CHAPTER 2

RHEOLOGY

Presented by,
Gazala Y. Ansari
Assistant Professor

DEPARTMENT OF PHARMACEUTICS
SMT. N. M. PADALIA PHARMACY COLLEGE
AHMEDABAD
 RHEOLOGY
❑ Rheology is defined as the science of flow and deformation of materials under influence of stress.
The term 'rheology' come from Greek rhee meaning to flow and logos means science.
❑ The scientist Bingham and Crawford brought the term of rheology in use during 1910 systemic
characterization of solids and liquids. From the viewpoint of rheology solids and liquids are
characterized differently.
❑ Solids have constant volume and permanent shape and can sustain applied stress whereas liquids
have constant volume at constant temperature but may vary in respect to their shapes and therefore
cannot sustain applied pressure.
❑ Liquids can only support the compressive kind of stresses and recover upon removal of pressure
stress.
❑ Different types of stresses cause infinite deformation if applied for long time as elastic and shear
module of the liquids is zero. Rheological properties are studied with viscometry and rheometry.
 CONTENTS
❑ Newtonian Systems
❑ Law of Flow
❑ Kinematic Viscosity
❑ Effect of Temperature
❑ Non-newtonian Systems, Pseudoplastic, Dilatant, Plastic,
❑ Thixotropy, Thixotropy in Formulation,
❑ Determination of Viscosity, Capillary, Falling Sphere, Rotational Viscometers
 SHEAR AND SHEAR STRESS
Shear: shear can be considered as an internal friction of a fluid
caused by molecular attraction which makes it resist a tendency to
flow.
❑ This friction becomes apparent when a layer of fluid is made to
move in relation to another layer. The greater the friction the
greater is the amount of force required to cause this movement
which is called shear.

Shear stress: The shear stress (F) is measure of the amount of force applied to sample per unit area.
❑ Stress is measured in units of Pascal (1 Pa = 1 N/m).
❑ The shear stress is expressed by the equation:
𝑭′
Shear stress (F) = 𝑨

Where, F is shear stress F’ is force and A is surface area

 RATE OF SHEAR
❑ Rate of shear is the velocity gradient (G) is defined as change in velocity with change in unit area
𝒅𝒗
G= 𝒅𝒓

❑ The higher viscosity then grater force per unit area required to produce certain rate of shear so.
𝒅𝒗 𝑭′ 𝒅𝒗 𝑭′ 𝒅𝒗
F ή
𝒅𝒓 𝑨 𝒅𝒓 𝑨 𝒅𝒓

𝒅𝒗 𝑨
ή= 𝒅𝒓 𝑭′

❑ ή is coefficient of viscosity, often called as viscosity which is expressed as ratio of shearing stress to the rate of
shear.
❑ Coefficient of viscosity is defined as the force per unit area required to maintain unit velocity difference
between two parallel layers in the liquid which are one cm apart.
❑ Viscosity is more commonly expressed as centipoises (cP).
❑ The cgs units for poise are dyne/cm2 or g/cm.sec and SI unit is Pascal-second (Pa.s)
1 P = 100 cP = 1 dyn.sec/cm2
 NEWTONIAN SYSTEMS
❑ Isaac Newton classified the fluids into two types:
Newtonian fluids and non-Newtonian fluids.
NEWTONIAN FLUIDS
❑ The fluids for which the shearing stress is linearly related to the rate of shear are designated as Newtonian
fluids.
❑ Fluids which obey Newton's law of fluid flow are called as Newtonian fluids.
❑ Newtonian materials are referred to as true liquids since their viscosity or consistency is not affected by shear
such as agitation or pumping at a constant temperature.
❑ These fluids start to flow when a stress is applied, and deformation stops instantly when the stress is removed.
Viscosity of these fluids is constant with respect to the time of shearing and it does not change in the retesting
condition.
❑ The Newton's equation for the flow of liquid is

F=ήG
 NON-NEWTONIAN SYSTEMS Con..
NON-NEWTONIAN FLUIDS
❑ In liquid polyphasic pharmaceuticals (dispersion of gums or other polymers) the rate of shear is not directly
proportional to the shearing stress and viscosity is not constant.
❑ A non-Newtonian fluid is one in which viscosity is not a constant parameter and it depends in some way on the
shear rate. It means the relationship between shearing stress and rate of shear is not constant.
❑ Fluids that do not follow Newton's law of fluid flow are known as non-Newtonian fluids.
❑ The size, shape and cohesiveness determine how much force is required to make them move. There are several
types of non-Newtonian fluid behavior, characterized by the way a fluid viscosity changes in response to
variation in shear rate.
❑ Based on shape of consistency curves of rheogram the non- Newtonian fluids are classified as follows.
• Plastic Flow
• Pseudo Plastic Flow
• Dilatant Flow
 NON-NEWTONIAN SYSTEMS Con..
Plastic Flow
❑ Fluids showing plastic flow behave as solid under static condition. Substances that undergo plastic flow are
called Bingham bodies, which can be defined as substances that exhibit a yield value.
❑ For example, clay suspension in water or flocculated particles in concentrated suspension of zinc oxide in
mineral oil, certain ointments, pastes and gels etc.
❑ Yield value (stress) is a point at which plastic flow curve intersects shear stress axis.
❑ Its units of dyne/cm2
❑ Yield value is an indicator of presence of forces of flocculation.
❑ The higher value of yield stress indicates greater degree of flocculation. Once the yield value is exceeded and
flow begins plastic fluid may show Newtonian, pseudo plastic or dilatant flow characteristics. The plastic flow
material does not begin to flow until shearing stress is equal to or exceeds the yield value.
 NON-NEWTONIAN SYSTEMS Con..
❑ The rheogram of plastic flow curve does not pass through the origin. Below yields value viscosity decreases
with decreasing shear rate. The slope of rheogram is called as mobility.
❑ The reciprocal of mobility is known as plastic viscosity.
❑ The rheological behavior of plastic materials is quantitatively expressed by the term plastic viscosity using
Bingham equation.
( 𝑭 −𝒇 )
U=
𝑮
❑ Where, U is plastic viscosity
F is shearing stress,
f is yield value and
G is rate of shear.

Rheogram of Plastic Flow

 NON-NEWTONIAN SYSTEMS Con..
Pseudo Plastic Flow
❑ Pseudo plastic flow is exhibited by polymeric solutions. Aqueous systems containing natural and synthetic
gums such as liquid dispersions of tragacanth, sodium alginate, methyl cellulose and sodium carboxymethyl
cellulose exhibit pseudo plastic flow properties.
❑ These fluids display continuous decrease in their viscosities with an increase in shear rate. This flow behavior is
called as shear thinning.
❑ For example, pharmaceutical products such as; emulsions, dilute polymeric solutions, slurries, ·shampoos,
blood, and some of the juices belong to shear thinning fluids.
❑ This type of systems does not exhibit a property of yield value or yield stress. Several expressions have been
derived and used to represent Pseudo plastic flow.
 NON-NEWTONIAN SYSTEMS Con..
❑ Pseudo plastic substances begin to flow upon application of shearing stress and as stress increases, the shear rate
also increases but the rheogram curve is non-linear in shape, Hence, viscosity. of such systems cannot be
expressed by single value.
FN = ή G
❑ Where, N is number given to exponent
ή is a viscosity coefficient of pseudo plastic fluid.

Rheogram of Pseudo plastic Flow

 NON-NEWTONIAN SYSTEMS Con..
Dilatant Flow
❑ Dilatant fluids display an increase in viscosity with increase in shear rate.
❑ The term dilatant is used to describe these substances because on application of shear, these systems increase
their volume and on removal of stress the system returns to its initial state of fluidity.
❑ Dilatant flow can be shown by dispersions containing high concentrations (~ 50%) of small and deflocculated
particles, concentrated slurries, for example, potato starch (52%) in water, kaolin (12%) in water and zinc oxide
30% in water.
❑ The mechanism of dilatancy can be described as follows. At rest, particles are closely packed with minimum
interparticle (void) volume. The small amount of liquid vehicle is enough to fill this volume.
❑ At low shear rates this volume permits the particles to move relative to one another and thus at rest the system
exhibits relatively low consistency. Therefore, the dilatant suspensions are fluid at low shear stress and can be
poured out from a bottle.
 NON-NEWTONIAN SYSTEMS Con..
❑ As the shearing stress is increased the bulk of the system dilates
(expands) and particles assume open form of packing with significant
increase in void volume.
❑ At higher stress the ·system shows paste like consistency.
❑ Dilatant materials may solidify under conditions of high shear.

Rheogram of Dilatant flow

 THIXOTROPY
❑ Thixotropy is defined as an isothermal and comparatively slow recovery on standing of material of a
consistency lost through shearing. It is an indication of fluffiness of the material. A good example of highly
thixotropic liquid is mayonnaise. It has a high viscosity if stirred slowly but much lower viscosity on quick
stirring. Since thixotropic liquids are non-Newtonian type the energy required to move them is not directly
proportional to the speed at which they are moved. Therefore, mayonnaise has high viscosity when sheared at
low speed and lower viscosity at high speed. The ratio of low speed viscosity to high speed viscosity is called
thixotropic index.
❑ Thixotropic behavior describes structural degradation during the shearing. When shearing stress is relieved the
original structure is recovered. The extent of structural recovery is dependent on the time allowed for recovery.
Thus, a thixotropic material will have a shear thinning behavior when a gradual increase in shear is applied.
❑ Thixotropic flow is a reversible gel-sol-gel transformation. The structural network formed at rest is of rigid
matrix type that stabilizes suspensions and gels but when sheared by simple shaking the matrix structure relaxes
to form a solution with characteristics of liquids.
 THIXOTROPY Con..
❑ Thixotropic property has great significance in the formulation of suspensions as particles remain uniformly
suspended during storage, but when required for use just by shaking the container it becomes liquid.
❑ Hysteresis loop is the up and down curves of the thixotropic systems. It is a region between curves for the
increasing decreasing shear rate ramps.

Thixotropy in (a) Plastic Flow (b) Pseudo Plastic Flow (c) Dilatant Flow
 THIXOTROPY Con..
Negative Thixotropy
❑ It is also known as anti-thixotropy which represents a time dependent increase in apparent viscosity rather than
decrease on application of a shearing stress. This property is also called as sol to gel transformation.
❑ At rest system consists of large number of individual particles and small size floccules. When the system is
sheared the molecules of dispersed phase colloids. The increase in collision frequency of these molecules causes
increase in interparticle bonding with time.

❑ At equilibrium state, very small number of large floccules exists therefore

system exhibit sol form. Again when system is at rest, the large size
floccules break up and gradually return to its original state of small size
floccules and individual particles.
❑ Negative thixotropy is observed with magnesia magma. when magnesia
magma was sheared with alternatively first by increasing and then by
Rheogram of Negative thixotropy
decreasing shears rates, it continuously gets thickened.
 KINEMATIC VISCOSITY
❑ Kinematic Viscosity Kinematic viscosity (v) is the ratio of viscosity of fluid to its density.
ή
V=
ρ

Where, ή is Viscosity
ρ is Density
❑ Kinematic viscosity is a measure of the resistive flow of the fluid under the influence of gravity. It is measured
using capillary viscometers.
❑ The SI unit of kinematic viscosity is m2/sec
 EFFECT OF TEMPERATURE ON VISCOSITY
❑ Viscosity is highly dependent on temperature. In case of liquids, viscosity decreases exponentially with increase
in temperature whereas for gases it increases with increase in temperature.
𝑬𝒗

ή =Ae(𝒌𝑻)
Where, ή is viscosity,
A is a constant depend upon molecular weight and molar volume,
k is Boltzmann's constant,
Ev is an activation energy required to make the molecules to flow
T is the temperature.
❑ The constants A and Ev exhibit a large variation between different fluids.
❑ In logarithmic form, equation
𝑬𝒗
log ή = log A + 𝟐.𝟑𝟎𝟑 𝒌𝑻
 EFFECT OF TEMPERATURE ON VISCOSITY Con..
❑ Plot of In ή versus 1/T yields straight line with slope equal to Ev/R and the intercept on y-axis is In A, Thus, the
values of the constant A and Ev can be obtained.
 DETERMINATION OF VISCOSITY
INSTRUMENT FOR MEASUREMENT OF
VISCOSITY

Falling and
Capillary Rotational Parallel plate
Rising body
viscometers viscometers viscometer
viscometers

Falling sphere
Rising sphere
Canon- viscometer - Cone and Plate
Ostwald's Ubbelohde viscometer – Cup and Bob
Flanske Hoeppler falling ball viscometer: Ferranti
viscometer viscometer Rheometer viscometer
viscometer viscometer Shirley viscometer

Couette (Cup) type -

Searle (bob} type
Mac Michael viscometer

Stormer viscometer Brookfield viscometer

 DETERMINATION OF VISCOSITY Con..
OSTWALD'S VISCOMETER
❑ The Oswald viscometer is a simple device for comparing the flow times of two liquids of known density. If the
viscosity of one liquid is known, the other can be calculated.
❑ Ostwald's viscometer is made up of U shaped glass tube, the left arm of which has
large diameter with large bulge in the lower region while right arm has small bulb
in the upper part. Below upper bulb it has capillary which extends towards the
curve of the tube at bottom. There are two marking A and B above and below the
upper bulb. The liquid is poured in the left arm and sucked up to the mark A and
hold at this level with thumb. The viscometer is then clamped vertically to the stand
and thumb is removed to allow the liquid to flow from mark A to mark B by force
of gravity. The time required to flow liquid from mark A to B is recorded.
❑ The time taken for the level of the liquid to pass between these marks is
proportional to the kinematic viscosity. Ostwald's Viscometer
 DETERMINATION OF VISCOSITY Con..
Ρ t
ή𝟏 = Ρ1 t1 X ή𝟐
2 2

Where, ή1 Viscosity of test liquid

ή1 Viscosity of water
Ρ1 Density of test liquid
Ρ2 Density of test liquid
t1 time required to flow test liquid
t2 time required to flow water
 DETERMINATION OF VISCOSITY Con..
UBBELOHDE VISCOMETER
❑ Ubbelohde viscometer consists of third vertical arm in addition to two arms of Ostwald's viscometer. The third
arm is attached to the right arm just above the reservoir bulb.

❑ The liquid under study is introduced through left arm to fill the lower reservoir
bulb. The viscometer is maintained at constant temperature by placing it in constant
temperature bath. After attaining the set temperature, the sample is sucked in to
middle arm up to mark A and allowed to drain through the middle arm from mark
A up to mark B. The time required for flow from A to B is recorded. The liquid
below lower capillary is ventilated by third arm for easy draining.
❑ Thereby liquid levels at the lower part of viscometer in left and middle arm are
maintained at same level. Ubbelohde viscometer and other suspended level
viscometers are used to measure viscosities of transparent liquids.
Ubbelohde Viscometer
 DETERMINATION OF VISCOSITY Con..
FALLING SPHERE VISCOMETERS
❑ These viscometers are used to determine viscosities by measuring the velocity of a falling or rolling ball, a falling
needle, or a rising air bubble in the liquid under test. This method is best suited for Newtonian fluids as it
measures viscosities at a single shear rate.
HOEPPLER FALLING BALL VISCOMETER
❑ Stokes' law is the basis of the falling sphere viscometer in which fluid is at stationary in a vertical glass tube.
❑ A body falling through a liquid experiences a viscous drag (resistance) which opposes the motion of the body. If
a body falls due to gravitational force in test solution a uniform terminal velocity can be achieved. This
instrument consists of long nearly vertical glass tube with large diameter having marks A and B on its outer
surface. A steel or glass sphere of known size and density is allowed to descend through the test liquid in the
instrument. The desired temperature is allowed to setup by means of a constant temperature outer jacket. The
ball loading pin is then released which is followed by inverting the apparatus to have ball at the starting position
and falls from known distance between mark A to B.
 DETERMINATION OF VISCOSITY Con..
ή = t (Sb – Sf) B
Where, ή is viscosity of test fluid,
t is time of flow, and
Sb and Sf are specific gravities of ball and test fluid, respectively.
B is a constant which depends upon material of the ball and its geometry.
❑ If the instrumerit constant is not given then it must be determined using liquid of known viscosity.
 DETERMINATION OF VISCOSITY Con..
ROTATIONAL VISCOMETERS
❑ In Rotational viscometers the force required to turn an object in a fluid indicate the viscosity. The viscometer
determines the required force for rotating a disk or bob in fluid at known speed. The great advantage of these
viscometers is their superiority over capillary and falling or rising body viscometers is that these operates with
wide range of shear rates.
CUP AND BOB VISCOMETER
❑ These viscometers consist of two co-axial cylinders of different diameters. The outer cylinder forms a cup where
as the inner cylinder or bob is fixed at center of the cup. The test fluid is sheared in the space between outer wall
of the bob and inner wall of the cup. There are two classical geometries in "cup and bob" viscometers,
 DETERMINATION OF VISCOSITY Con..
COQUETTE TYPE VISCOMETER
❑ A coquette viscometer is an instrument used for measuring the viscosity of a fluid. It consists two concentric
cylinders. The fluid is placed between the cylinders, and the outer cylinder is then made to rotate with constant
angular velocity.
❑ At steady state, the torque required to keep the outer cylinder in motion is noted and using this information the
viscosity of fluid is calculated. It is assumed that the density and viscosity of fluid is constant and fluid follow
laminar flow of steady state. This viscometer is used to calculate apparent viscosity of pseudo plastic and plastic
fluid systems

coquette viscometer
 DETERMINATION OF VISCOSITY Con..
MAC MICHAEL VISCOMETER
❑ In this instrument the cup is rotated and the viscous drag on the bob is produced by liquid that result into a
torque which is proportional to viscosity of liquid under test. The number of revolutions per minute (r.p.m.) and
torque represents rate of shear and shearing stress, respectively.
❑ The viscosity is calculated by following equation.
𝑾
ή = Kv 𝑽

Where, ή is apparent viscosity

W is weight paced on hanger (shearing stress)
V is shear rate in r.p.m,
Kv is constant

Mac Michael Viscometer

 DETERMINATION OF VISCOSITY Con..
SEARLE TYPE VISCOMETER
❑ Searle Type viscometers work opposite to the Coquette type such that the bob is rotated while cup is at
stationary. Brookfield viscometer and Stormer viscometer are the examples of this type of viscometers.
STORMER VISCOMETER
❑ The Stormer viscometer is a rotation instrument used to determine the
viscosity of natural gums, and synthetic gums and other Newtonian systems.
This viscometer is used to obtain fundamental rheological properties such as
yield value, plastic viscosity and thixotropic index.
❑ In Stormer viscometer bob is rotating and cup is stationary. During operation
the test sample is placed in the gap between the cup and the bob. The desired
temperature is set by circulating water from the constant temperature bath.
A known weight is attached to hanger and placed in sample followed by
rotations of the bob to have some specified number of revolutions.
Stormer viscometer
 DETERMINATION OF VISCOSITY Con..
❑ The rotor speed can be adjusted by changing the amount of load supplied onto the rotor. The viscosity can be
found by adjusting the load until the rotation velocity is 200 r.p.m. The time required for the number of
revolutions is recorded.
❑ The hanger along with the bob is then taken-up to add higher weight and again on dipping in sample similar
determinations are carried out. The weights are increased gradually and the cycle of determinations is
performed to have number of data values. By using calculated _values of shear rates and shear stress rheogram
is plotted.
𝑾
ή = Kv 𝑽
 DETERMINATION OF VISCOSITY Con..
BROOKFIELD VISCOMETER
❑ It consists of a cup, which is at stationary and a different size rotating bob (spindle/disc). Selection of suitable
spindle is based on viscosity of material. Since, viscosity is inversely proportional to spindle size; for liquids
having low viscosity the large size spindles are used while for highly viscous liquids small size spindles are
suitable.
❑ The principal of this viscometer is to drive a spindle which is
immersed in the test fluid through a calibrated spring. The viscous
drag· of the fluid against the spindle is measured by the spring
deflection. Spring deflection is measured with a rotary transducer.
The measurement range of this viscometer is in cP which is
determined by the rotational speed of the spindle, the size and
shape of the spindle, container the spindle is placed in, and the
full scale torque of the calibrated spring. Brookfield Viscometer
 DETERMINATION OF VISCOSITY Con..
❑ At practical determinations of viscosities suitable spindle is attached to the hanger and is placed in sample
holder that contains required quantity of the test sample,
❑ Temperature of test material is maintained constant using thermostat. The spindle is rotated using a
synchronous motor by a beryllium-copper torsion spring. Different models of Brookfield viscometers are
available.
❑ Movement pointer shows dial reading which is net effect of stiffness and viscosity of sample. Viscosity is
obtained from dial reading, spindle number and speed of rotation.
𝟏𝟎𝟎
ή = ( 𝒓.𝒑.𝒎. ) X TK X SMC X T

Where, r.p.m. is current viscometer spindle speed

TK is viscometer torque constant
SMC is current spindle multiplier constant
T is current viscometer torque (%) expressed as a number between 0-100.
 DETERMINATION OF VISCOSITY Con..
CONE AND PLATE VISCOMETER
❑ As the name implies 'Cone and Plate' viscometers essentially use a cone of very shallow angle in theoretical
contact with and placed centrally above a flat circular plate.
❑ With this system the shear rate beneath the plate is constant to a modest degree of precision; a graph of shear
stress (torque) against shear rate (angular velocity) yields the viscosity.

❑ The Spindle or rotor is attached directly to the shaft. High speed

microprocessors measure the speed from a digital encoder and calculate
the current required to drive the rotor at the test speed. The current
required is proportional to the viscosity of the sample under test.
❑ During analysis the test sample is placed exactly at the center on the
plate, which is then raised in to position under cone. The sample fills
the narrow triangular gap between cone and plate. The surface tension
of the sample prevents it from spreading on the plate. Cone and Plate Viscometer
 DETERMINATION OF VISCOSITY Con..
❑ The plate is maintained at constant temperature by circulating water under the plate. The cone is driven by
variable speed motor.
❑ The sample is sheared between cone and plate within the narrow gap. By varying the speed of cone (i.e. rate of
shear, r.p.m.) the torque produced on the cone is measured. The rheogram is obtained by plotting rate- of shear
(r.p.m.) against shear stress (dial reading).

The viscosity of Newtonian fluid The plastic viscosity is

𝑻 𝑻 − 𝑻𝒇
ή = Kv 𝑽 𝑼 = Kv 𝑽

Where, ή is viscosity of test sample Where, T is torque observed as dial reading

T is torque Tf is torque at the shear stress
V is speed of cone in r.p.m. V is angular velocity (r.p.m.)
Kv is instrument constant. Kv is instrument constant.
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