Chapter seven

Rheology

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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 arena

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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.
– Tensile stress: when the stress is applied perpendicular to the
surface of the body.
– 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….
• The deformation of any pharmaceutical system can be
arbitrarily divided into two types:
• Elastic Deformation: it is a spontaneous and
reversible deformation.
• Plastic deformation: it is a permanent or
irreversible deformation.
• Plastic deformation: promotes flow and exhibited by
viscous bodies.
 Great importance in any liquid dosage forms like
suspensions, solutions, emulsions, etc.
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 Introduction…

• 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.
• The energy required for the deformation is dissipated
within the fluid in the form of heat and cannot be
recovered simply by removing the stresses.

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

Viscosity of 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 between the wall and the flowing

layers.
– 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…

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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 difference 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 because its
molecular makeup gives it a lot of internal 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 Aabsolute viscosity

F ' dv F' dv F'

S Shearing Stress
  
dv
A  
A dr A dr dr
G Rate of Shear

 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.

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 Newtonian fluids: Kinematic
Viscosity
• It is the absolute viscosity divided by the density of
liquid at a specified temperature.

KV  η
ρ
• The preferred unit when the shear stress and shear
rate of the fluid are influenced by the density is:
 Stock (s) or centistokes

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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

 A non-Newtonian fluid is defined as one for which

the relationship between F’ and S is not a constant.
• In other words, Substances that fail to follow the
Newtonian equation of flow.
• The viscosities of non-Newtonian fluids vary with
shear rate.
– stating a single viscosity is misleading : apparent
viscosity

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 Non-Newtonian fluids…

• It can be seen in liquid and solid heterogeneous

dispersions such as colloids, emulsions, liquid
suspensions and ointments.
• Three classes:
Plastic flow
Pseudo-plastic flow
Dilatant flow

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 Plastic flow (Bingham bodies)

• A plastic material does not flow until a certain

minimum shearing stress, the yield value, is
applied.
• 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.

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 Plastic flow…

• The slope of the

rheogram is termed
mobility, analogous to
fluidity in Newtonian
systems and its
reciprocal is known as
the Plastic viscosity, U

F  f
U 
G
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 Plastic flow…

• Extrapolations of the linear plot gives ‘x’ intersect:

yield value
– This curve does not pass through the origin
– Intersects the shear stress axis at a particular
point, yield value
– As the curve above yield value tends to be
straight, the plastic flow is similar to the
Newtonian flow above yield value.

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 Flocculated Suspension: Mechanism of
Plastic Flow
 Flocculated particles in a concentrated suspensions
usually show plastic flow.

Shear

09/23/2025 Rheology 27
 Plastic flow…

• The yield value represents the stress required to

break the inter-particular contacts so that
particles behave individually.
• Thus, it is indicative of the forces of
flocculation
 increased by the increased concentration

of the dispersed phase.

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 Plastic flow…

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 Plastic flow…
• Other examples of plastic flow:
– Solid powder materials
– Topical ointments
– Pastes
• Powder materials that are compressed easily
have low yield point (highly compressible at
minimum shear stress).
• Materials with low yield value compressed easily
so this materials can be used as a binder.
• Granulation of powder materials causes increased
compressibility due to porosity and lowering of
yield value.
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 Pseudo-plastic Flow (shear-
•
thinning)
The relationship between shear stress and the shear
rate is not linear and the curve starts from origin.
• The viscosity of these liquids can not be expressed
by a single value.
• Pseudo plastic flow is exhibited by polymer
dispersions like:
– Tragacanth in water
– Sodium alginate in water
– Methyl cellulose in water
– Sodium carboxy methyl cellulose in water
• Most of Cream (o/w or w/o), gellies and semisolids
lotion
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 Pseudo-plastic Flow…
• The viscosity of a pseudo-
plastic substance
decreases with increasing
G (shear-thinning systems)

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Pseudo-plastic flow behavior; Structural
reasons
• At rest, the linear polymers dispersed at random in
the dispersion medium.
• As shearing stress is applied, the macromolecules
become aligned with the long axis parallel to the
direction of flow.
• With this ordered alignment the molecules pass one
another with less frictional resistance, and the
viscosity is decreased.

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Pseudo-plastic Flow…

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Pseudo-plastic Flow…

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 Pseudo-plastic Flow…

• If the S is decreased, the orientation of the

macromolecules becomes more random.
• Greater frictional resistance to the flow is reflected
in an increased viscosity.
• Since only a molecular alignment is involved: no
lag time.
• E.g. Emulsions and dispersions of many types:
shear-thinning.

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 Dilatant Flow

• Resistance to flow (viscosity) increases with increase

in shear stress.
– When S is applied their volume increases and hence, they are
called Dilatant.
– This property is also known as shear thickening.

• Dilatant flow is observed in suspensions containing

more than 50% W/V of solids, deflocculated
particles.
– Deflocculated with less than or equal to 5% or 10% shows
psudo-plastic flow.
– Suspending agent such as hydrophillic colloids like
bentonite, magnisium almunium silicate shows dilatant flow.
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 Dilatant Flow…

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 Dilatant Flow…
• At rest, the particles are closely packed with a
minimum inter-particle volume, or voids.
• The vehicle is sufficient to fill this volume.
• As the shear stress is increased, the bulk of the
system expands or dilates.
 Increase in the inter-particle void volume
 Vehicle become insufficient to fill the increased voids.
 The resistance to flow increases: This process is
reversible.

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 Dilatant Flow…

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 Summary of time independent
flows

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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 sol (fluid) and on standing they slowly
turn to gel (semisolid).

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 Reason for thixotropic property
• 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

Solutio
n

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.

09/23/2025 Rheology 46
 Thixotropy…
• Rheogram of
thixotropic materials
depends on:
– Applied shear rate or
shearing force.
– The length of the
time a sample is
subjected to
shearing or
kinematic history.
 The previous history of the sample has significant
effect on the rheologic properties of a thixotropic
system.

09/23/2025 Rheology 47
 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.

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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

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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
• Antithixotropy is believed to result from an increased collision

frequency of the dispersed particles in suspensions which results in

an increased inter-particle bonding with time.

• 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: solution

 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…

• At rest the large floccules break up and gradually

return to the original state of small floccules and
individual particles
viscosity decreases: Solution

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 Rheopexy

• Rheopexy is the conversion of solids to gel up on

application of shearing stress.
• Substances with low melting point shows rheopectic
property.
• Example: polymers with low melting point
• Rheopectic fluids are rarely encountered
• Are time-dependent dilatant behavior.

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 Measurement of Viscosity
• Different equipments called viscometers are used to
measure viscosity of different 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

09/23/2025 Rheology 56
 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 between 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

 1 t1
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.

09/23/2025 Rheology 59
 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 2 (  s  l ) g

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
09/23/2025 Rheology 60
 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
• A temperature increase usually produces a rapid
viscosity decrease.
• 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.

09/23/2025 Rheology 66
 Pharmaceutical applications…
2. Quasisolids (semisolids)
- Spreading and adherence on the skin
- Removals from jars or extrusion from tubes
- Release of drug 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
09/23/2025 - Processing efficiency
Rheology 67
 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 between 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
bsorption so maintain therapeutic so maintain )absorption (
Level for short time
Therapeutic Level for longer time

:The formation of depot depends on

a- high yield value
09/23/2025 .b-fast thixotropic recovery
Rheology after injection 69
 (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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• A thixotropic agent such as sodium bentonite
magma, colloidal silicon dioxide, is incorporated
into the suspensions or emulsions to confer a
high apparent viscosity or even a yield value .

• The agitation breaks down the thixotropic

structure so reducing the yield value to zero &
lowering the apparent viscosity. This facilitates
pouring.

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 Thank you

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