ANNEX II-F: GENERALIZED MAXWELL MODEL.

RHEOLOGICAL
ELEMENTS

Pot element or Dashpot.—

ηv
t

A) B)

Figure 0.6: A) Dashpot element. B) Deformation vs. time representation when a

constant stress is applied

This element is a frictionless piston which represents the viscous behavior

(Figure 0.6-A). If a stress σ is applied between times t0 and t1, the
deformation ɛ will vary linearly with time of application of stress (Figure 0.6-
B).

𝑑𝜀 𝜎
= Eq. 0.59
𝑑𝑡 𝜂𝑣

if σ is constant (Creep case):

𝜎
𝜀= 𝑡 Eq. 0.60
𝜂𝑣

where ηv is the viscosity constant.

When the applied stress σ stops acting, deformation ɛ remains (irreversible)

because the work provided by the external force is not stored by the material
and it is dissipated as heat (internal friction). Deformation is faster for smaller
values of viscosity.

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Elastic solid. Spring model.—

Ee
e t

A) B)

Figure 0.7: A) Elastic Spring. B) Deformation vs. time representation when a

constant stress is applied

The elastic solid follows Hooke's law σ=Ee.ɛ (Figure 0.7-A). When a load is
applied, the instantaneous strain originated is due to changes in the length
and angles of atomic bonds (Figure 0.7-B). The solid stores all the energy
supplied by the external forces. When the load is removed, the stored energy
is able to restore the original shape instantly (reversible deformation)

Maxwell model.—

ɛ
Ev
ɛve=/Ev

ηv
ɛve=/Ev ɛvv=t1*σ/ηv

t1 t

A) B)

Figure 0.8: A) Maxwell models representation. B) Creep case (σ is constant)

Maxwell models loading and unloading representation. The model is unloaded at
time t1.

Most polymers exhibit elastic and viscous behavior together (only glassy
polymers are perfectly elastic solids and thermoplastics; high temperature

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shows a viscous behavior only), which can be assimilated to the juxtaposition
of the models described above.

Maxwell's element or model is formed by connecting in series a dashpot and

a spring (Figure 0.8-A). By applying the spring force F, it instantly lengthens
the magnitude ɛ and the dashpot moves to the speed σ/η while applying the
load (between to and t1). By stopping the application of the load, the elastic
component is recovered instantaneously while the viscous component of the
deformation remains indefinitely (Figure 0.8-B).

The total deformation is therefore distributed between the two elements,

which are subjected to the total stress. Thus,

𝜎𝑣 = 𝜎𝑣𝑒 = 𝜎𝑣𝑣 Eq. 0.61

𝜀𝑣 = 𝜀𝑣𝑒 + 𝜀𝑣𝑣 Eq. 0.62

Where subscripts ve, vv and v indicate the stresses σ and strains ɛ in the
elastic spring, dashpot and the totals of the Maxwell element.

The spring is the elastic component of the model and behaves according to
Hooke's law:

1
𝜀𝑣𝑒 = ( ) 𝜎𝑣 Eq. 0.63
𝐸𝑣𝑒

and the dashpot is the viscous component of the model and behaves
according to Newton's law:

𝑑𝜀𝑣𝑣 1
= ( ) 𝜎𝑣 Eq. 0.64
𝑑𝑡 𝜂𝑣

The total strain variation over time is obtained by differentiating the Eq. 0.62:

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𝑑𝜀𝑣 𝑑𝜀𝑣𝑒 𝑑𝜀𝑣𝑣
= + Eq. 0.65
𝑑𝑡 𝑑𝑡 𝑑𝑡

Substituting in Eq. 0.65 the Eq. 0.64 and Eq. 0.63 derivative with respect to
time yields:

𝑑𝜀𝑣 1 𝑑𝜎𝑣 1
=( ) + ( ) 𝜎𝑣 Eq. 0.66
𝑑𝑡 𝐸𝑣𝑒 𝑑𝑡 𝜂𝑣

which is the equation that governs the behavior of the Maxwell model.

A simple viscous or standard viscoelastic solid model: Zener model.—

ɛ
ɛe ɛv

Eve
Ee
ηv

Figure 0.9: Three elements model. It is known as the Zener or standard linear solid
(SLS) model.

A response closer to a real polymer is obtained by adding a second spring of

modulus Ee in parallel with Maxwell unit (Figure 0.9). This model is known as
Zener model [4].

𝜀 = 𝜀𝑒 = 𝜀𝑣 Eq. 0.67

𝜎 = 𝜎𝑒 + 𝜎𝑣 Eq. 0.68

where:

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 𝜎𝑒
𝜀= Eq. 0.69
𝐸𝑒

Using these relationships, their time derivatives and the above stress-strain
relationships for the spring and the dashpot elements, the system can be
modelled as follows:

𝑑𝜀 𝐸𝑒 𝐸𝑣𝑒 𝑑𝜎 𝐸𝑣𝑒
(𝐸𝑒 + 𝐸𝑣𝑒 ) + 𝜀= + 𝜎 Eq. 0.70
𝑑𝑡 𝜂 𝑑𝑡 𝜂𝑣

Generalization of the Maxwell model.—

This model is based on the Zener model. One or more Maxwell chains are
added to that model to improve the fitting of experimental data (Figure 0.10).

σ ɛ

Eve1 Eve2 Even

Ee …
ηv1 ηv2 ηvn

Figure 0.10: Generalization of the Maxwell model.

Considering a relaxation test, the total stress in this model will be obtained
with the addition of the elastic stress to the solitary spring of stiffness Ee
which is known as E, plus the sum of stresses in each Maxwell element.

These viscoelastic models can be written so that they can characterize the
mechanical behavior as a function of both time and frequency. When these
models are written according to time, they can be used for characterizing the
creep and stress relaxation tests. This thesis will examine the last mentioned
tests because this latter is the most related to the objectives of the thesis.

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Maxwell models stress relaxation behavior.—

In this mode of time-dependent stress, ɛ is constant, then Eq. 0.66 is

converted into:

1 𝑑𝜎𝑣 𝜎𝑣
( ) +( )=0 Eq. 0.71
𝐸𝑣𝑒 𝑑𝑡 𝜂𝑣

Where,

𝑑𝜎𝑣 𝐸𝑣𝑒
= − ( ) 𝑑𝑡 Eq. 0.72
𝜎𝑣 𝜂𝑣

The solution of the previous differential equation between the initial time of
application of stress σ until it takes a time t gives:

−𝐸𝑣𝑒 𝑡 −𝑡 −𝑡
𝜎 = 𝜎𝑣0 𝑒 𝜂𝑣 = 𝜎𝑣0 𝑒 𝜏 = ɛ𝑣0 𝐸𝑣𝑒 𝑒 𝜏 Eq. 0.73

And,

−𝑡
𝐸(𝑡) = 𝐸𝑣𝑒 𝑒 𝜏 Eq. 0.74

The initial stress is defined entirely by the elastic spring, and the initial
condition for the differential equation is the load acting on the body is
disappearing gradually and disappears completely after an infinite time
(Figure 0.11). This equation shows that the stress decays exponentially with
a characteristic time constant:

𝜂𝑣
𝜏= Eq. 0.75
𝐸𝑣𝑒

where  is called the “relaxation time”.

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 σ(t)

σv0=Eveɛv0

𝜎∞
t

Figure 0.11: Stress relaxation phenomenon: Maxwell model.

This model is too simple to explain the actual behavior of polymers since it
has two major limitations: the strain rate is constant while applying the
constant load and also the relaxed stress σ=0 at constant strain conditions.

The complex modulus E*(ω) can be determined by solving Eq. 0.66 for a
steady-state sinusoidal strain history,

𝜀 ∗ = 𝜀0 𝑒 𝑖𝜔𝑡 Eq. 0.76

Inserting a trial solution,

𝜎 = 𝐶𝑒 𝑖𝜔𝑡 Eq. 0.77

into Eq. 0.66 yields in the stationary solution,

𝑖𝜔 𝑖𝜔𝜏
𝐶 = 𝐸𝑣𝑒 𝜀0 = 𝐸𝑣𝑒 𝜀 Eq. 0.78
𝑖𝜔 + 𝐸𝑣𝑒 /𝜂 𝑖𝜔𝜏 + 1 0

Finally the complex modulus can be written as follows,

𝑖𝜔𝜏
𝐸 ∗ (𝜔) = 𝐸𝑣𝑒 Eq. 0.79
1 + 𝑖𝜔𝜏

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Zener models stress relaxation behavior.—

σ(t)

𝜎0 = 𝜀0 (𝐸∞ + 𝐸𝑣𝑒 )

𝜎∞ = 𝜀0 𝐸∞
t

Figure 0.12: Stress relaxation phenomenon: Zener model.

The total stress is given by,

𝜎 = 𝜎∞ + 𝜎𝑀𝑎𝑥𝑤𝑒𝑙𝑙 Eq. 0.80

Once the material is relaxed, the stress is not zero (Figure 0.12), but it
reaches a value depending on the additional spring (compared to the
Maxwell model).

In this case, integrating the Eq. 0.70 from the initial time of application of
stress σ until it takes a time t gives:

−𝑡
𝜎(𝑡) = ɛ0 (𝐸∞ + 𝐸𝑣𝑒 𝑒 𝜏 ) Eq. 0.81

Then, Young’s relation modulus can be written as follows:

−𝑡
𝐸(𝑡) = 𝐸∞ + 𝐸𝑣𝑒 𝑒 𝜏 Eq. 0.82

The stress is given by inserting the Maxwell stress Eq. 0.79 into Eq. 0.80
according to,

𝑖𝜔𝜏
𝜎 ∗ (𝜔) = 𝐸∞ 𝜀 ∗ + 𝐸𝑣𝑒 𝜀∗ Eq. 0.83
1 + 𝑖𝜔𝜏

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Hence, the Zener models complex modulus yields in,

𝑖𝜔𝜏
𝐸 ∗ (𝜔) = 𝐸∞ + 𝐸𝑣𝑒 Eq. 0.84
1 + 𝑖𝜔𝜏

Generalization of the Zener model or generalized Maxwell model.—

The generalized Maxwell model (Figure 0.10), widely used to characterize

the modulus functions of linear viscoelastic media, consists of a spring and N
Maxwell units connected in parallel Tschoegl [5].

𝜎0 = 𝜎∞ + ∑ 𝜎𝑣𝑒,𝑖 Eq. 0.85

𝑖=1

𝑁
−𝑡
𝜎 = ɛ0 (𝐸∞ + ∑ 𝐸𝑣𝑒,𝑖 𝑒 𝜏𝑖 ) Eq. 0.86
𝑖=1

𝑁
𝑡
−
𝐸𝑣𝑒(𝑡) = 𝐸∞ + ∑ 𝐸𝑣𝑒,𝑖 𝑒 𝜏𝑖 Eq. 0.87
𝑖=1

where i is the relaxation time for each Prony component Evei.

In this model, when the time is zero (t=0), the instantaneous modulus Eo is,

𝐸0 = 𝐸∞ + ∑ 𝐸𝑣𝑒𝑖 Eq. 0.88

𝑖=1

where the long term or the relaxed modulus (t=) is 𝐸∞ . Evei and  are the
relaxation modulus and relaxation time respectively; the relaxation time of the
ith Maxwell element defined by 𝜏𝑖 = 𝜂𝑖 /𝐸𝑣𝑒𝑖 where 𝜂𝑖 is the viscosity of the
dashpot unit. The typical term under the summation symbol in the previous
equation, represents the relaxation modulus of the ith Maxwell unit. The
series expression in the equation is often referred to as a Prony series.

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Findley et all [6] studied some common models including the generalized
Voigt model and generalized Maxwell model.

This model can be used to simulate sinusoidal dynamic tests. If the

mentioned test is simulated with the latter model, the dynamic modulus does
not change with the loading strain amplitude (Figure 0.13):

σ
E

t ɛ

A) B)

Figure 0.13: Sinusoidal Dynamic test: Linear viscoelasticity. The dynamic modulus
does not change with the load strain amplitude. A) Two sinusoidal loads with
different strain amplitude are presented. B) The dynamic modulus is the same in both
load strain cases presented in Figure A.

The complex modulus for the generalized Zener model can be derived in a
similar manner that made before in Eq. 0.84,

𝑛
∗ (𝜔)
𝑖𝜔𝜏𝑗
𝐸 = 𝐸∞ + ∑ 𝐸𝑣𝑒𝑗 Eq. 0.89
1 + 𝑖𝜔𝜏𝑗
𝑗=1

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