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Rheology

Learning Objectives:
At the end of 3-hour leacture discussion, the students
will be able to:
Define rheology.
Provide examples of fluid pharmaceutical products
exhibiting various rheologic behaviors.
Describe the application of of rheology in the the
pharmacuetical science.
Undertsand anf define the different concepts in
rheology.
Appreciate the fundamentals of practical
determination of rheologic properties using the
four types of viscometers.
Content Outline:
Definition
Classification of Rheologic Systems
Thixothropy
Determination of Rheologic Properties
Application o Rheology in Pharmacy
Rheology
rheo to flow
logos science
Science of describing the flow and deformation of
matter under stress.

Viscosity ( )
- the resistance of fluid to flow
- the higher the viscosity, the greater the
resistance.
Significance
formulation of medicinal and cosmetic creams,
pastes and lotion.
formulation in emulsion, suspension, suppositories
and tablet coatings
fluidity of solutions for injection
in mixing and flow of materials, their packing into
containers, their removal prior to use ( whether by
pouring from a bottle, extrusion from a tube or
passage through a single syringe needle).
affect patient acceptability, physical stability and
even biological availability.
Classification of Rheologic Systems

Newtonian System

Non-Newtonian System
Newtons Laws
1. Every body continues in its state of rest or uniform
motion in a straight line unless it is acted upon by
another force.

2. The rate of change of momentum is proportional


to the applied force and in the direction of the
applied force.

3. For every action there is equal and opporiste


reaction.
Newtonian System
Newtonians Law of Flow
Newtonian Flow
Definitions
Shear
- the movement of material relative to parallel
layer
Shear Stress ( F )
- the force per unit area required to bring about
a flow
Shear rate ( G )
- the difference in velocity (dv) between two
planes of liquids separated by distance (dr)
The rate of shear should be directly
proportional to the shearing stress.
The unit of viscosity is poise.
- the shearing force required to produce a
velocity of 1 cm/sec between two parallel
planes of liquid each 1 cm2 in area and
separated by a distance of 1 cm.

Poise = dyne sec / cm2


cgs = g / cm sec
Definitions
Fluidity
the reciprocal of viscosity
Definitions
Kinematic Viscosity
- the absolute viscosity divided by the
density of liquid at a specific
temperature

Where p is the density of the liquid


The unit is Stoke (s) or centistoke (cs).
Definitions
Relative Viscosity
- the relation of the solution viscosity
to the viscosity of the solvent standard
o.
Examples
1. The viscosity of acetone at 25 C is 0.313
cp, its density at 25 C is 0.788 g/cm3. What
is the kinematic vsicosity at 25 C?

2. Water is usually used a standard of liquids. Its


viscosity at 25 C is 0.89 cp. What is the
viscosity of acetone relative to that of water at
25 C ?
Non-Newtonian Systems
Non-Newtonian fluid
- one in which the relationship between
shear stress and shear rate is not a constant
When the shear rate is varied, the shear stress
doesnt very in the same proportion. The viscosity
of such fluids will therefore change as the shear rate
is varied.
Seen in liquid and solid heterogenous dispersions
such as colloids, emulsions, liquid suspension and
ointments.
Non-Newtonian Systems
Three Classes
Plastic Flow
Pseudoplastic Flow
Dilatant Flow
Plastic Flow
known as Bingham bodies
A Bingham body does not begin to flow until
a shearing stress corresonding to the yield
value is exceeded.
Yield value (f) is an indication of the force
that must be applied to a system to convert it
to a Newtonian System.
- an indication of the force of flocculation
- the more flocculated the suspension, the
higher will be the yield.
Plastic Flow
At stresses below the yield value, the
substance acts as elastic material.
Substances that exhibit a yield value solid
Substances that begin to flow at the smallest
shearing stress and show no yield liquid
Plastic flow is associated with the
preparation of flocculation and aggregation
of particles in concentrated suspension.
Plastic Flow
Plastic Flow
The slope of the rheogram is termed
MOBILITY, analogous to fluidity in Newtonian
system and its reciprocal is known as Plastic
Viscosity (U).

where f is the yield value


Example
A plastic material was found to have a yield
value of 5200 dyne/cm2. At a shearing stress
above the yield value, F was found to
increase linearly with G. If the rate of shear
was 150 sec -1 when F was 8000 dyne/cm2.
calculate the plastic viscosity of the sample.
Pseudoplastic Flow
known as shear-thinning
the curve begins at the origin, there is no yeild
value
occurs in dispersion of polymers ( synthetic or
natural gum)
As the shearing-stress is increased, disarranged
molecules orient themselves to thee direction of
flow. This orientation reduces internal friction and
resistance of the molecules an allows a greater rate
of shear at each stress.
Dilatant Flow
known as shear-thickening
Certain suspension with a high percentage of
dispersed solids exhibit an increase in resistance to
flow with increasing rates of shear.
System has increase in volume when sheared and
hence DILATANT.
Type of flow is is the inverse of the the flow
properties possessed by the pseudoplastic system.
When stress is removed, a dilatant system returs to
its original state of fluidity.
Reasons for Dilatency
1. At rest particles are closely packed with minimal
inter-particle volume (void), so the amount of
vehicle to fill in voids and permits particles to move
at low rate of shear.
2. Increase shear stress, the bulk of the system
expand (dilate) and the partciles take an open form
of packing.
3. The vehicles becomes insufficient to fill the viods
between particles. Accordingly, particles are no
longer completely wetted (lubricated) by the
vehicle.
Reasons for Dilatency
4. Finally, the suspension will set-up as a firm
paste.
5. This process is reversible.
Characteristics of Dilatent System
Resting Sheared

-Closed packed -Open packed particles


particles - Increased void volume
- Minimum void - Insuffiecient vehicle
volume - Relatively high
- Relatively low consistency
consistency
Significance of Dilatency
Suggests appropriate precautions used
during the processing of dilatent materials.
Mixing ( powder + granulating liquid) is
usually conducted in high speed mixers,
dilatent materials may solidify under these
consditions thereby damage the
equipments.
Review
1. What is rheology?
2. What are the classifications of rheological
systems? Describe each.
3. What are the 3 classes of non-newtonian
systems?
Assignment
1. What is thixothropy?
2. What are the apparatus used in the
determination of rheologic properties? What
are the principles involved in the use of each
apparatus?
3. What are the applications of the principles
of rheology in pharmacy?
RECAP
1. Rheology
2. Classifications of rheological systems.
3. 3 Classes of non-newtonian systems.
- Psuedoplastic
- Plastic
- Dilatant
Thixotropy
The decrease in viscosity as a
function of time upon shearing, then
recovery of original viscosity as a function of
time without shearing.
Thixotropy
The system contain asymetric particles
forming a loose network through sample.
At rest, this structure impart rigidity to
system resembling gel.
As shear is applied, the structure begin to
break and the material undergo Gel-to-Sol
transformation and exhibit shear thinning.
Finally, at rest the structure is restored again
Sol-to-Gel.
Thixotropy
Thixotropy
Thixotropic samples
- ketchup, paints, yoghurt, mayonnaise
- suspension
- emulsion, lotions, creams and ointments
Measurement of Thixotropy
2 approaches
First To determine structural breakdown with
time at constant rate of shear

Second To determine the structural


breakdown due to increasing shear rate.
Measurement of Thixotropy
2 approaches
First To determine structural breakdown with
time at constant rate of shear

Thixotropic coefficient, B
U1 - U2 plastic viscosities
t1 and t2 time, seconds
Measurement of Thixotropy
2 approaches
Second To determine the structural
breakdown due to increasing shear rate.

Thixotropic coefficient, M, dynes sec/ cm2


U1 - U2 plastic viscosities
t1 and t2 time, seconds
Negative Thixitropy
An increase in viscosity with time

Rheopexy
Solid forms a gel more readily when gently
shaken or sheared than allowed to form a
gel while the materials is kept.

Rheopectic system gel is the equilibrium form


Antithixotropy sol is the equilibrium form
Determination of Viscosity
Newtonian System
- Capillary viscometer
- Falling Sphere viscometer

Newtonian and Non-Newtonian System


- Cup-and-Bob viscometer
- Cone-and-Plate viscometer
Capillary Viscometer
also known as ostwald viscometer
determined by measuring the time required
for the liquid to pass between two marks as
it flows by gravity through a vertical capillary
tube
the time of flow of the liquid under test is
compared with the time required for a liquid
of known viscosity (usually water) to pass
between the 2 marks.
Capillary Viscometer
Example
What is the viscosity of acetone at 25 C when
the time required for acetone to flow between
two marks on the capillay viscometer was 45 sec
and for water the time was 100 sec at 25 C.
The density of acetone is 0.786 g/cm3 and that
of water is 0.997 g/cm3 at 25 C.
Falling - Sphere Viscometer
A glass or steel ball rolls down an almost
vertical glass tube containing the test liquid
at known temperatue.
the rate at which a ball of particular density
and diameter falls is an inverse function of
the viscosity of the sample.
the time required for the ball to fall
between two marks is accurately measured
and repeated several times.
Falling - Sphere Viscometer

t the time interval in


seconds for the ball to fall
between two points
Sb Sf - specific gravities of
the ball and fluid
B constant for a particular
ball and is supplied by
manufacturer.
Cup-and-Bob Viscometer
a sample is sheared in the space between
the outer wall of a bob and the inner wall of
a cup to which the bob fits.
popular instrument is the Stormer
instrument.
Stormer Instrument
the test system is placed between the cup
and the bob and allowed to make reach
temperature equilibrium.
a weight is placed in the hanger and the
time required for the bob to make 100
revolutions is recorded.
the data is converted to revolutions per
minute
the weigh is incresed and the whole
procedure is repeated.
Stormer Instrument

U plastic viscosity in poises


Wf yield value in grams
Stormer Instrument
A driving weight, w, of 450g produced a bob
velocity v, of 350 rpm. A series of velocities
was obtained using other driving weights.
The yield value intercept, Wf , extrapolating
the curve to the shearing stress axis where v
= o and the value of Wf was found to be
225g. The instrument constant Kv is 52.0
and Kf is 20.0 . What is the plastic viscosity?
Cone Plate Viscometer
Ferranti-Shirley , popular example
the sample is placed at the center of the
plate, which is then raised into position
under the cone.
a variable speed motor drives the cone and
the sample is sheared in the narrow gap
between the stationary plate and the
rotating cone.
Cone Plate Viscometer
the rate of shear in revolutions per minute
is increased and decreased by a selector dial
and the viscous traction or torque (shearing
stress) produced on the cone is read on the
indicatpr scale.
Cone Plate Viscometer
Newtonian Liquid
C instrument constant
T torque reading
v speed of the cone in revolutions per minute

Non-Newtonian ( Plastic flow)


Tf torque at the shearing stress axis
Cf instrymental constant
Cone Plate Viscometer
A new ointment base was designed and
subjected to rheology analysis at 20C in a
cone-plate viscometer with instrument
constant, C, 6. 277 cm-3. At a cone velocity
of v=125 rpm the torque reading, T, was
`287.0 dyne cm. The torque tf, at the
shearing stress axis was found to be 63.5
dyne cm. What is the plastic viscosity of the
ointment base?
Pharmaceutical Area in which
Rheology is Significant
1. Fluids
Mixing
Particle-size reduction of disperse system with
shear
Passage through orifices, including pouring,
paackaging on bottles and passage through
hypodermic needles.
Fluid transfer, including pumping and flow
through pipes
Physical stability of disperse system
Pharmaceutical Area in which
Rheology is Significant
2. Quasisolids
Spreading and adherence on the skin
Removal from jars or extrusion from tubes
Capacity of solids to mix with miscible liquids
Release of the drug from the base
Pharmaceutical Area in which
Rheology is Significant
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
processing capacity of the equipment
processing effeciency
Assignment
1. Define the three classes of complexes.
2. What are chelates and their physical
properties?
3. What are the uses of chelates?