PS, 3/1-2018

Introduction to simple linear models for viscoelastic materials

Kinematics and deformation
The Newtonian fluid
For flow in thin gaps or with high viscosity, µ, we have a linear velosity profile:

V (t)
vx (y, t) = y = γ̇yx (t)y
H
Here γ̇yx is the strain-rate and an element in

γ̇ = ∇v + ∇vT

Moving plate

Velocity V (t)
-
6 -
- y
H - 6
-
? -
x
Fixed plate
z
The total deformation becomes:
∫ t
∂
ux (y, t0 , t) = vx (y, t′ )dt′ ⇒ vx (y, t) = ux (y, t0 , t)
t0 ∂t

The Hookean solid

Moving plate

Displacement U (t0 , t)
-
6 -
- y
H - 6
t′ =t0 - t′ =t
? -
x
Fixed plate
z

1
The total deformation is given by:

U (t0 , t)
ux (y, t0 , t) = y = γyx (t0 , t)y
H
Here γyx is the deformation gradient or strain and an element in

γ = ∇u + ∇uT , γyx (t0 , t0 ) = 0

Stress expressions
The Newtonian fluid
The stress in a Newtonian fluid can be described by the following expression:
∂vx
τyx (t) = −µγ̇yx (t) = −µ
∂y
This expression is valid for any deformation. The parameter µ is the viscosity. As the stress
τyx (t) = f (γ̇yx (t)) the fluid has no memory (De=0).

The Hookean solid

For an elastic material that follows Hookean behaviour the stress can be described by
∂ux
τyx (t) = −Gγyx (t0 , t) = −G
∂y
This expression is only valid for small deformation gradients. The parameter G is the shear
modulus. As τyx depends on both t0 and t there is a memory build in. A specified stress gives
an immediate finite deformation (De→ ∞).

No memory:
∂
γ̇yx (t) = γyx (t0 , t)
∂t
Memory: ∫ t
γyx (t0 , t) = γ̇yx (t′ )dt′
t0

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Mechanical equivalents
Linear viscous: Dashpot, friction, damping.

τyx = −µ ∂v
∂y
x

= −µγ̇yx µ
?
τ
Linear elastic:

τyx = −G ∂u x
∂y Spring, elasticity, memory.
= −Gγyx
and

∂τyx G
= −Gγ̇yx
∂t
?
The Maxwell model τ

The idea behind the Maxwell viscoelastic

model is to combine a Newtonian element µ
with a Hookean element in a series con-
nection. The choice is arbitrary; it is an G
empirical model. Later we consider the
parallel connection which leads to the so- ?
τ
called Voigt-Kelvin model.
Neglecting inertia, the consequence of a series coupling is that the stress is uniform and equal in
each element:
τyx,N = τyx,H = τyx
As we have the following expressions,

τyx,N = −µγ̇yx,N
τyx,H = −Gγyx,H
γyx = γyx,N + γyx,H

we find,
1 1 ∂τyx,H
γ̇yx = γ̇yx,N + γ̇yx,H = − τyx,N −
µ G ∂t
Inserting the uniform stress expression we obtain the Maxwell model:
( µ ) ∂τ
yx
+ τyx = −µγ̇yx
G } ∂t
| {z
λ
Here, we have defined the relaxation time λ. As λ → 0 we recover the Newtonian model and if
λ → ∞ we obtain the Hookean model. The Maxwell model is the simplest viscoelastic model for
liquid like materials.

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The Voigt-Kelvin model
Corresponding to the Maxwell model we
µ G
use a mechanical analogy. In the Voigt-
Kelvin model we replace the series connec- ?
tion by a parallel coupling. τ

By combining in parallel a dashpot and a spring we have a system with equal deformation in the
two elements and additive stresses:

γyx = γyx,N = γyx,H ⇒ γ̇yx = γ̇yx,N = γ̇yx,H

and
τyx = τyx,N + τyx,H = −µγ̇yx,N − Gγyx,H = −µγ̇yx − Gγyx
The Voigt-Kelvin model is the simplest viscoelastic model for solid like materials.

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Maxwell equivalent integral form and the generalised linear viscoelastic model
The linear Maxwell model in differential form
∂τyx
λ + τyx = −η0 γ̇yx
∂t
can be integrated and written as an integral stress expression:
∫ t [
η0 −(t−t′ )/λ ]
τyx (t) = − e γ̇yx (t′ )dt′
−∞ | λ {z }
G(t − t′ )
The function G(t) is called the relaxation modulus and can be used to define a generalised linear
viscoelastic model: ∫ t
τyx (t) = − G(t − t′ )γ̇yx (t′ )dt′
−∞

The step-strain shear experiment

γyx γ̇yx
6 γ0 6 γ̇0 = γ0 /ϵ

- -
t0 −ϵ t0 t t0 −ϵ t0 t

The associated stress for the above experiment can be calculated for t > t0 :
∫ t
τyx (t) = − G(t − t′ )γ̇yx (t′ )dt′
−∞
∫ t0−ϵ ∫ t0 ∫ t
= − G(t − t′ )γ̇yx (t′ )dt′ − G(t − t′ )γ̇yx (t′ )dt′ − G(t − t′ )γ̇yx (t′ )dt′
−∞ t0−ϵ t0
∫ t0
= −γ̇0 G(t − t′ )dt′
t0−ϵ
∫ t0
γ0
= − G(t − t′ )dt′
ϵ t0−ϵ

As ϵ → 0 we use l’Hôpitals rule to determine the limit:

{ ∫ t0 }
− t0−ϵ G(t − t′ )dt′
τyx (t) = −γ0 lim
ϵ→0 ϵ
{ }
−G(t − (t0 − ϵ)) · (−1)
= −γ0 lim
ϵ→0 1
= −γ0 G(t − t0 )
In particular for t0 = 0 we have:
τyx (t) = −γ0 G(t)
We have now shown that the relaxation modulus can be determined directly from this step strain
shear experiment.

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Time-temperature superposition
In isothermal conditions we have calculated the stress in the step strain shear experiment:

τyx (t) = −γ0 G(t)

Assuming a Maxwell type spectrum, the relaxation modulus may be written as the following
sum:
∑N
G(t) = Gi e−t/λi ; Gi = ηi /λi
i=1

In non-isothermal conditions the spectrum can be written as:

∑
N
G(T, t) = Gi (T )e−t/λi (T )
i=1

The temperature dependency are described by so-called shift factors for time and modulus:
Time shift factor:
λi (T )
aT =
λi (Tr )
Modulus shift factor from rubber elasticity:
ρT
bT =
ρr Tr
The relaxation modulus at temperature T is then related to the value at some reference temper-
ature Tr :
G(T, t) = bT G(Tr , tr ); tr = t/aT
From linear viscoelastic theory we have the viscosity expressed as:

∑
N
η0 = Gi λi
i=1

The viscosity may therefore be shifted in a similar procedure:

η(T )
= bT aT
η(Tr )

From experimental data it is possible to realise so-called master curves. It is also possible to
predict the time shift factor from models. One such model is the Williams-Landel-Ferry (WLF)
model.

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The Willams-Landel-Ferry (WLF) equation
A polymeric material may contain a temperature dependent free volume defined by the linear
equation below:
f = α(T − T∞ )
Th so-called Doolitle equation predicts the viscosity from the free volume f :

η = η0 exp(B/f )

If we take the previous expression for the temperature shifted viscosity we have:

η(T )
= bT aT
η(Tr )

Assuming bT ≈ 1 we obtain:
{ }
η(T ) B B
aT = = exp −
η(Tr ) f fr
{ ( )}
B fr
= exp −1
fr f
{ ( )}
B fr − f
= exp
fr f
{ ( )}
B T − Tr
= exp −
fr T − T∞

Hence,
ln aT B T − Tr −c1 (T − Tr )
log10 aT = =− =
ln 10 fr ln 10 (Tr − T∞ ) + T − Tr c2 + T − Tr
Typically, the glass transition temperature is chosen as reference (Tr = Tg ).