 What is rheology?

 Describe the application of rheology in the pharmaceutical

sciences and practice of 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, hysteresis and viscoelasticity.
 Define and understand Newton's law of flow and its
application.
 Differentiate flow properties and corresponding rheograms
between Newtonian and non-Newtonian materials.
 Rheology is Greek word, Rheo means flow and
Logos means science.

 Rheology is the study of flow properties of

fluids and deformation of solids i.e. the
viscosity characteristics of powders , solids and
semisolids.

 Rheometry describes measuring methods and

techniques used to determine the rheological
properties.
 The term rheology was introduced by EUGENE C.
BINGHAM, in 1929 for physics and chemistry.

 Scott-Blair recognized the importance of rheology

in pharmacy and studied the importance for various
dosage forms like emulsions, suspensions, pastes
and tablet coatings.

 Now a days, rheology is been studied for paints, ink,

building materials, cosmetics and dairy products.
 Rheology measurement is involved in:

 Mixing
 Flow of material
 Filling and Packaging
 Removal
 Topical application on to skin
 Physical stability of suspension, emulsion and semisolids
 Bioavailability
 Release of drug from dosage form
 The rheology of a particular product can effect:
 Patient acceptability
 Physical stability
 Biological activity

 The rheological properties of a pharmaceutical

system can also influence the choice of
manufacturing equipment and method.
 Shear Stress
Shear stress is force F acting on area A to effect the
movement in liquid element between two plates.
The velocity of the movement at a given movement
is controlled by the internal forces of the material.
It is represented as:
𝐹
𝜏=
𝐴
 Shear Rate
Shear rate is defined as the difference of velocity dv
between two planes of liquid separated by thickness
difference dh of two layers.
It is represented as:
𝑑𝑣
𝛾=
𝑑ℎ

dv = velocity differential between adjacent velocity layers

dh = thickness differential of flow layers
 On the basis of flow rate and deformations,
materials are classified into two class:

 Newtonian System
 Non-Newtonian System
 Newton was the first person to study the flow
properties of liquid in a quantitative way.

 He recognized that viscosity is directly proportional

to shear stress i.e. greater the viscosity of liquid,
greater the shear stress required to produce certain
rate of shear.

 Or we can say is shear rate is directly proportional to

shear stress.
 Consider a block of liquid
consisting of parallel plates
of molecules.
 Bottom layer is considered
to be fixed in place.
 If the top plane is moved at
a constant velocity, each
lower layer will move with a
velocity directly
proportional to its distance
from stationary bottom
layer.
 This can be mathematically represented as

𝐹 𝑑𝑣
=ή
𝐴 𝑑𝑟
 Here
 F’/A is the force applied to top layer to result in flow
and is called shearing stress (F), dv/dr is the velocity
gradient or rate of shear (G) and ή is viscosity.
 The equation can be written as
𝐹
ή=
𝐺
Viscosity
Defined as the shearing force required to produce a
velocity of 1 cm/sec between two parallel planes of liquid
each 1 cm2 in area and separated by a distance of 1 cm.
The unit of viscosity is the poise.
The cgs units for poise are dyne sec cm-2 or g cm-1 sec-1 .
These units are readily obtained by rearranging the
viscosity coefficient equation.
Kinematic viscosity
 It is defined as the absolute viscosity divided
by the density of the liquid at a definite
temperature.
 Mathematically it is represented by:
ή
Kinematic viscosity =
ρ

 Unit is stoke or centistoke.

 Viscosity of the liquid decreases with an increase in
temperature and fluidity is increased as fluidity is
1
∅ =
ή

 The relationship is mathematically represented by the

equation:
ή = 𝐴𝑒 𝐸𝑣𝑅𝑇
 Where:
 A = constant depending on molecular weight
 Ev = Activation energy
 The substances that fail to follow Newton’s
Equation of flow are know as non-
Newtonian system.
 Pharmacists deals more with non-Newtonian
systems as compared to Newtonian systems.
 Liquid and solid heterogeneous dispersions
such as colloidal solutions, emulsions
suspensions, ointments and similar products
belongs to the same class.
 Non-Newtonian systems are classified into
three classes:
Time independent Time dependant
 Plastic flow Thixotropic
 Pseudo-plastic flow Antithixotropic
 Dilatant flow
 Plastic flow is represented by the rheogram shown in figure:
 The materials which exhibit the plastic flow are know as
Bingham bodies.

 The plastic flow curve does not pass through the origin
rather intersects the shearing stress axis at a point
known as Yield value.

 Bingham bodies begin to flow only when the shear

stress value exceeds the yield value.

 At stress below the yield value the substance acts as

elastic material.
 The slope of the rheogram is know as mobility,
which is analogous to fluidity in Newtonian
system.
 And its reciprocal is plastic viscosity, represented
by:
𝐹 −𝑓
𝑈=
𝐺
 Where f is yield value, F is shear stress and G is
shear rate.
 The Bingham bodies are classified into two
types:

 Solids, the substances that exhibit a yield value

 Liquids, the substances which begin to flow at
smallest shear stress and show no yield value.
Explanation of Plastic Flow
 Plastic flow is associated with presence of flocculated
particles in a suspension.
 The yield value is present because of the contacts
between the adjacent particles which must be broken
down before the flow can occur.
 Once the yield value is exceeded, the increase in shear
stress become directly proportional to shear rate.
 So plastic system resembles Newtonian system at
shear stress above the yield value.
Pseudo-Plastic Flow
Pseudo-Plastic Flow
 A large number of natural and synthetic gums e.g. liquid
dispersions of tragacanth, sodium alginate exhibit pseudo-
plastic flow.
 The rheogram of pseudoplastic systems starts from origin
and there is no yield value.
 No part of the curve is linear, so viscosity can not be
measured by any single value.
 The viscosity of pseudo plastic substance decreases with
increase of shear rate. That’s why they are also called as
shear thinning systems.
 Most of the pseudo plastic materials consist of long
chain molecules or complex structure which are
disarranged at rest or low shear rate.
 When shear rate is increased they begin to align their
long axis in direction of flow.
 This arrangement reduces the internal resistance and
allows greater shear rate at each successive shear
stress point.
 Some of the solvent associated with molecules may
be released, resulting in lowering of concentration
and size of dispersed molecules.
 Pseudoplastic flow can be measured by using Martin’s
exponential formula:
𝐹𝑁 = ή G
 Where F is shearing stress and G is shearing rate. Exponent
N is indicative of non-Newtonian behaviour.
 When N assumes the unity, we have simple Newtonian
equation of flow. As the value increases above unity, the
pseudoplastic character tics increased.
 The equation can also be written as:
Log G = N log F - Log ή
 This equation is for straight line.
 Dilatants are the systems which increase in
volume when sheared and viscosity increases
with increasing shear rates.
 Hence are called as shear thickening systems.
 Certain suspensions with high percentage of
dispersed solids exhibit an increase in resistance
to flow with increasing shear rate.
 When the stress is removed the system returns
to its original state of fluidity.
 The rheogram present in the figure shows
dilatant flow.
 Dilatancy is represented by the equation

𝐹𝑁 = ή G

 In this case N is always less than 1 and

decreases as the degree of dilatancy
increases.

 As value approaches 1, the system becomes

increasingly Newtonian in behaviour.
Explanation
 Dilatant flow is exhibited by the suspensions having high
concentration of very fine particles. The particles, although
in close packed arrangements are in state of deflocculating.
 Flocculated suspensions on the other hand tend to show
plastic flow rather than dilatancy.
 When the undistributed settled deflocculated particle mass
is vigorously agitated the bulk is increased as the particle
force pat one another.
 The expansion results in large volume between the particles
and insufficiency of the vehicle to fill the voids.
 Thus the unlubricated particles show an increased
resistance to flow and a rigid paste results.

 Dilatancy does not occur in dilute suspensions.

 Dilatancy may prove to be troublesome during

processing of dispersion and granulation of tablet
mass when high speed mixers and mills are employed.

 If the material becomes dilatant, the resulting

solidification can cause overload and damage to
motor.
 It is defined as:
An isothermal and comparatively slow
recovery, on standing of a material, of
consistency lost through shearing

 This is only applied to shear thinning systems

Explanation

 Thixotropic systems usually contains asymmetric

particles that through numerous points of contact, set
up a loose three dimensional network throughout the
system.

 At rest the structure confers to the rigidity of the

system and resembles a gel.

 As shear is applied, flow starts and structure begins to

breakdown as particles become aligned.
 The material undergoes gel to solution
transformation and show shear thinning.
 When stress is removed, reformation starts and
the process is not instantaneous as the
asymmetric particles come in contact with
random Brownian movement.
 The rheogram obtained for thixotropic system
are highly dependent on shear rate and time for
which shear rate was applied.
 Rheogram of thixotropic system is shown in
the figure.

 The down cure for non-Newtonian systems is

displaced with regard to upper curve and is
displace to left of the up-curve showing that
the material has low consistency at any point
than the up-curve.
Measurement
 Quantitative measurement of the thixotropy can be done
by many ways. The most apparent characteristic of
thixotropic system is hysteresis loop, formed with up and
down curves of rheogram. Based on that a thixotropic
coefficient B is calculated as:
𝑈1 − 𝑈2
𝐵= 𝑡
𝐼𝑛 1
𝑡2
 Where U1 and U2 are plastic viscosities of two down
curves after shearing at a constant rate for t1 and t2
seconds.
 Negative thixotropy or
antithixotropy, which
represents an increase rather
than a decrease in
consistency on the
downcurve.
 The material is sheared at
repeated increasing and then
decreasing rates of shear. At
stage D, further cycling no
longer increased the
consistency, and the
upcurves and downcurves
coincided.
 Rheopexy is a phenomenon in which a solid forms a
gel more readily when gently shaken or otherwise
sheared than when allowed to form the gel while the
material is kept at rest.
 In a rheopectic system, the gel is the equilibrium form,
whereas in antithixotropy, the equilibrium state is the
sol.
 Antithixotropy should not be confused with dilatancy
or rheopexy. Dilatant systems are deflocculated and
ordinarily contain greater than 50% by volume of solid
dispersed phase, whereas antithixotropic systems
have low solids content (1%–10%) and are flocculated.
 There are various instruments used for the measurement of
rheological properties of the substances:
 Capillary viscometers (Single Point Viscometer)
 Glass capillary viscometer
 Cannon-Fenske Viscometer
 Ubbelhode Viscometer
 Ostwald Viscometer
 Rotational Viscometer (Multipoint Viscometer)
 Coaxial-cylinder Viscometer
 Stromer viscometer
 Hoake roto Viscometer
 MacMicheal Viscometer
 Couette Viscometer
 Cone-plate Viscometer
 Fluids
 Mixing
 Particle-size reduction of disperse systems with shear
 Passage through orifices, including pouring, packaging in bottles, and passage through
hypodermic needles
 Fluid transfer, including pumping and flow through pipes
 Physical stability of disperse systems
 Quasisolids
 Spreading and adherence on the skin
 Removal from jars or extrusion from tubes
 Capacity of solids to mix with miscible liquids
 Release of the drug from the base
 Solids
 Flow of powders from hoppers and into die cavities in tabletting or into capsules during
encapsulation
 Packagability of powdered or granular solids
 Processing
 Production capacity of the equipment
 Processing efficiency
 Rheology has applications in:
 material science to determine viscoelastic
properties of polymers & biopolymers.
 Solo-gel science for glass & ceramic production.
 geophysics to determine flow of molten lava or
debris as well as plasticity of granite etc.
 physiology esp. hemorheology i.e. study of flow
properties & viscosity of blood.
 food rheology.
 concrete rheology.