1

RHEOLOGY
 Define rheology, describe the application of rheology in
pharmacy.
 Understand and define the following concepts: shear rate,
shear stress, viscosity, kinematic viscosity, fluidity,
plasticity, yield point, pseudoplasticity, shear thinning,
dilatancy, shear thickening, thixotropy, antithixotropy,
Rheopexy, Viscoelasticity.
 Differentiate Newtonian and Non-Newtonian materials.
 Describe various types of viscometers and their utility in
determining rheologic properties of various systems.
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 RHEOLOGY
 The term “rheology,” has been derived from two Greek
words Rheo meaning to “ flow” and logos meaning
“science”. The term was first suggested by Bingham and
Crawford to describe the flow of liquids and deformation
of solids.
 The branch of science which deals with deformation of
matter under the influence of an applied stress is called
Rheology.
 The stress may be applied perpendicularly to the surface of a
body , tangentially to the surface of the body or at any angle
to the surface of the body.
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Rheology

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Rheology

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WHY WE STUDY RHEOLOGY
 Study of flow properties of liquids is important in the
manufacture of several dosage forms i.e. simple liquids, gels,
creams, pastes. These system can change their flow behavior
when exposed to different stress conditions. FOR EXAMPLE
 Rheology is involved in the mixing and flow of materials, their
packaging into containers, and their removal prior to use,
whether this is achieved by pouring from a bottle, extrusion
from a tube, or passage through a syringe needle.
 The rheology of a particular product, which can range in
consistency from fluid to semisolid to solid, can affect its patient
acceptability, physical stability, and even biologic availability.
 For example, viscosity has been shown to affect absorption rates
of drugs from the gastrointestinal tract

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 REVERSIBLE & IRREVERSIBLE DEFORMATION

When the stress is applied to the fluids; two type of deformation

take place:
 Reversible deformation: The type of deformation in which
when applied stress is removed the fluid comes back to original
structure, then it is called reversible deformation or elastic
deformation.
 Irreversible deformation: The type of deformation in which
after removing stress the fluid does not comes back to original
structure, then it is called irreversible deformation or plastic
deformation. The work spent for this deformation is dissipated
as heat. Plastic deformation is also referred to as flow and is
exhibited by viscous bodies.

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TYPE OF FLUIDS ACCORDING TO TYPES OF FLOW

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 NEWTONIAN AND NON-
NEWTONIAN FLOW
• The liquids which obeys the Newtonians law of
flow are called the Newtonian Liquids.
• The liquids which doesn't obeys the Newtonians
law of flow are called the Non- Newtonian
Liquids.
• Viscosity of Newtonian fluids remain constant,
while that of non Newtonian fluids changes with
change in applied shear force.
• Sample liquids like water, true solutions and dilute
suspensions are examples of newtonian liquids.

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 NEWTONIAN AND NON-
NEWTONIAN FLOW
 Most of pharmaceutical formulations like colloidal
dispersions, emulsions, ointments and gels are examples
of Non-Newtonian liquids.
 Some examples of newtonian liquids are :

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FLOW CHARACTERISTICS OF NEWTONIAN FLUIDS

NEWTONIAN LAW OF FLOW

Fig 1 : Shear stress is parallel to the cross section of material.

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 NEWTONIAN LAW OF FLOW
 Newton's viscosity law's states that, the shear stress between adjacent
fluid layers is proportional to the velocity gradients between the two
layers.
 Consider a “block” of liquid consisting of parallel plates of molecules,
similar to a deck of cards, as shown in Figure 1. If the bottom layer is
fixed in place and the top plane of liquid is moved at a constant
velocity, each lower layer will move with a velocity directly proportional
to its distance from the stationary bottom layer.
 The difference of velocity (dv) between two layers of liquid separated
by an distance ( dx) is the velocity gradient or rate of shear, dv/dx.
 The difference in velocity (dv) between two layers of liquids each of
areas “A” separated by distance (dx) is directly proportional to the
applied force per unit area i.e. Shear Stress.
 The force per unit area, F/A, required to bring about flow (shearing
stress) is given the symbol F.

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 NEWTONIAN LAW OF FLOW
 Newton was the first to study flow properties
of liquids in a quantitative way. He
recognized that the higher the viscosity of a
liquid, the greater is the force per unit area
(shearing stress) required to produce a
certain rate of shear.
 Rate of shear is given the symbol G. Hence,
rate of shear should be directly proportional
to shearing stress.
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NEWTONIAN LAW OF FLOW

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NEWTONIAN LAW OF FLOW

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NEWTONIAN LAW OF FLOW

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NEWTONIAN LAW OF FLOW
 The rheological properties of liquids are expressed in
terms of flow diagram or RHEOGRAMS which
consists of graphs showing the variation of shear rate
with shear stress.
 The plot of newtonian liquids like water, true
solutions and dilute suspensions and emulsions is a
straight line , the slope of which is equal to reciprocal
of viscosity, a value termed to as the fluidity.

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NEWTONIAN LAW OF FLOW
 The linear curve for Newtonian liquids passes to the origin
indicating that even a mild force can induce flow in these
systems.
 Also the linear nature of the curve shows that the viscosity
of a Newtonian liquid is a constant unaffected by the value
of the rate of shear.
 Thus a single determination of viscosity from the shear
stress at any given shear rate is sufficient to characterize the
flow properties of a Newtonian liquid.
 Figure gives a graphical representation of the effect of rate
of shear on the viscosity of Newtonian liquid. As seen from
the figure the viscosity of Newtonian liquid remains
constant with change in the rate of shear.

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Graph A between Shear Stress and Shear rate is a straight
line and passes through origin

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Rheology

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 VISCOSITY
Flow property of simple liquid is expressed in terms of viscosity.
Viscosity is an expression of resistance to flow of liquid. It is also
defined as the internal friction of fluid.
The more viscous the liquid, more the friction is, hence the greater
force in required to make it follow at a particular rate.
FOR EXAMPLE
Honey or syrups all resist the flow more in comparison to water or
alcohol . On molecular level, the motion is transferred between
molecules of syrups is slower than molecules for water.
The CGS unit of viscosity is the poise.
The SI unit of viscosity is the pascal second (Pa·s) or N/m2 . S OR
kg m−1s−1 (kg/m.sec)
One pascal is equivalent to one newton (1 N) of force applied over
an area of one meter squared (1 m2). That is, 1 Pa = 1 N / m 2

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 VISCOSITY
Poise is defined as the shearing force required to produce a
velocity of 1 cm/sec between two parallel planes , 1 cm2 in area
and separated by a distance of 1 cm.
Poise is equal to dyne sec cm−2 (i.e., dyne sec/cm2) or g/cm sec).
These units are readily obtained from analysis of viscosity
coefficient.

A more convenient unit for most work is the centipoise 1 cp

being equal to 0.01 poise.
The dyne was originally defined as the force necessary to produce an
acceleration of 1cm/sec² in a mass of 1 gram. That is dyne = g. cm/sec2
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 FLUIDITY
Fluidity, φ, is defined as the reciprocal of viscosity.
It is ability of materials to flow or their quality of being
fluid .

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 KINEMATIC VISCOSITY
 Two types of viscosities are often encountered: dynamic viscosity
OR absolute viscosity and kinematic viscosity.
 Kinematic viscosity is defined as the dynamic viscosity divided by the
density of the fluid of the liquid at a specific temperature:

 kinematic viscosity is the preferred unit when the shear stress and
shear rate of the fluid are influenced by the density.
 The CGS unit of Kinematic viscosity is given in units of centistoke,
while the dynamic viscosity is given in centipoise.
 The conversion from dynamic to kinematic is given by dividing the
dynamic viscosity by the fluid density in grams per cubic centimeter.
 Any viscometer that uses gravity in its measurement design is
measuring kinematic viscosity.
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UNIT OF KINEMATIC VISCOSITY

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UNIT OF KINEMATIC VISCOSITY

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EXAMPLE

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 EFFECT OF TEMPERATURE ON VISCOSITY
The viscosity of a liquid decreases as temperature is
raised, and the fluidity of a liquid (the reciprocal of
viscosity) increases with temperature. The dependence
of the viscosity of a liquid on temperature is expressed
approximately for many substances by an equation
analogous to the Arrhenius equation of chemical
kinetics:

Where A is a constant depending on the molecular weight

and molar volume of the liquid and Ev is an “activation
energy” required to initiate flow between molecules. R is the
gas constant and T is the temperature in kelvin. 28
29
Representative flow curves for various materials

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 NON-NEWTONIAN SYSTEMS

 The majority of pharmaceutical products does not follow

Newtonian law of flow. These systems are referred to as
non-Newtonian.
 Non-Newtonian behavior is generally exhibited by
colloidal dispersions, emulsions, suspensions and
ointments.
 Three classes of flow, are recognized:
1. Plastic
2. Pseudoplastic
3. Dilatant

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 Plastic Flow
A plastic material does not flow until a certain minimum
shearing stress, the yield value, is applied. Therefore, the plastic
flow curve does not pass through the origin but rather
intersects the shear stress axis at a particular point referred to as
the yield value.
At stress below yield value the material acts like an elastic
material. The yield value, therefore, becomes an important
property of some dispersions.
Materials which exhibit plastic flow are known as Bingham
Bodies in honor of the pioneer of modern rheology and the first
investigator to study plastic substances.
A Bingham body does not begin to flow until a shearing stress
corresponding to the yield value is exceeded.

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 PLASTIC FLOW

It is often more satisfactory to use lower yield value, in

practical applications of plastic materials since this
indicates when actual flow begins. In addition , higher
yield value is sometimes used. This corresponds to the
shear stress beyond which the flow curve becomes linear. 33
 PLASTIC FLOW
The slope of the rheogram in Figure is termed as
Mobility, analogous to fluidity in newtonian system
and its reciprocal is known as the plastic viscosity,
U. The equation describing plastic flow is
U= (F-f) / G
Where f is the yield value in dynes/cm2, F is
shearing stress and G is rate of shear.

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 Plastic Flow
Plastic flow is associated with the presence of flocculated
particles in concentrated suspensions. As a result, a
continuous structure is set up throughout the system.
A yield value exists because of the contacts between
adjacent particles (brought about by van der Waals
forces), which must be broken down before flow can
occur. Consequently, the yield value is an indication of
force of flocculation. The more flocculated the
suspension, the higher will be the yield value.
Frictional forces between moving particles can also
contribute to yield value along with force of flocculation.

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 Plastic Flow
Once the yield value has been exceeded, any further increase in
shearing stress causes flow to begin. Moreover, rate of shear is
directly proportional to the force in excess of yield value ( F-f).
Hence, a plastic system resembles a Newtonian system at shear
stress above the yield value.

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 Plastic Flow
 Other examples of materials exhibiting plastic flow are
suspension of zinc oxide in mineral oil.
 Certain paints and printing inks also fall in this class.
 Contrary to newtonian liquid, Bingham body does not
flow until a definite shearing stress, the yield value is
applied.

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 PSEUDOPLASTIC FLOW
Pseudoplastic flow is typically exhibited by polymers in
solution, in contrast to plastic systems, which are
composed of flocculated particles in suspension.
Many pharmaceutical products, including liquid
dispersions of natural and synthetic gums (e.g.,
tragacanth, gelatin sodium alginate, methylcellulose,
and sodium carboxymethyl cellulose) and other water
soluble mucilages and gums exhibit pseudoplastic flow.
The rheological curve for a pseudoplastic material
begins at the origin. Therefore, these materials exhibits
no yield value as there is in a plastic system.
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 PSEUDOPLASTIC FLOW
 However, unlike the curve of newtonian materials,
the pseudoplastic curve is non-linear. The shear stress
F does not increase linearly with the shear rate G and
therefore, the viscosity does not remain constant at
different rate of shears.
 Hence, Pseudoplastic systems are also referred to as
shear- thinning systems.
 Figure show the effect of rate of shear on the viscosity
of pseudoplastic materials. Similar decrease in
viscosity with increasing rate of shear is also seen in
plastic system.

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Pseudoplastic Flow

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 Pseudoplastic Flow
Newtonian systems are completely described by viscosity, η, and plastic
systems are adequately described by yield value, f . However, several
approaches have been used to obtain meaningful parameters that will
allow different pseudoplastic materials to be compared.

Above expression has been used most frequently for pseudoplastics.

Where F is shearing stress and G is the rate of shear. The term η is a
viscosity coefficient. The exponent N is the indication of non-newtonian
behavior.
When N = 1 ( unity) equation reduces to newtonian equation and flow is
Newtonian.
When exponent N rises above unity, i.e. N > 1 flow becomes non-
Newtonian and materials exhibit pseudoplastic behavior.

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 Pseudoplastic Flow
Following rearrangement, we can write pseudoplastic
equation in the logarithmic form.

Many pseudoplastic systems fit this equation when log G is

plotted as a function of log F. However some of important
pseudoplastic materials such as methyl cellulose and alginic
acid derivatives do not fit into this equation.

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 Pseudoplastic
 Most of the pseudoplastic materials consists of long chain
molecules or other complex structure which are dispersed at
random in the dispersion medium at rest.
 As shearing stress is applied , the macromolecules become
aligned with the long axis parallel to the direction of flow.
 With this ordered alignment the molecules pass one another
with less frictional resistance, and the viscosity is decreased.
 If the shearing stress is decreased, the orientation of the
macromolecules becomes more random, and greater frictional
resistance to the flow is reflected in an increased viscosity.
 Since only a molecular alignment is involved, there is no lag
time.

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Pseudoplastic Flow

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 Dilatant Flow
Dilatancy is also referred to as shear-thickening flow
behavior.
Materials exhibits an increase in resistance to flow
with increase rate of shear.
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.
This type of flow is the inverse of that possessed by plastic or
pseudoplastic systems. Whereas these materials are
frequently referred to as “shear thinning systems,” dilatant
materials are often termed “shear thickening systems.” When
stress is removed, a dilatant system returns to its original
state of fluidity.

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Dilatant Flow

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 Dilatant Flow

Dilatancy can be described by the exponential expression of

above equation.
In dilatancy, N is always less than 1 or unity i.e. N < 1.
As N approaches 1 (unity) i.e. N = 1, the system becomes
increasingly Newtonian in behavior.
Substances possessing dilatant flow properties are invariably
suspensions containing a high concentration (about 50%
or greater) of small, deflocculated particles.

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 Dilatant Flow
Dilatant behavior can be explained as follows.
 At rest, particles are closely packed with minimal interparticle volume
(voids). The amount of vehicle in the suspension is sufficient, however,
to fill voids and permits particles to move relative to one another at
low rates of shear. Thus, a dilatant suspension can be poured from a
bottle because under these conditions it is reasonably fluid.
 As shear stress is increased, the bulk of the system expands or dilates;
hence the term dilatant.
 The particles, in an attempt to move quickly past each other, take on an
open form of packing, as depicted in Figure. Such an arrangement
leads to a significant increase in interparticle void volume.
 The amount of vehicle remains constant and, at some point, vehicle
becomes insufficient to fill the increased voids between particles.
 Accordingly, resistance to flow increases because particles are no
longer completely wetted, or lubricated, by the vehicle.
 Eventually, the suspension will set up as a firm paste.
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 Dilatant Flow
Dilatancy may prove to be troublesome during processing of
dispersions containing solid particles when high-speed
mixers, blenders, or mills are employed.
Dilatant materials have a tendency to solidify under
condition of high shear, thereby overloading and damaging
processing equipment. Behavior of this type suggests that
appropriate precaution be used during processing of dilatant
materials.
Concentrated suspensions i.e. titanium dioxide suspension,
zinc oxide paste are examples of system showing dilatant
flow. It can also be observed by mixing 50% weight of
potassium silicate or starch with cold water and
deflocculating agent to prepare concentrated suspension.
Dilatancy is not exhibited by dilute suspensions.
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Dilatant Flow

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 Thixotropy
Non-Newtonian system such as plastic, pseudo plastic and
dilatant system at a given temperature show time
dependent changes in the viscosity at varying shearing
stress. This behavior is known as thixotropy and may be
explained in the following manner.
Thixotropy in plastic and pseudoplastic systems
In plastic and pseudoplastic systems, the viscosity is
gradually decreases on increasing the shearing stress at
any given temperature. On removing the shearing stress,
the viscosity is regained but not immediately but after some
time lag. The term thixotropy is given to this phenomenon.
It maybe described as a reversible isothermal
transformation from gel to sol.

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 Thixotropy
 Time-dependent changes in viscosity have also been
reported for a number of polymer solutions .
 Although most polymer solution do not show any
measurable time-dependency of viscosity. However, in
a few cases, disentanglement of polymer molecules
during shear can cause time-dependent effects,
particularly when a dynamic physical network (gel) is
dynamically formed and broken during stirring.
 In most cases, time-dependent changes in viscosity are
reversible, but in a few cases, shearing the polymeric
material can cause irreversible changes.

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 THIXTROPY
If a rheogram is plotted between the rate of shear at various
shearing stresses, a hysteresis loop is obtained.
As the shearing stress is increased an upward curve is
obtained. On reducing the shearing stress gradually, a
downward curve is obtained. However, unlike Newtonian
system, the upward curve and downward curve are not
super imposable. The down curve is shifted to the left side
meaning that the viscosity of the down curve is lower than
that of the up curve. This implies that the gel structure of the
system is not reformed immediately but only after a lag time.

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THIXOTROPY

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 THIXOTROPY
 Thixotropic systems contain asymmetric particles
having loose three-dimensional structure. This
structure confers a certain rigidity on the system
and it resembles a gel.
 As shearing is applied to the system, the
structure breaks down and then material changes
from gel to sol structure.
 Upon removal of the stress the structure begins to
reform slowly and initial structure is formed after
a lag time.

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 THIXOTROPY
 Examples of plastic system is showing thixotropy
Bentonite Gel and petrolatum .
 Examples of pseudo plastic systems showing
thixotropy include dispersions of synthetic
suspending agents.
 Bentonite gel is made up of random network of hydrated
elongated particles. On the application of shearing stress
the elongated particles align with the long axis parallel to
the direction of flow therefore the inter particle link is
broken. The network therefore disintegrate and the
apparent viscosity decreases.
 On removal of shearing forces the arrangement of
dispersed particles gradually become less orderly under the
influence of Brownian motion and the gel network is
reformed after a time-lag. 60
THIXOTRPY

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 Thixotropy in Formulation
Thixotropy is a desirable property in liquid pharmaceutical
systems that ideally should have a high consistency in the
container, yet pour or spread easily.
For example, a well formulated thixotropic suspension
will not settle out readily in the container, will become fluid
on shaking, and will remain long enough for a dose to be
dispensed. Finally, it will regain consistency rapidly enough
so as to maintain the particles in a suspended state.
A similar pattern of behavior is desirable with emulsions,
lotions, creams, ointments, and parenteral suspensions
to be used for intramuscular depot therapy.
With regard to suspension stability, there is a relationship
between degree of thixotropy and rate of sedimentation the
greater the thixotropy, the lower the rate of settling.
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 Thixotropy in Formulation
Concentrated parenteral suspensions containing from 40% to
70% w/v of procaine penicillin G in water were found to
have a high inherent thixotropy and were shear thinning.
Consequently, breakdown of the structure occurred when the
suspension was caused to pass through the hypodermic
needle. Consistency was then recovered as rheologic
structure reformed. This led to formation of a depot of drug
at the site of intramuscular injection where drug was slowly
removed and made available to the body.

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Thixotropy in dilatant systems
In dilatant systems, an increase in the shearing stress
causes an apparent increase in viscosity at a given
temperature. On the removal of shearing stress ,the
viscosity decreases but after a lag time . This
phenomenon is known as thixotropy in dilatant system
and may be described as a reversible isothermal
transformation from sol to gel to sol.
Example includes Quick sands which exhibit
thixotropic behavior of . Quicksand is
a colloid consisting of fine granular material (such
as sand or clay) and water.

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 Irreversible Thixotropy
This is in effect similar to Thixotropy. Application of
Shearing forces cause breakdown of structure within the
system. Hence, the structure does not reform on
removal of shear stress or the time lag is so long that
from practical point of view the effect is irreversible.
Examples of such systems include gels produced from
high molecular weight polysaccharides which are
stabilized by large number of secondary bonds.
On the application of high shear, the three-dimensional
structure of the polysaccharides is reduced to a two-
dimensional one and the original gel like structure is
never recovered.

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Irreversible Thixotropy

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 Rheopexy
The process of re-formation of the gel
structure after it has been deformed can be
accelerated by applying gentle and regular
movements (rolling or rocking motion).
This phenomenon is known as rheopexy.
The gentle rolling and rocking motion
provides a mild turbulence which helps the
dispersed particles to acquire a random
orientation and the network is
re-established.
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Thixotropy and Rheopexy

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Thixotropy Vs Rheopexy

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Anthixotropy or negative thixotropy
Anthixotropy is a phenomenal similar to
thixotropy but there is an increase rather than a
decrease in the consistency on the down
curve. Thus in a plastic or pseudo plastic
system the viscosity first decreases on
increasing the shearing stress at any given
temperature.
On removing the shearing stress the viscosity
obtained of the down curve is greater than that
of up curve.
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 Antithixotropy or negative thixotropy
This increase in thickness or resistance to flow with increase
time of shear has been observed during the rheological
analysis of Magnesia Magma. It was observed that when
magnesia magma was alternately sheared at increasing and
decreasing rates of shear, the magma continuously thickened
but at a decreasing rate and it finally reached an equilibrium
state in which further cycles of increasing-decreasing shears
rates no longer increased the consistency of the
material.
It was detected at shear rates of greater than 30 sec−1; below
30 sec−1 the magma showed normal thixotropy, the
downcurve appearing to the left of the upcurve.

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 Anthixotropy or negative thixotropy
Anthixotropy is believed to result from an increased
collision frequency of the dispersed particles in
suspension which results in an increased
interparticle bonding with time.
This changes the original state of the system from a
network of a large number of individual particles
and small floccules to the equilibrium state consisting
of a small number of relatively large floccules.
When allowed to stand , however, the material returned
to its original state of sol-like properties i.e. small
floccules and individual particles.

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Anthixotropy

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Anthixotropy or negative thixotropy
 Antithixotropy or negative thixotropy should not be
confused with dilatancy or rheopexy.
 Dilatant system are deflocculated and ordinarily
contain greater than 50% by volume of solid dispersed
phase whereas antithixotropy systems have low solid
content (1 to 10%) and are flocculated.
 Rheopexy is a phenomenon in which a solid forms a
gel more readily when gently shaken . In a rheopectic
system, the gel is the equilibrium form , whereas in
antithixotropy, the equilibrium state is the sol.

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Anthixotropy or negative thixotropy
An example of an anti-thixotropic liquid is
polymethacrylic acid (PMA). It shows a 350 fold
increase in viscosity when sheared for one minute. It
was concluded that simultaneously occurring
hydrophobic and hydrophilic interactions between PMA
molecules, that are dynamically formed and broken
during shearing, cause anti-thixotropic behavior.

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 Viscometers
A viscometer is an instrument used to measure the viscosity of
a fluid. The three viscometers that we have listed here are
capillary viscometer, Falling and Rising body viscometer and
Rotational viscometer.

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What type of Viscosity do different viscometers
measure
 Dynamic (absolute) viscosity: Dynamic viscosity is also
known as absolute viscosity and most often relates to non-
Newtonian fluids. It refers to the fluid’s internal resistance
to flow when force is applied.

 Kinematic viscosity: Kinematic viscosity is a measure of the

viscosity of a (usually Newtonian) fluid in motion. It can be
defined as the ratio of dynamic viscosity to density. Any
viscometer that uses gravity in its measurement design is
measuring kinematic viscosity.

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What type of Viscosity do different viscometers measure
 Not every viscometer is the same, the type of viscosity it
measures depends on its design.
 Capillary viscometers: Capillary viscometers use gravity to
measure how long it takes a fluid sample to travel the
length of a tube. They also measure kinematic viscosity.
 Rotational viscometers: A rotational viscometer measures
how much torque is required to turn a spindle immersed in
a fluid. The spindle applies stress to the fluid, resulting in a
measurement of dynamic viscosity.
 Falling ball viscometers: A falling ball viscometer measures
the force required for a ball to fall through a fluid. The ball
applies stress to the fluid, giving a measurement of
dynamic viscosity. 82
 Capillary viscometers
Capillary instruments are very accurate for the measurement of
viscosity of Newtonian fluid having low viscosity. During
measurement the time for the fluids to flow by gravity from one
mark in a capillary column to the second mark is measured.
The time of flow of the liquid under-test is compared with the
time required for the liquid of known viscosity (usually water) to
pass between the two marks. If η1 and η2 are the viscosity of the
unknown and standard liquid , ρ1 and ρ2 are the densities of the
liquid and t1 and t2 are the respective flow times in seconds. The
absolute viscosity of the unknown liquid η1 is determined by
substituting the experimental value in the equation:

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 Capillary viscometers
Above Equation is based on Poiseuille’s law for a liquid flowing through a
capillary tube

where r is the radius of the inside of the capillary, t is the time of flow, ΔP is the
pressure head in dyne/cm2 under which the liquid flows, l is the length of the
capillary, and V is the volume of liquid flowing.
The radius, length, and volume of a given capillary viscometer are
constant and can be combined into a single constant, K.
Equation based on Poiseuille’s law can then be written as

84
 Capillary Viscometers
The pressure head P depends on density the ρ of the
liquid being measured, the acceleration of gravity, and
the difference in heights of liquid levels in the two
arms of the viscometer.
Acceleration of gravity is a constant, however, and if the
levels in the capillary are kept constant for all liquids,
these terms can be incorporated in the constant and the
viscosities of the unknown and the standard liquids can
be written as

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 Capillary Viscometers

Therefore, when flow periods for two liquids are

compared in the same capillary viscometer, the division
of η1= Kt1ρ1 by η2=Kt2ρ2 gives equation

The United States Pharmacopeia suggests a capillary

apparatus for determining the viscosity of high-viscosity
types of methylcellulose solutions.

86
 Capillary Viscometers
Viscometers with capillary of varying diameters are available
commercially for the measurement of fluids over the a wide
range of Viscosity.
Examples of different capillary viscometers include
 Ostwald’s viscometer
 Ubbelohde viscometer
 Cannon Fenske viscometer

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90
Falling and rising body apparatus
Falling sphere viscometer
The principle of this instrument is based on Stokes law which states that
when a body falls through a viscous medium it experiences resistance on
viscous drag which opposes the motion of the body at the initial stage, the
body experiences acceleration due to the influence of gravity but soon
this acceleration is balanced by the viscous drag and the body falls with a
uniform terminal velocity. Thus,
Viscous drag on the body = force responsible for the downward movement
3𝜋ηdv= (π / 6 )d3g(ρs- ρ1)
Where,
η is the coefficient of viscosity
d is the diameter of the sphere
g is the acceleration due to gravity
v is the terminal velocity
ρS is the density of the sphere
ρ 1 is the density of the liquid
Rearranging the above equation we get:

η = 𝑑2𝑔(ρs- ρ1)/18v

91
 Falling sphere viscometer
The diameter of the sphere is obtained using a vernier calliper, the density
of the liquid is determined using a specific gravity bottle and the terminal
velocity is determined using the falling sphere viscometer. The density of
the material of which sphere is made can be obtained from the literature.
The value of the viscosity of the liquid is then calculated using below
equation
η = 𝑑2𝑔(ρs- ρ1)/18v
WORKING
A falling sphere viscometer is shown in figure . It consists of a tube having
two markings A and B on the outer surface. The tube is filled with the
liquid whose is viscosity is to be determined. The tube is clamped
vertically inside a constant temperature bath . A ball of suitable materials
such as steel or glass is then allowed to fall through the guide tube inside
the falling tube. The time taken for the sphere to fall from point A to B is
noted and the terminal velocity is obtained by dividing the distance
between the two marks and the time. By substituting all the values in
the above equation, the viscosity of the liquid is determined.
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Falling sphere viscometer

93
HOEPPLER BALL VISCOMETER
It is an example of falling sphere
instrument which uses a short , nearly
vertical glass tube of large diameter and
closely fitting ball of either steel or glass.
The sample and the ball are loaded into
the inner cylinder and brought to the
temperature of measurement by means of
a constant temperature outer jacket.
The time for the ball to transverse the
distance between two marks is measured.
A minimum 30 sec time is used for best
result.
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 Rotational Viscometer
Rotational viscometers measure viscosity by immersing
a rotating spindle in the fluid to be tested. The amount
of power (torque) required to turn the spindle
indicates the viscosity of the fluid, and because
rotational viscometers do not use gravity to function,
their measurements are based on the fluid's internal
shear stress.

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CUP AND BOB VISCOMETER

98
 CUP AND BOB VISCOMETER
In cup-and-bob viscometers, the sample is sheared in the space
between the outer wall of a bob and the inner wall of a cup into
which the bob fits. The various instruments available differ mainly
in whether the torque results from rotation of the cup or of the
bob.
 In the Couette-type viscometer, cup is rotated and bob is
held stationary. The viscous drag on the bob produced by the
liquid causes it to turn. The resultant torque produced is
proportional to the viscosity of the liquid. An example of this
type of viscometer is Mac Michael viscometer.
 In the Searle type viscometer , inner bob rotates while the cup
is held stationary. The torque resulting from the viscous drag of
the system under examination is generally measured by a spring
or sensor in the drive to the bob. Examples of Searle type
instruments include the Brookfield viscometer and stormer
viscometer.

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CUP AND BOB VISCOMETER

100
 Brookfield viscometer
The Brookfield viscometer is a rotational viscometer of
the Searle type that is popular in the quality-control
laboratories of pharmaceutical manufacturers. A
number of spindles (bobs) of various geometries,
including cylinders, T-bars, and a cone–plate
configuration, are available to provide scientific
rheologic data for Newtonian and non-Newtonian
liquids and for empirical viscosity measurements on
pastes and other semisolid materials. Various models of
the Brookfield viscometer are available for high,
medium, and low viscosity applications.

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Brookfield viscometer

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 Cone-and-Plate Viscometer
In operation, the sample is placed at the center of the plate,
which is then raised into position under the cone . A variable
speed motor drives the cone, and the sample is sheared in the
narrow gap between the stationary plate and the rotating
cone. The rate of shear in revolutions per minute is increased
and decreased by a selector dial and the viscous traction or
torque (shearing stress) produced on the cone is read on the
indicator scale. A plot of rpm or rate of shear versus scale
reading or shearing stress can thus be constructed in the
ordinary manner.

103
Cone-and-Plate Viscometer

104
 Viscoelasticity
Viscoelastic behavior describes materials which
show behavior somewhere between that of an
ideal liquid (viscous) and ideal solid (elastic).
Most of the pharmaceutical semisolid such as
creams , lotions , ointments, suppositories,
suspensions and colloidal dispersions exhibit
viscoelastic properties. Many biological fluids
such as blood and sputum also show
viscoelastic properties.

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 Viscoelasticity
 When viscoelastic materials are subjected to stress for
a short period of time they undergo a slight
deformation under the influence of the stress but
once the stress is removed, they exhibit their elastic
behavior by returning to their original shape with
little deformation.
 However, if the stress applied continued for a long
period of time, the deformation increases and
becomes more permanent. When the stress is finally
removed, only a small fraction of the deformation is
recovered. This behavior approaches that of a viscous
liquid.

106
 Viscoelasticity
The viscoelastic behavior of a semisolid may be represented by the use of
mechanical models.
The ELASTIC PROPERTIES that a semisolid exhibits can be represented by an
ideal spring. Since spring obeys hook’s law ,it is also known as HOOK’S BODY.
According to Hooke’s law, applied stress is proportional to the resultant strain as
long as the elastic limit is not exceeded, and will return to its initial shape when
the stress is removed. If the elastic limit is surpassed the spring will be
permanently distorted.
The VISCOUS FLOW that a semisolid exhibits can be represented using a
dashpot which obeys Newton’s law. A dashpot is mechanical device consisting of
a plunger moving through a viscous Newtonian fluid. When a stress (or force) is
applied to a dashpot, the dashpot immediately starts to deform and goes on
deforming at a constant rate (strain rate) until the stress is removed . When stress
is removed , dashpot stops at its position and does not return to the starting point
unlike a Hook’s body, that returns to its starting point as a force becomes zero.
The energy required for deformation or displacement is dissipated within the
fluid (usually as heat) and the strain is permanent.
The behavior of semisolid as the viscoelastic body may therefore be described by
the combination of a dashpot and spring as shown in Figure 19.20. 107
Viscoelasticity

108
Viscoelasticity

109
 Maxwell element
When the dashpot and spring are
combined in series, the model obtained is
known as Maxwell element. If a stress is
applied to a Maxwell model then at very
short times the response is predominantly
elastic and governed by G, while at much
longer times viscous behavior prevails and
is governed by η. Removal of the stress
leads to complete recovery of the spring,
but the viscous flow shows no recovery, that
is, no tendency to return to its original
state.
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 Voigt model
This second model for viscoelasticity is known as a Voigt
model, in which the spring and the dashpot are attached in
parallel rather than in series. When a constant stress is
applied to a voigt model, having spring and dashpot being
attached in parallel, strain takes time to develop since the
presence of the dashpot retards the response of the spring
and the system behaves like a viscous liquid initially and then
elastically over longer time scales, as the spring becomes
more stretched.

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 PSYCHORHEOLOGY
In addition to desirable pharmaceutical and pharmacologic
properties, topical preparations must meet criteria of feel,
spreadability, color, odor, and other psychologic and sensory
characteristics. Workers in the food industry have long tested
products such as butter, chocolate, mayonnaise, and bread
dough for proper consistency during manufacture,
packaging, and end use.
Sensations in the mouth, between the fingers, and on the
skin are important considerations for manufacturers of
foods, cosmetics, and dermatologic products. This is called
PSYCHORHEOLOGY.

112
 APPLICATION OF RHEOLOGY
Study of flow properties of liquids is important for
pharmacist working in the manufacture of several dosage
forms i.e. gels, ointments, creams, and pastes. These systems
change their flow behavior exposed to different stress
conditions
MANUFACTURING OF DOSAGE FORMS
Materials undergo process such as mixing, flowing through
pipes, filling into the containers etc. Flow related changes
influence the selection of mixing equipment.
HANDLING OF DRUGS FOR ADMINISTRATION
The syringebility of the medicines, the pouring of the
liquids from containers, extrusion of ointment from tubes, all
depend on the changes in flow behavior of dosage forms.
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 APPLICATION OF RHEOLOGY
RHEOLOGY OF EMULSIONS
Most of emulsion systems encounter in the field of pharmacy
such as lotions and creams are non-newtonian but dilute ones
exhibit Newtonian behaviour. The fluid emulsions such as
lotions are usually pseudo plastic. The semisolid creams are
usually viscoelastic. Different rheology behaviour can be
conferred on these emulsions by merely varying the
concentration of the dispersed phase . Thixotropic lotions
exhibit considerable consistency when allowed to stand at rest in
the bottle . Once the bottle is shaken, they lose their consistency
and easily pour from the bottle.
RHEOLOGY OF SUSPENSION
Most of the pharmaceutical systems exhibit plastic or pseudo
plastic characteristics along with thixotropic properties. The
rheological properties depend on the degree of flocculation of
the dispersed phase as well as on the type and quality of the
suspending and thickening agent added to the system. The
product thus becomes thick on standing. On shaking , product
becomes fluid and pouring of suspension from the bottle and 114
hence dosing becomes easier.
 APPLICATION OF RHEOLOGY
RHEOLOGY OF OINTMENTS AND GELS
The rheological characteristics of gels and ointments directly
affect the stability elegance and the extrudability from tubes.
This also affect the adherence and spread of the products on
the skin and in some cases the release of active drug from the
base.
Hydrocarbons such as petroleum exhibit plastic flow with
varying degrees of thixotropy. Some pastes exhibit dilatancy.
Pharmaceutical pastes, toothpastes, ophthalmic ointments
exhibit different flow behaviors ranging from plug flow to
complete streamline flow when extruded from tubes.

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 APPLICATION OF RHEOLOGY
RHEOLOGY OF POWDERS
Good flow properties of powders and granular solids are required to ensure
uninterrupted flow from hopper and into the die cavities in high speed tableting
machines. Flow properties are also important during encapsulation of solid materials
into capsules and during the packing of powdered and granular masses. The most
important factor affecting the flow properties of particulate solid is the surface
characteristic of the particles. Improvement in the flow can be achieved by reducing
the surface roughness of particle and also by reducing the stickiness between
particles. Surface roughness is generally reduced by the presence of fines in powders
or granular material which fills the irregularities. Stickiness is generally reduced by
the addition of lubricant such as talc, starch and magnesium stearate.
RHEOLOGY AND PROCESSING
Rheological considerations of the materials are important to ensure their proper
mixing. For example, a large impeller operating at a low shear rate is required by
shearing thinning systems since a small impeller operating at a high speed will not
produce complete fluid turnover and effective mixing. Semi solid material exhibiting
dilatant properties should be processed with the low shear mixer to prevent a
consistency build up during processing which may cause overloading of the
equipment.
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