Rheology

Objectives
At the end of this session you will be able to know:
 definition of rheology
 fundamentals of rheology
 Newtonian flow
 Plastic flow
 Pseudoplastic flow
 Dilatant flow
 Thexotropy
 Viscoelasticty
 Pharmaceutical applications of rheology
 Introduction
 Rheology is the branch of physics that deals with the flow
of liquids and the deformation of solids.
 It is derived from, the Greek word rheo (“to flow”) and
logos (“science”)
 Rheology, the study of flow/viscosity characteristics of
powders, fluids, and semisolids.
 Viscosity is an expression of the resistance of a fluid to flow.
Thus, the reciprocal of viscosity is fluidity.
 Viscosity is internal friction in the fluid, resistance of the
fluid to the relative motion of adjacent layers of liquid.
 The higher the viscosity, the greater is the resistance to
flow.
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 Introduction...........cont’d
 Drug release from dosage forms is often controlled
by rheological properties of the formulation matrix.
 Rheological principles govern transit of luminal
contents through GIT,
 Rheological principles stem from two fundamental
laws: Robert Hooke’s law of elasticity and Issac
Newton’s law of viscous flow.
 The corresponding equations, which symbolize
these laws, characterize Hookean and Newtonian
materials.

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 Fundamentals
 In rheology, stress means a system of forces
whether applied in a compressive, extensional, or
shear mode.
 Strain means a change in size or shape.
 When a force is applied to a body, the two
rheological extremes of behaviour are the pure
elastic deformation of a Hookean solid and the
pure viscous flow of a Newtonian liquid.

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 Fundamentals……..cont’d
 Pure (ideal) elasticity means that the body
returns to its original form once the stress is
removed.

 While pure (ideal) viscosity means that the liquid

flows even under the smallest stress and does not
return to its original shape/form once the stress is
removed.

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 Fundamentals……....cont’d
 The resistance to deformation is described by the
modulus of elasticity or Young’s modulus, E, for an
elastic body undergoing extension.
 Elastic deformation of solids is described by
Hooke’s law,

dl is the elastic deformation or extension in length L

caused by application of stress, σ.

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 Fundamentals……..cont’d
 Fluid materials are divided into two:
 Newtonian and non-Newtonian, depending on their flow
characteristics.

 Newtonian flow is characterized by constant viscosity,

regardless of the shear rates applied.
 Non-Newtonian flow is characterized by a change in
viscosity characteristics with increasing shear rates.

 Non-Newtonian flow includes plastic, pseudoplastic,

and dilatant flow.
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 Newtonian system
 Simple liquids follow Newton’s law ( ) of direct
proportionality between shear stress and rate of
shear, so that their viscosity is independent of the
shear stress or the rate of shear.
 Their flow behaviour is thus referred to as
Newtonian.
 Substances such as water, ethanol, ethyl ether,
glycerin are Newtonian fluids.

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 Newtonian system..........
 Plots of shear stress (y-axis) as a function of the
rate of shear (x-axis) are referred to as flow curves
or rheograms of two liquids, A & B.

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 Newtonian system..........
 The rheograms of Newtonian liquids, like those of figure above,
are straight line going through the origin.
 Viscosity is the slope of such a line or the tangent of the angle it
makes with the horizontal axis.
 Viscosity (y-axis) against shear rate
(x-axis) gives a straight line parallel
to the x-axis.
Newtonian system.........cont’d
 Its unit is dynes/cm2 sec-1 or g/cm.s, which is called
a poise.
 Because many liquids including water have
viscosities of the order of 1/100 of a poise, their
viscosity is often expressed in centipoises.
 In the SI system, the unit of viscosity is Newton x sec /m2
or Pascal.s, which equals 10 poise.

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 Non-Newtonian system

 Fluids that do not obey Newton’s Law ( ) are

often termed as non- Newtonian fluids.
 Non- Newtonian behaviour is generally exhibited
by liquid and solid heterogeneous dispersions
such as colloidal dispersions, suspensions,
and ointments.
 There are three general types of non-Newtonian
materials: plastic, pseudoplastic, and dilatant.

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Plastic flow
 Semisolids that do not flow at low shear stresses
(exhibiting reversible deformation like elastic solids)
but flow like liquids above their yield value (i.e., yield
stress) are termed plastic or Bingham bodies.
 This type of rheological behaviour is termed as
plasticity, i.e., elastic solid at low shear but liquid-like at
higher shear stress.
 Plastic flow curves do not pass through the origin,
but rather intersect the shearing stress axis (or will if
the straight part of the curve is extrapolated to the
axis) at a particular point referred to as the yield
value.
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 Plastic flow………...cont’d
 Plastic flow is often exhibited by semisolids
characterized as structured media, i.e, semisolids that
have a cross-linked three-dimensional network of
polymers, macromolecules, or particulates extending
throughout the system.

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 Plastic flow......cont’d
 A yield value exists because of the contacts between
adjacent particles (brought about by van der Waals
forces), which must be broken down before flow can
occur.
 Frictional forces between moving particles can also
contribute to yield value.
 Once the yield value is exceeded, any further
increase in shearing stress (i.e., σ−σyield) brings about
a direct proportional increase in rate of shear.
 In effect a plastic system resembles a Newtonian
system at shear stresses above the yield value.
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Pseudoplastic flow (shear -thinning
fluids)
 Many colloidal systems, especially polymer solutions,
and flocculated suspensions become more fluid the
faster they are stirred.
 In shear-thinning fluids, the viscosity decreases with
increasing shear. This shear-thinning behaviour is
referred to as pseudoplasticity.
 As the increase in shear rate is greater than the
increase in the corresponding shear stress, the flow
curve is concaved toward the shear rate axis.
 There is an apparent viscosity for each value of
shear rate or shear stress.
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Pseudoplastic flow (shear thinning
fluids)
 Pseudoplastic flow (shear thinning
fluids).......cont’d
 Many pharmaceutical products, including liquid
dispersions of natural and synthetic gums e.g.,
tragacanth, sodium alginate, methylcellulose and
sodium carboxymethylcellulose exhibit pseudoplastic
flow.

 The shear-thinning behaviour of polymer or

macromolecule solutions arises from the alignment
of neighbouring macromolecules and the degree of
their entanglement.

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 Pseudoplastic flow (shear thinning
fluids)........cont’d
 When shear is applied, the randomly coiled,
entangled macromolecules tend to disentangle
themselves and to align themselves in the direction
of flow.

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 Pseudoplastic flow (shear thinning
fluids)......cont’d
 The imposition of increasing shear in these systems
enables the macromolecule “chains” to uncoil
progressively and become elongated, thereby offering
less resistance to flow than the original.
 At very high shear rates, the dissolved polymer
chains are wholly disentangled and well align in the
direction of flow, and the aggregates of particles are
broken up as far as possible.
 There is no residual structure left which can be
broken up by further increment in shear rate: the
viscosity levels off at a constant value called the
upper Newtonian viscosity, ηinfinity.
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 Dilatant flow (shear -thickening)
 Certain suspensions with a high percentage of
dispersed solids exhibit an increase in resistance to
flow with increase in shear.
 Viscosity increases with increasing shear rate. This
shear-thickining effect is known as dilatancy.
 When concentrated suspension is poured or
stirred slowly, there is just enough liquid to
lubricate the slipping of one particle past another,
and the viscosity is low.
 When stirred fast, the particles get into each
other’s way, block each other and bunch up rather
than slipping past each other. 22
 Dilatant flow……………….(cont’d)

 When high shear is followed by low shear or rest,

the particles that had been crowded together
separate again, the interparticle void volume
decreases, and the viscosity drops as the
suspension appears wet again.

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Dilatant flow……………….(cont’d)
 Wet sand offers small resistance to slow flow or
penetration, but stiffens and appears dry when
deformed fast.
 Substances possessing dilatant flow properties are
invariably suspensions containing a high
concentration (about 50% or greater) of small
deflocculated particles.

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 Thixotropy (Time dependent non-
Newtonian flow)
 Materials whose consistency depends on the
duration of shear and rate of shear are said to be
thixotropic or to exhibit thixotropy.
 If a suspension is viscous and/or the particles are
large and heavy, their Brownian motion is too slow
to restore the broken interparticle links
“instantaneously.”
 Likewise, the entanglement of polymer chains are
slow to be reestablished by Brownian motion if
their solution is viscous.

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 Thixotropy (Time dependent non-
Newtonian flow)....cont’d
 If the rate of restoration of the link is lower than the
rate of breakdown by shear, the apparent viscosity
decreases even while the system is under constant
shear.
 The number of the particles aggregates or the
extent of macromolecular entanglement is
progressively reduced.
 Furthermore, the apparent viscosity at a given shear
rate is lower if the system is stirred recently at high
speed than if the shear rate was approached from
low speed or from rest.
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Thixotropy (Time dependent non-
Newtonian flow).......cont’d
 The apparent viscosity depends not only on
temperature, composition, rate of shear or shear
stress, but on the previous shear history and time
under shear.
 The differences between the top and bottom
branches of a flow curve illustrates a common
phenomenon called hysteresis.
 The area enclosed by two branches and the stress
axis is called hysteresis loop.
 Its size is the measure of the extent of thixotropic
breakdown in the structure of the system.
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Thixotropy (Time dependent non-
Newtonian flow).....cont’d
 The decrease in the hysteresis loop corresponds a
decrease in the amount of structural breakdown of
the system,
 Because each cycle leaves intact less residual
structure to be broken dawn in the next cycle.
 When no structure remains, the Newtonian flow
curve results.
 The absence of hysteresis in the flow curves is due
to the rebuilding of structure by Brownian motion.

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 Viscoelasticity
 When stressed, viscoelastic materials simultaneously
exhibit some of the properties of elastic solids and
some of the properties of viscous liquids:
 Viscoelasticity may be viewed as a combination of
viscous and elastic properties when undergoing
deformation.
 Some deformation occur instantaneously upon the
application of stress and continuous as long as the
stress is applied.
 Upon the removal of the stress, there is partial
recovery of the original shape.
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Viscoelasticity………...cont’d

 In effect, viscoelastic systems are capable of storing

part of the deformation energy elastically and
reversibly.

 Viscoelastic materials are molten polymers, chewing

gums, and most gels.

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Pharmaceutical applications of
rheology
1. Fluids
 Mixing
 Particle size reduction of disperse 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 of
rheology.........cont’d
2. Semisolids (Quasisolids)
 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
 Processing efficiency
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