Chapter seven

Rheology
By Dinberu B (B Pharm, Msc Pharmacology)

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 Objectives

At the end of this lesson you will be able to:

 define rheology

 differentiate newtonian and non-newtonian systems.

 determine thixotropy.

 differentiate factors affecting rheology

 determine viscosity

 apply rheology in pharmaceutical area

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 Introduction
• Rheology (Greek words), rheo ‘to flow’ and logos
‘science’.
• Defined as the science concerned with the flow of
matter under the influence of shearing stress.
• The flow of fluids (liquids and gases) and the
deformation of solids under the influence of shearing
stress.
– Shearing stress: when the stress is applied
tangentially to the surface of a body.
– Shear deformation: is a measure of the samples
deformation (strain)
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 Introduction….
– Deformation describes the change of matter in terms of shape or
volume, or both.
– If the changes due to deformation are at least partly nonreversible,
then matter flows
• The deformation of any pharmaceutical system can be arbitrarily
divided into two types:
• Elastic Deformation: it is a spontaneous and reversible
deformation.
• The work spent for the deformation is recoverable when the
body returns to its original position
• Plastic deformation: it is a permanent or irreversible
deformation.
• The work spent for the deformation is dissipated as heat.
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 Introduction…
• plastic deformation: promotes flow and exhibited by
viscous bodies.
➢ Great importance in any liquid dosage forms like suspensions,
solutions, emulsions, etc.

• Ideal solids deform elastically

✓ The energy required for the deformation is fully recovered
when the stresses are removed.
• Ideal fluids such as liquids and gases deform
irreversibly, then they flow.

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 Recoverable vs permanent deformations
The deformation is recoverable if the Deformation is permanent if the
material returns to its initial shape material remains deformed
when the stress is removed. when the stress is removed.

While elastic deformation is recoverable, plastic deformations are not.

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 Types of materials based on flow

❖ Materials are classified into two general types

depending upon their flow properties:
✓ Newtonian
✓ Non-Newtonian
❖ The flow of liquids or semisolids is described by
viscosity.

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 Newtonian fluids: Viscosity

A fluid’s internal resistance to flow

and may be thought of as a
measure of fluid friction.

Measure of the resistance of

Viscosity liquid to deformation under
shear stress.

The resistance offered when one

part of the liquid flows past
another.
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 Newtonian fluids: Viscosity…
• The phenomenon of viscosity is best understood by a
consideration of a hypothetical cube of fluid made up of
infinitely thin layers (laminae) which are able to slide
over one another like a pack of playing cards.

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 Newtonian fluids: Viscosity…
• The bottom layer is considered to be fixed in place.

– The adhesive force b/n the wall and the flowing layers

is inter-molecular cohesive forces

• This inter-molecular force (viscous forces): viscosity

– Viscosity is the opposing force to flow, it is

characteristic of the medium.

– In other words, viscosity describes the internal friction

of a moving fluid.

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 Newtonian fluids: Viscosity…

• Shear rate
• The rate of change of velocity at w/c one layer of
fluid passes over an adjacent layer.
• As an example, consider that a fluid is placed b/n
two parallel plates that are 1.0 cm apart, the upper
plate moving at a velocity of 1.0 cm/sec and the
lower plate fixed

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 Newtonian fluids: Viscosity…

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 Newtonian fluids: Viscosity…

• When a tangential force is applied to the uppermost

layer
– Each subsequent layer will move at progressively
decreasing velocity that the bottom layer will be
stationary.
• A velocity gradient will therefore exist,
– equals to the velocity (ms-1 ) of the upper layer /
the h (m) of the cube.

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 Newtonian fluids: Viscosity…

❖ The d/ce in velocity (dv) b/n two planes of a liquid

separated by an infinitesimal distance (dx) is the velocity
gradient or a rate of shear (dv/dx or G).

Shear rate (G) = dv/ dx

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 Newtonian fluids: Viscosity…
• The force required for one layer of a liquid to slip past
over another layer with a given velocity depends
– Directly on the viscosity of the liquid and on the areas
of layers exposed to each other and
– Inversely on the distance separating the two surfaces.
• A fluid with high viscosity resists motion
– b/c its molecular makeup gives it a lot of internal friction when it
is in motion.

• A fluid with low viscosity flows easily because its molecular

makeup results in very little friction when it is in motion.
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 Newtonian fluids: Viscosity…

❖ The force per unit area (F/A) needed to bring about this
flow is known as the shearing stress, S.

Shear stress (S) = F/ A

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 Newtonian fluids: Viscosity…
• Newton recognized that: the higher the viscosity of a
liquid, the greater the force per unit area required to
produce a certain rate of shear.
• Thus, the rate of shear is  to the shearing stress
Newtonian law
Absolute viscosity

F ' dv F' dv F'

 = =
dv
A S Shearing Stress
= =
A dr A dr G Rate of Shear
dr
❖ Where (eta) is a constant known as coefficient of
viscosity, usually referred to simply as viscosity or
absolute viscosity.
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 Newtonian fluids: Viscosity…
• Where,
– S is the shearing stress ([Link]−2)
– G is the rate of shear (sec−1)
• Units: dynes-sec/cm 2 or poise
• SI unit: N-sec/m2
• 1 N-sec/m2 = 10 poise

• 1 poise is defined as the F required to produce a velocity

difference of 1 cm/sec between two parallel layers of
liquids of 1cm2 area each and separated by 1 cm distance.
• Viscosity of water is 1 centipoise(0.01 poise) at 20 oC 1 poise=100
centi poise
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 Newtonian fluids
Liquids that obey Newton’s law of flow: Newtonian liquids
• Newton’s equation for the flow of a liquid is:

S=η*G
• Plot of shear stress Vs shear rate: the slope gives the
viscosity.
– The curve always passes through the origin
• The reciprocal of viscosity is called fluidity:

1/η = Slope
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 Characteristics of Newtonian flow

• The passage through the origin indicates that even a mild

force can induce flow in these systems.
• The linear nature of the curve shows that the viscosity (η)
of a Newtonian liquid is a constant unaffected by the
value of the rate of shear.
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 Newtonian fluids…
• 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.
• Examples of Newtonian fluids include:
– Water
– Air
– Glycerin and most mineral oil
– True solutions
– Very dilute suspension and emulsions
– Liquid paraffin

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 Non-Newtonian fluid

• Substances that fail to follow the Newtonian equation of

flow.
• The viscosities of non-Newtonian fluids vary with shear rate.
• The viscosity of such fluids will therefore change as the shear rate is
varied.
• Apparent viscosity mean the viscosity keeps on changing.
• But in the case of Newtonian fluid the viscosities is constant
with varied shear rate

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 Non-Newtonian fluid

• The relationship b/n shear stress and the shear rate is not
linear and the curve starts from origin.
• The substance initially behaves like an elastic body and fails
to flow when less amount of stress is applied.
• Further increase in the stress leads to a nonlinear increase
in the shear rate which then turns to linearity.
• Resistance to flow (viscosity) increases with increase in shear
stress.

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 Cont’d

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 Non-Newtonian fluid

– Examples of Non-Newtonian fluid

– Solid powder materials
– Topical ointments
– Pastes

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 Thixotropy

Non-Newtonian, Time Dependent behavior

• Definition: Thixotropy is the decrease in viscosity as a

function of time upon shearing, then recovery of original
viscosity as a function of time without shearing.

• It is characteristics feature of pseudo-plastic flow.

• Defined as the isothermal slow reversible conversion of gel

to solution.

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 Thixotropy…

• Thixotropic substances on applying shear stress convert to fluid and

on standing they slowly turn to gel (semisolid).
• Macromolecules which are capable of interacting by numerous secondary
bonds to produce a loose three-dimensional structure, so that the material
is gel-like when unsheared

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 Cont’d

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• Thixotropic systems contain asymmetric particles which
set up a loose three dimensional structure which is rigid
and resembles a gel which is broken down on applying
shear:---→ Solution
• On removing the applied stress, the material reform its
original structure of state:-→ Gel

Solution

Gel
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 Reason for thixotropic…

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 Thixotropy…
• Rheogram : show a hysteresis where, as the S is increased
an up-curve is obtained, on reducing the S gradually, a
down curve shifted to the left side is obtained.

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 Thixotropy…

• Rheogram of thixotropic materials depends on:

– Applied shearing force.
– The length of the time a sample is subjected to
shearing

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 Thixotropy…

• Thixotropic substances are now a day’s more used in

suspensions to give stable suspensions.

– On storage turn to gel: viscosity increases infinitely, do

not allow the dispersed particles to settle down
– stable suspension.

– When shear stress is applied they turn to solution and

thus are easy to pour and measure for dosing.
– Solve the problems of stability and pourability.
– Stable suspension should sediment slowly and
redisperse rapidly dinberub1980@[Link]
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 Thixotropy…

• Examples of gels that show thixotropic flow include

– aluminum hydroxide gel and bentonite magma.

– Paints are also another example of thixotropic fluids.

• When modern paints are applied, the shear created by the

brush or roller will allow them to thin and wet out the
surface evenly.

• Once applied the paints regain their higher viscosity which

avoids drips and runs.

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 Irreversible Thixotropy

• Application of F causes breakdown of structure within the

system but

– The structure does not reform on removal of the F, or

– The time lag is so long that from a practical point of

view the effect is irreversible.
• Example: gels produced from higher [Link] polysaccharides

- b/c which are stabilized by large number of secondary bonds

eg yoghurt, it becomes thinner when stirred.

does not returns to its original thickness. So it does not exhibit thixotropic
flow behavior
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 Irreversible Thixotropy….

– On application of high shear,

– The 3D structure of the polysaccharides is

reduced to a 2D one and

• The original gel-like structure is never

recovered

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 Negative thixotropic
• Deflocculated suspensions of a solid content of less than 10%

shows,

– increase in viscosity through shearing are termed as anti thixotropy

• Example: magnesium magma and milk of magnesium

• Antithixotropy

– result from increased collision frequency of the dispersed

particles in suspensions
• which results in an increased inter-particle bonding with time.

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 Negative thixotropic…

• This changes the original state of the system from a network

of a large number of individual particles and small floccules
to an equilibrium state consisting of a small number of
relatively large floccules

• Which helps the dispersed particles to acquire a random

orientation and the network is established: Gel

❑ Antithixotropic systems have low solid content(1-10%) and

are flocculated

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 Negative thixotropic…

➢ Antithixotropy is essentially the opposite of thixotropy, in that

the fluid’s viscosity ↑ with time as it is sheared at a constant rate

➢ The gentle rolling or 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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• Rheopexy(Antithixotropy, negative thixotropy)

• is the continuum mechanics that is rare property of some

non Newtonian fluids to show time dependent increase in
viscosity, the longer the fluid undergoes shearing force,
the higher its viscosity.

• Substances with low melting point shows rheopectic

property.
• Rheopectic fluids are rarely encountered

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 Cont’d

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 Measurement of Viscosity
• Different equipments called viscometers are used to measure
viscosity of d/t fluids and semisolids.

• Successful determination of viscosity depends on the choice of

the correct instrument.

– For a Newtonian system;

• Instruments that operate at a single rate of shear such as

capillary viscometers can be used.

– For non-Newtonian systems

• Multi-point instruments that can operate at different rates

of shear are required.
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 Ostwald Viscometer

• It is a type of capillary viscometer

• This is ‘U’ shape tube with two bulbs and two marks

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 Ostwald Viscometer…
• It is used to determine the viscosity of Newtonian liquids

❖ Principle:
• When a liquid flows by gravity, the time required for the
liquid to pass b/n two marks, upper mark and lower mark,
through a vertical capillary tube is determined.
• The time of flow of the liquid under test is compared with
the time required for a liquid of known viscosity (usually
water).

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 Ostwald Viscometer…

 The viscosity of unknown liquid η1 can be determined

using the equation
1t1
1 = 2
 2t 2
ρ1= Density of unknown liquid
ρ2= Density of known liquid
t 1= Time of the unknown liquid
t 2= Time of the known liquid
η 2= Viscosity of known liquid
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 Falling Sphere Viscometer
• Consists of cylindrical transparent tube having graduated
section near the middle of its length and generally a steel
ball that is allowed to fall through the tube.

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 Falling Sphere Viscometer…

• The tube is filled with the liquid whose viscosity is to be

determined and the ball is allowed to fall.
• The velocity of the falling ball is measured and viscosity is
calculated using stoke’s law.

d (  s − l ) g
2
=
18V
where d= Diameter of the falling ball; ρ s =Density of the sphere;
ρ l=Density of liquid; g= Gravitational acceleration; v = Terminal settling
velocity

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 Falling Sphere Viscometer….

• As d2g/18 is constant, can be replaced by another

constant ‘K' Therefore, the equation will be:
K ( s − l )
=
V

• Stoke’s law states that when a body falls through a

viscous medium, it experiences a resistance which
opposes the motion of the body

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 Factors affecting rheological properties

Chemical factors

Extent of Polymer Hydration

• In hydrophilic polymer solution, the molecules are

regarded as completely surrounded by immobilized water
molecules forming a solvent layer.

• Such hydration of hydrophilic polymers gives rise to an

increased viscosity.

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 Factors affecting rheological…

Impurities, Trace Ions and Electrolytes

• Chemical impurities are the major factors in changing
the viscosity of natural polymers.
• At high conc. compete for adsorbed water
molecules surrounding the hydrated polymer
the polymer become dehydrated the
viscosity of the dispersion decreased finally
precipitation occurs.

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 Factors affecting rheological…

Physical factor

Temperature

• As temperature increase usually produces rapid decrease

in viscosity.

• Prolonged heating may produce drastic decrease in

viscosity due to decomposition of the polymer.

e.g., gelatin

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 Factors affecting rheological….

Concentration

• In concentrated suspensions: a decrease in particle size

or an increase in the surface area of the solid phase
produce an increase in the viscosity of the system.

– This is due to immobilization of the vehicle with an

increase in the fraction of the suspension volume
occupied by the solid.

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Pharmaceutical applications of rheology
1. Fluids
• Mixing
• Particle size reduction of dispersed systems with
shear.
• Passage through orifices, including pouring,
package in bottles, and passage through
hypodermic needles.
• Fluid transfer, including pumping and flow
through pumps.
• Physical stability of disperse systems.

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 Pharmaceutical applications…
2. semisolids
- Spreading and adherence on the skin
- Removals from jars or extrusion from tubes
- Release of drug(API) from base
3. Solids
- Flow of powders from hoppers and into die cavities
in tableting or into capsules during encapsulation.
- Packagability of powdered or granular solids
4. Processing
- Production capacity of the equipment
- Processing efficiency

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 Pharmaceutical applications…

1- Prolongation of Drug Action:

• The rate of absorption of an ordinary suspension

differs from thixotropic suspension.

• Example: procaine penicillin G, a form of penicillin, of

relatively low water solubility.
– Aqueous suspensions containing b/n 40 and 70% w/v of milled or
micronized procaine penicillin G + small amount of sodium
citrate & polysorbate 80 are thixotropic pastes & are of depot
effect when injected intramuscularly.

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 Ordinary suspension of Thixotropy suspension of
pencillin G pencillin G

I.M injection

Forms spherical deposits at site of

Forms no depot, fast dispersion injection which resists disintegration
& by tissue fluids& Small surface area
absorption so maintain therapeutic ( absorption) so maintain
Level for short time
Therapeutic Level for longer time

The formation of depot depends on:

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 )2( Effect on Drug Absorption:

• The viscosity of creams and lotions may affect the rate

of absorption of the products by the skin.

• A greater release of active ingredients is generally

possible from the softer, less viscous bases.

• The viscosity of semi-solid products may affect

absorption of these topical products due to the effect
of viscosity on the rate of diffusion of the active
ingredients.

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(3) Thixotropy in Suspension and Emulsion
Formulation:
• Thixotropy is useful in the formulation of pharmaceutical
suspensions and emulsions.
• They must be poured easily from containers (low viscosity)
• Disadvantages of Low viscosity:
– Rapid settling of solid particles in suspensions and rapid
creaming of emulsions.
– Solid particles, which have settled out stick together, producing
sediment difficult to redisperse ("caking or claying").
– Creaming in emulsions is a first step towards coalescence.
(break down of emulsion)

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 Thank you

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