21-Feb-16

CONTENTS
 Introduction
 Definition
 Importance
 Newton's laws
 Types of flow
 Viscosity
 Measurements of viscosity
 Pharmaceutical applications

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INTRODUCTION
 rheo – to flow
 logos – science
 Rheology is the study of the flow and deformation of matter under
Stress (shear).

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DEFINITION OF RHEOLOGY
 Rheology is the science/physics that concerns with the flow of
liquids and the deformation of solids.

 Study of flow properties of liquids is important for pharmacist

working in the manufacture of several dosage forms, viz., simple
liquids, gels, ointments, creams, and pastes.

 These systems change their flow behavior when exposed to different

stress conditions.
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IMPORTANCE & FUNDAMENTALS

 Formulation of medicinal and cosmetic creams, pastes and lotions.
 Formulation of emulsions, suspensions, suppositories, and tablet
coating.
 Fluidity of solutions for injection.
 In mixing and flow of materials, their packaging into the
containers,
their removal prior to use, the pouring from the bottle.
 Extrusion of a paste from a tube .
 Passage of the liquid to a syringe needle.
 Influence the choice of processing equipments in the pharmaceutical
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• Can affect the patient’s acceptability of the product, physical stability,
biologic availability, absorption rate of drugs in the gastrointestinal
tract.
• 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 syringibility 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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NEWTONS LAW
 According to NEWTONS LAW higher the
viscosity of a liquid, the greater is the force per
unit area (shearing stress F) required to produce
a certain rate of shear( G).
 rate of shear α shearing stress
 F= ῃ G
Where F= F’/ A
G= rate of shear
ῃ= viscosity

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Rheology of solids and liquids:-

Rheology of solids involves deformation of solids and

their [Link] rheology of liquids involve the flow
of liquids.
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TYPES OF FLOW

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NEWTONIAN FLOW:
 A Newtonian fluid (named for Isaac Newton) is a fluid whose stress
versus rate of shear curve is linear and passes through the origin. The
constant of proportionality is known as the viscosity.
 Examples :
 Water,
 chloroform,
 Castor oil,
 ethyl Alcohol etc.

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VISCOSITY

 Itis defined as resistance to the flow.

 ῃ is the coefficient of viscosity. And is calculated
as
ῃ=F/ G
Where F= Shearing stress
G= Rate of shear
o Unit of viscosity is
Poise or [Link]/cm2.
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KINEMATIC VISCOSITY

 It
is defined as absolute viscosity divided by
density of liquid at specific temperature.

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NON NEWTONIAN FLOW

• A non newtonian flow is defined as one for which the relation
between F and G is not linear.
• In other words when the shear rate is varied, the shear stress is not
varied in the same proportion. The viscosity of such a system thus
varies as the shearing stress varies. (Viscosity is not constant)
• It can be seen in both liquid and solid heterogeneous dispersions
such as emulsions, suspensions, colloids and ointments.

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NON NEWTONIAN SYSTEMS

Three classes:
 PLASTIC FLOW
 PSEUDOPLASTIC FLOW
 DILATENT FLOW

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PLASTIC FLOW: (Bingham Bodies)

• In which curve does not pass through the origin, but intersects the
shear stress on X-axis (Yield value)

• Elastic body and it fails to flow when less amount of stress is applied.
• As increase the stress, leads to non-linear increase in shear rate but after
that
curve is linear.

So, plastic flow shows Newtonian flow above the yield value.

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•The curve represents plastic flow, such materials are called as Bingham
bodies.
•Bingham bodies does not flow until the shearing stress is corresponding to
yield Value exceeded.
•So, yield value is important property of certain
dispersions.
•The reciprocal of mobility is Plastic viscosity

 EXAMPLES: ZnO in mineral oil, certain pastes , paints and ointments.

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Plastic flow explained by flocculated particles in

concentrated suspensions, ointments, pastes and
gels.

F/A
Increase
Yield value stress
Flow
Flocculated Individual
Particles particles

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PLASTIC FLOW

The curve for the plastic flow is as fallows.

Slope =

mobility
Rate of shear,
G Yield value

Shearing
stress, F

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The equation describing plastic flow is,

U=F–f/G

Where,
f = Yield
value

F = Shearing stress
G = Rate of shear
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PSEUDO PLASTIC FLOW

Many Pharmaceutical products liquid dispersion of natural and

synthetic gums show pseudo plastic flow.

eg. 1. Tragacanth in water

2. Sod. Alginate in water

3. Methyl cellulose in water

4. Sodium CMC in water

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• With increase in the shearing stress the disarranged molecules

orient themselves in the direction of flow, thus reducing friction
and allows a greater rate of shear at each shearing stress.
• Some of the solvent associated will be released resulting in
decreased viscosity.
• This type of flow behavior is also called as shear thinning
system.

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Graph for pseudo plastic flow is like this

Rate of shear,
G

Shearing
stress,
F

 In which curve is passing from origin (Zero

shear stress), so no yield
value is Obtained.
 As shear stress increases, shear rate increases but
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 Pseudo plastic flow can be explained by Long chain

molecules of polymer.
Polymer &
water molecules
align on
direction of
force
Stress
Water

Polymer long chain

with water molecules

 In storage condition, arrange randomly in

dispersion.
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 On applying F/A, shearing stress molecules ( water

&
polymer) arrange long axis in the direction of force applied.
 This stress reduces internal resistance & solvent
molecules released form polymer molecules.
 Then reduce the concentration and size of molecules
with
decrease in viscosity.

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The exponential equation shows this flow

FN = η G

N = no. of given exponent

η = Viscosity coefficient

The exponent N rises as flow becomes increasingly non-Newtonian

 In case of pseudo plastic flow, N > 1.

i.e. More N >1, the greater pseudo plastic flow of material.

 If N = 1, the flow is Newtonian.
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Taking Log on both sides,

i.e. N log F = log η + log

G
On rearrangement, we get

log G = N log F - log

η
This equation gives straight line,

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DILATANT FLOW
 Certain suspensions with high % of dispersed solids shows an
increase in resistance to flow with increasing rates of shear.

 Such system increase in volume when sheared, such system called as

dilatant flow.

 Also, called as “ Shear thickening system” i.e. when stress is

removed, dilatant system return to its original position

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Graph for dilatant flow is like this

Rate of shear, G

Shearing stress, F

 In which curve is passing from origin (Zero shear stress), so no yield

value is Obtained.
 Non-linear increase in rate of shear.
 Increase resistance to flow on increase rate of shear

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 In which, particles are closely packed with less voids

spaces, also amount of vehicle
is sufficient to fill the void
volume.

Increase rate of
shear

At rest close packed Less Open packed High void

void volume Sufficient volume Insufficient
vehicle Low consistency vehicle High
consistency
This leads particles to move relative to one another at low rate of shear.

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 So therefore, dilatant suspension can be poured from bottle because in

these
condition it is fluid.
 When stress is increased, the particles shows the open packing and bulk of
system (void volume is increase) is increased.
 But the amount of vehicle is insufficient to fill this void space.
 Thus particles are not wetted or lubricated and develop resistance to flow.
 Finally system show the paste like consistency.

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 Because of this type of behavior, the dilatant suspension can be

process by high speed mixers, blenders or mills.

The exponential equation shows this flow

FN = η G
N = no. of given exponent
η = Viscosity coefficient

In which N < 1, and decrease as the dilatancy increase.

If N = 1, the system is Newtonian flow

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THIXOTROPHY (GEL-SOL-GEL)

It is defined as, isothermal and comparatively slow recovery on standing of

material of a consistency lost through shearing.

It is shear thinning system, when agitated and kept aside it is expected to

return its original state of fluidity, but takes longer time to recover
compared to the time taken for agitation.

Thixotropic behavior can be shown by plastic and pseudo plastic system.

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THIXOTROPHY CONCEPT (PARTICLE – PARTICLE

INTERACTIONS) (GEL – SOL – GEL TRANSFORMATION)

Multi point contacts

At rest Gel state
( On storage) (High consistency
or high viscosity)
Rapid
process
On shear Contacts break down
(equilibrium) (low consistency Sol state
or low viscosity)
slow process
Set aside
(removal of Particle contacts formGel state
stress)
due to brownian motion
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The Rheogram of thixotropic material depends on:

 Rate at which shear increased or decreased.

 Length of time during which sample is subjected to any one rate

of shear.

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 From the graph up curve ab is
obtained, up to maximum point b.
The thixotrophy phenomena can be
If the rate of shear is reduced,
observed by constructing
consistency curves. then down curve bc is obtained.
 In Non-Newtonian system,
Pseudo plastic
system b the
down curve is displaced to left of
Rate of shear, G

the up curve.
In this graph, the material has
Plastic
low consistency at any rate of shear
c
system on down curve compared to that
a
Shear stress, F
shown on up curve.

InNewtonian system, down curve

superimposed to up curve.
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ANTI-THIXOTROPHY (-VE
THIXOTROPHY)
Anti-thixotrophy represents an increase in consistency (high viscosity)

The increasein thickness or resistance to

flow with increasetime of shear observed for (magnesia
magma).

Anti – thixotrophy is flocculated system containing low solid content ( 1 – 10

%).

Dilatancy system is deflocculated system containing solid content ( > 50 %).

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Individual particles
(in large no. Of small flocs)
At rest
(Low viscosity)
( On storage)

Particle collision &

On shear contacts are more Sol state
(equilibrium) (Large flocs in small no.)
( High viscosity)

Set aside Flocs contacts break

(removal of individual particles
stress) (Low viscosity)
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THE ANTI - 2 1-Fe b -16
From the Rheogra m i t is
THIXOTROPHY observed
PHENOMENA CAN that,
BE SHOWN BY  When Magnesia
alternatively magma
sheared was
at sing
MAGNESIA MAGMA
and sing rate of shear, magma
got thick continuously.
Finally, reach the equilibrium
Rate of shear, G

A B C
D
state in which, further cycling
of sing and sing rate of shear
no
longer sing consistency
of material.
Shear stress, F Equilibrium state where gel was

found.
UP
curve When allow to stand, material
Down return to sol like property.
curve
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RHEOPEXY

Rheopexy is phenomena in which a sol forms a gel more readily

when shaken or sheared than when allow to form the gel while the
material is kept at rest.

e.g. Magnesia magma, Clay suspension

In rheopectic system, the gel is the equilibrium state.

In anti – thixotropic system, the sol is the equilibrium state.

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