RHEOLOGY:

Rheology is the study of paints, inks, doughs, building

materials, cosmetics, diary products.

It also deals with the analysis of pharmaceutical products:

emulsions, pastes, suppositories and tablet coatings.

Non-Newtonian systems: colloidal solutions, emulsions, liquid

suspensions, ointments,

Plastic Flow: The slope of the rheogram is its mobility and the
reciprocal is known as plastic viscosity. The flow starts only after reaching
yield value. The yield value is present due to the presence of Van der
Waals forces and friction. The more flocculated the suspension the higher
is the yield value.
Pseudo plastic Flow: A large number of pharmaceutical products,
natural and synthetic gums, liquid dispersions, sodium alginate,
methylcellulose and sodium carboxymethylcellulose. Exhibited by
polymers in soln.
The viscosity decreases with increasing rate of shear.
Pseudo plastic materials are referred to as “shear thinning systems

Dilatant Flow: Certain suspensions with a high percentage of

dispersed solids exhibit an increase in resistance to flow with increasing
rates of shear. Such systems actually increase in volume when sheared
and are hence termed dilatant. It should be immediately obvious that this
type of flow is the inverse of that possessed by pseudo plastic systems.
Whereas pseudo plastic materials are referred to as “shear thinning
systems”, dilatant materials are often termed “shear-thickening systems”.
When the stress is removed a dilatant system returns to its original state
of fluidity.

Substances possessing dilatant flow properties are invariably suspensions

containing a high concentration (about 50% or greater) of small,
deflocculated particles. Particulate systems of this type that are
flocculated would be expected to possess plastic, rather than dilatant flow
characteristics. Dilatant behavior may be explained as follows. At rest, the
particles are closely packed with inter particle volume or voids being at a
minimum. The amount of vehicle in the suspension is sufficient however,
to fill this volume and permits the particles to move relative to one
another at low rates of shear. Thus one may pour a dilatant suspension
from a bottle since under these conditions it is reasonably fluid. As the
shear stress is increased, the bulk of the system expands or dilates. The
particles, in an attempt to move quickly past each other, take on an open
form of packing.
Such an arrangement leads to a significant increase in the interparticle
void volume. The amount of vehicle remains constant and at some point,
becomes insufficient to fill the increased voids between the particles.
Accordingly, the resistance to flow increases because the particles are no
longer completely wetted, or lubricated, by the vehicle.
Eventually, the suspension will set up as a firm paste. Behavior of this
nature necessitates that great care be taken in processing dilatant
materials. Conventionally the processing of dispersions containing solid
particles is facilitated by the use of high speed mixers, blenders or mills.
Although this is advantageous with all other rheologic systems, dilatant
materials may solidify under these conditions of high shear, thereby
overloading the processing equipment.
Thixotropy is the property of some non-Newtonian pseudoplastic
fluids to show a time-dependent change in viscosity; the longer the fluid
undergoes shear stress, the lower its viscosity. A thixotropic fluid is a
fluid which takes a finite time to attain equilibrium viscosity when
introduced to a step change in shear rate. However, this is not a universal
definition; the term is sometimes applied to pseudoplastic fluids without a
viscosity/time component. Many gels and colloids are thixotropic
materials, exhibiting a stable form at rest but becoming fluid when
agitated.

The distinction between a thixotropic fluid and a shear thinning fluid:

 A thixotropic fluid displays a decrease in viscosity over time at a

constant shear rate.
 A shear thinning fluid displays decreasing viscosity with increasing
shear rate.

Some fluids are anti-thixotropic: constant shear stress for a time causes
an increase in viscosity or even solidification. Constant shear stress can
be applied by shaking or mixing. Fluids which exhibit this property are
usually called rheopectic. They are much less common.

The several types of behavior observed when the rate of shear is

progressively increased and plotted against the resultant shear stress,
has been discussed. It was tacitly assumed that if the rate of shear was
reduced once the desired maximum has been reached, the down curve
would be identical with the one superimposed on the up curve. While this
is so with Newtonian systems the down curve for non-newtonian systems
can be displaced with regard to the up curve. With shear thinning
systems (i.e.,pseudoplastic) the down curve is frequently displaced to the
left of the up-curve, showing the material has a lower consistency at any
one rate of shear on the down curve than it had on the up-curve. This
indicates a breakdown of structure (and hence shear thinning) that does
not reform immediately when the stress is removed or reduced. This
phenomenon is known as Thixotropy, may be defined as an isothermal
and comparatively slow recovery, on standing of a material, of a
consistency lost through shearing. As so defined, thixotropy may be
applied only to shear thinning systems. Thixotropic systems usually
contain asymmetric particles that, through numerous points of contact
set up a loose three dimensional network throughout the sample. At rest,
this structure confers some degree of rigidity on the system, and it
resembles a gel. As shear is applied and flow starts, this structure begins
to break down as the points of contact are disrupted and the particle
becomes aligned. The material undergoes a gel-to-sol transformation and
exhibits shear thinning. Upon removal of the stress, the structure starts
to reform. This process in not instantaneous: rather it is a progressive
restoration of consistency as the asymmetric particles come into contact
with one another by undergoing random Browning movement. The
rheograms obtained with thixotropic materials are therefore highly
dependent on the rate at which shear is increased or decreased and the
length of time a sample is subjected to any one rate of shear.

In other words , the previous history of the sample has a significant effect
on the rheologic properties of a thixotropic system. For example suppose
that in fig 17-5 the shear rate of a thixotropic material is increased in a
constant manner from a to point b and is then decreased at the same rate
back to e. Typically this would result in the so-called hysteresis loop abe.
If, however, the sample was taken to point b and the shear rate held
constant for a certain period of time say t1 secs,the shearing stress, and
hence the consistency, would decrease to an extent depending on the time
of shear, the rate of shear, and the degree of structure in the sample.
Decreasing the shear rate would then result in the hysteresis loop, abce.
If the sample had been held at the same rate of shear for t 2 secs, the loop
abcde would have been observed. Obviously, therefore, the rheogram of a
thixotropic material is not unique but will depend on the rheologic history
of the sample and the approach used in obtaining the rheogram. This is
an important point to bear in mind when attempting to obtain a
quantitative measure of thixotropy.
MEASUREMENT OF THIXOTROPY:

A quantitative measurement of thixotropy can be attempted in several

ways.The most apparent characterstic of a thixotropic system is the
hysteresis loop, formed by the up-and down-curves of the rheogram. This
area of hysteresis has been proposed as a thixotropic breakdown; it may
be obtained readily by means of a planimeter or other suitable technique.
With plastic(Bingham) bodies, two approaches are frequently used to
estimate the degree of thixotropy. The first is to determine the structural
breakdown at a constant rate of shear. The type of rheogram needed for
this estimation is shown in fig.17-5. Based on such a rheogram, a
thixotropic coefficient B,the rate of breakdown with time at constant
shear rate, is calculated as follows:

B = U1 - U2
ln t2/t1

In which U1 and U2 are the plastic viscosities (Slopes) of the down-curves,

after shearing at a constant rate for t1 and t2 secs. respectively.

DETERMINATION OF RHEOLOGIC PROPERTIES :

The determination and evaluation of the rheologic properties of a

particular system depend, in large part, on choosing the correct
instrumental method. Since the rate of shear in a Newtonian system is
directly proportional to the shearing stress, one can use instruments that
operate at a single rate of shear.These “one-point” instruments provide a
single point on the rheogram; extrapolation of a line through this point to
the origin will result in a complete rheogram. In a non-Newtonian system
however, the “one-point’ determination is virtually useless in
characterizing the flow properties of the system. It is therefore,essential
that, with non-Newtonian systems, the instrumentation used must be
able to operate at a variety of rates of shear.Only by the use of “multi-
point” instruments is it possible to obtain the complete rheogram for
those systems.

The important conclusion is that while all viscometers can be used to

determine the viscosity of Newtonian systems, only those with variable
shear stress controls can be used for non-Newtonian materials.

The Viscometers used for non-Newtonian systems are:

1.Capillary viscometer
2.Falling Sphere viscometer
3.Cup and Bob viscometer
4.Cone and Plate viscometer