RHEOLOGY

PRASHANT PANDEY
M.Pharm (Pharmaceutics)
CONTENTS :
 Introduction
 Importance of Rheology
 Types of Rheological systems
 Thixotropy
 Measurement of thixotropy
 Rheopexy
 Measurement of viscosity by different types of viscometers.
 INTRODUCTION
 The term rheology was derived from two Greek words namely rheo
(to flow) and logos(science) was suggested by BINGHAM
 Rheology is the science that deals with deformation of matter under
the influences of stresses.
 Rheology describes the flow of liquids and deformation of solids.
 Viscosity is defined as frictional force(F) exerted unit area(A)
between successive layers of liquid and seperated by unit
distance(dx) possessing variable velocity(dv)
Fα A.dv/dx
F=η A dv/dx
η=F/A . dv/dx
 Reciprocal of Viscosity called Fluidity .
 viscometer is an instrument used to measure viscosity.
viscosity which vary with flow conditions, an
instrument called Rheometer is used.
 Viscosity play major role in pouring from the bottles,
extrusion from tubes, passage through syringe needle
 Units of viscosity is
 Kinematic viscosity is defined as viscosity/density
(η/ρ)
 Units : stoke and centistokes.
 Ex : lotions having viscosity - 300 cp
paste or ointments viscosity – 1200 poise
IMPORTANCE OF RHEOLOGY :
 Rheological properties like viscosity are more
important in liquid solutions, dilute and concentrated
colloidal systems.
 They are important in manufacturing of emulsions,
suppositories, paste, tablet coating.
 Rheology is involved in mixing and flow of materials
their packing into containers and their removal prior
to use.
 Rheology is important in ink industries, paint
industries, road welding materials, manufacturing of
cosmetics and dairy materials.
• Viscosity plays a major role in pouring from the bottle,
extrusion from the tube, passage through the syringe nee
RELATION BETWEEN SHEAR STRESS
AND RATE OF SHEAR
 SHEAR STRESS: It is defined as unit force require to
induce unit area

 RATE OF SHEAR: It is the change in velocity with

respect to change in time.
G=dv/dx
 The relation between the F&G is

F
Types of Rheological systems:
 It broadly classified into two types:
1. Newtonian system
2. Non Newtonian system

Newtonian Flow Of System:

 Liquid that obeys the newtons law of flow called
Newtonian fluids.
 The system which follows a linearity relationship
are called Newtonian fluids
 Ex: water, glycerin, chloroform, solutions of syrup
and very dilute colloidal solutions.
Shear stress-shear rate relationship
for Newtonian flow

G slope= fluidity
Rate of
shear

shear stress F
Non Newtonian flow of system:

 The substance which does not follow Newton's law are

said to be Non Newtonian flow system.
 Generally they analyzed in rational viscometer

 This is classified into three types:

1. Plastic flow
2. Pseudo plastic flow
3. Dilatent flow
 PLASTIC FLOW :

 The material which exhibit plastic flow is called BINGHAM BODIES

 A plastic body behaves as elastic bodies and fails to flow when less
amount of stress is applied, after increases the shear stress leads to
non linear increase in shear rate which progressively get linearised, it
gives yield value(f)
 Therefore plastic flow resembles to Newtonian flow above yield value
 Plastic flow express in terms of yield value
Slope of plastic flow gives mobility of particular system or fluidity
Reciprocal of fluidity will give about plastic viscosity(U)

Ex: Floculated particles in concentrated suspensions, ointments,

pastes, gels
 PSEUDO PLASTIC FLOW :
 As the shear stress increase progressively, shear rate also
increases, viscosity of pseudo plastic material decreases. and
curve is not linear
 Viscosity of pseudo plastic system cannot be expressed by
single value
 The consistency curve for pseudo plastic material begins at
the origin. there fore no yield value like plastic system,
because no part of curve is linear
 Ex; system containing natural and synthetic gums.
system containing dispersing agents like tragacanth,methyl
cellulose,sodium cmc.
 It is exponentially given by
where N= 1 system ready to flow
N>1 MORE PSEUDO PLASTIC
N<1 DILATANT FLOW SYSTEM

N log F = log η + log G

logη = N log F –log G
 All thixotropic system may claimed as- pseudo plastic system
But all pseudo plastic systems are not –thexotropic system
 It is also called shear thinning system
DILATANT FLOW:
 It is also called shear thickening system
 The system exhibit enhance resistant to flow with increasing rate of
shear
 Actually increasing in volume when sheared hence termed as dilatant
system
 The flow is inverse to pseudo plastic flow
 Ex: starch powder in water, Concentrated deflocculated suspension
 Here, the molecules are not completely wetted by the solvent as the
stress applied the bulk of system expand or dilate. If shear stress is
removed, the dilatent system returns to its original state of fluidity
This equation can be used to describe dilatancy in this case
N is always less than 1 and decreases as degree of dilatency
increases as an N approaches 1 the system becomes increasingly
Newtonian in behavior
THIXOTROPY
• It is an isothermal and comparatively slow recovery on standing
of material, of a consistency loss through shearing
• Assume that rate of shearing was reduced, in Newtonian
flow the down curve would be identical with super imposable up
curve but in non Newtonian flow down curve, will displaces
relatively the up curve
 In pseudo plastic system the down curve is displaced to the left
of up curve showing that the material has a lower consistency,
this indicates the break down of structure that does not reform
immediately even when stress is removed
 This phenomenon is said to be thixotrophy
 Ex: gel-sol-gel
sol-gel-sol
 . This process is not instantaneous rather it is progressive
restoration of consistency as asymmetric particles come into
contact with one another by under going random Brownian
moment
NEGATIVE THIXOTROPY :
The increase in thickness of the resistance to flow with
increased time of shear is said to be negative thixotrophy.
 Ex: rheological analysis of magnesia magma, clay
 In this rheogram the down curve shifts to right side of up
curve
BULGES
 Ex:Conc.aqueous magma of bentonite.
 It produces hysteresis loop
SPURS

 A sharp point of structural breakdown at low

shear rate in up curve called spur value.
• Ex: procaine penicillin gel
 MEASUREMENT OF THIXOTROPHY

At single rate of shear

 The structural break down
with respective time at
constant rate of shear .
 Thixotropic coefficient
B=(U1-U2)/ln (t2/t1)
 At a different rates of shear
 The structural breakdown with respect to time having
different shear rates. In this plastic viscosities (U1&U2)
having shear rates of (V1&V2)

 Thixotropic coefficient M=2(U1-U2)/ln (v2/v1)2

RHEOPEXY
 The phenomenon in which sol transforms into gel state more
readily
 The time period to regain its original viscosity may be
reduced by applying rolling and tumbling motion.
 It is two types
 positive rheopexy
 Negative rheopexy
INSTRUMENTATION

viscometer

Single point Multi point

viscometer viscometer

capillary viscometer Cup and bob viscometer

Falling sphere Cone and plate
viscometer viscometer
 Ostwald’s viscometer
 It follows poiseuille’s law

• It is also called
capillary visco meter
 Principle;-viscosity of unknown liquid determined by
equation.
η1 = ρ1t1/ρ2t2 .η2
η=k’ t1 ρ1

Applications
 Used for formulation and evaluation of dispersion system
such as colloids , suspensions , emulsions.
 Study of flow of liquids through capillary tube throw light
upon the circulation of blood
FALLING SPHERE VISCOMETER
• It follow’s stroke’s law.
• The instrument can be used over a range of 0.5 to
200000 poise.
• Viscosity drag on sphear = force responsible for
downward moment due to gravity.

• The viscosity of Newtonian liquid calculated by

η = t ( Sb- Sf) B
ROTATIONAL VISCOMETERS
ADVANTAGES
 It is possible to vary the shear rates over a wide range of
values.
 Measurement can be made continuously for extended period
at given shear rate.
 Viscosity of non Newtonian system exhibited by this at with
accurate temperature control
 Examples:
 cup and bob
 cone and plate
CUP AND BOB VISCOMETER
 This is Multi point viscometer.
• Couette type : cup rotate –Mac Michael viscometer
Searle type : Bob rotate - stormer viscometer.
• For systems of viscosity more than 20 centi poise
• A rheogram obtained by plotting Rpm vs wt,added
• Viscosity of pseudo plastic system calculated by
η = kv w/v
• Viscosity of plastic system calculate by
U= kv w-wf/v
• Yield value of Bingham body expression
f = kf.wf
CUP AND BOB VISCOMETER
DIS ADVANTAGES
 No uniform rate of shear.
 Frictional heating may developed at high rate of shear
 Cleaning is difficult.
 Plug flow development
minimized by – decreasing gap between cup and bob
Increasing the shear rate.
CONE AND PLATE VISCOMETER
 The cone to plate angle is less than
10 centigrade
 sample required is small 0.1 to 0.2 ml
 Principle:
pseudo plastic Viscosity estimated by
η = C. T/v
plastic viscosity estimated by
U = T –T f/v.
CONE AND PLATE VISCOMETER
ADVANTAGES
 Rate of shear is constant,no chance for plug flow.
 Temperature stabilization is good.
 It needs to vary little samples for the study
sample volume of 0.1 to 0.2 ml
• Valuble aid for det.of hysteresis loops obtained in
thixotropic system,and det. The thixotropic coefficient.
RHEOLOGY OF SUSPENTIONS
 The flow property of suspension depend upon their
rheological characters
 The rheological properties of suspension decide the
pourability, easy of injection, sedimentation, its
redispersibility.
 The viscosity of flocculated suspension greater than
deflocculated particles in same suspension.
 The flocculated suspension has yield value and behave like a
plastic or pseudo plastic system.
 Example: conc.parenteral suspension contain 40- 70 % w/v
of procain pencillin G
RHEOLOGY OF EMULSIONS
 Dilute emulsions shows Newtonian type flow
Highly conc.emulsions and creams shows plastic flow.

The important properties influencing the emulsions :

 Aggregation of particles
 Viscosity of continuous phase
 Globule size and size distribution
 Nature and proportion of emulsifying agent
RHEOLOGY OF OINTMENTS AND CREAMS
 Ointments and creams show plastic and thixotropic
behaviour.
 Determination of rheological behavior and thixotropic
coefficient of a standard preparation compare with
subsequent batches serves as guide for quality control
measurement, for stability, spreadability ,performance
and elegance of the preparation