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Oh Lord who provides Joy, takes away

Sadness and removes all “vighnas” (obstacles) in life.

He who kneels before God can stand before anyone.

~Author Unknown
Applied Rheology in Polymer
Processing
 Relationship between the rheological parameters

• The mathematical relationship

between stress, strain and the rate of
strain is known as constitutive
equation of a body or the rheological
equation of state. A mathematical
function of the form
f (σ, γ, ῠ) = o
represents a general function
between different rheological The science of rheology has
parameters. developed from two different
directions
i) Theoretical analysis of
response of the system to
applied stimuli
ii) Analysis of experimental
data to develop the
empirical correlations.
The theoretical analysis involves the
relationships between stress, strain and
rate of strain tensors resulting in highly
complex generalized equations and only
their simplified forms find the practical
applications.
However, these equations give better
insight into the combined effects of
different types of stresses and the
corresponding response.

The experimental approach on the other hand

results in simple applicable equations
containing few material parameters or
constants.
 Rheological systems
Purely Elastic Behaviour

• Purely elastic response of materials is characterized by their stress

strain curves

• Different materials give different stress-strain curves, for example

brittle materials and metals and alloys are characterized by high
stress and low strain but brittle plastic suffer the brittle failure
whereas the metals undergo yield i.e. the ductile failure.

• The rubber and rubber like materials show low stress and very
high elongation and their stress strain curves pass through a number
of stages.

• The cross linking or vulcanization increase the stress values but

reduces the elongation where as the fillers give the similar effect but
to the lesser extent.
 Rheological systems...
Purely Viscous Behaviour

• Purely viscous behavior is characterized

by the dependence of shear stress on the
rate of shear (also sometimes written as
the rate of deformation or the shear rate).
• The behavior of such fluids can
• The liquids are capable of sustaining be best demonstrated by shearing
infinite deformation and the linear a fluid between two parallel plates
relationship between shear stress, τ and
the rate of shear γ◦ is the well known
Newton’s law of viscosity representing the
Newtonian flow behaviour.

Viscous deformation
 Purely Viscous Behaviour...

If the distance between the plates is y and a force F is

applied to the top of surface area A so that it moves
with a velocity of Vx with the lower plate being
fixed, the shear stress and the rate of shear can be
calculated and the relationship between them can be
written

• Most of the low molecular weight liquids organic

solvents and dilute solution of polymers follow this
equation. The viscosity for these liquids is constant
over the entire range of rate of shear at a particular
temperature.

• A plot of shear stress and rate of shear gives a

straight line passing through the origin and the slope
of the line is the viscosity of the fluid.
 Time independent non-Newtonian fluids

A large no of liquids like polymer and rubber

melts, concentrated polymer solutions, solid
suspensions and slurries invariably do not follow
the Newtons law but show the viscosity to be a
function of rate of shear, γ◦ only. Such fluids are
known as the time independent non Newtonian
fluids.
• For these fluids the viscosity is either found to decrease
with rate of shear as in the case of pseudoplastic fluids or to
increase in the case of dilatent fluids.

• The Bingham plastic fluids on the other hand demonstrate

the existence of yield stress , i.e. to say that these fluids
require a definite amount of energy before they start flowing
and then flow as Newtonian fluids.

• Some polymer melts may flow as pseudoplastic liquids after

yielding, these are known as plastoviscous or viscoplastic
fluid.
 Pseudoplastic fluids

Eg: Ketchup (Sauce), Nail polish, paper pulp in water

The viscosity of these fluids reduces with the shear

rate and the curve of shear stress versus rate of
shear is concave downwards.

A log log plot of shear stress and rate of shear

clearing show three different regions. These are

•A low shear region of a small range with the

slope of the line =1, known as the first
Newtonian region

•An intermediate shear region with line of slope

<1 known as pseudoplastic or shear thinning
region and
Plot of ln Ʈ versus ln γ◦ for
•A high shear region with slope of the line again Pseudoplastic fluids
=1 known as second Newtonian region
 Pseudoplastic fluids...

• Depending on the type of polymer the slope of

the line in the intermediate region may vary
from just <1 to very close to zero.

• The extent of pseudoplasticing or the shear

thinning behavior increases with the decrease in
the value of slope below 1.

• The viscosity and shear stress or rate of shear

plot for such fluids shows a general nature with
the viscosity being constant at low shear region,
continuously falling in the intermediate region
and the again constant in the high shear region
particularly for the polymer solutions and low
molecular weight polymer melts.
Variation of viscosity with rate of
shear
• Such a behavior can be explained by Pseudoplastic fluids...
assuming that in the polymer melts and
solutions, which show shear thinning •As the shear rate increases the polymer molecules
nature the macromolecules or the start orienting in the direction of flow. As the
particles are completely random in the polymer system contains a molecular weight
spatial orientation when at rest Fig a) and distribution the small molecules, which require less
are bound by weak intermolecular forces. energy to change the direction start orienting,
initiating the reduction in the viscosity. The high
•When the applied stress is relatively low molecular weight molecules have very long coiled
the molecules maintain their randomness chains, which are entangled with each other. These
and the molecular forces do not allow molecules require higher energy for
them to be oriented in the direction of disentanglement, uncoiling and then orientation.
force resulting in constant viscosity in this
region.

Pseudoplastic fluids under shear

deformation
• As the shear stress and shear rate Pseudoplastic fluids...
increases further the system is subjected to
increasingly higher energy for deformation
resulting in more and more molecules
being oriented.

•The resistance to the flow of the oriented

molecules is reduced due to the fact that
the oriented molecules can slip past each
other with relative ease. This gives a
continuous decrease in the viscosity till all
the molecules are oriented at some higher •Beyond this value of rate of shear there is no
value of rate of shear. further increase in the extent of orientation of
molecules and the systems show a constant
viscosity or the second Newtonian region.
 Dilatent fluids
Eg: Mixture of cornflour and water

• The rheological behaviour of dilatent fluids is exactly opposite to that of

pseudoplastic fluids, i.e., their viscosity increases with rate of shear or shear
stress and the plot of τ and γ◦ gives concave upward curve.

• These fluids show a constant viscosity at low shear rate, increasing viscosity
with increasing rate of shear in the intermediate region but at high shear
region the behavior is not well established due to experimental difficulty in
collecting the reliable rheological data.

•Examples of such fluids are not very common and only some highly filled
polymer propellant systems like hydroxyl terminated polybutadiene
propellants or the suspensions of beach sand or the PVC plastisols display this
nature.
 Dilatent fluids...

•The shearing of suspensions in which the amount of solids

present is so high that the liquid is just enough to fill the voids,
will tend to release the solids out of fluids contact due to
expansion during shearing there by increasing the viscosity.

•At very low shear rate the liquid fills the voids causing
lubrication effect and giving constant viscosity.

Dilatent fluids under shear deformation