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SCH 2464 - Mechanical Propeties of Polymers (1)

Mechanical properties of polymers

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11 views8 pages

SCH 2464 - Mechanical Propeties of Polymers (1)

Mechanical properties of polymers

Uploaded by

dnnsmoso
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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1.

0 MECHANICAL PROPERTIES OF POLYMERS

1.1 Overview of the basic terminologies

1.1.1 Rheology

Rheology is the science of the flow and deformation of matter


(liquid or “soft” solid) under the effect of an applied force
(or under controlled testing conditions). In practice, the word
"rheology" typically refers to the flow and deformation of "non-
classical" materials such as rubber, molten plastics, polymer
solutions, slurries and pastes, composites, paints and many
others.

1.1.2 Viscoelasticity

Viscoelasticity is the property of materials that exhibit both


viscous and elastic characteristics when undergoing deformation
(strain). Viscous materials resist shear flow and strain
linearly with time when stress is applied. Elastic materials
strain instantaneously when stretched and just as quickly return
to their original state once the stress is removed.

Viscoelastic materials have elements of both of these properties


and, thus, exhibit time-dependent strain. Whereas elasticity is
usually the result of bond stretching along crystallographic
planes in an ordered solid, viscosity is the outcome of the
diffusion of atoms or molecules inside an amorphous material.

Depending on the change of strain rate versus stress inside a


material, viscosity may be categorized as a linear, non-linear,
or plastic response. In rare cases, viscosity decreases as the
shear/strain rate remain constant, and the materials are said to
be thixotropic. When stress is independent of strain rate, the
material exhibits plastic deformation. Many viscoelastic
materials exhibit rubbery behavior explained by the
thermodynamic theory of polymer elasticity. Inelastic materials
(a subset of Viscoelastic materials) have a unique equilibrium
configuration and ultimately recover fully after removal of a
transient load.

1.1.2.1 Stress relaxation

Stress relaxation is the observed decrease in stress in response


to an equal amount of strain generated in the structure. This is
mainly due to keeping the structure in a strained condition for
some finite interval of time and hence causing some amount of
plastic strain.

The amount of relaxation that takes place is a function of time,


temperature and stress level, as such, the actual effect it has
on the system is not precisely known, but can be bounded. Stress
relaxation describes how polymers relieve stress under constant
strain.

1.1.2.2 Creep

Creep (also called cold flow) is the tendency of a solid


material to move slowly or deform permanently under the
influence of mechanical stresses. In material science, this also
refers to the constant state of stress with an increasing amount
of strain. It may occur due to long-term exposure to high levels
of stress that are still below the yield strength of the
material. Creep is much more severe in materials that are
subjected to heat for extended periods of time and increases as
they near their melting point.

1.1.2.2.1 How creep relates to stress relaxation

Stress relaxation describes how polymers relieve stress under


constant strain. Because they are viscoelastic, polymers behave
in a nonlinear, non-Hookean fashion. This nonlinearity is
described by both stress relaxation and a phenomenon known as
creep, which describes how polymers strain under constant
stress.
1.2 Toughness and strength of a typical polymer

1.2.1 Toughness

The toughness of a material is the area under a stress-strain


curve (Figure 1). The stress is proportional to the tensile
force on the material, and the strain is proportional to its
length.

Figure 1: Stress-strain curve (toughness)

The toughness is a measure of the energy a sample can absorb


before it breaks. There is a difference between toughness and
strength, as is illustrated in Figure 2.

Figure 2: Stress-strain curve (toughness vs. strength)

A material that is strong but not tough is said to be brittle.


Brittle substances are strong, but cannot deform very much.
1.2.2 Tensile Strength

The tensile strength is the stress needed to break a sample


(Figure 3). It is expressed in Pascals or psi (pounds per square
inch). Tensile strength is an important property of polymers
that are going to be stretched such as fibers that must have
enough tensile strength.

Figure 3: Stress-strain curve (tensile strength)

1.3 The Boltzmann superposition principle

In the linear viscoelastic regime, the stress responses to


successive deformations are additive. Similarly, in the linear
viscoelastic regime the strain responses to successive stresses
are additive.

1.4 An idealized stress strain curve for typical polymer/s

The ratio between stress and strain is constant; hence modulus


is obtained from the slope of the curve (Figure 4). Point L
represents the stress beyond which a brittle material will
fracture. For a brittle polymer, it obeys the curve to point L
(energy for brittle fracture) and breaks around this region. If
the polymer is not brittle, it will continue to curve until the
point of inflection, Y where strain decreases which is called
the yield point. At this point, the polymer increases in length
(stretches) until it breaks at point B; break point. However, if
the polymer is tough (rubbery), it will continue to point B of
the curve.

Figure 4: Idealized stress strain curve for a typical crystalline


olefin polymer

1.5 Maxwell model

The Maxwell model can be represented by a purely viscous damper


and a purely elastic spring connected in series, as shown in the
diagram (Figure 5).

Figure 5: The Maxwell model

Under this model, if the material is put under constant strain,


the stresses gradually relax. When a material is subjected to
constant stress, the strain has two components. First, an
elastic component occurs instantaneously, corresponding to the
spring, and relaxes immediately upon release of the stress. The
second is a viscous component that grows with time as long as
the stress is applied. The Maxwell model predicts that stress
decays exponentially with time, which is accurate for most
polymers.

1.6 Mechanical properties of polymers

1.6.1 Bulk properties

The bulk properties of a polymer are those most often of end-use


interest. These are the properties that dictate how the polymer
behaves on a macroscopic scale.

a. Tensile strength
The tensile strength of a material quantifies how much
elongating stress a material can endure before suffering
permanent deformation. This is critical in applications that
rely upon a polymer's physical strength or durability. For
example, a rubber band with a higher tensile strength will hold
a greater weight before snapping. In general, tensile strength
increases with polymer chain length and also the cross-linking
of the polymer chains.

b. Young’s modulus
Young's Modulus quantifies the elasticity of the polymer. It is
defined, for small strains, as the ratio of the rate of change
of stress to strain. Like tensile strength, this is highly
relevant in polymer applications involving the physical
properties of polymers, such as rubber bands. The modulus is
strongly dependent on temperature. In designing a material, it
should be noted the temperature that you are using.

c. Diffusivity
It relates to how rapidly molecules move through polymer matrix
and it’s important in applications such as films and membranes
e.g. surface coatings and soft drinks bottle (PVC) carbonated
drinks. Plasticizers have a higher diffusion rate in the polymer
that allows them to move freely within the polymer.
Flexibilizers are also highly diffusive and move well within the
polymer.

d. Melting point
The term melting point, when applied to polymers, suggests not a
solid–liquid phase transition but a transition from a
crystalline or semi-crystalline phase to a solid amorphous
phase. Though abbreviated as simply Tm, the property in question
is more accurately called the crystalline melting temperature.
Among synthetic polymers, crystalline melting is only discussed
with regards to thermoplastics, as thermosetting polymers will
decompose at high temperatures rather than melt.

e. Boiling point
High polymers with a high degree of polymerization don’t exhibit
boiling point because they tend to decompose before theoretical
boiling point. For short oligomers, a boiling transition may be
observed.

f. Glass transition temperature


Tg is the temperature at which amorphous polymers undergo a
second order phase transition from rubbery, viscous, amorphous
solid or from crystalline solid (depending on the degree of
crystallization) to a brittle glassy amorphous solid (Figure 6).

Figure 6: Relationship between elastic modulus and temperature


Altering Tg of a material is important. It’s altered by
increasing branching of the polymer, cross-linking and by the
addition of plasticizers. The addition of plasticizers to
polymers tends to lower the Tg and increases polymer
flexibility. Plasticizers are small molecules and are chemically
similar to polymers and create gaps within the polymer chains
for greater mobility and reduced interchain interaction.
Plasticizers that are compatible with polymer material act as
spaces between polymer chains and space them out from each
other. We call this increasing the free volume. They slide past
each other more easily and can move around at lower temperatures
than they would without the plasticizer. In this way, the Tg of
a polymer can be lowered, to make a polymer more pliable, and
easier to work with the polymer.

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