynamic

mechanical analysis, which records the stress response to an application of a

sinusoidal strain.

Unlike fatigue tests, dynamic mechanical properties are measured at low strain

such that deformation is not permanent.

Commercial
C i l dynamic-testing
d i t ti i t
instruments
t are available
il bl for
f operation
ti i severall
in

modes of deformation (e.g., tensile, torsion, compression, flexure and shear)

and over a several decades of frequencies (0.1 ~ 100 Hz).

Theory

For a tensile strain that is a sinusoidal function of time, the strain function is

expressed as

= o sin (t)
( )

where o is the amplitude of the applied strain

is the angular frequency of oscillation (= 2 f).

The
Th stress resulting
li f
from the
h applied
li d sinusoidal
i id l strain
i is
i also
l a sinusoidal
i id l

function, which can be written as

= o sin (t + )

where o is the amplitude of the stress response

is the phase angle between the stress and the strain.

strain
o
o
 The phase angle (= 0 ~ /2) is a measure of the viscoelastic response of the

polymer material to dynamic strain.

In the case of an ideal elastic solid,

solid the stress is always in phase with strain (i.e.,
(i e

=0).

= E = E o sin (t) = o sin (t)

where o is the magnitude (o = Eo) of the resulting stress function.

In the case of an viscous fluid, the stress is always 90 out of phase (i.e., =/2)

with the strain. This can be shown to result from Newtons law of viscosity

given as

= d/dt

By using
i the
h equation
i ( = o sin
i (t)), we can obtain
b i

= o cos (t) = o sin (t + /2)

where o = o
 At temperatures below Tg, polymer materials behave more as Hookean solids,

but at higher temperatures (i.e., in the vicinity of Tg) their behavior is

distinctly viscoelastic.
viscoelastic At temperatures far higher than Tg, the mechanical

behavior of polymer materials is viscous.

Over these temperatures, will have a value between 0 (totally elastic) and

90 (totally viscous).
 An alternative and more useful approach to discuss the dynamic response of a

viscoelastic material to an applied cyclical strain is by use of complex number

notation by which a complex strain,

strain *, can be represented as

* = o exp (it)

The resulting complex stress, *, can be written as

* = o exp [ i(t + ) ]

A complex modulus (E*)

(E ) can be defined as the ratio of complex stress to

complex strain as

This complex modulus can be resolved into two components

 The above equation can be written in the form given as

where
h E is
i the
h storage modulus
d l

and E
E is the loss modulus.
modulus

The ratio of loss and storage

g moduli defines another useful p
parameter in

dynamic-mechanical analysis called tan , where

 Since the dynamic tensile-compliance (D*) is inversely related to the dynamic

tensile-modulus(E*),

The
h above
b equation
i can be
b written
i i the
in h form
f

where D is called the storage compliance

and D is called the loss compliance

A in
As i the
th case off dynamic
d i modulus,
d l t
tan i related
is l t d to
t the
th components
t off

complex dynamic compliance as

 Mechanical Models of Viscoelastic Behavior

An insight into the nature of the viscoelastic properties of polymers can be

obtained by analyzing the stress or strain response of mechanical models

using an ideal spring as the elastic element and a dashpot as the viscous

element.
element

The elemental models are a series combination of a spring and dashpot in the

Maxwell element, and a parallel combination of a spring and dashpot in the

Voigt element, as illustrated in Figure 5-7.

In the following sections, relationships for the transient responses of Maxwell

g models are developed.

and Voigt p
 = 1 + 2 = 1 = 2
= 1 = 2 = 1 + 2

=E

= d/dt
1.
1 Maxwell Element

In the case of a series combination of spring

p g and dashpot,
p the total strain is a

summation of the individual strains of the spring and dashpot,

= 1 + 2

F
From H
Hookeslaw
k l (( = E
E),
) th
the strain
t i rate
t off an id
ideall elastic
l ti spring
i can b
be

written as

while the strain rate for the dashpot is obtained by Newtons law of viscosity
 Therefore, the basic equation for strain rate in the Maxwell model is the

summation of the strain rates for the spring

p g and dashpot
p as

This differential equation can be solved for creep, stress relaxation and

dynamic response by applying the appropriate stress or strain function.

function
A. Creep

= [kg m/s] = [Pa s ]

E = [Pa]
 0

0
 creep

stress
relaxation
B. Stress
Stress--Relaxation
2.
2 Voigt Element

This is also known as the Kelvin model.

For a parallel combination of a spring and dashpot in the Voigt model, the

strain on each element must be equal while the stress is additive.

= 1 = 2

and = 1 + 2

The fundamental relation for the Voigt model is therefore,

 = 1 + 2 = 1 = 2
= 1 = 2 = 1 + 2

=E

= d/dt
A. Creep

The Voigt model is particularly useful in describing the behavior during creep

where the stress is held constant at = o

The Voigt equation for creep deformation becomes a linear differential

equation;

Solving
g for (t) g
gives the compliance
p function as,

(t) = (o/E)[1-exp(-t/)]
where D = 1/E

This
Thi behavior
b h i isi shown
h in
i Fig
Fi 5.8
5 8 (a)
( ) and
d it clearly
l l represents
t the
th correctt form
f

of behavior for a polymer undergoing creep.

 creep

stress
relaxation
B. Stress
Stress--Relaxation

On the other hand,

hand the Voigt model is unsuccessful in predicting the stress

relaxation behavior of a polymer.

p y In this case, the strain is held constant at o

and since d/dt = 0

Then,

= E o

which is the linear elastic response indicated in Fig. 5.8 (b)

3. Multi-
Multi-element Models

The Maxwell model describes the stress relaxation of a polymer to a first

approximation whereas the Voigt model similarly describes creep.

A logical step forward is therefore to find some combinations of these models

which can account for both phenomena.

A multi-element model, particularly suited for modulus, is called the Maxwell-

Wiechert model, which is a parallel combination of multiple Maxwell elements.

In this model, the strains on each Maxwell element are equal and the stresses

experienced by each Maxwell element are additive, as they are in the case of

the single spring and dashpot in the simple Voigt model.

Creep Stress relaxation
 For the two-element Maxwell-Wiechert model illustrated in Figure 5-8, the

stress-relaxation
l i modulus
d l isi given
i as

where 1 = 1/E1 and 2 = 2/E2.

By
B appropriate
i t selection
l ti off values
l f Ei and
for d i, a reasonable
bl representation
t ti

of the g
glass and rubber p
plateau regions
g of the stress-relaxation modulus is

obtained, as illustrated in Figure 5-9.

 There have been many attempts at devising more complex models which can

give a better representation of the viscoelastic behavior of polymers.

As the number of elements increases, the mathematics becomes more complex.

It must be stressed that the mechanical models only give a mathematical

representation of the mechanical behavior and as such so not give much help

in interpreting the viscoelastic properties on a molecular level.

creep
 Time--Temperature
Time p Superposition
p p

It is important to know how a material will behave (e.g., creep or stress

relaxation) at a fixed temperature, but over a long time period (perhaps years)

that may not be realistically accessible.

Fortunately,
Fortunately long
long-time
time behavior can be evaluated by measuring stress
stress-

relaxation or creep data over a shorter period of time but at several different

temperatures.

Information from each of these different temperature curves may then be

combined to yield a master curve at a single temperature by horizontally

shifting each curve along the log time scale. This technique is called time-

p
temperature superposition.
p p
 It is
i possible
ibl to interrelate
i l the
h time
i and
d temperature dependence
d d off the
h

viscoelastic p
properties
p of p
polymers,
y , since there is a g
general equivalence
q

between time and temperature.

For instance, a polymer which displays rubbery characteristics under a given

set of testing conditions can be induced to show glassy behavior by either

reducing the temperature or increasing the testing rate.

Building
ildi on these
h id
ideas, the
h time-temperature
i superposition
ii principle
i i l states

tthat
at data at o
one
e te
temperature
pe atu e ca
can be supe
superimposed
posed o
on data at a
another
ot e

temperature by shifting the curves along the log time axis.

 Fig.
Fi 10 14 illustrates
10.14 ill t t th time-temperature
the ti t t superposition
iti principle
i i l using
i

polyisobutylene data. The reference temperature of the master curve is 25 oC.

The reference temperature is the temperature to which all the data are

converted by shifting the curves to overlap the original 25 oC curve.

The
Th material
i l is
i rubber-like
bb lik with
i h a low
l modulus
d l at high
hi h temperatures and
d low
l

frequencies and becomes glassy with a high modulus as the temperature is

reduced and the frequency is increased.

It is found empirically that all the curves can be superposed by keeping one

fixed and shifting all the others by different amounts horizontally parallel to

g
the logarithmic time axis.
 The
Th shift
hift factor
f t (a ( T) is
i defined
d fi d as the
th ratio
ti off time
ti t reach
to h a particular
ti l value
l off

modulus at some temperature

p to the reference-scale time coordinate, tr,

corresponding to the same value of modulus in the master curve at the

reference temperature, Tr.

Stated more concisely,

concisely the time-temperature superposition principle says that

The procedure of horizontal shifting is illustrated for stress-relaxation and

torsional creep data for polycarbonate in Figure 5-16.

@ low temperature

@ hi
high
h ttemperature
t
 The dependence of the shift factor (aT) on temperature is given by the

WilliamsLandel-Ferrry(WLF) relationship

where C1 and C2 are constants for a given polymer

and Tr is the reference temperature.

The WLF equation is originally developed empirically.

When Tr is taken to be the polymer Tg, as it often is,

is C1 and C2 may be

approximated by the universal values of 17.44 and 51.6, respectively.

However, significant deviations from these values may exist for some polymers,

as shown by values given for some common polymers in Table 5.3.

53