POLYMER PHYSICS
Section 3. Properties
Unit 3.5 Viscoelasticity behavior and viscoelastic models.
Matteo Arioli
Univ. Politècnica Catalunya (2024)
[email protected]
Overview
Viscoelasticity and rheological behavior
• Viscoelasticity
• Models of viscoelastic behavior
• Molecular interpretation of the viscoelastic behavior
• Time – temperature equivalence
• Rheological behavior of polymers
Viscoelasticity
• Viscoelasticity can be defined as a complex response of mechanical behavior
that is strongly dependent on time and is characteristic of plastic materials.
This behavior is intermediate between an elastic solid and a viscous fluid.
• Viscoelastic fluid exhibit recovery from deformations that occur during flow
• Typical characteristics of viscoelastic fluids
• Slow flow-partial recovery of the initial size
• Stress relaxation Slow recovery Stress relaxation
Viscoelasticity
• In some temperature range, polymers display a combination of liquid (viscous)
and solid (elastic) behavior simultaneously → viscoelasticity
• Stretching to fixes ε0 and hold → observe decrease in stress
Viscoelasticity
The variation with temperature of the stress
relaxation
Models of viscoelastic behavior
Elastic (solid-like) response Viscous (liquid-like) response
𝜎 = 𝐸𝜀 𝜎 = 𝜂𝜀
ሶ
E = Young’s modulus
𝜂ሶ = Young’s modulus
Spring Dash-pot
(piston)
Models of viscoelastic behavior
Elastic (solid-like) response Viscous (liquid-like) response
• A material is perfectly elastic, if the • The viscous flow of a material can be
equilibrium shape is attained instantly represented by the Newtonian model, by
when a stress is applied. using a “dashpot” mechanical analog.
• In a cyclic elastic deformation, strain and • The dashpot is really a piston that moves
energy are completely recovered. inside a chamber filled with a viscous
fluid.
• The simplest elastic solid model is the
Hookean model, which we can represent • Unlike elastic behavior, viscous flow is
by the “spring” mechanical analog. irreversible and produces permanent or
nonrecoverable strain.
• In viscous behavior, the deformation rate
becomes instantaneously zero when the
stresses are set equal to zero.
Elastic (solid-like) behavior
Creep test: a constant
stress is instantly applied
to the material and the
resulting strain is followed
as a function of time.
Stress relaxation test: a
constant strain is suddenly
applied to the sample and
the corresponding stress as
a function of time
measured.
Viscous (liquid-like) behavior
Creep test: a constant
stress is instantly applied
to the material and the
resulting strain is followed
as a function of time.
Stress relaxation test: a
constant strain is suddenly
applied to the sample and
the corresponding stress
as a function of time
measured.
Models of viscoelastic behavior
One can build up a model of linear viscoelasticity by considering combinations
of the linear elastic spring and the linear viscous dash-pot.
• Maxwell model
• Voigt - Kelvin model
• Burgers model
• Multiple and combinative models
Models of viscoelastic behavior
• Maxwell model
• Serial combination of a dash-pot and a elastic spring
• σspring = σdashpot
• Good stress relaxation model
• Bad slow-flow model
• q is defined as the relaxation time.
• It is given by h / E and corresponds to the necessary time for the stress to be reduced to
37% of its initial value
𝑡
𝜎 = 𝜎0 exp −
𝜃1
Models of viscoelastic behavior
Maxwell model
When force is applied there is an instant
energy deformation due to a stretching of
spring. Further deformation takes place due
to deformation of dash-pot.
Once the force is removed, spring returns
to its original shape leading to recovery of
the deformation.
Maxwell model is very good in understanding the deformation and
recovery behavior of soft solids like thermoplastic polymer in the vicinity
of their melting point.
Models of viscoelastic behavior
• Voigt Model
• Parallel combination of a dashpot and a spring
• It is assumed there is no bending in this type of parallel arrangement, so that
the strain experienced by the spring is the same as that experienced by the
dash-pot
• Bad stress relaxation model
• Good slow-flow model 𝜎𝑜 − 𝐸∙𝑡
flowing: 𝛾 = 1 − exp
𝐸 𝜎
Models of viscoelastic behavior
Voigt Model
Once the force is applied, there is no
instantaneous deformation since dashpot
cannot deform instantaneously.
At constant stress the model is quite
realistic as it predicts strain to decrease
with time. But regards to relaxation the
model is much less accurate.
However, this model can be used to predict
the deformation behavior at low loading for
organic polymers rubber and Wood.
Models of viscoelastic behavior
• Burgers Model
• Serial combination of Maxwell and Voigt models
g = so / E1 + so t / h1 + so / E2 (1- exp (- t / q2))
• Good slow flow model
• Good stress relaxation model
• Multiple models → combination of several springs and dashpots
Molecular interpretation of the viscoelastic
behavior
The deformations of the bonds determine
the elastic behavior defined by E1.
Reversible conformational deformations
are responsible for E2 and σ2.
The molecular movement occur at great
deformations and define η.
Time - temperature equivalence
Time and temperature are variables that operate in the same way on the
responses of a viscoelastic material. An increase in temperature is
equivalent to shortening the time since h and q diminish very accurately
with the temperature.
The determined module values can be converted to several temperatures,
in values corresponding to the same work temperature, making the right
changes in the time scale.
The displacement factor, aT, corresponds to the relationship between the
relaxation time q at a temperature T and the relaxation time q0 at a
reference temperature T0. Among the most used empirical relationships is
the glass transition temperature used as a reference:
−17.44 (𝑇 − 𝑇𝑔 )
log 𝑎𝑡 =
51.6 + 𝑇 − 𝑇𝑔
Rheological behavior of polymers
The rheological behavior of a polymer
can be considered as a three-
dimensional surface (s, g (e), t).
The projections on different planes in
which a variable is kept constant
correspond to
1. tensile-deformation graphics (at
different test times)
2. relaxation of stress (to different
deformations)
3. flow diagrams (to different applied
stress).
Rheological behavior of polymers
The results of the flowing
tests (polypropylene and
vinyl polychloride) can be
transformed into
isochron diagrams that
can be constructed from
the previous ones.
polypropylene
vinyl polychloride
