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Applied Rheology in Polymer

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 valves 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 liquids are capable of sustaining
infinite deformation and the linear
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.
•The behavior of such fluids can
be best demonstrated by shearing
a fluid between two parallel plates
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
• 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
• 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
• 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
Pseudoplastic fluids
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
•A high shear region with slope of the line again
=1 known as second Newtonian region
Plot of ln Ʈ versus ln γ◦ for
Pseudoplastic fluids
Pseudoplastic fluids...
• Depending on the type of polymer the slope of
the line in the intermediate region many vary
form 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
Pseudoplastic fluids...
• Such a behavior can be explained by
assuming that in the polymer melts and
solutions, which show shear thinning
nature the macromolecules or the
particles are completely random in the
spatial orientation when at rest Fig a) and
are bound by weak intermolecular forces.
•When the applied stress is relatively low
the molecules maintain their randomness
and the molecular forces do not allow
them to be oriented in the direction of
force resulting in constant viscosity in this
Pseudoplastic fluids under shear
•As the shear rate increases the polymer molecules
start orienting in the direction of flow. As the
polymer system contains a molecular weight
distribution the small molecules, which require less
energy to change the direction start orienting,
initiating the reduction in the viscosity. The high
molecular weight molecules have very long coiled
chains, which are entangled with each other. these
molecules require higher energy for
disentanglement, uncoiling and then orientation.
Pseudoplastic fluids...
• As the shear stress and shear rate
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
value of rate of shear.
•Beyond this value of rate of shear there is no
further increase in the extent of orientation of
molecules and the systems show a constant
viscosity or the second Newtonian region.
The greatest man of our times.
- Einstein called Gandhiji
The real hero of Mine.
- Obama called Gandhiji
Mohandas Karamchand Gandhi was the
preeminent leader of Indian independence
movement in British-ruled India.
Born: October 2, 1869, Porbandar
Assassinated: January 30, 1948, New Delhi
Spouse: Kasturba Gandhi (m. 1883–1944)
Parents: Karamchand Gandhi, Putlibai Gandhi