Applied Rheology in Polymer

Processing
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 and 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 and voids causing
lubrication effect and giving constant viscosity.
Dilatent fluids...
Dilatent fluids under shear deformation
Bingham plastic fluids require a certain
force to develop what is known as yield
stress,
y
before they start flowing and
then flow like Newtonian liquids, i.e.,
the plot of and is a straight line and
it intercepts the stress axis at some finite
value equal to the yield stress.
The viscosity of these fluids is constant
during the flow at shear stresses higher
than yield stress, >
y
and increases
sharply as the stress approaches yield
stress.
Bingham plastic fluids
These fluids, when at rest, are believed to
develop a three-dimensional structure due
to the presence of intermolecular or inter
particle forces. This structure resists the
deformation to such an extent that it does
not allow the fluid to deform till the
applied force gives enough energy to break
it down and once the fluid begins to
deform it flows like a Newtonian liquid.
After the deforming force is removed the
structure forms again when at rest.
These liquids also show yield stress
but during flow do not follow the
Newtons law of viscosity but show a
shear rate dependent viscosity
beyond the shear stress >
y
.
Viscoplastic fluids
The time dependent fluids are those
liquids, which show either a decrease or
increase in the viscosity with time at a
particular rate of shear, i.e., if these
fluids are subjected to a constant shear
rate then the shear stress will either
decrease or increase. These fluids are
respectively thixotropic fluids and
rheopectic fluids.
Time dependent fluids
and versus time plots for time dependent fluids
Thixotropic fluids are essentially
pseudoplastic type where the orientation
of molecules at a particular shear rate is
a time dependent process as compared
to being instantaneous for the
pseudoplastic liquids.
The rheopectic fluids are dilatent type
where the dilatency is time dependent.
Time dependent fluids...
Both these fluids, when deformed first
with increasing shear stress and then
with decreasing, do not follow the same
path back but show hysteresis.
The area under the hysteresis curves
represents the loss of energy during the
cycle of deformation.
This energy is consumed in the changes
in the molecular configuration and other
structural changes, these liquids might
have undergone as a result of shearing.
Hysteresis curves for i) thixotropic and ii) rheopectic fluids
As the name implies these fluids posses
both purely elastic and purely viscous
characteristics, i.e., they store a part of
the deformational energy and dissipate
the remaining as heat due to viscous
drag.
Viscoelastic fluids.
Weissenberg demonstrated these effects
by shearing such fluids in a cone and
plate rheogoniometer, which is fitted
with a set of piezometric tubes.
The stored elastic energy manifests
itself in the form of normal stresses
resulting in the climbing of fluid in the
tubes.
The intensity of normal stresses is
maximum at the center and minimum at
the periphery.
Normal stresses as observed in a rheogoniometer