Rheology

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Objectives
By the end of this lecture, the student
will be able to:
1. Define rehology
2. List the types of flow
3. Compare and differentiate between Plastic
flow, Pseudo-plastic and Dilatant flow
4. Describe different types of viscometers in
determining rheologic properties of various
systems 2
 Rheology
 Rheology is defined as the study of flow and
deformation of matter.
 The deformation of any pharmaceutical system
can be divided into two types:
1. The spontaneous reversible deformation,
called elasticity and
2. Irreversible deformation, called flow.

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 Rheology
 Generally viscosity is measured as a part of
rheological studies because it is easy to measure
 Viscosity (inter-molecular cohesive forces) is the
proportionality constant between the shear rate
and shear stress, it is denoted by η.
 SᶑD→S=η.D
η = S/D
Where,
S = Shear stress, D = Shear rate
 Viscosity is the opposing force to flow
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 Rheology
Kinematic Viscosity:
 It is defined as the ratio of viscosity (η) and the
density (ρ) of the liquid.
Relative Viscosity:
 The relative viscosity denoted by ηr . It is defined
as the ratio of viscosity of the dispersion (η) to
that of the vehicle, η.

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 UNITS OF VISCOSITY
Poise (P) = [Link]/cm2 or centiPoise (cP) = 0.01
poise
Pascal-second (Pa.s) = N·s/m2 or milliPascal-second
(mPa.s)
1P = 0.1 Pa·s & 1 cP = 1 mPa·s
KINEMATIC VISCOSITY
Stokes (St) = P/[Link]-3 = cm2 /s or
centiStokes (cSt) = cP/[Link]-3 0.01 St
1 St = the viscosity in poise divided by the density of
the fluid in grams per cubic centimetre (g/cm3).
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 Types Of Flow
 Flow pattern of liquids can be divided
mainly in two types

[Link] Flow
[Link]-Newtonian Flow

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 1. Newtonian Flow
 Liquids that obey Newton’s law of flow are called
Newtonian liquids, e.g. simple liquids.
 Newton’s equation for the flow of a liquid is
S=ηD
Where,
S = Shear stress
D =Shear rate
 For Newtonian liquids, viscosity is constant (at a
given temperature)
 Increase temperature decrease the viscosity of
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liquids
1. Newtonian Flow

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 2. Non-Newtonian Flow
 Emulsions, suspensions and semisolids have
complex rheological behavior and thus do not
obey Newton’s law of flow and thus they are
called non Newtonian liquids.
 They are further classified as under
A. Plastic flow
B. Pseudo-plastic flow
C. Dilatant flow

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 A. Plastic flow (Bingham plastic)
 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.
 ex: ointments, creams, toothpaste, butter,
ketchup

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 Slope of the rheogram (straight part) is equal to
the viscosity (plastic viscosity U).
 plastic viscosity U: is shearing force in excess of
the yield value required to induce a unit rate of
shear D
U =S-SB/D
Where,
SB = the yield value in dynes/cm2
S = Shear stress
D =Shear rate

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[Link]-plastic Flow (shear thinning)
 Here the relationship between shear stress and
the shear rate is not linear and the curve starts
from origin
 Thus the viscosity of these liquids cannot be
expressed by a single value.
 No yield value

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 Normally, pseudo-plastic flow is exhibited by
polymer dispersions like: Tragacanth water,
Sodium alginate in water , proteins, blood, gels,
nail polish
SN = η D
Where,
S = Shear stress
D =Shear rate
η = viscosity
N = is indicative of non-Newtonian behavior
When N = 1 → Newtonian behavior
As the value of N rises above unity → the greater the
pseudoplastic character of the material 14
 [Link] Flow (shear thickening)
 In this type of liquids resistance to flow
(viscosity) increases with increase in shear rate.
 When shear stress is applied their volume
increases and hence they are called Dilatant
(shear thickening)
 Dilatant flow is observed in suspensions
containing more than 50% v/v of solids.
 As in case of pseudo-plastic flow:
SN = η D
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Where N is less than one
 Theories behind shear thickening behavior
 Shear thickening behavior is highly dependent
upon the volume fraction of solid particulate
suspended within the liquid.
 The higher the volume fraction, the less shear
required to initiate the shear thickening behavior.
 The shear rate at which the fluid transitions from a
Newtonian flow to a shear thickening behavior is
known as the critical shear rate.
 Dilatancy does not occur in a dilute suspension,
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where the vehicle is in great excess
 Explanation of shear thickening behavior
 Order to disorder transition
 Hydroclustering

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Order to disorder transition
• When shearing a concentrated stabilized solution
at a relatively low shear rate, the repulsive
particle-particle interactions keep the particles in
an ordered, layered, equilibrium structure.
However, at shear rates elevated above the critical
shear rate, the shear forces pushing the particles
together overcome the repulsive particle-particle
interactions, forcing the particles out of their
equilibrium positions. This leads to a disordered
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structure, causing an increase in viscosity.
Hydroclustering
• Transition from an immobile state to mobile state,
leads to small groupings of particles form
hydroclusters, increasing the viscosity.
• Small quantity of the vehicle is needed to fill the
voids between the clusters but it is not sufficient
to allow the suspension to flow like a liquid.
• The expansion → larger volume –b- the particles
and insufficiency of vehicle to fill the voids.
• Thus the un-lubricated clusters show an increased
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 Thixotropy
 Thixotropy is defined as the isothermal slow
reversible conversion of gel to sol.
 By applying shear stress convert to sol (fluid) and
on standing they slowly turn to gel (semisolid).
 Thixotropic substances are used in suspensions
to give stable suspensions.

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 The area enclosed by the up and down curve is
referred to as hysteresis loop
 when the structure does not reform on the
removal of shear stress or the lag time is so long
this indicates irreversible thixotropy
shear stress standing
 Gel Solution Gel

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Negative thixotropy and rheopexy:
 Negative Thixotropy is a time dependent
increase in the viscosity at constant shear
shear stress standing
 Solution Gel Solution
 Rheopexy is the phenomenon where sol forms a
gel more rapidly when gently shaken than when
allowed to form the gel by keeping the material at
rest.
 In negative Thixotropy, the equilibrium form is sol
while in Rheopexy, the equilibrium state is gel.
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Application of thixotropy in formulation
 Prolongation of drug action (procaine
penicillin G I.M injection)
 Improve the formulation
 Increase the stability

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Determination of rheological properties
 For a Newtonian system, instruments that operate
at a single rate of shear such as capillary
viscometers can be used
 Such instrument of one point of determination is
not useful in non-Newtonian systems where the
viscosity varies with the change in shearing rate
 For such systems multi point instruments that
can operate at different rate of shear are used

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Determination of rheological properties
 The viscometers used for determining the
viscosity of different systems can be broadly
divided into the following types:
 Capillary instruments
 Falling and rising body instruments
 Rotational Viscometers
 While Capillary and falling and rising body
instruments can only be used for Newtonian
systems, the rotational viscometers are also
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suitable for non-Newtonian systems.
 Capillary viscometers
η1 = ρ1 t1 η2
ρ2 t 2

ρ1 =Density of unknown liquid

t1 =Time of the unknown liquid

ρ2= Density of known liquid

t 2 = Time of the known liquid

η2 = Viscosity of known liquid

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Falling and rising Body Apparatus
η = t (Sb – Sf)

η = viscosity of the sample

t = time in seconds for the
ball to fall between the two
points
Sb , Sf = specific gravities of

the ball and the liquid

under examination
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 Rotational viscometers
1. Cup and Bob viscometer
2. Cone and plate viscometer

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1. Cup and Bob viscometer

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 2. Cone and plate viscometer
Newtonian liquids:
η = CT/V
Non-Newtonian liquids:
η = CT – Tf / V

Where,
C = instrumental constant
T = force reading
Tf = yield value

V = speed of cone (rpm) 30

 Viscoelasticity
 Materials which exhibit both the viscous
properties of Iiquid as well as the elastic property
of solids, such as; creams, lotions, ointments,
and many biological fluids such as blood
 When subjected to stress for a short period of
time they undergo slight deformation but once the
stress is removed, they exhibit their elastic
behavior by returning to their original shape
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 Application of Rheology in pharmacy

 Viscosity and spreading of creams or ointment

 Viscosity and pouring of solutions, suspensions
or emulsions
 Viscosity and difficulty in syringeability or
injectability
 Viscosity and packaging into containers

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