NON-NEWTONIAN

SYSTEMS
VISCOSITY
DETERMINATION
*For non-Newtonian systems of great
relevance during viscosity measurement is
the effect of shear rate and time.
*Dynamic viscosity takes into account these
effects, it is measured with dynamic
instruments; either rotating (shearing) or
oscillating.
*Instruments capable only of measuring
shearing viscosities are typically refereed to
as viscometers, and the oscillating type are
called rheometer
*Rotational viscometers instruments rely on
the viscous drag exerted on a body when it
is rotated in the fluid to determine the
viscosity of the fluid.
*The major advantage of such instruments is
that wide ranges of shear rate can be
achieved, and often a programme of shear
rates can be produced automatically
Cup and bob viscometer
*Two coaxial cylinders of different
diameters; the outer forming the cup
containing the fluid in which an inner
cylinder the bob is positioned centrally.
*The outer cylinder is rotated and the viscous
drag exerted by the fluid is transmitted to the
inner cylinder as a torque, such that it
rotates against a transducer that is in form of
a fine torsion wire.
*The stress on this inner cylinder is
indicated by the angular deflection, θ,
once equilibrium (i.e. steady flow) has
been attained.
*The torque, T, can then be calculated from:

where C is the torsional constant of the wire.

*The viscosity is then given by:

*where r1 and r2 are the radii of the inner and

outer cylinders, respectively, h is the height
of the inner cylinder and ω is the angular
velocity of the outer cylinder
Cone and plate viscometer
*This is composed of a flat circular plate with a
wide-angle cone placed centrally above it

*The tip of the cone just touches the plate and

the sample is loaded into the included gap.
*When the plate is rotated the cone will be
caused to rotate against a torsion wire in
the same way as the inner cylinder
described above.
*Provided the angle is small (of the order of
1 °) the viscosity will can be expressed as:

where ω is the angular velocity of the plate,

T is the torque, r is the radius of the cone
and α is the angle between the cone and
the plate.
Procedure for obtaining rheogram
*Whether cone-plate or concentric cylinder
geometry is used, instruments have been
modified to make measurements both easier
and more accurate.
*The common modification is to make one
part of the geometry, usually the plate or
the outer cylinder, stationary and to rotate
the other member at a constant speed.
*A torque sensor can then measure the
developed shear stress.
*An alternative is to rotate the upper
member under a constant stress when the
developed shear rate is measured
*Such controlled stress instruments consist
of a specially designed induction motor
which generates a torque that is
independent of the degree or rate of
rotation.
*The torque is not measured, as it is defined
by the way the power is fed to the motor,
which is connected to the measuring
geometry through a rigid drive chain so that
no motion is lost in the deflection of a
torque sensor.
*It is then necessary only to detect the
movement of the drive system and its
associated measuring geometry by, for
example, an optical encoder, in order to
obtain the shear rate or strain.
*Both designs have been the subject of
considerable sophistication, including the
use of microcomputers for programming
and data analysis.
*Also, having one part of the geometry
stationary means that it can be circulated
with water or other fluid at a temperature
appropriate to the measurement.
*Concentric cylinder viscometers are very
useful for Newtonian and non-Newtonian
fluids provided the latter are not too solid-
like in nature.
*Wide ranges of shear rate can be achieved
by varying the diameters of the cylinders.
*However, this geometry does suffer from
disadvantages, the major one being that
the shear rate across the gap is not
constant, and this is especially the case
when the gap is large.
*Also, the end effects can be significant
since the equation only takes into account
the surfaces of the walls of the cylinders
and not the ends.
*These end effects are usually accounted
for by calibration of the instrument with a
fluid of known viscosity.
*Frictional heating can also be a problem at
high shear rates, and so temperature
control is essential with such instruments.
*Filling and cleaning are often difficult
when the gap is small, but if it is large then
the volume of sample required may be
prohibitive.
Effect of temperature
*Viscosity decreases sharply with increasing
temperatures.
*The temperature dependency on viscosity
is expressed by the following equation;
η = A exp E /RT
V

*Logarithmic form as
ln η = ln A + EV/R(1/T)
*where A is a constant of same units as
viscosity EV is the activation energy required
to initiate flow of molecules and R the
universal gas constant, T is absolute
temperature
APPLICATION OF RHEOLOGY
Laminar, transitional and turbulent flow
*The conditions under which a fluid flows
through a pipe markedly affect the
character of the flow.
*Reynolds experiments could be used to
describe the types of flow that occur.
*The experiments utilizes apparatus
consisting of a straight glass tube through
which a fluid flows under the influence of a
force provided by a constant head of water.
*At the centre of the inlet of the tube a fine
stream of dye is introduced.
*At low flow rates the dye forms a coherent
thread that remains undisturbed in the
centre of the tube and grows a little in
thickness along the length.
*This type of flow is described as
streamlined or laminar, and the liquid is
considered to flow as a series of concentric
cylinders in a manner analogous to an
extending telescope.
*If the speed of the fluid is increased a
critical velocity is reached at which the
thread begins to waver and then to break
up, although no mixing occurs.
*This is known as transitional flow.
*When the velocity is increased further to
high values, the dye instantaneously mixes
with the fluid in the tube, as all order is
lost and irregular motions are imposed on
the overall movement of the fluid.
*Such flow is described as turbulent.
* In this type of flow the movement of
molecules is totally haphazard, although
the average movement will be in the
direction of flow.
* Reynolds' experiments indicate that the
flow conditions are affected by four
factors,
- diameter of the pipe
- viscosity
- density
- velocity of the fluid.
*These factors could be combined to give
the following equation:

where ρ is the density, u is the velocity and

η is the dynamic viscosity of the fluid; d is
the diameter of the pipe.
*Re is known as Reynolds' number and,
provided compatible units are used, it will
be dimensionless.
*Values of Reynolds' number have been
determined that can be associated with a
particular type of flow.
- If it is below 2000 then streamline
flow will occur
- If it is above 4000 then flow will be
turbulent.
*In between these two values the nature of
the flow will depend upon the surface over
which the fluid is flowing.
- if the surface is smooth then
streamline flow may not be disturbed and
may exist at values of Reynolds'
number above 2000.
- if the surface is rough or the channel
tortuous then flow may well be
turbulent at values below 4000, and
even as low as 2000.
*The application of knowing the type of flow
lies in the fact that with streamline flow
there is no component at right-angles to
the direction of flow, so that fluid cannot
move across the tube.
*This component is strong for turbulent flow
and interchange across the tube is rapid.
*Thus in this case, mass will be rapidly
transported, whereas in streamline flow
the fluid layers will act as a barrier to such
transfer, which can only occur by molecular
diffusion
RHEOLOGY OF PHARMACEUTICAL SYSTEMS
Rheology of mixing
*Many solution dosage forms are Newtonian
fluids in which the mixing of solute and
solvent occurs at molecular level to form
homogeneous systems.
*Since the shear forces of mixing do not
affect the viscosity of the product, solutions
tend to be uniformly mixed and provide dose
uniformity
*Suspensions and emulsions however tend
to exhibit a non-newtonian rheological
profile and the mixing process can affect
the viscosity of a formulation.
*Drug incorporation into ointments and
other semi-solid dosage forms is also
affected by the shear stress induced during
mixing.
*Depending on method used for drug
incorporation (i.e. roll mill verses a hand
mixer), the content uniformity of a drug
may be affected.
Rheology of suspensions and emulsions
*Settling and aggregation of solid particles in
suspensions are viscosity dependent.
*Nevertheless the final suspension should be
pourable or Injectable based on the ultimate
site of administration.
*Emulsion stability is also dependent on the
viscosity of the formulation.
*Apparent viscosity values of suspensions
and emulsions are applied to design systems
that can provide optimum stability and dose
uniformity upon administration.
Removal and spreading of ointments
*The increase in apparent viscosity upon the
addition of drugs and expients in the dosage
form can affect the removal of product from
the container and spreading on the skin
surface