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RHEOLOGY

Pharmaceutics-I (Physical Pharmacy)

By:
AMK
CONTENTS
Definition & basic concepts
Newtonian systems
Non-Newtonian systems
Thixotropy/ Anti-thixotropy/Rheopexy
Rheology of emulsions & suspensions
Determination of rheological properties- Viscometers
Application of rheology
INTRODUCTION
It is derived from Greek word rheo means to flow and logos means science as
suggested by BINGHAM.
Scientifically, it is defined as:
the study of flow of fluids under applied stress (deformation forces)

Oil and water flow in familiar, normal ways, whereas honey, mayonnaise,
peanut butter flow in complex and unusual ways. In rheology, we study the
flows of unusual or interesting materials.
The two-plates model mathematically describes this definition.
All materials range on an imaginary scale from solid to liquid. In
scientific terms, solid materials are specified as elastic, while liquids
are viscous. However, most materials are not purely elastic, nor
entirely viscous, but viscoelastic. Depending on their properties,
substances can be classified as viscoelastic solids (like e.g. gels) or
viscoelastic liquids (like e.g. hair shampoo).
Viscometry deals with ideally viscous
fluids, and - with certain limitations - also
with viscoelastic liquids, i.e. viscous
substances with an elastic portion.
If a fluid flows easily, its resistance to
deformation is low. It is a low-viscosity
fluid. Fluids with greater resistance to
deformation do not flow easily. They are
highly viscous. At the same temperature high-viscosity fluids
flow more slowly than low-viscosity fluids
But how the flow of liquids is affected by stress or
deformation forces?????

A body may deform as a result of force applied to it:


The stress may be:
Tensile stress
If the stress is applied perpendicular to the body
Shear stress
If the force is applied tangentially (at any other angle) to the
body
The deformations that result from the application of stress may be:
REVERSIBLE or ELASTIC deformations:
The work used in producing this deformation is recoverable when the
body returns to its original shape after removal of the applied stress
IRREVERSIBLE or PERMANENT deformations:
These are referred as flow and are exhibited by viscous bodies.
The work used in producing this deformation is dissipated as heat and
is non-recoverable when the stress is removed
The Two-plates Model
This model consists of two imaginary plates with the fluid in-between.
Two conditions must be met to allow for accurate calculation of the
viscosity-related variables.
The fluid adheres to both plates and does not slip or slide along them.
There are laminar flow conditions. That means the flow takes the shape
of infinitesimally thin layers, no turbulence occurs.
A stack of beer mats gives a good idea of how laminar flow works.
Shear Stress (F)
While the lower plate stands still, the upper plate very slowly moves
along. Even the slow movement causes stress that is parallel to the
fluid's surface and which is called shear stress.
The shear stress is defined as the force F applied to the upper plate
divided by this plate's area A.
The force is measured in Newton, the area in square meters.
The shear stress tau is force divided by area. This calculation results in
the unit N/m2, which is called pascal [Pa] after Blaise Pascal.
Shear Rate (G)
A second variable that can be derived from the two-plates model is
the shear rate gamma-dot. In older literature the shear rate is
sometimes given as D.
To obtain the shear rate OR velocity gradient, the velocity v (or dv) of
the upper plate, in meters per second, is divided by the distance h (or
dr) between the two plates in meters.
This gives the unit [1/s] or reciprocal second [s-1].

Or G = dv/dr
When we talk about liquid flow, concept of
viscosity comes in our mind..
VISCOSITY ()
The term 'viscosity' simply means fluid's thickness.
A measure of fluids resistance to flow by an applied stress or deformation force.
It describes the internal friction of moving liquids and therefore its thickness.
Fluids with high viscosity resist motion because its structure and morphology results in lot of
internal friction between neighboring molecules that are moving with different velocities. E.g
Honey
In case of less viscous liquids, there is very little internal friction (between layers) when the
liquid is in motion. E.g. Water
Relationship between shear stress (F) is shear rate (G) is the basis of viscosity .i.e.

= F/G
where is the coefficient of viscosity, usually referred to simply as viscosity.
Fluidity, , a term sometimes used, is defined as the reciprocal of
viscosity:
= 1/

The shear rate is an important parameter in defining viscosity (refer


to the two-plates model) and also in specifying a substance's flow
behavior.
The vital question is whether a change of shear rate does or does
not change a fluid's viscosity. This question draws the line between
Newtonian and non-Newtonian fluids.
TYPES OF RHEOLOGICAL SYSTEMS:
1) Newtonian systems
2) Non- Newtonian systems
a. Plastic systems
b. Pseudoplastic systems
c. Dilatant systems
Newtonian Liquids
If a fluid's internal flow resistance is independent of the shear rate acting upon the fluid, it is
ideally viscous.
Such fluids are named Newtonian liquids after Sir Isaac Newton, Newtonian fluids are the
simplest type of fluid.
A Newtonian fluid is a fluid or dispersion whose rheological behaviour is described by
Newtons law of viscosity. He recognized that the higher the viscosity of a liquid, the greater
is the force per unit area (shearing stress) required to produce a certain rate of shear.
Newtonian flow is characterized by constant viscosity, regardless of the shear rates applied.
In an Newtonian fluid, such as water or oil, the shear stress is directly proportional to the
shear rate, while the fluid is in laminar flow.
A viscosity function means plotting the
viscosity over the shear rate. The
viscosity function of a Newtonian
liquid is a straight line.
Examples: water or salad oil.
Non-Newtonian Liquids
If a substance is not ideally viscous, its viscosity changes with the shear
rate. Such substances are called Non-Newtonian Liquids
Non-Newtonian flow is characterized by a change in viscosity
characteristics with increasing shear rates.
Non-Newtonian substances are those that fail to follow Newtons
equation of flow.
Example: materials include colloidal solutions, emulsions, liquid
suspensions, and ointments.
There are three general types of Non-Newtonian materials:
a. Plastic
b. Pseudoplastic
c. Dilatant
RHEOGRAM
A rheogram is a plot of shear rate (G) as a function of shear stress (F).
Rheograms are also known as consistency curves or flow curves.
The rheologic properties of a given material are most completely
described by its unique rheogram.
The simplest form of a rheogram is produced by Newtonian systems,
G=fF
The slope, f, is known as fluidity and is the reciprocal of viscosity, :
f = 1/
Therefore, the greater the slope of the line, the greater is the
fluidity or, conversely, the lower is the viscosity.
The rheogram of Newtonian systems can easily be obtained with a
single-point determination.
A non-Newtonian system can only be fully characterized by
generating its complete rheogram, which requires use of a multipoint
rheometer.
The majority of fluid pharmaceutical products are not simple liquids and do not
follow Newtons law of flow. These systems are referred to as non-Newtonian.
Non-Newtonian behavior is generally exhibited by liquid and solid
heterogeneous dispersions such as colloidal solutions, emulsions, liquid
suspensions, and ointments.
When non-Newtonian materials are analyzed and results are plotted, various
consistency curves, representing three classes of flow, are recognized:
a. Plastic
b. Pseudoplastic
c. Dilatant
a. Plastic Flow
In Figure, the curve represents a body that exhibits
plastic flow.
Such materials are known as Bingham bodies.
Plastic flow curves do NOT pass through the origin but
rather intersect the shearing stress axis at a particular
point referred to as the yield value.
IMPORTANT A Bingham body requires
certain amount of shear stress (Yield value) before it
begins to flow.
The slope of the rheogram is termed the
Mobility, and its reciprocal is known as the
plastic viscosity, U.
The equation describing plastic flow is:

Where:
f = yield value, or intercept, on the shear stress
axis
(dynes/cm2), and
F = Shear stress
G = Shear rate
At stresses below the yield value, the substance
acts as an elastic material.
Those substances that exhibit a yield value
(Bingham bodies) Solids,
Substances that begin to flow at the smallest
shearing stress and show no yield value Liquids.

A plastic system resembles a Newtonian system at


shear stresses above the yield value.

Once the Yield value has been exceeded, any


further increase in shearing stress (i.e., F f )
brings about a directly proportional increase
in G, rate of shear.
Example:
Plastic flow is associated with the presence of flocculated particles in
concentrated suspensions.

Yield value is an indication of Force of flocculation:


The more flocculated the suspension, the higher will be the yield value.

A continuous structure is set up throughout the system. 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
An example of a plastic material is toothpaste. It is necessary that
toothpaste will stay on the brush but it must be easily extrudable.
b. Pseudoplastic Flow
As seen in Figure, the consistency curve for a pseudoplastic material
begins at the origin therefore NO yield value.
NO part of the curve is linear, therefore the viscosity of a
pseudoplastic material cannot be expressed by any single value.
(entire consistency curve is used)

The viscosity of a pseudoplastic substance decreases with


increasing rate of shear. (Shear THINNING systems) i.e.
the more stress is applied, the more freely it flows

As shearing stress is increased, normally disarranged


molecules begin to align their long axes in the direction of
flow. This orientation reduces internal resistance of the
material.
Some of the solvent associated with the molecules may be
released, resulting in further decrease in viscosity.
The most frequently used exponential formula for
pseudoplastics is given as:

--------(1)
Where;
F = Shear stress
G = Shear rate
= viscosity coefficient
N = exponent
N rises as flow becomes increasingly non-Newtonian.
When N = 1, the above equation reduces to equation (
) and flow is Newtonian.
Following rearrangement, we can write the previous equation in the
logarithmic form:

--------(1)

Many pseudoplastic systems fit this equation when log G is


plotted as a function of log F.
Example:
Pseudoplastic flow is typically exhibited by polymers in
solution.
Many pharmaceutical products, including liquid dispersions
of natural and synthetic gums (e.g., tragacanth, sodium
alginate, methylcellulose, and sodium carboxymethyl
cellulose) exhibit pseudoplastic flow.

Plastic and pseudoplastic behaviors can be explained as


follows:
The decrease in apparent viscosity is due to the
disentangling of aggregates of dispersed particles
of the systems.
Modern paints are examples of pseudoplastic materials.
When modern paints are applied the shear created by the brush or
roller will allow them to thin and wet out the surface evenly. Once
applied the paints regain their higher viscosity which avoids drips and
runs.
Quick sand.?
c. Dilatant Flow
Certain suspensions with a high percentage of dispersed solids exhibit an increase in
resistance to flow with increasing rates of shear.
Such systems actually increase in volume when sheared and are hence termed
dilatant or Shear THINKENING systems.
Inverse of pseudoplastic systems.
When stress is removed, a dilatant system returns to its original state of fluidity.
Equation (1) can be used to describe dilatancy:

In this case,
N is always less than 1 and decreases as degree of dilatancy increases.
As N approaches 1, the system becomes increasingly Newtonian in behavior.
In short, the value of n or N indicates the type of flow:

N = 1 (Newtonian flow)
N > 1 (Pseudoplastic flow)
N < 1 (Dilatant flow)
Dilatant behavior can be explained as follows:
At rest; particles are closely packed with minimal
interparticle volume (voids). The amount of vehicle in
the suspension is sufficient, however, to fill voids and
permits particles to move relative to one another at low
rates of shear. Thus, a dilatant suspension can be poured
from a bottle because under these conditions it is
reasonably fluid.
At increased shear stress; As shear stress is increased,
the bulk of the system expands or dilates; hence the
term dilatant. The particles, in an attempt to move
quickly past each other, take on an open form of
packing, as depicted in Figure 193.
Such an arrangement leads to a significant increase in interparticle void
volume. The amount of vehicle remains constant and, at some point,
becomes insufficient to fill the increased voids between particles.
Accordingly, resistance to flow (viscosity) increases because particles are no
longer completely wetted, or lubricated, by the vehicle. Eventually, the
suspension will set up as a firm paste.
Behavior of this type suggests that appropriate precaution be used during
processing of dilatant materials.
IMPORTANT PRECAUTION Processing of dispersions containing solid particles
is facilitated by the use of high-speed mixers, blenders, or mills.
Although this is advantageous with all other rheologic systems, dilatant materials
may solidify under these conditions of high shear, thereby overloading and
damaging processing equipment.
Example:
Substances possessing dilatant flow properties
are suspensions containing a high concentration
(about 50% or greater) of small, deflocculated
particles.
This can readily be seen with a mixture
Oobleck.????
Corn starch and water (oobleck)
Cornstarch is a common thickening agent used in cooking. It is also a
very good example of a shear thickening system. When a force is
applied to a 1:1.25 mixture of water and cornstarch, the cornstarch
acts as a solid and resists the force.
Quicksand
Quicksand is a natural case of a shear thinning, non-Newtonian fluid.
This is the opposite of a dilatant. As its strain rate increases, its
resistance to shear will decrease causing the system to act more like a
liquid than a solid. Hence, as one thrashes about in quicksand one
sinks faster as the mixture's resistance decreases.
THIXOTROPY
Viscosity of a system not only depends on shear rate but is also time
dependent.
It may have been assumed that if the rate of shear were reduced
once the desired maximum had been reached, the down curve
would be identical with, and superimposable on, the up curve.
Although this is true for Newtonian systems, the down curve for
non-Newtonian systems can be displaced relative to the up curve.
Typical rheograms for plastic and
pseudoplastic systems exhibiting this
behavior are shown in Figure.
With shear-thinning systems (i.e.,
pseudoplastic), the down curve is
frequently displaced to the left of the
up curve (as in figure)
This indicates a breakdown of
structure (and hence shear thinning)
that does not reform immediately
when stress is removed or reduced.
The discussed phenomenon is known as thixotropy or shear duration
thinning, and can be defined as:

an isothermal and comparatively slow recovery (on standing of a


material) of a consistency lost through shearing.

As so defined, thixotropy can be applied only to shear-thinning


systems.
At rest, such structure confers some degree of rigidity on the system,
and it resembles a gel.
As shear is applied and flow starts, this structure begins to break
down. The material undergoes a gel-to-sol transformation and
exhibits shear thinning.
On removal of stress, the structure starts to reform. This process is
NOT instantaneous; rather, it is a progressive restoration of
consistency as asymmetric particles come into contact with one
another by undergoing random Brownian movement.
Rheograms obtained with thixotropic
materials (thixotropic curve or hysteresis
loop) is not unique but are highly
dependent on
Changes in rate of shear
Duration of time involved (at a particular
rate of shear)
In other words, the previous history of the
sample has a significant effect on the
rheologic properties of a thixotropic
system.
For example, suppose that in Figure 195 the shear rate of a
thixotropic material is increased in a constant manner from point a to
point b and is then decreased at the same rate back to e.
Typically, this would result in the so-called hysteresis loop abe.
If, however, the sample was taken to point b and the shear rate held
constant for a certain period of time (say, t1 seconds), shearing stress,
and hence consistency, would decrease to an extent depending on
time of shear, rate of shear, and degree of structure in the sample.
Decreasing the shear rate would then result in the hysteresis loop
abce and so on
Difference..
Rapid recovery of viscosity after disturbance classic shear-thinning
or pseudoplasticity.
Measurable time taken for the viscosity to recover thixotropic
behavior.
When describing the viscosity of liquids, however, it is therefore
useful to distinguish shear-thinning (pseudoplastic) behaviour from
thixotropic behaviour, where the viscosity at all shear rates is
decreased for some duration after agitation: both of these effects can
often be seen separately in the same liquid.
Measurement of thixotropy
This area of hysteresis has been proposed as a measure of thixotropic
breakdown.
With plastic (Bingham) bodies, two approaches are frequently used to
estimate degree of thixotropy:
i. The first is to determine structural breakdown with time at a constant rate
of shear. (Time is varied)
ii. The second approach is to determine the structural breakdown due to
increasing shear rate (Shear rate is varied)
i) The first is to determine structural breakdown with time at a
constant rate of shear.

Where,
B = Thixotropic coefficient (which indicates the rate
of break down with time at constant shear rate)
U1, U2 = Plastic viscosities
t1, t2 = time duration
ii) The second approach is to determine the structural breakdown
due to increasing shear rate

Where,
M = Thixotropic coefficient
U1, U2 = Plastic viscosities
V1, V2 = shear rates
Bulges & Spurs
Dispersions employed in pharmacy may yield complex
hysteresis loops when sheared in a viscometer. Two such
complex structures Includes:

Bulges
A concentrated aqueous bentonite gel (10% to 15% by
weight), produces a hysteresis loop with a characteristic
bulge in the up-curve.
It is presumed that the crystalline plates of bentonite form
a house-of-cards structure that causes the swelling of
bentonite magmas.
This three-dimensional structure results in a bulged
hysteresis loop as observed in Figure.
Bulges & Spurs
Spur
In still more highly structured systems, such as a procaine
penicillin gel, the bulged curve may actually develop into a
spur-like protrusion.
The structure demonstrates a high yield or spur value, ,
that traces out a bowed up-curve when the three
dimensional structure breaks in the viscometer, as observed
in Figure.
The spur value represents a sharp point of structural
breakdown at low shear rate.
It is difficult to produce the spur, and it may not be
observed unless a sample of the gel is allowed to age
undisturbed in the cup-and-bob assembly for some time
before the rheologic run is made.
Negative thixotropy or Antithixotropy
Generally, thixotropic systems are shear thinning i.e.
with a decrease in consistency in the down curve.
But some materials like magnesia magma (1-10%)
shows deviation from suggested behavior.
The down curve falls to the right of up-curve and it
continuously thickened and finally reached
equilibrium at which the up and down curves overlap
each other.
After reaching equilibrium, the system was found
to have gel-like property and showing greater
suspendability.
When allowed to stand, however, the material
returned to its sol-like properties.
It is believed that antithixotropy results from an increased
collision frequency of dispersed particles or polymer molecules
in suspension, resulting in increased interparticle bonding with
time.
This changes an original state consisting of a large number of
individual particles and small floccules to an eventual
equilibrium state consisting of a small number of relatively
large floccules.
At rest, the large floccules break up and gradually return to the
original state of small floccules and individual particles.
Rheopexy
Rheopexy is:
a phenomenon in which a sol forms a gel more readily when gently shaken or
sheared.

The system exists in gel state at equilibrium unlike antithixotropic substances


which exists in sol form.
Magnesia magma and clay suspensions may show a negative rheopexy,
analogous to negative thixotropy.
Thixotropy in formulations
Various pharmaceutical dosage forms like suspensions, emulsions,
creams, gels show thixotropic behavior, which helps in easy
spreadability and pourability from containers.

Example:
Gel preparation stored in a tube; gel from the tube does not start
flowing on opening the cap or inverting the tube. It only flows with
application of pressure. The reason behind is nothing but
thixotropy (i.e. shear thinning)
Same principle also apply for suspensions.
At rest high viscosity, with well suspended particles.
Upon shaking viscosity gets reduced which supports easy pouring from
the container.

In case of Procaine penicillin G in water (40-70% w/v), structural


breakdown occurs when it passes through the needle results in
easy flowability. After injection, it restores its consistency and
forms a depot at the site of injection which helps in maintaining the
sustain levels of drug in the body.
Determination of rheological properties
Viscometer is an instrument used to measure the viscosity of a fluid.
The selection of an appropriate viscometer is necessary for successful
determination of viscosity.
This selection depends upon the type of system whose viscosity is to be
determined.
Viscometers can be broadly classified as:
1) Single point viscometers
2) Multi point viscometers
1) Single point viscometers:
In case of Newtonian systems, where F is directly proportional to G, a
single point viscometer can be used.
These equipment work at single rate of shear
These viscometers provide a single point on rheogram; extrapolation of which
gives a complete rheogram.
It includes:
a) Capillary viscometer b) Falling sphere viscometer

2) Multi point viscometers:


In case of non-Newtonian systems, these types of viscometers are used.
(may be used for Newtonian systems as well).
These viscometers act at different shear rates to get the entire rheogram.
These include:
a) Cup and bob viscometer b) Cone and plate viscometer
Single point viscometers:
a) Capillary viscometer
Viscosity determination by
measuring Time required by the
liquid to pass between 2 marks
under the influence of gravity
through a vertical capillary tube
known as an Ostwald viscometer.
Principle:
The liquid is made to flow between two points X and Y.
The time of flow of liquid under test is noted and compared with the time of
flow of known liquid (usually water).
The equation that governs the flow of liquid through capillary tube is based
on law known as Poiseuilles law:

Where,
r = radius of the inside of the capillary (cm)
t = time of flow,
P = pressure head (dyne/cm2)
l = length of the capillary
V = volume of liquid flowing
The absolute viscosity of unknown liquid is obtained by using following
equation:

Where,
1 = viscosity of the unknown liquid
2 = viscosity of standard liquid
1 and 2 = respective densities of the liquids
t1 and t2 = respective flow times (sec)

This viscometer is most suitable for the liquids of low viscosity.


Single point viscometers:
b) Falling sphere viscometer

In this type of viscometer, a glass or steel ball rolls down


an almost vertical glass tube containing the test liquid at a
known constant temperature.
Rate at which a ball falls 1/ Viscosity of the sample

Example:
Hoeppler viscometer
Principle:
It consists of glass tube, which is positioned vertically.
The glass tube is filled with test sample.
A ball (steel or glass) is dropped in the tube as soon as temperature equilibrium
is achieved (between inner tube and outer jacket).
The tube and jacket assembly is then inverted, which places the ball at the top
of inner tube.
The time for the ball to fall between 2 marks is accurately measured.
The viscosity is then calculated as:

Where,
t = time interval taken by ball to fall between the two points (sec)
Sb and Sf = specific gravities of the ball and fluid, respectively.
B = constant for a particular ball

Reliable viscosity values range: 0.5 20,000 poise


For best results, a ball whose t > 30 seconds should be used.
Multi point viscometers:
a) Cup and bob viscometer
In cup-and-bob viscometers, the sample is sheared in the
space between the outer wall of a bob and the inner wall
of a cup into which the bob fits.

If the cup is rotated Couette type (Example: MacMichael


viscometer)
If the bob is rotated Searle type (Example: Rotovisco
viscometer, Stormer viscometer, Brookfield viscometer)
Principle:
In operation, the test system is placed in the space between the cup and the
bob and allowed to reach temperature equilibrium.
A weight is placed on the hanger, and the time required for the bob to make
100 revolutions is recorded. These data are then converted to revolutions
per minute (rpm).
The weight is increased and the whole procedure repeated.
In this way, a rheogram can be constructed by plotting rpm versus weight
added.
Here,
Number of revolutions (rpm) = rate of shear
Torque (weights added) = shear stress
For pseudoplastic systems:

For plastic viscosity:

Where,
Kv is a constant for the instrument
W = weight placed on hanger (g)
V = rpm or shear rate
U = plastic viscosity (poise)
Wf = yield value intercept (g)

The yield value of a plastic system is obtained by use of the expression:

Disadvantage Plug flow


Plug flow
In a viscometer of the Searle type:
Shear stress close to the rotating bob = sufficiently high so as to exceed the yield
value.
Shear stress at the inner wall of the cup = lie below the yield value.
Material in this zone would therefore remain as a solid plug and the measured
viscosity would be in error.
Major contributing factor the gap between the cup and the bob.
(use largest bob possible with a cup of a definite circumference)
Multi point viscometers:
b) Cone and plate viscometer

In this type of viscometer, the sample is placed at


the center of the plate, which is then raised into
position under the cone.

Example:
FerrantiShirley viscometer,
Brookfield viscometer
Principle:
the sample is sheared in the narrow gap between
the stationary plate and the rotating cone.
The speed of cone can be varied using variable -
speed motor.
The rate of shear in rpm is increased and decreased
by a selector dial and the viscous traction or torque
(shearing stress) produced on the cone is read on
the indicator scale.
A plot of rpm (rate of shear) versus scale reading
(shearing stress) can thus be constructed.
For Newtonian liquids:

Where,
C = instrumental constant,
T = torque reading,
v = speed of the cone in rpm

For plastic systems:

Where,
Tf = torque at the shearing stress axis (extrapolated from the linear portion of the curve)
Cf = instrumental constant.
f = Yield value =
Types of Viscosity
Absolute Viscosity (Shear/ Dynamic Viscosity)
= F/G

Units: Poise, Centipoise (1P= 100cP or 0.01P= 1cP)


The cgs units for poise= dyne . sec/cm2 or g/cm . sec
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.
Kinematic Viscosity
When Newtonian (absolute) viscosity is divided by density, it gives kinematic viscosity.
= /

Units: Stoke (S), Centistoke (CS)


Relative Viscosity
It is the ratio of viscosity of dispersion to that of solvent.
r = / o
Temperature dependence and the
theory of Viscosity
A fluid's viscosity strongly depends on its
temperature. Along with the shear rate,
temperature really is the dominating influence.
Viscosity of a liquid decreases as temperature
is raised, and the fluidity of a liquid (the
reciprocal of viscosity) increases with
temperature.

Factors influencing a substance's flow


behavior
For some fluids a decrease of 1C causes a 10 % increase
in viscosity.
The dependence of the viscosity of a liquid on
temperature is expressed by an equation analogous to the
Arrhenius equation of chemical kinetics:
-1C in temperature => +10 % in
viscosity

Where,
A = constant depending on the molecular weight and molar
volume of the liquid
Ev = activation energy required to initiate flow between
molecules.
R = Gas constant
T = Temperature (K)
RHEOLOGY OF SUSPENSIONS

The flow property of suspension depend upon their rheological


characters
The rheological properties of suspension decide the pourability, easy
of injection, sedimentation, its redispersibility.
The viscosity of flocculated suspension is greater than deflocculated
particles in same suspension.
The flocculated suspension has yield value and behave like a plastic or
pseudo plastic system.
Example: conc.parenteral suspension contain 40- 70 % w/v of procain
pencillin G
RHEOLOGY OF EMULSIONS
Dilute emulsions Newtonian type flow
Highly concentrated emulsions Plastic flow

The important properties influencing the emulsions :


Aggregation of particles
Viscosity of continuous phase
Globule size and size distribution
Nature and proportion of emulsifying agent
Applications of Rheology
Understanding the fundamental nature of a system (basic science)
Quality control (raw materials and products, processes)
Tuning rheological properties of a system has many applications in
every day's life
Pharmaceutics
Cosmetics
Chemical industry
Oil-drilling
etc
SUMMARY
Rheology
Shear stress (F/A)
Shear rate (dv/dx)
Viscosity (= F/G)
Types of Viscometers

1. Single point 2. Multi point


viscometer viscometer

Capillary Cup and bob


viscometer viscometer

Falling Cone and


sphere plate
viscometer viscometer
Interesting Fact
(Rheology)
Worlds Longest Running Laboratory
Experiment The Pitch Drop Experiment
1927 Prof Parnell in University of
Queensland Australia heated a sample of
pitch and poured it into a glass funnel with a
sealed stem. Three years where allowed for it
to settle, after which the stem was cut.
Examine the viscosity of the pitch by the
speed at which it flows from a funnel into a
jar.
Only eight drops has fallen in 80 years.
The viscosity is approximated as 100 billion
times that of water.

Dr. Aldo Acevedo - ERC SOPS


REFERENCES
Martins Physical Pharmacy And Pharmaceutical Sciences, (6th
Edition)
Cooper and Gunns Tutorial Pharmacy (6th Edition)
World of Rheology (http://www.world-of-rheology.com)
Viscopedia (http://www.viscopedia.com)