RHEOLOGY

STUDY OF FLOW OF LIQUIDS & DEFORMATION

OF SOLIDS AS A RESULT OF APPLIED PRESSURE
 INTRODUCTION
Derived from Greek word
Rheo to flow

Logos science

Suggested by Bingham & Crawford to describe

Flow of liquid &

Deformation of solids
 Applications
Manufacture of dosage forms
Handling of drugs for administration
 TYPES OF FLOW

Newtonian

Non- Newtonian

Choice depends on whether or not their flow properties are in accord

with Newtons law of flow

NEWTONIAN
SYSTEMS
Newtonian systems: Obey Newtons law of flow

Examples

Homogenous liquids s.a. water, glycerin, alcohol, chloroform, oil etc

Newton was the first to study flow properties of liquid in quantitative

way.
He recognized that higher the viscosity of a liquid, greater the force

per unit area required to produce a certain rate of shear.

Thus, rate of shear should be directly proportional to shearing stress.
 NEWTONS LAW
Consider a block of liq & assume that it is made up of parallel layers
of liquids.

Bottom layer is fixed to plane so that it is stationery

Let force F be applied horizontally onto topmost layer.

Liq begins to flow.

Topmost layer moves with higher velocity.

While moving ahead, topmost layer induces flow in 2nd layer

Velocity of 2nd layer is less than 1st layer, because of viscous drag offered by
3rd layer

Phenomena continues & velocity decreases as they approach bottom

stationary layer

Thus, liq resists flow when force is applied

Rate of Shear: Difference of velocity (dv) b/w 2 layers of liq separated by
a change in distance (dr)

Shearing Stress: Force applied per unit area reqd to bring about flow

Acc to Newtons law, rate of shear is directly proportional to shearing

stress; thus

or

Where, = coefficient of viscosity

 Thus, Newtons law of flow can be stated as:

Higher the viscosity of a liquid, greater the shearing stress

required to produce a certain rate of shear
 NEWTONIAN SYSTEMS

Rheogram or Flow curve

The rheogram passes through the origin and the slope gives the
co.efficient of viscosity.
NON-NEWTONIAN
SYSTEMS
 NON-NEWTONIAN SYSTEMS
Substances that fail to follow Newton's equation of flow

Most pharmaceutical fluids do not follow this law because viscosity

of fluid varies with rate of shear

Examples

Liquid & solid heterogeneous dispersions such as colloidal solutions,

emulsions, liquid suspensions, ointments & similar products
 TYPES OF NON-NEWTONIAN
SYSTEMS
Depending on how viscosity changes with shear rate flow behavior is
characterized as follows:

1. Plastic systems: exhibit a so-called yield value, i.e. a certain shear

stress must be applied before flow occurs

2. Pseudoplastic systems: viscosity decreases with increased shear

rate. Also called as Shear thinning fluids.

3. Dilatant systems: viscosity increases with increased shear rate.

Also called as Shear thickening fluids.

 PLASTIC FLOW
Materials that exhibit plastic flow are called as Bingham bodies in
honor of pioneer of modern rheology & 1st investigator to study
plastic substances in a systematic manner.

Consistency curve for plastic flow does not pass through origin.

Subs initially behaves like an elastic body & fails to flow when less
amt of stress is applied.

Further increase in shear stress leads to non-linear increase in shear

rate, which progressively gets linearised.

Linear portion when extrapolated intersects shearing stress axis at a

point called Yield value
Below yield value subs is elastic

Rheogram or Flow curve

Resembles Newtonian system above yield value

Plastic flow can be adequately expressed in terms of yield value &
plastic viscosity

Acc to consistency curve:

Slope of rheogram = Mobility (1/U)

Reciprocal of mobility = Plastic viscosity (U)

Where, F = Shear stress; G = Rate of shear; f = Yield value

Yield value is the intercept of shear stress axis & expressed in

dynes/cm2
Plastic flow is associated with presence of flocculated particles in
concentrated suspensions, butter, certain ointments, pastes & gels

MECHANISTIC REPRESENTATION FOR CONC FLOCCULATED SUSPENSION

MECHANISTIC EXPLANATION FOR CONC FLOCCULATED SUSPENSION

In flocculated suspensions, at zero stress or at rest, floccules are present.

When stress is applied initially, suspension fails to flow, until sufficient stress is
applied that is reqd to break inter-particle contacts, so that particles behave
individually.

Thus, yield value is indicative of forces of flocculation.

Frictional forces b/w moving particles also contribute to yield value.

More conc or flocculated the suspension, higher will be the yield value.

Once the yield value exceeds, further increase in shearing stress will bring about a
proportional increase in rate of shear.

Thus at shear stresses above yield value, plastic system resembles Newtonian
systems.
 PROBLEM
A plastic material was found to have a yield value of 1800
dynes/cm2. If the shear rate was 180/sec at a shear stress of 2900
dynes/cm2, calculate plastic viscosity of the sample?
 PSEUDOPLASTIC FLOW
Consistency curve for pseudoplastic flow begins at origin.

There is no yield value.

As shear stress increases progressively, shear rate also increases.

No part of the curve is linear.

Viscosity of pseudoplastic system cannot be determined by single

value.

Viscosity of pseudoplastic subs decreases with increase in rate of

shear thus described as SHEAR THINNING SYSTEMS

Example:

Paint, Shampoo, Slurries etc

Rheogram or Flow curve
Newton eq is modified as follows:

Where, = viscosity coefficient for pseudoplastic system

N = Index of pseudoplasticity

For pseudoplastic systems N >1 & rises as flow becomes

increasingly non-newtonian

Taking log on both sides

On rearrangement, we get
Pseudoplastic flow is shown by natural & synthetic gums, e.g. liquid
dispersions of tragacanth, sodium alginate, methylcellulose &
sodium carboxymethylcellulose.
MECHANISTIC REPRESENTATION FOR SYSTEM WITH PSEUDOPLASTIC
FLOW
MECHANISTIC EXPLANATION FOR SYSTEM WITH PSEUDOPLASTIC FLOW

Under normal storage conditions, long chain molecules of polymers are randomly
arranged in dispersion.

On applying shear stress, molecules that are disarranged, begin to arrange or align
their long axis in direction of force applied.

This stress induced orientation reduces internal resistance of material.

In addition, solvent molecules which were earlier associated with polymer

molecules will also be released.

Thus effective conc & size of molecules are lowered.

This too will lower apparent viscosity.

Now the material allows greater shear rate on progressive increase in shear stress.
 DILATANT FLOW
Consistency curve for dilatant flow begins at origin.
There is no yield value.
System exhibits enhanced resistance to flow with increasing rate of shear.
These systems increase in volume when sheared hence termed as
Dilatant.
No part of the curve is linear.
Viscosity of dilatant system cannot be determined by single value.
Viscosity of dilatant subs increases with increase in rate of shear thus
described as SHEAR THICKENING SYSTEMS.
When stress is removed, system returns to its initial state of fluidity.
Example:
Suspensions with high % of dispersed solids (>50%); Wet sand; Conc starch
suspensions .
Rheogram or Flow curve
Newton eq is modified as follows:

Where, = viscosity coefficient for dilatant system

N = Index of dilatancy

For dilatant systems N < 1 & decreases as degree of dilatancy

increases

Taking log on both sides

On rearrangement, we get
Dilatant flow is shown by Suspensions with high % of dispersed
solids (>50%)

MECHANISTIC REPRESENTATION FOR DILATANT SYSTEM

MECHANISTIC EXPLANATION FOR DILATANT SYSTEM

When dilatant system is at rest, molecules are closely packed. Minimum void
volume is available & amt of vehicle in system is sufficient to fill void vol.

This situation allows particles to move relative to one another.

Thus, system at rest exhibits relatively low consistency.

Hence, one may pour a dilatant suspension from a bottle, because under these
conditions, it is reasonably fluid.

When shear stress is applied, particles assume open form of packing & bulk of
system expands or dilates i.e. void volume significantly increases because
particles try to move quickly.

But amt of vehicle is insufficient to fill this expanded void space.

Thus, particles are not wetted & develop resistance to flow.

Finally system will show a paste-like consistency.

CAUTION FOR DILATANT SYSTEM

1. Since dilatant systems form a paste-like consistency, one has to be cautious in

selecting equipment in mfr of dispersion systems of a dilatant type.

2. In mixing & size reduction: Processing of dispersions containing solid

particles is facilitated by use of high speed mixers, blenders or mills.

But dilatant materials may solidify under these conditions of high shear, thereby
overloading & damaging processing equipment.

Hence, for dilatant materials, larger container is reqd & equipment is operated at
slow rate.

3. Sediment in deflocculated suspension is dilatant & resists an attempt of stirring

or shaking. This effect is known as caking or claying of suspension. This
behavior should be avoided.
 RHEOGRAMS

DO NOT GET CONFUSED

Here Shear rate is on x-axis & Shear stress is on y-axis. Thus
curves are inverted.
In previous curves, Shear rate was on y-axis & Shear stress
 THIXOTROPY
Isothermal & comparatively slow recovery, on standing

of a material, of a consistency lost through shearing

Shear thinning systems, when agitated & kept aside are expected to

return to its original state of fluidity.

But it takes longer time to recover, when compared to time taken for

agitation.

This behaviour is called as THIXOTROPY.

This phenomena is observed with plastic & pseudoplastic systems.

Phenomena is observed by constructing consistency curves.

Rate of shear is progressively increased & corresponding stress is measured

using a suitable instrument.

When these readings are plotted, a up-curve is obtained.

From desired maximum, if rate of shear is reduced gradually, down-curve is

obtained.

In Newtonian systems down-curve would be identical &

superimposed on up-curve.

In Non-Newtonian systems down-curve can be displaced with regard

to up-curve.
 With shear-thinning systems (i.e. Plastic & Pseudoplastic) down-curve is

frequently displaced to the left of up-curve.

Figure shows that material has a lower consistency at any one rate of

shear on the down-curve than it had on up-curve.

This indicates a breakdown of structure that does not reform immediately when

stress is removed or reduced. This phenomenon, known as Thixotropy, which

may be applied only to shear-thinning systems.
Phenomenon of Thixotropy can be explained in terms of Particle-particle
interaction.
At rest, particles in dispersion impart rigidity on system through multi

point contacts. System behaves like a gel.

As shear is applied, contacts begin to break down, particles are aligned

& flow starts. Material undergoes gel-to-sol transformation, inducing

system to exhibit shear thinning.
Upon removal of stress, system starts regaining its original state. This

process is not instantaneous. Particles slowly come in contact with one

another owing to random Brownian movement & progressively original
consistency will be restored.
If system is viscous or consists of large, heavy particles, brownian motion
will be too slow to re-establish broken links.

More or less, extensive period of rest is reqd to rebuild original structure &
reach initial viscosity.

Events GEL-SOL-GEL TRANSFORMATION

 DEVIATION OF THIXOTROPY
Deviation from std rheogram takes place resulting in complex hysteresis
loops.

1. BULGES:

E.g. Concentrated aqueous magma (gel) of bentonite (10-15% by weight)

Mechanism: Bentonite absorbs water, swells & forms a 3-dimensional

structure of higher consistency resulting in a characteristic bulge in up-
curve.
2. SPURS:

E.g. Procaine Penicillin gel

Mechanism: Here, bulged curve develops into a spur like protrusion.

Structural breakdown is indicated by High Spur Value Y in up-curve.

Spur value represents a sharp point of structural breakdown at a low shear

rate in up-curve.

Procaine penicillin gels exhibiting definite

Spur value Y produce prolonged blood

levels of drugs, as they form i.m depots

on injection.
Rheogram of thixotropic material depends on:

1. Rate at which shear is increased or decreased.

2. Length of time during which a sample is subjected to any one rate of

shear.

In a thixotropic system, Hysteresis Loop is formed by up & down curves

of rheogram.

Higher the area of hysteresis loop, higher is the thixotropy.

Area of hysteresis thixotropic breakdown

It can vary with history of conditions to which system is subjected.

 MEASUREMENT OF THIXOTROPY
A quantitative measurement of thixotropy can be attempted in several ways.

The most apparent characteristic of a thixotropic system is the hysteresis

loop, formed by up- & down-curves of rheogram.

Area of hysteresis has been proposed as a measure of thixotropic

breakdown.

It can be obtained readily with help of planimeter.

With plastic (Bingham) bodies, two approaches are used:

1. Determination of structural breakdown with time at a constant rate of

shear.

2. Determination of the structural breakdown due to increasing shear rate.

Determination of structural breakdown with time at constant rate of shear:

Based on such a rheogram, a thixotropic coefficient B, rate of breakdown

with time at constant shear rate, is calculated as follows:

U1 & U2 plastic viscosities of two down curves, calculated after shearing at a

constant rate for t1 & t2 seconds, resp.

For accurate measurement, rheograms

should be obtained at several rates of shear
Choice of shear rate is arbitrary
More meaningful though time
consuming
EXPLANATION:

Consider a material that follows plastic flow.

Suppose shear rate is increased at a constant rate on system from

point a to a point b & then decreased at same rate back to point
e; it results in a hysteresis loop abe.

If shear rate is maintained at point b for a time t 1 sec & then

decreased; abce rheogram is obtained.

Similarly, at point b if shear rate is maintained for time t 2 sec & then
decreased, abde curve is obtained.

The structural breakdown with respect to time at constant rate of

shear gives the rheogram.
Determination of the structural breakdown due to increasing shear rate:

In this case, a thixotropic coefficient M, loss in shearing stress per unit

increase in shear rate, is obtained from (diff max rates of shear v1 & v2):

Where, M is in dynes sec/cm2 & U1 & U2 are plastic viscosities for two
separate down-curves having maximum shearing rate of v1 & v2, resp.
 THIXOTROPY IN FORMULATION
1. Formulation of suspensions:

Well formulated suspension should have high consistency in container

during storage, so that suspended particles do not settle rapidly.

On moderate shaking, suspension should become fluid, so that contents can

be poured easily from container. Thus thixotropy is useful in dispensing
& admn of a dose.

Finally, at rest, suspension should regain its original consistency such that
particles are maintained in a suspended state.

Thus thixotropy rate of sedimentation improved physical stability.

[Similar behavior is desirable in emulsions & parenteral suspensions]

2. Formulation of ointment:

At rest, ointment should be within the tube.

On applying force to tube, ointment should become fluid so that it oozes

out of tube.

After removal of stress, ointment should remain consistent inside the tube
at rest.

3. Formulation of semisolids & fluids meant for application on skin:

If thixotropic, spreading becomes easier i.e. due to friction.

Semisolids liquefy & spread.

After application, they remain at site of application for longer time because
they regain consistency slowly.
4. Formulation of injections:
Parenteral suspensions containing 40-70% of procaine penicillin G in water
have high thixotropy.
At rest, it remains as a gel so that particles are uniformly distributed in
container.
On application of stress, it becomes fluid so that it can pass through the
needle.
Slow regaining of consistency gives sufficient time to inject.
While injecting, structure of suspended particles break down so that the pdt
can pass through the needle.
After injection, original structure of gel is rebuilt.
Slow rebuilding of rheological structure leads to formation of depot at site
of injection in muscle, from which drug is slowly released, so as to
provide sustained levels of drug in body.
Limitations of Thixotropy:

1. Degree of thixotropy may change over a period of time or due to

ageing.

Thus it is necessary to study effect of ageing & carefully follow

changes in parameters such as plastic viscosity, area of hysteresis

loop, yield value & spur value.

2. Thixotropy may change due to change in temp.

 NEGATIVE THIXOTROPY
Also known ANTI-THIXOTROPY

Represents an increase in consistency on down curve than up-curve

at a particular rate of shear.

Rate of structure building is faster than rate of structure breakdown.

Thus, in rheogram, down-curve shifts to the right of up-curve.

Anti-thixotropy is observed with flocculated suspensions containing low
conc (5-10%) of solids
E.g. Magnesia magma i.e. Magnesium hydroxide mixture
At rest, it shows sol-like properties.
On application of stress, it behaves like a gel & imparts greater
suspendability.
At eqm, it is readily pourable.
When magnesia magma is sheared alternatively with increasing & then
decreasing rate of shear, the magma thickens.
As cycles continue, extent of increase in thickening reduces gradually &
finally reaches eqm state.
There will be no change in consistency
curves on further cycles of shear rate.
ANTI-THIXOTROPY should not be confused with dilatancy.

Dilatant systems are deflocculated & volume of solids is high

(>50%).

Whereas, negative thixotropy is seen in flocculated systems

containing low solid content (1-10%).

Phenomenon of Anti-thixotropy can be explained in terms of Particle-
particle interaction.
At rest, system consists of a large no. of individual particles & small

floccules.
As shear is applied, polymer molecular collisions are increased at a

greater frequency. As a result, inter particle bonding increases.

At eqm, large floccules are available in small no. System exhibits sol

form.
When pdt is allowed to rest, large floccules break up & gradually return

to its original state of small floccules & individual particles.

Events
 RHEOPEXY
Phenomena in which sol transforms to gel state more rapidly rather
than keeping a sol at rest.

It is a phenomena where regaining of structure is made faster due to

gentle shaking or swirling. i.e. gentle shaking or low rate of shear
is sufficient to transform a sol into a gel.

On shaking, particles are made to collide with each other & thus
increasing points of contact. Hence, regaining consistency
becomes faster.

Systems which exhibit rheopexy are known as Rheopectic systems.

VISCOSITY
 VISCOSITY
Viscosity is an index of resistance of a liquid to flow.

Higher the viscosity, greater is the resistance.

Coefficient of viscosity: Force per unit area reqd to maintain unit

difference in velocity b/w two parallel layers in liquid, one cm
apart
 UNITS OF VISCOSITY
Unit of viscosity is Poise

Poise is defined as the shearing force required to produce a velocity

of 1 cm/sec b/w two parallel planes of liquid each 1 cm2 in area &
separated by a distance of 1 cm.

CGS unit for poise are dyne sec cm-2 or g cm-1 sec-1.

These units are readily obtained by a dimensional analysis of

viscosity coefficient.
In SI system, unit of viscosity is Newton/m2 sec-1, which is equal to
10 poise.

Since many common liquids including water have viscosities of the

order of 1/100 of a poise, it is convenient to employ a centipoise.

1 cp = 0.01 poise

FLUIDITY is defined as the reciprocal of viscosity

In other words: = slope of rheogram in Newtonian System

Newtonian Viscosities of Common Liquids

Liquids Temperature Viscosities

(C) (poise)
Water 20 0.0100
50 0.0055
99 0.0028

Ethanol 20 0.0120
50 0.0070

Benzene 20 0.0065
50 0.0044
Glycerin 20 15

Castor oil 20 10.3

 KINEMATIC VISCOSITY
It is the absolute viscosity divided by density of liquid at a definite
temperature

Where,

= density of liquid

Units of kinematic viscosity: stokes or centistoke

 RELATIVE & SPECIFIC VISCOSITY
Einstein developed an equation of flow applicable to dilute colloidal
dispersions of spherical particles, namely,

Where, = volume fraction of colloidal particles present,

0 = viscosity of dispersion medium

= viscosity of the dispersion

According to definition, is equivalent to a concentration term

Relative viscosity (rel) of a solution or dispersion is the ratio of
solution or dispersion viscosity () to viscosity of solvent or
dispersion medium (0):

Where specific viscosity (sp) is given by:

Since volume fraction is directly related to concentration

where c = grams of colloidal particles per 100 ml of total dispersion

 INTRINSIC VISCOSITY
If sp/c , the viscosity number or reduced viscosity is determined at
a range of polymer concentrations & plotted along y-axis as a
function of concentration, c (x-axis):

Then a linear relationship should be obtained,

i. Intercept produced on extrapolation of line will yield constant k 1

which is limiting viscosity number or intrinsic viscosity [] ,

ii. Intrinsic viscosity may be used to determine approximate

molecular mass (M) of polymer using Mark-Houwink equation
Mark-Houwink equation:

Where K & are constants characteristic of particular polymer-solvent

system, obtained at given temp for specific polymer-solvent system.

These constants are independent of MW & are obtained initially by

determining [] for polymer fractions whose MWs have been determined
by other methods such as light scattering, osmotic pressure or
sedimentation.

Once these constants are known then viscosity determinations provides a

quick & precise method of molecular mass determination of pharm
polymers s.a dextran, bio-polymer formed from enzyme technology,
which is used as blood plasma volume expanders.
 Temperature Dependence & Theory
of Viscosity
While viscosity of gas increases with temp, it can be observed that viscosity
of liq decreases as temp is raised, & fluidity of a liq increases with temp.

Dependence of viscosity of liq on temp is expressed approximately for

many subs by an eq analogous to Arrhenius equation of chemical
kinetics:
Ae Ev / RT

Where, A = Arrhenius factor or frequency factor, depending on molecular

weight & molar volume of liquid

Ev = activation energy reqd to initiate flow b/w molecules

R = Gas constant, 1.987 calories/deg mole

T = Absolute temperature
Arrhenius equation can be written in logarithmic form as follows:

Ev 1
ln ln A
RT
Energy of vaporization of a liq is energy reqd to remove a molecule from a
liq, leaving a hole behind equal in size to that of the molecule that has
departed.
A hole must also be made available in a liq if one molecule is to flow past
another.
Activation energy for flow has been found to be about one-third that of
energy of vaporization, & can be concluded that free space reqd for flow
is about one-third the vol of a molecule.
This is because a molecule in a flow can come back, turn & maneuver in a
space smaller than its actual size.
More energy is reqd to break bonds & permit flow in liqds composed of
molecules that are associated through hydrogen bonds.
These bonds are broken at higher temp by thermal movement & Ev
decreases markedly.
 DETERMINATION OF VISCOSITY

Instrument used to measure viscosity for rheological study are called

VISCOMETERS

They are classified into 2 types:

1. Single point viscometer

2. Multiple point viscometer

Single point viscometer

Capillary Viscometer

E.g. Ostwalds viscometer

Falling sphere (ball) Viscometer

E.g. Hoeppler viscometer

Multiple point viscometer

Cup and Bob Viscometer

Couette type. E.g. Mac Michael viscometer

Searle type. E.g. Stormer viscometer

Cone and plate Viscometer

E.g. Ferranti Sherly viscometer

 Choice of Viscometer

1. Newtonian systems:
Rate of shear is directly proportional to shearing stress, thus one can use
instruments that operate at a single rate of shear.
Thus one point instruments provide a single point on rheogram;
extrapolation of a line through this point to origin will result in the complete
rheogram.
Capillary & falling sphere viscometers are commonly used for Newtonian
materials.
2. Non-Newtonian systems:
The instrumentation used must be able to operate at variety of rates of shear.
Only by use of multi-point instruments is it possible to obtain complete
rheogram for these systems.
Cup and bob & cone and plate viscometers are commonly used for Non-
Newtonian materials.
 SINGLE POINT VISCOMETER
They work at a single rate of shear.

Since rate of shear in a Newtonian system is directly proportional to

shearing stress, single point viscometers can be used for
Newtonian systems.

This instrument provides a single point on rheogram.

Extrapolating of a line through this point to origin will result in

complete rheogram.
 CAPILLARY VISCOMETER
Ostwald viscometer

Used to determine viscosity of Newtonian liq.

Both dynamic & kinematic viscosities

can be obtained.

Here, liq flows under force of gravity

& not rate of shear.

Hence called as single point viscometer.

Construction: Consists of 2 arms with one bulb each.

Bulbs are placed at different levels.

Narrower limb has a capillary.

Principle: When fluid flows by gravity, time reqd for liq to pass b/w
2 marks through a vertical capillary tube of viscometer is
determined.

Time of flow of liq under test is compared with time reqd for a liq of
known viscosity.

Viscosity can be determined using the foll eq:

1=viscosity of unknown liquid

2=Viscosity of known liquid

1& 2= viscosity of each liquid respectively

t1 & t2 = Time required to flow each liquid respectively.

Derivation: Derived from Poiseuilles law

It expresses relationship for flow of liq through capillary viscometer.

Where,

= viscosity of liq

r = radius of inside capillary

t = time of flow

v = vol of liq flowing

l = length of capillary
For a given Ostwald viscometer, radius, length & volume are
constants & may be combined into a single constant K

Thus eq can be written as =KtP

Where, P represents shearing stress; which depends on density of

liq being measured, acceleration due to gravity & difference in
heights of liq arms of viscometer.

P=gh

Acceleration due to gravity is a constant & levels in capillary tube

can be made constant by taking accurately measured identical vol
of all liq.

Hence P =
If all these constants are incorporated into above eq, viscosity of liq
may be expressed as,

= K t

Where, K = constant of viscometer

Above eq can be directly used to determine viscosity of a liquid.

Thus, viscosity of unknown liq 1 & known liq 2 is:

1 = K t1 1 & 2 = K t2 2

Combining above 2 eq gives:

Ostwald viscometer gives only mean value of viscosity because only
one value of pressure head is possible.

It is applicable for less viscous solutions.

It is not applicable for highly viscous liq, due to difficulty of filling

viscometer with accurate vol. & drainage errors during filling
procedure may result in overfilling.

Thus suspended level viscometer is used.

E.g. Methylcellulose dispersions.

Method: Refer module

Application:

1. Quality control purposes in formulation & evaluation of pharm

dispersion systems s.a colloids, dilute suspensions, emulsions etc.

2. Official in IP for evaluation of liquid paraffin & dextran 40

injection.

3. Study of flow of liq through a capillary tube throw light upon

circulation of blood.

Re- Dvd/
 FALLING SPHERE VISCOMETER
Principle involved is based on Hoeppler viscometer.

Construction:

Consists of a glass tube positioned vertically.

Constant temp jacket with provision for

water circulation arranged around a glass tube.

Test liq is placed in glass tube.

Steel/ glass ball is dropped into the liq & allowed to

reach eqm with temp of outer jacket.

Tube with jacket is inverted, which places ball

at the top of inner glass tube.

Time taken for ball to fall b/w 2 marks is measured.

For Newtonian liquid

t = Time in sec for ball to fall b/w two points

Sb = Specific gravity of ball

Sf = Specific gravity of test fluid

B = Constant for ball (supplied by manufacturer)

https://www.youtube.com/watch?v=wmQTjtKOmCQ
Derivation: Derived from Stokes equation

Where, v = Rate of fall of ball

h = Height at which ball falls,
t = Time for ball to fall
d = diameter of ball
= viscosity of medium
s & o = density of ball & medium resp.
g = acceleration due to gravity

Here, d, g & h are constants denoted by B, Thus

Advantages:

1. Simple to operate

2. Measurement is of shorter duration

3. Since a variety of balls of different material & different diameter

are available, it can be used to determine a wide range of viscosity
i.e. 0.5 2,00,000 poise.

Metal balls are suitable for highly viscous solution & glass balls are
used for less viscous solutions.

Ball must be chosen such that time taken for a ball to fall b/w 2
points should be > 30 sec. Thus larger possible diameter ball
should be employed.
 MULTIPLE POINT VISCOMETER
Used for evaluation of newtonian & non-newtonian fluids.

Newtonian systems Determine viscosity when maintained at

constant rate of shear.

Non-newtonian Determine apparent viscosity at several rates of

shear to get entire consistency curve.

 CUP & BOB VISCOMETER
Rotational viscometer

Method:
Sample is placed in a cup.

Bob is placed in the cup up to an appropriate height.

Sample is sheared in space b/w outer wall of bob & inner wall of cup into
which the bob fits.

Either the cup or bob is made to rotate & torque resulting from viscous drag
is measured by a spring or sensor in the drive of the bob.

Various instruments are available which differ mainly whether torque set up
in bob results from cup or bob caused to revolve.
Thus, Cup & Bob viscometers can be of 2 types:

1. Couette type: Revolving cup type & bob is left free.

E.g. Mac Micheal viscometer

Here, viscous drag on bob due to sample causes it to turn. The

resultant torque is proportional to viscosity of sample.

2. Searle type: Stationary cup & Rotating bob type

E.g. Stormer viscometer

Here, torque resulting from viscous drag of system under examn is

measured by a spring or sensor in the drive to the bob.
Stormer viscometer
Std liq or sample liq is placed in a space b/w cup & bob & is allowed to
reach temp eqm with help of water jacket.
Bob is connected to a hanger through torsion wire.
Weights are hung on hanger.
Weights added represent shearing stress.
Time reqd for bob to make 100 revolutions is recorded.
Data is converted to rpm.
Weight is increased & whole procedure repeated.
Rheogram can be constructed by plotting rpm vs wt added.
Using appropriate constants, rpm values can be converted to actual shear
rates in sec-1.
Weights added can be converted into units of shear stress (dynes/cm2)
For rotational viscometers, shear stress shear rate relationship can
be expressed as follows (for pseudoplastic flow):

Where, =Angular velocity (radians/sec)

T= torque (dynes/cm2)

h = depth of bob immersion

Rb & Rc = Radii of bob & cup resp.

h, Rb & Rc are combined as Kv = constant for instrument.

Where, w = weights added & v = corresponding rpm

For rotational viscometers, shear stress shear rate relationship can
be expressed as follows (for plastic flow):

Where, U = plastic viscosity (poise)

wf = yield value (grams)

w = weights added

v = rpm
NOTE: Viscous drag of sample on base of bob is not taken into account.
Either an end correction must be applied, or base of bob is recessed.
In this case, pocket of air is entrapped b/w sample & base of bob, rendering
contribution from base of bob negligible.
Disadvantage of cup & bob viscometer:

Variable shear stress exerted across the sample between cup & bob.

Material near the inner wall of cup can form a solid plug. E.g. Plastic system.

Kind of flow where a system as a whole does not exhibit a uniform flow is known
as Plug Flow

Operator should use largest bob possible with a cup of definite circumference so as
to reduce the gap & minimize chances of plug flow.

Increasing speed of rotation of bob so that stress at outer wall of cup is above yield
value & system undergoes laminar flow.

Cone & plate viscometer minimizes plug flow.

Plug flow is imp in flow of pastes.

E.g. extrusion of toothpaste & ointment from tube.

 CONE & PLATE VISCOMETER
E.g. Ferranti- Shirley viscometer

Rotating cone & stationary plate type.

Sample placed at centre of plate.

Raised up to position under the cone.

Variable speed motor drives the cone.

Sample sheared in the narrow gap between stationary plate & rotating
cone.

Rate of shear (rev/min) is increased & decreased by a selector dial.

Shearing stress (torque or viscous traction) is recorded on indicator

scale.
Viscosity in poise of Newtonian liquid is estimated by:

Where, C = Instrumental constant; T = Torque; v = Speed of cone (rpm)

Plastic viscosity is estimated by:

Where,

Cf = Instrumental constant

f = Yield value = Cf x Tf

Tf is torque at the shearing stress axis (extrapolated from linear portion of

curve)
ADVANTAGES

1. Rate of shear is constant throughout entire sample sheared.

Thus, Plug flow avoided.

2. Cone angle is generally from 0.3 to 0.4 (small angle preferred)

3. Ease in cleaning & filling.

4. Less Time reqd for temp stabilization of sample run.

5. Cup & bob requires 20-50ml sample while cone & plate requires
0.1-0.2 ml.

6. Suitable attachment can increase or decrease rate of shear in a

predetermined reproducible manner & thus help in estimation of
thixotropy.
 APPLICATIONS OF RHEOLOGY
In case of Fluids:

Mixing of fluids: In case of dispersion of polymers, suspensions etc, it is used

to adjust speed of apparatus(as viscosity changes at diff rates)

It mainly affects dilatant systems.

Flow of fluids: Plastic system does not flow if stress of shear is less than yield
value. Thus rheology is necessary for choosing appropriate shear stress.

In Particle size reduction: Dilatant systems have to be sheared at low speeds.

Passage through orifice: Pouring of liq from containers; passage through

hypodermic needle. For this pseudoplastic & thixotropic systems will be ideal.

In fluid transfer including pumping & flow through pipes.

In formulation & Physical stability of dispersed systems.

Packaging into containers

In case of semisolids:

Spreading & adherence of ointments, gels, pastes etc on skin.

Mech: Thixotropy.

Removal from jars or Extrusion from collapsible tubes.

Mech: Plug flow.

Release of drug from base Sustained release of drug.

E.g. Procaine penicillin G injection

Mfr of medicinal & cosmetic creams, pastes etc.

Capacity of solids to mix with miscible liquids.

In case of solids:

Flow of powders from hopper into die cavity in mfr of tablets &
into capsules in mfr of capsules.

Filling & packing of powders or granules in bottles.

In case of Processing:

Production capacity of equipment.

Processing efficiency.