OBJECTIVE: Polymer viscoelasticity

Tayab Ali

(21bschem57)

Teacher:

Dr. Sidra Ameen

DEPARTMENT OF CHEMISTRY
Faculty of Natural Science and Technology
Shaheed Benazir Bhutto University (SBBUSBA)
Benazir Abad/Nawabshah, Sindh

29/ 4/ 2024
 CONTENT

S.NO. TOPIC PAGE NO.

1 Introduction 1to 3
I. Background
2 Viscoelastic Properties 3 to 4
I. Introduction to Plastic Deformation and Viscous Flow
3 Viscoelasticity Experimental Measurements – The Relaxation Modulus 4 to 5

4 Types of viscoelastic behavior: 5 to 7

I. Linear Viscoelasticity
II. Nonlinear Viscoelasticity

5 Factors Affecting Viscoelastic Behavior: 7

6 Applications of Viscoelastic Materials 8

References 4

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 1. Introduction :

In materials science and continuum mechanics, viscoelasticity is the property of materials that exhibit
both viscous and elastic characteristics when undergoing deformation. Viscous materials, like water,
resist shear flow and strain linearly with time when a stress is applied. Elastic materials strain when
stretched and immediately return to their original state once the stress is removed.

Viscoelastic materials have elements of both of these properties and, as such, exhibit time-dependent
strain. Whereas elasticity is usually the result of bond stretching along crystallographic planes in an
ordered solid, viscosity is the result of the diffusion of atoms or molecules inside an amorphous material.

I. Background:

In the nineteenth century, physicists such as James Clerk Maxwell, Ludwig Boltzmann, and Lord Kelvin
researched and experimented with creep and recovery of glasses, metals, and rubbers. Viscoelasticity was
further examined in the late twentieth century when synthetic polymers were engineered and used in a
variety of applications. Viscoelasticity calculations depend heavily on the viscosity variable, η. The
inverse of η is also known as fluidity, φ. The value of either can be derived as a function of temperature
or as a given value.

Depending on the change of strain rate versus stress inside a material, the viscosity can be categorized as
having a linear, non-linear, or plastic response. When a material exhibits a linear response it is
categorized as a Newtonian material. In this case the stress is linearly proportional to the strain rate. If the
material exhibits a non-linear response to the strain rate, it is categorized as non-Newtonian fluid. There is
also an interesting case where the viscosity decreases as the shear/strain rate remains constant. A material
which exhibits this type of behavior is known as thixotropic. In addition, when the stress is independent
of this strain rate, the material exhibits plastic deformation.Many viscoelastic materials exhibit rubber like
behavior explained by the thermodynamic theory of polymer elasticity.

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Some examples of viscoelastic materials are amorphous polymers, semicrystalline polymers,

biopolymers, metals at very high temperatures, and bitumen materials. Cracking occurs when the strain is
applied quickly and outside of the elastic limit. Ligaments and tendons are viscoelastic, so the extent of
the potential damage to them depends on both the rate of the change of their length and the force applied.

1) Viscoelastic Properties:
I) Introduction to Plastic Deformation and Viscous Flow:

When a material sample is subject to external loading deformations that exceed its elastic limit, or yield
strength, the material will cease to deform linearly, elastically and reversibly. Instead, the sample will
gradually start undergoing the phenomenon of plastic deformation, otherwise known as yielding.
Contrary to the regime of elasticity, plasticity is both non-linear and permanent. This implies that its
effects on the material cannot be recovered and undone once the external stress at the source of the
deformation is removed. Fundamentally, plastic deformation is the consequence of large number of atoms
or molecules moving relative to one another, which results in the breaking of their original bonds and the
reforming of new ones. This bond-switching mechanism cannot in fact be energetically reversed upon
release of the external load.

Representation of the viscous flow of a liquid or fluid glass in response to an applied shear force

In general, the microscopic mechanisms by which such plastic deformation occurs is different for the two
cases of crystalline and amorphous materials. Within the former category, plasticity is accompanied by
the nucleation and propagation of crystalline defects known as dislocations. In non-crystalline solids on

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the other hand, plastic flow and deformation unfolds in very much the same way as the flow of liquids.
This consists specifically in a viscous flow mechanism. It includes therefore the case of amorphous and
semi-crystalline polymers. This is a direct result of the lack of regular atomic structure within this class of
materials. Under this regime of viscous flow, the rate of deformation is typically proportional to the
applied stress.

For the common case where the applied stress consists in shear stress, the atoms will slide next to each
other by the breaking and re-forming of interatomic bonds, in a very unpredictable fashion. The figure
below illustrates the main features of viscous flow on a macroscopic scale. Here, the decreasing velocity
of the flow as a function of increasing distance, and therefore decreasing magnitude of the applied shear
force, is clearly apparent.

The fundamental quantity defining viscous flow is called the viscosity η of the amorphous material or
liquid under consideration, which is measured in units of pascal-seconds. Considering the above image,
viscosity can be defined as the ratio of the applied shear stress F and the change in velocity dv of the
substance with distance dy perpendicularly from the surface A across which the shear stress is applied.
Therefore, the higher the viscosity, the higher essentially will be the material’s resistance to the flow
induced by such shear forces. Typically, liquids have much lower viscosities than the amorphous
materials for which viscous flow is relevant, such as glasses.

For example, the viscosity of water at room temperature is only around 10 -3 Pa-s, whereas for solid
glass the value at an equivalent temperature can have an order of magnitude as high as 10 16 Pa-s, due to
their strong interatomic bonding. For the case of amorphous polymers considered here, the value of the
viscosity is of order 10 8. Despite such vastly different orders of magnitude, it is important to highlight
that the concept and mechanism of viscosity and viscous deformation apply equally well to both liquids
and amorphous materials in their solid state. These values for the viscosity will generally decrease with
increasing temperature, as a result of such bonding forces becoming weaker under thermal effects, and the
flow of atoms thus being made easier.

3 Viscoelasticity Experimental Measurements – The Relaxation Modulus

The viscoelastic behaviour of polymeric materials can be investigated and characterized experimentally in
a number of different ways. One such method consists in stress relaxation measurements. Under this
approach, the polymer sample is firstly strained rapidly in tension to some fixed strain value, whilst its
temperature is kept constant. The experiment then consists in measuring the stress required for

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maintaining this strain level across the polymer sample at its fixed and predefined value, which typically
decreases with time owing to the time-dependent nature of viscoelasticity and its associated molecular
relaxation processes.

The ratio between this measured time-dependent stress profile and the fixed predefined value of the strain
is called the relaxation modulus of the viscoelastic polymer. This quantity therefore plays the same role as
the conventional elastic Young’s modulus in linear elasticity, but this time in the context of time-
dependant and partially-inelastic mechanical response properties. The relaxation modulus is also typically
temperature-dependant, decreasing with increasing temperature as the material becomes correspondingly
softer. Another time-dependant mechanical phenomenon which affects numerous polymers is that of
viscoelastic creep. Under these circumstances, the polymer sample will gradually undergo a time-
dependant deformation, when this time it is the externally-applied stress level which is fixed and
predefined.

A classical example of this phenomenon is when car tyres develop flat spots, when cars are left parked
over long periods of time on hot asphalt surfaces during warm summer days. Similarly to the afore-
mentioned relaxation modulus, we may therefore define also the time-evolving and isothermal creep
modulus, as the ratio between the fixed applied stress and the resulting time-dependant strain affecting the
polymer. This quantity also decreases with increasing temperature of the sample.

4 Types of viscoelastic behavior:

I. Linear Viscoelasticity

Linear viscoelasticity is a type of viscoelastic behavior where the stress and strain of a material are
proportional to each other. This means that the material exhibits a linear response to stress, and the
resulting strain is directly proportional to the applied stress.

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In linear viscoelasticity, the material’s behavior can be described using the following equation:

Σ (t) = E ε (t)

Where σ (t) is the stress at time t, E is the modulus of elasticity, and ε (t) is the strain at time t.

Linear viscoelastic materials exhibit the following characteristics:

The stress-strain curve is a straight line. The material’s behavior is independent of the loading history

The material’s behavior is reversible (i.e., it returns to its original shape after the load is removed)

Examples of materials that exhibit linear viscoelastic behavior include metals, ceramics, and some
polymers

.II. Nonlinear Viscoelasticity

Nonlinear viscoelasticity is a type of viscoelastic behavior where the stress and strain of a material are not
proportional to each other. This means that the material exhibits a nonlinear response to stress, and the
resulting strain is not directly proportional to the applied stress.

In nonlinear viscoelasticity, the material’s behavior cannot be described using a simple linear equation.
Instead, more complex equations and models are required to describe the material’s behavior.

Nonlinear viscoelastic materials exhibit the following characteristics:

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The stress-strain curve is nonlinear (e.g., curved or sigmoidal). The material’s behavior depends on the
loading history. The material’s behavior may be irreversible (i.e., it does not return to its original shape
after the load is removed)

Examples of materials that exhibit nonlinear viscoelastic behavior include many polymers, such as
rubbers, plastics, and biological tissues. It’s worth noting that many materials exhibit a combination of
linear and nonlinear viscoelastic behavior, depending on the specific conditions and loading history.

5. Factors Affecting Viscoelastic Behavior:

I. Temperature: Temperature has a significant impact on the viscoelastic behavior of polymers. As

temperature increases, the polymer chains gain energy and move more freely, leading to
increased creep and stress relaxation.

II. Time: Time is a critical factor in viscoelastic behavior, as it affects the degree of creep and stress
relaxation. Over time, polymers may exhibit increased deformation and stress relaxation.

III. Frequency: The frequency of loading and unloading cycles affects the viscoelastic behavior of
polymers. Higher frequencies can lead to increased energy loss and hysteresis.

IV. Molecular Structure and Weight: The molecular structure and weight of polymers influence
their viscoelastic behavior. Polymers with higher molecular weights tend to exhibit greater creep
and stress relaxation.

V. Cross-Linking and Branching: Cross-linking and branching in polymer chains can affect their
viscoelastic behavior. Cross-linking can reduce creep and stress relaxation, while branching can
increase it.

6. Applications of Viscoelastic Materials:

A material is usually thought of as just a solid or just a liquid. One that is viscoelastic may have both
properties to some extent. Though not technically true, the material flows like a liquid in certain situations
but performs like a solid in others. There are a number of different materials that count as viscoelastic,
each behaving in the same or similar manner.

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Discovered and developed in the late twentieth century, viscoelastic materials have been used in a number
of different applications including as a buffer under heavy loads to prevent or reduce the damage that can
be seen from moving those items or from operating them in place. The material developed by Sorbothane
was introduced in the early 1980’s and is meant to flow under loads like a liquid.

The dual behavior of the materials allows it to resist shear flow as well as strain. Elastic for example, may
undergo strain when it is stretched at all but will return to its normal, resting state once that stressing
factor is removed from it. Viscosity, on the other hand, gives the material a little more stability and resists
flowing. Additional synthetic polymers will help to stabilize and keep the material behaving like it was
supposed.

Viscoelastic materials also help to deal with the concept of creep. Creep is the tendency of otherwise solid
materials to move or to deform with certain stresses or properties. This deformity may be permanent and
may also represent a potential or imminent failure, depending on the material that is represented. Creep is
almost always more severe in the types of materials that are exposed to or subjected to heat for long
periods. There are some materials where a fair amount of creep is considered to be a good thing- for
instance in concrete roadways or sidewalks, a small amount of creep prevents the stress buildup that can
crack or otherwise damage it.

The viscoelastic polymer materials that were created by Sorbothane in 1982 are used to reduce the
damages that can be caused by machine vibration and by reducing shock damages that are generated by
working machinery parts. For instance, NASA used a version of the material during a launch to protect a
delicate camera from the many different shocks, vibrations and other forces that would be exerted on it.
This same material was also used to help the Air Force Memorial to be safely built. Soaring over two
hundred feet in the air, this structure incorporated specialized dampers that displaced the wind energy that
could have caused the whole thing to topple.

Viscoelastic polymer materials reduce noise transmissions as well which makes working in factories safer
and more pleasant for the employees. Noise reduction can also reduce the amount of down time in the
factory which can lead to increased productivity and efficiency and an overall happier workforce. That
translates to an improvement for the factory, the employees and the surrounding areas.

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References:

I. Paul C. Hiemenz , Polymer chemistry the basic concepts, published by Marcel Dekker, INC Ali
Rights Reserved.
II. L . H. Sperling , Introduction to physical polymer science , fourth edition, 2006, Published by
John Wiley & Sons, INC.
III. https://link.springer.com
IV. https://www.materialssquare.com

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