By pharmacist Muhanad S.

Al Ani
The term rheology from the Greek rheo ( to
flow ) and logos ( science ) was suggested
to describe the flow of liquids and the
deformation of solids.
The importance of rheology in pharmacy
and its’ applications :
1.  Rheology is important for the formulation
and analysis of pharmaceutical products
as emulsions, suppositories, cosmetic
creams, lotions and tablet coatings.
2.  Rheology is involved in the mixing and
flow of materials, their packaging into
containers and their removal prior to use,
whether this is achieved by pouring from
bottle, extrusion from a tube or passage
through a syringe needle.
 Viscosity : is an expression of the resistance of a
fluid to flow, the higher the viscosity the greater
the resistance to flow.
FACTORS INFLUENCING THE VISCOSITY
Intrinsic Factors
1. Molecular size or molecular weight: the heavier the
molecule of the given liquid, the greater will be the
viscosity.
2. Shape: Liquids with large and irregularly shaped molecules
are generally known to be viscous compared to small and
symmetric molecules.
3. intermolecular forces : as the intermolecular interactions are
stronger the molecules tend to stick to each other thereby
increasing the viscosity of the liquid. The higher the
intermolecular forces, the higher is the viscosity.
Extrinsic Factors
1.  Pressure: An increase in pressure enhances the
cohesive forces of interaction leading to an
increase in the viscosity.
2. Added substances: In general, small
quantities of non electrolytes like sucrose, glycerin
and alcohol when added to the water, the solution
exhibits increased viscosity. Similarly, polymers
and other macromolecules enhance the viscosity
of solvents such as water. On the other hand,
small amounts of strong electrolytes decrease the
viscosity.
 3.Temperature :
As the temperature increases, the system acquires

thermal energy which facilitates the breaking of the

cohesive forces. The viscosity of liquid decreases. In case

of gases, an increase in temperature increases the

viscosity owing to the increased molecular collisions and

interactions .
The unit of viscosity is the Poise : which is
the shearing force required to produce a
velocity of 1cm/sec between two parallel
planes of liquid each 1 cm² in area
separated by a distance of 1 cm.
Centipoise (cp) = 0.01 poise
Fluidity (Φ) : is the reciprocal of the viscosity
1
Φ= η
Substances, such as hydrocolloids and polymers,
are dispersed in water and utilised as vehicles in
the formulation of several dosage forms. These
substances are termed as suspending agents or
bodying agents. Such as methylcellulose and
bentonite.
Substances, such as glucose, fructose and sucrose, in
water increase the viscosity of water to an appreciable
extent. Honey is highly viscous and contains a large
proportion of fructose. Simple syrup (sucrose in water)
is also viscous. Polymer solutions are still more
viscous. The viscosity of polymer solutions increases
almost many folds with concentration, i.e., the increase
in viscosity is exponential with concentration.

For example, methylcellulose USP in the concentration of

2.0 % w/w in water shows an apparent viscosity of 80
poise at room temperature. The viscosity of water is
0.01 poise.
In other words, the increase in viscosity of water is 8000
fold. Normally, such polymers are used in low
concentrations.
 Mechanism of enhanced viscosity
The lower sugars, such as glucose and sucrose
contain many alcohol functional groups. These
react with water molecules through hydrogen
bonding. The higher numbers such as starch
and other cellulose polymers also react with
water.
For example, methylcellulose has three to four
ether groups and one to two hydroxyl groups.
When water is added to it, the groups get easily
hydrated in solution. When the polymer molecule
moves, the hydrated solvent sheath also moves.
As a result, the size of polymer unit increases
and hence, increases the resistance to flow.
 The classification of material
according to
types of flow and deformation.

This classification depends on whether or

not their flow properties are in accord with
The difference of velocity dv
between tow planes of
liquids separated by an
infinitesimal distance dr is F’
A
the velocity gradient or the
rate of shear
dv
G = dv/dr
dr
The force per unite area
F`/ A , required to bring
The higher the viscosity of the liquid
about a flow is called the
the greater is the force per unit area
shearing stress = F
( shearing stress ) required to
produce a certain rate of shear.
Rate of shear Shearing stress
F` = η dv dv = G (rate of shear)
A dr dr

F` = F ( shearing stress )
A
F =ηG η = F
G
A representative flow curve or rheogram, obtained
by plotting F versus G
For Newtonian system a straight
line passing through the origin is
obtained.
G
Slope = fluidity

F
Most of pharmaceutical fluid products are
not simple liquids and do not follows
Newtonian law of flow . Example colloidal
solutions, emulsions, suspensions and
ointments.
These systems can be classified into 3
classes of flow.
1.  Plastic flow.
2.  Pseudoplastic flow.
3.  Dilatant flow.
 Plastic flow
The substance that exhibits plastic flow are known as
Bingham bodies.
Plastic flow curves do not
pass through the origin, but
intersect the shearing
stress axis at a particular
point referred to as the
yield value. Rate of Slop = mobility
shear
The Bingham bodies does
not begin to flow until a
shearing stress exceed the f = yield value
yield value .
Shearing stress
At a stress below the yield
Plastic flow
value the substance act as
an elastic material.
 How the plastic flow is produced
Plastic flow is associated with the presence of
flocculated particles in concentrated suspensions,
so in this case the yield value results from the
contacts between adjacent particles which must
be broken down before flow can occur .
So the yield value indicate the force of flocculation
in that the higher the flocculated suspension the
higher the yield value.
At a value of shearing stress above the yield value
the plastic systems become resemble Newtonian
systems in that there is a direct relation ship
between the shearing rate and shearing stress.
The slop of the rheogram in plastic flow is
termed as the mobility which analogous to
the fluidity in Newtonian system, and its`
reciprocal is known as plastic viscosity (u)
F-f
u =
G
F : is the shearing stress.
G: is the shearing rate.
f : is the yield value.
 Pseudoplastic flow
Pseudoplastic flow is typically exhibited by polymers in
solution, example natural and synthetic gums as tragacanth,
methyl cellulose and sodium carboxymethyl cellulose.
The curve of the pseudoplastic flow
begins at the origin therefore there is no
yield value as there is in the plastic
flow.
G
The viscosity of the pseudoplastic
material can not be expressed by any
single value, in that it will be decreased
F
with increasing the rate of shear. HOW?
As the shearing stress is increase , normally disarranged molecule
begin to arrange their long axis in the direction of flow, this
orientation reduces the internal resistance of the material and
allows a greater rate of shear at each successive shearing
stress.

In addition some of the solvent associated with the molecule may

be released resulting in effective lowering of the conc. And size
of dispersed molecules, this will lead to reduce the apparent
viscosity.
The viscosity of the pseudoplastic material cannot be expressed
by any single value, it can be obtained at any rate of shear from
the slop of the tangent to the curve at the specified point

tangent
 Dilatant flow
This flow is the inverse of the pseudoplastic
flow in that there is an increase in the
resistance to flow with increasing the rate
of shear .
These systems actually increase in volume
when sheared and hence termed Dilatant.
So dilatant materials are referred to as shear
thickening systems while pseudoplastic
materials referred to as shear thinning systems.
Why ?
Usually dilatant flow are
produced by suspension G

that contain a high conc.

( 50% or more ) of small
deflocculated particles. F
The dilatant flow can be explained as follows

By increasing
shear stress

Closed – packed
particles, Open packed ( dilated )
particles,
minimum void volume,
Increased void volume,
sufficient vehicle,
Relative high consistency
relative low consistency
Particles are closely packed with minimal
interparticle volume ( void ), the amount of
vehicle in suspension is sufficient to fill the
voids and permits particles to move relative
to on another at low rate of shear.
As shear stress is increased the particles is
in an attempt to move quickly past each
other, taking an open form of packing
which leads to a significant increase in
interparticle void volume.
The amount of vehicle remains constant and at
some points becomes insufficient to fill the
increased voids between particles, accordingly
resistant to flow increases because particles are
no longer completely wetted or lubricated by the
vehicle, eventually the suspension will set up as
a firm paste.
Thixotropy : it is an isothermal and comparatively
slow recovery, on standing of a material, of a
consistency lost through shearing. i.e. shear-
thinning systems
Plastic
Pseudoplastic

Thixotropy in Newtonian Thixotropy in plastic and pseudoplastic

system systems
 For Newtonian systems:
When the shear stress were reduced once the
desired maximum had been reached, the down
curve would be identical with and super imposable
on the up curve .
For the non Newtonian systems (plastic and
pseudoplastic ):
The down curve is frequently displaced to the left
of the up curve showing that the material has a
lower consistency at any one rate of shear on the
down curve than it hade on the up curve.
This indicates the break down of structure that does not
reform immediately when stress is removed or reduced.
The phenomenon of thixotropy is explained in terms of particle-particle
interactions
At rest, particles in the dispersion
AT REST Multipoint contacts Gel state
(On storage) (high consistency
or high viscosity)

ON SHEAR Contacts break down sol state

(Equilibrium) (low consistency
or low viscosity)

SET ASIDE particle contacts are Gel state

(Removal of stress) re- established due to
Brownian motion
( high viscosity)
 Thixotropy in Dilatant Systems
In dilatant systems, an increase in the shearing
stress causes an apparent increase in viscosity at a
given temperature. On removal of the shearing
stress, the viscosity decreases but after a lag time.
This phenomenon is known as thixotropy in
dilatant systems and may be described as a
reversible isothermal transformation from sol to
gel.
Application of Removal of
shear stress shear stress
Sol Gel Sol
G

Thixotropy in dilatant system

 Negative Thixotropy
Antithixotropy or negative thixotropy represents an
increase in consistency on the down curve. For
example, magnesia gel exhibits an enhanced
resistance to flow with increased time of shear
compared to resting state. In the rheogram, the
down-curve shifts to the right of the up-curve.
When magnesia gel is sheared alternatively with
increasing and then decreasing rates of shear,
the gel thickens. As these cycles continue, the
extent of increase in the thickening reduces
gradually and finally reaches equilibrium state.
There will be no change in the consistency
curves on further cycles of shear rate.
 D
A B C

Rheogram of antithixotropic behavior. Example is

Magnesia gel
In the resting state, the system consists of a
large number of individual particles and
small floccules. When the product is
sheared, the polymer molecular collisions
are increased at a greater frequency. As a
result, interparticle bonding increases. At
equilibrium, large floccules are available in
small numbers. However, the system
exhibits sol form at equilibrium. When the
product is allowed to rest, the large
floccules breakup and gradually return to
the original state of small floccules and
individual particles.
Negative thixotropy should not be confused
with the term 'dilatancy'. Dilatant systems
are deflocculated and the volume of solids
is high (more than 50%), whereas
negative thixotropy is seen in a flocculated
system containing low solid content (1 to
10%).
AT REST Individual particles are
(On storage) in large number
Small flocs
(low viscosity)

ON SHEAR Particle collisions

(Equilibrium) particle contacts are
more; Large flocs in
small numbers
(high consistency)

SET ASIDE Flocs contacts break

(Removal of stress) individual particles
(low consistency)

Particle-particle interactions in an antithixotropic material