PolyE-501

ADVANCED POLYMER RHEOLOGY

Dr. M. Shafiq Irfan
Assistant Professor
Department of Polymer and Process Engineering
University of Engineering and Technology, Lahore
PRINCIPLES OF LINEAR
VISCOELASTICITY*
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* I M Ward and J Sweeney, The Mechanical Properties of Solid Polymers: Chapter 4
Viscoelasticity as a phenomenon
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Viscoelasticity as a Phenomenon
The behaviour of materials of low relative
molecular mass is usually discussed in terms of
two particular types of ideal material: the elastic
solid and the viscous liquid.
One of the most interesting features of polymers
is that a given polymer can display all the
intermediate range of properties between an
elastic solid and a viscous liquid depending on the
temperature and the experimentally chosen
timescale. This form of response is termed
viscoelasticity.
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Linear Viscoelastic Behaviour
Hookes law describes the behaviour of a linear
elastic solid and Newtons law that of a linear
viscous liquid. A simple constitutive relation for
the behaviour of a linear viscoelastic solid is
obtained by combining these two laws:
1. For elastic behaviour
2. For viscous behaviour
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Linear Viscoelastic Behaviour
A simple possible formulation of linear
viscoelastic behaviour combines these equations,
making the assumption that the shear stresses
related to strain and strain rate are additive:
The equation represents one of the simple
models for linear viscoelastic behaviour, the
Kelvin or Voigt model.
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Linear Viscoelastic Behaviour
For elastic solids Hookes law is valid only at small
strains, and Newtons law of viscosity is restricted to
relatively low flow rates, as only when the stress is
proportional either to the strain or the strain rate is
analysis of the deformation feasible in simple form.
A comparable limitation holds for viscoelastic
materials: general quantitative predictions are
possible only in the case of linear viscoelasticity, for
which the results of changing stresses or strains are
simply additive, but the time at which the change is
made must be taken into account.
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Creep
Creep is the time-dependent change in strain
following a step change in stress.
The responses to two levels of stress for linear
elastic and linear viscoelastic materials are
compared in Figure 4.2.
In the former case the strain follows the pattern
of the loading programme exactly and in exact
proportionality to the magnitude of the stresses
applied.
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9
Creep
For the most general case of a linear viscoelastic
solid the total strain e is the sum of three
essentially separate parts:
e
1
the immediate elastic deformation
e
2
the delayed elastic deformation
e
3
the Newtonian flow, which is identical with the
deformation of a viscous liquid obeying Newtons
law of viscosity.
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Creep
Because the material shows linear behaviour the
magnitudes of e
1
, e
2
and e
3
are exactly
proportional to the magnitude of the applied
stress, so that a creep compliance J(t) can be
defined, which is a function of time only:
where J
1
, J
2
and J
3
correspond to e
1
, e
2
and e
3
.
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Creep
Linear amorphous polymers show a significant J
3
above their glass transition temperatures, when
creep may continue until the specimen ruptures, but
at lower temperatures J
1
and J
2
dominate.
Crosslinked polymers do not show a J
3
term, and to a
very good approximation neither do highly crystalline
polymers.
The maximum insight into the nature of creep is
obtained by plotting the logarithm of creep
compliance against the logarithm of time over a very
wide time-scale (Figure 4.3).
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Creep
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Creep
It is convenient to define a retardation time in
the middle of the viscoelastic region to
characterize the time-scale for creep. The
distinction between a rubber and a glassy plastic
is then seen to be somewhat artificial, because it
depends only on the value of at room
temperature.
Compared with typical experimental response
times, which can rarely be less than 1 s, for a
rubber is very small at room temperature,
whereas the opposite is true for a glassy polymer.
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Creep
As the temperature is raised the frequency of
molecular rearrangements increases, so reducing
the value of .
Thus at sufficiently low temperatures a rubber
behaves like a glassy plastic, and will shatter
under impact conditions; correspondingly a
glassy plastic will become rubber-like at a
sufficiently high temperature.
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Stress Relaxation
When an instantaneous strain is applied to an
ideal elastic solid a finite and constant stress will
be recorded. For a linear viscoelastic solid
subjected to a nominally instantaneous strain the
initial stress will be proportional to the applied
strain and will decrease with time (Figure 4.4), at
a rate characterized by the relaxation time . This
behaviour is called stress relaxation.
For amorphous linear polymers at high
temperatures the stress may eventually decay to
zero.
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Stress Relaxation
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Stress Relaxation
Making the assumption of linear viscoelastic
behaviour we can define the stress relaxation
modulus G(t) = (t)/e. Where there is no viscous
flow the stress decays to a finite value (Figure
4.5), to give an equilibrium or relaxed modulus G
r
at finite time.
As with creep we see that there are regions of
glassy, viscoelastic, rubberlike and flow
behaviour; similarly, changing temperature is
equivalent to changing the time-scale.
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Stress Relaxation
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Mathematical representation of
linear viscoelasticity
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The Boltzmann superposition principle
Boltzmann proposed, as long ago as 1876, that:
1. The creep is a function of the entire past loading
history of the specimen.
2. Each loading step makes an independent
contribution to the final deformation, so that
the total deformation can be obtained by the
addition of all the contributions.
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The Boltzmann superposition principle
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The Boltzmann superposition principle
The total creep at time t is then given by
where J(t - ) is the creep compliance function.
The summation of above Equation can be
generalized in integral form as
Separating out the instantaneous elastic response
in terms of the unrelaxed modulus G
u
gives
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The Boltzmann superposition principle
The integral in last Equation is called a Duhamel
integral, and it is a useful illustration of the
consequences of the Boltzmann superposition
principle to evaluate the response for a number
of simple loading programmes.
The Duhamel integral is most simply evaluated by
treating it as the summation of a number of
response terms.
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Single-step loading of a stress
0
at time = 0
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Two-step loading of a stress
0
at time = 0 ,
followed by an additional stress
0
at time = t
1
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Creep and Recovery
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Mechanical models, retardation and
relaxation time spectra
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Mechanical Models
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Mechanical Models
We have seen that the Maxwell model
describes the stress relaxation of a viscoelastic
solid to a first approximation, and the Kelvin
model the creep behaviour, but that neither
model is adequate for the general behaviour
of a viscoelastic solid where it is necessary to
describe both stress relaxation and creep.
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The Standard Linear Solid
A response closer to that of a real polymer is
obtained by adding a second spring of
modulus Ea in parallel with a Maxwell unit
(Figure 4.12). This model is known as the
standard linear solid and is usually attributed
to Zener.
It provides an approximate representation to
the observed behaviour of polymers in their
viscoelastic range.
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The Standard Linear Solid
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The Standard Linear Solid
In creep, both springs extend, so that
but in stress relaxation E
a
is unaffected, giving
The stressstrain relationship is
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Multi-element models
For real materials a simple exponential
response in creep or stress relaxation is not an
adequate description of the time dependence.
A good representation can be obtained by
simulating creep with an array of Kelvin
models in series and simulating stress
relaxation with an array of Maxwell models in
parallel (Figure 4.13).
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Multi-element models
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Multi-element models
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Retardation and relaxation time spectra
Let the number of individual units in multi-
element models tend to infinity. For creep, an
infinite number of Kelvin units gives an infinite
number of retardation times: this is called the
spectrum of retardation times.
The analagous development for stress
relaxation leads to the spectrum of relaxation
times.
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