t e

that
w h e n

at
zero sshear rate
during
2.6
m e a n s v i s c o s i t y

(Unit-I) viscosity.
It
lubrication.
High

11. Ophthalmic formulations should also have 4ppropriate

leads
to temperature.
viscosity at high shear rate during blinking of eyes, it visCosih
at
rectal
d e c r e a s e
in with
non-blinking of eyes, prevents the fuid from flowing a a * ofdrug
s h o w e d

en decreases
12. the
release
It a n d ther again
Suppositories having a fatty base, helps to influence
e m u l s i o n s .

54°C

(TEAS)
in extent
at
I state. At 54°C, the gel
state.

13. To study about the behaviour of tr Olamine

stearate

increases
to a
small
f o r m a t i o n ofgel
the
an increase in temperature up to 48°C. viscosity due to
of T E A S
is
rith increasingtemperature. This unusual property viscosity
decreases the
formed is destroyed gradually which again
14. To study about solidified sodium stearate in cosmetology
May-16, (R13), Q8(a) mis
2 NEWTONIAN SYSTEMS

04. What is Newton's law of flow? Explain with equations.

on Jan.-14/Suppl., (RO9), Q8(a) m[3%|

What are Newtonian systems?

or

Define and explain Newton's law of flow and its

applications. Dec.-13/Suppl., (R09), 01(a) m[Tk|

Answer:
Law of Flow liquids. This law has been
known as Newtonian
Newton's law offlow
are
Liquids which exhibit laminar flow i.e..
illustrated as follows.
in terms of laminar layers (which have negligible thickness).
Consider a liquid flowing through a laminar glass tube considered to be stationary. As we
beneath the inner wall of glass tube is
The layer of liquid which is present immediately
successive layers of the liquid keeps on
from the stationary layer of the liquid, the velocity of the
move gradually away
the z-axis. If the distance between
the two laminar layers is
increasing. This leads to build up of velocity gradient along
and faster moving layer moves with a velocity v
+
considered to be r, then the slow moving layer moves with a velocityv
rdvldz. Hence, when the molecules move from the slower layer to the
faster layer, momentum of the molecules of the faster
faster layer to the slower layer, the momentum gets transferred
layers gets retarded, and when the molecules move from
it up. This leads to the development of friction between the layers, thereby increasing
tothe slower layer therebyspeeding
the velocity.
Glass tube
Stationary layer V

Faster layer
Stationary layer-
Laminar layers of liquids
Figure: Newtonian Liquids Exhibiting Laminar
Flow
To maintain velocity gradient, external
orce appied
is to inauce the tiuid flow. According to the force
Newton's law, the
Newton's
is directly proportional to area ofthe layer
and
difference in velocity between two cording
to the difference between two adjacent layers. Theve sign is due to the viscous adjacent layers, but inversely
ely proportion
of flow of fluid. force acting opposite to the direv n
FaAdz
F' = n 4 .
dz
dv

. (1)
(Newton's law of viscosity)
- . ( 2 )

teaonving of this bookis a CRIMINAL act A

 Wherc,

n-Constant of proportionality known as

F'=Force viscosity or coefficient of viscosi1y.
A = Area

FA Shearing stress (i.e., force per unit area

dv/dz= Velocity gradient or rate represented by the symbol F)
of
shear (represented by the symbol G)
Equation (2) represents Newton's law of viscosity. Hence, this is equation applicable to Newtonian systems (which
wNewton's law) which exhibit only laminar flow. Newtonian
liquids are independent of the velocity gradient
On applying the parameters in equation (2)
Force Distance
AreaArea Velocity
Substituting the units of the parameters,
Massx LengthxTime2 Length
Length2 Length xTime
n Massx Length-lx Time' or ML-'T' (FPS system)
or

n= Gram x cm-l x sec-l or dyne sec. cmor poise (C.G.S system).

or

n=kg x ml x sec' (S.I system)

I Poise =
0.l kg m-' sec
dv
Applying the parameters F'/A = F and Gin equation (1),;
dz

F=n *G
.(3)
or

Shearingstress
Coefficient of viscosity= Rate of shear

The relationship between the shear stress and

shear rate
is given by rheogram or consistency curve. When a rheogram
stress on x-axis and rate of shear on y-axis, a straight line is obtained which
consistency
asses
Curve
through the
is between shearing
plotted
The slope of the
curve
cient of viscosity.
gives the value of coefficient v All those fluids which show such
rough origin.
anear Telationship are kiown as Newtonian fluids. E.gs: water, cniororOTm, gIycerin, benzene, syrup solution etc

Lineargraph
(Consistency
curve)
Rate of Slope
shear(G)
(sec-)

x
Shearingstress (F) (dynes/cm2)
Curve for Newtonian ow
Flow
Figure:
 (nit-
3. NON-NEWTONIAN SYSTEMS
Q5. Write a short note on,
(16), GARMv)
mfs+]
(a) Plastic flow Apri18,

(b) Dilatant flow.

01g) m2
or Apri18, (R16),

What is yield value?

(Refer Only Topic: Plastic Flow/Bingham Bodies)

or May-17, (R15), 9(b) m5]
Write a note on rheological behaviour of non-Newtonian system
or
May-17, (R15), 01(g) m1
Define dilatant flow.
(Refer Only Topic: Dilatant Flow/Shear Thickening System)
or
May-15, (R13), 09 m[101
neat diagrams.
Explain different types of flow with suitable examples and
or
May-15, (R13), Q1(g) m
value.
What is 'yield value'? Write the method to determine yield
Refer Only Topíc: Plastic Flow/Bingham Bodies)
or

Explain non-Newtonian systems with rheograms. Jan-14/Suppl., (ROB), Q6(a) m[34]

Answer:
Liquids which exhibit turbulent flow ie, do not obey Newton's law of fow are said to be non-Newtonian fluids.
These generally include suspensions, gels, ointments, colloidal solutions and emulsions.
As non-Newtonian liquids exhibit turbulent fow, the equation of Newton's law of viscosity does not apply to them
when rheogram is plotted between shearing stress on X-axIS and rate of shear on y-axis, it gives rise to various consistency
curves. This is because the velocity gradient varies in non-Newtonian liquids. Hence, non-Newtonian liquids are categorized
into three types based on their flow property as follows.

1. Plastic flow/Bingham bodies

E.g: Concentrated floccular suspensions

2. Pseudoplastic flow/Shear thinning system

solution
E.g: Polymers in
3. Dilatant flow/Shear thickening system
E.g: Non-flocculated suspension
Plastic Flow/Bingham Bodies
1.

Rate of
shear (G) Slope Mobility
(sec-)

Yield value(f)
Shearing stress (F) (dynes/cm2) X
Figure: Plastic Flow Curve for non-Newtoni

book is a CRIMINA
AINAL act. Anyone found
w P h o t o c o p y i n g

ofthis guilty is LIABI Ftt

 When a rheo
plotted between
from the
es not start
origin. shearing stress on X-axis and rate of (Unit-I) 2.9
ress. However Initially, the substance
mount of stres shear
shea Y-axis, the curve for plastic
on
when the shiows elas
lastic behaviour and does
ich ultimately becomes shearing stress is incrcased not flow on
application of a

the yield valie (Unit: linear. When ed further,

the linear non-linear increase in the shear stress is
a
part the graph is
of
tonian
ysluc, Newtonian iflow is dynes/cm'). Below the yield extrapola
olated onto the x-axis, it meets at
poin
observed. The valuc, the substances show
a

splastic viscosity
slope of the
plastic flow curve is referred
clastic nature. Above
the yie d
eferred to as t mobility and its reciprocal is known
Plastic viscosity (U)= hearing stress(F)- Yield
Rate of shear(G)
value(S)
Yield value is
considered to be
the yicld value. plastic flow
an
important property of dispersion agents i.e.,
Bingham bodies are classified into solids andconcentrated floccular suspensiO
d
Sased on
or
seld value are known as Solids, whereas those that do not
preld liquids. Substances exhibiting the
exhibit the yield value
ascof concentrated floccular suspensions, the known as liquids (as liquids flow). In
are
particles are bound by van der Waal's forces. The force or stress
vrak those forces is represented by the yicld value.
rea required to
Once the yield value exceeds, then
ees leads to a proportional increase in the rate any further increase in the shearing
of shear.
Pseudoplastic Flow/Shear Thinning Systemn

Rate of
shear (G)
(sec)

X *

Shearing stress(F) (dynes/cm)

Flow Curve for non-Newtonian Flow
Figure: Pseudoplastic
stress on x-axis and rate of shear on y-axis,
the curve of pseudoplastic
When a graph is plotted between shearing the rate of shear increases but does not show any
of origin. As the shearing stress increases,
ON starts from the point cannot be obtained (i.e.. apparent viscosity
an exact value of viscosity
the does not show any linearity, An increase
ity. As graph in the dispersion are randomly arranged.
the polymer
the molecules of
Oaned). Under normal conditions, unordered molecules
of the dispersion according to the
direction of flow. This
of the
nhe
k rate of shear leads to alignment
resistance of the substance, but
also results in the release of water molecules
internal the size ofdispersed molecules and
ngement not only decreases the
concentration
molecules. Due to this,
with the polymer
CTe found to be associated
dss decreases.

flow
tquationfor pseudoplastic (1

FN = n'G

Where.
F Shearing stress

N= Exponent
=Coeflicient of viscosity

G- Rate of shear
.(2)
F= n'
hen N= 1, then

or L t act.Anyonefound guilty is LIABLE to face LEGAL proceedings.

 Physical Pharmaceutics-
2.10 (Unit-m N 1 , pseudonl .

Equation (2) resembles it can

be said
that
when
doplastic
substances show Newtonian Newtonian flow equation (n =
F/G). Hence,
flow.
Rearranging equation (1) gives G=
Applying log on both sides of equation (3),
log G Nlog F- log .(4)
However most
of the pseudoplasti
n doog Gvs log Fis plotted on a graph. the equation (4) gives a straight line. a
substances not follow the ab
do
the above
equation.

log G

logF
3. Dilatant Flow/Shear Thickening System
DIlatant substances exhibit flow properties which are considered to be an inverse of pseudoplastic substances. Dilatant
OW1Sexhiited by substances which have high concentration (50%) of dispersed solids. As the rate of shear increases,
R resistance toffow also increases. When shearing stress is applied, they show an increase in volume and hence termed
dilatant. When the stress is
removed, they return to their original state. Examples of dilatant substances are defiocculated
or
non-flocculated suspension. The dilatant behaviour of deflocculated systems can be explained by considering closely
packed and open packed systems. At rest, the dilatant system consists of closely
void spaces are minimum which are packed molecules. This means that the
completely filled with the vehicle. The particles are able to move freely and thus the
system exhibits low viscosity and can be easily poured from a bottle.
On the contrary, when shear stress is
applied, the particles tend to move past one another and the system dilates
(the molecular packing loosens). As a result, the interparticle void volume increases and the vehicle is insufficient to fill
these void spaces. Due to this reason, the particles are not
completely wetted. Due to this the viscosity of the
increased resistance to flow and acquires the consistency
resembling that óf a paste. Examples of fluid system shows
dilatant, flow are suspension of starch in water, suspension containing more than systems exhibiting
100% of solids etc.
Particles
Particles
Force (stress)
is increased Large void spaces
o 0. O Sufficient
vehicle
Insufficient vehicle
Minimum
void spaces

(a) Closely Packed Particles

(b)
Open/Loosely Packed Particles
A graph plotted between shearing stress on x-axis and rate of shear vy-axis for
on

Y dilatant substancess appears as

follows,

Rate
shear (G)
(sec-

Shear stress(F) (dynes/cm?)

Figure: Dilatant Flow Curve
Equation
for
dilatant flow is given as,
FN =n'G
this book is a CRIMINA
ofthis
ng of act.
Anyone foundguilty is LIABI Et
Xerox/Photocopying

WG:
gu
 Curve Yield value Shearing stress(F)
(a) Rheogram pas
through the origin.
Shearing stress (F) through
passes pseudoplasticcurn
(a) Rheogram does not pass (a)
Rheogram
Inverse of
the origin. curve.
(b)
(b)
yield
value.
through the of origin. in the No
No linearity (c)
(b) Curvilinear graph. (6)
value.
(c) No yield (d) exhibit plastic
(c) Yield value is obtained. Does not
(d) Slope = Mobility. (d) (e)
exhibit plastic viscosity.
Does not
(e) Depicts plastic viscosity. (e) IfN is n e a r e r to
viscosity. Here N<1.
resembles Newtonian
FN = n' G When N= 1, it 1then it shows
Newtonian flow. flow property.
50% concentration
50%
Examples Concentrated floccular Polymers in (i.e., gums,|
solution
o f non-flocculated
tragacanth mucilage, jellies,
Suspensions. or deflocculated
sodium alginate, methyl
suspensions.
cellulose).

4. THIXOTROPY
Q8. What is
V
negative thixotropy? Dec.-17, (R15), a1(h) m
(Refer Only Topic:Antithixotropy/Negative Thixotropy)
or
Explain why bulges and spurs are observed in
rheogram of certain samples. Dec-17, (R15), Q9(b) m[E
(Refer Only Topic: Appearance of Bulges and
Spurs in Thixotropic Hysteresis Loops)
or
Write a note on
thixotropy.
or
May-17, (R15), Q9(b) m[E
What is thixotropy? How is it measured?
or May-16, (R13), Q9(a) m[E
Define thixotropy. How will you determine the thixotropic
Answer behaviour of the given
system?
Definition
anamenon wherein a material which Jan.-14/Suppl., (RO9), a6(b) m[
iponstanding exhibited a has
slower recovery of its been subjected to stress and
comparatively
agitated and allowed to stand for some time, the time taken consistency. For showed
han the time taken for agitation. The phenomenon of by the example, snowed aa decrease in in viscosit-
viscosit
system to achieve when a
thixotropy can be explained as its original state is pseudoplastic
system
system i
WARNING: Xerox/Photocopying of this book Is a act.CRIMINAL
follov
Anvone fa
lows, relatively longe-
 (Unit-11 2.13
Under normal conditions, the
system
multiple contacts with each other. exists in gel state i.c. has high viscosity as the particles o

When shear is applied, these

contacts break, which decrcases the viscosity of the system and it undergoes
transformation. E
3 When the Stress is
removed, the particles again slowly start to
acquire the contacts with each other due to
tnei
random Brownian motion. Hence, the system
gradually starts to regain its original consistency.
SolApplication

(At rest)
of shear RemovalSol
of shear

However, the time taken by viscous systems or those containing large and heavy particles, is more due to siow
Brownian motion. Hence, such systems require considerably longer time period to regain their original consistencles.

Thixotropy in Newtonian and Non-Newtonian System

1. Thixotropy in Newtonian System

Rheogram for Newtonian fluids does not show any variation in viscosity when force (shear) is applied. The thixotropic
curve obtained for Newtonian system is linear (straight line). Due to linearity ofthe graph, the upward movement from the
point of origin coincides with the downward movement back to origin.

Rate of
shear (G)
(sec-1)
X
Shearing stress
F(dynes/cm)

in Newtonian Flow
Figure: Graph Depicting Thixotropy

. Thixotropy in Non-Newtonian System is applied, as the graph

shows variation in the viscosity when force (shear)
The rheogram for non-Newtonian systems movement of the curve does not coincide with
to the type of fiow. The upward
obtained is non linear and varies according or
particles is disrupted upon application of force (shear). The
the downward movement, as the structural arrangement the for few minutes, hours or days.
left undisturbed
structural form when
particles come back to their original
Flow
Plastic Flow and Pseudoplastic decreases. When the shearing stress is removed.
the viscosity ot the substance shear
is increased, shearing stress (F) on x-axis and rate of
When shearing stress (G) after s o m e t i m e .
A graphical plot of
is regained
viscosity ofthe substance
the
loops.
Gony-axis gives hysteresis

ementApplicationofshear Rate of

(Umopwarvemdent) Shear (G)

(sec-)
Rate of
shear (G)
(sec-1)

Shearing Stress (F) .

Shearing stress (F)
(dynes/cm
(dynes/cm)

Curve
Figure: Pseudoplastic Flow Curve
Flow
Plastic

Figure:

ofthis
book is a
CRIMINAL act. Anyone found guityis LIABLE toface LEGAL proceedings.
CRIMINAL
ac
 Physical
curve. Kemovat of
2.14 (Unit-I movement
of the
curve is toward
upward of the
In both the above exhibits a n
obtained. The
movement

graphs, increase in the shearing

shearing stress ( g
stress dowmward are

shearing stress (G) steadily, xhibit

exhibit aa dou
downward movement of the
Thecurve.

lower
values of
viscosity

the left side the up-

e of
of the up-curve which indicates that on removal ofshearing
stress,
removal ot su ced hy Brownia
motion.

substance regains its dt on by

Brownian

original state after a short as it is

delay, mu
Appearance of Bulges and Spurs in first and then
decreased
Thixotropic Hysteresis Loops increased
shear () is
The material to be tne rate of
If the
experimented ise viscometer. If
taken in a viscometer.
in ia
n
spurs the hu
it gives rise to or spurs in the
gCSbulges Or hysteresis loop.
Bulge

Rate of Down
Curve
shear (G)
(sec-l) Bulged portion
i i n the up-curve

Up-Curve

Shearing stress (F)

(dynes/cm)

Figure: Graph of Aqueous Bentonite Gel

When agraph for concentrated aqueous bentonite gel (10-15% by weight) is plotted by taking shearing stress
on x-axis and rate of shear (G) on y-axis, it gives a characteristic bulge in the curve.
Such characteristic bulge in the hysteresis loop occurs because under normal conditions, the crystalline plates of the
magna are randomly arranged but upon application of shearing stress, these plates arrange themselves as a pack of cards
which results in the swelling of the magma. The bulged loop in the curve is due to the 3-dimensional structure acquired
by the magma.

Spur

1
Rate of
shear G)
(sec-")
S-Spur
Shearing stress (F)
(dynes/cm )
Figure: Graph of Procaine
Penicillin Gel
Rheogram of procaine penicillin gel (intramuscular injection) exhibits a spur in th
Formation ofspur
spur indicates the structural breakdown of the molecules. The bOw h t n e thixotropic hysteresis loo.
indicates tnesu procaine penicilin has aa specific spurvalueit ach of up-curve represents the cnr
value or high yield value (S). Since aine penicillin has
administration.
specific spur value it
achieves high levels in
formation of depot on the site of blood due to the
Measurement of Thixotropy
and the
In a thixotropic system, the up-curve down-curve form
the
the thixotropic breakdown and can be measured using a planimeter. rheogram. The area of
hysteresis loop indicates
The substances exhibiting plastic
fow exhibit thixotropy by two wa
When a graph of
plastic flow substances (Bingham bodies) plotted,
is
increased,
thena when shear rate isit
is obtained. Consequently, when gives hysteresis
rate is
rate 1s n ws held for aa certain period of time , at constant rate o
or
certa nstant decreased
eased then h loop dbc.
DC. When shear
Whe
e
held
the substance was held for
If the for a ocertain
longer
rate of shear at then b'c is obtained.
is a'bdc. ame
t, at a point
b', then Suppose
o b t a i n e d is
a'bde'e.
constant rate of the hyste
obtained

loop ysteresis loop

hysteresis shear at b', then tne
WARNING:Xerox/Photocopying ofthis
thi book isaCRIMINAL act. Anyone fo
found guilty is
LIABLE to face
LEGAL prot
 Ot Solids

(Unit-) 2.15

Rate of
shear (G)
Decatascd
Au,
shearra t e

(8CC 1) Increased
shear
ate

Figure: Graph Shearing

stress (F) (dynes/cm/)
Depicting Measurement of
The hysteresis loops are obtained when the Thixotropy at Constant shear Kate
the sample. shearing stress is
Disruption in the structural arrangement of the decreased, which in turn decreases the consistcn
molecules is expressed by thixotropic coefficient B.
Thixotropic coefficient (B) =
Plastic viscosit yof d'e(U)-Plastic viscosity of e'c(U2
In 2
Where,
,Time for down curve d'c
Time for down curve e'c
U = Plastic viscosity of d'c

U,= Plastic viscosity of e'c

The above equation is applicable when rate of shear is constant. This method of
measuring thixotropy is more
appropriate.
3. The material which exhibits plastic flow is taken in a rotational viscometer and subjected to experimentation. The
values obtained for the upward curve are plotted. Similarly the values obtained for the downward curve are also
plotted. v, is plotted on y-axis at the meeting point ofupward and downward curve i.e., at point A. The same material
is again subjected to experimentation at a higher rpm and upward and downward curves are obtained. v, is plotted
on y-axis at the meeting point of upward and downward curve i.e., at point B. The slopes of the curves bA and Bce,
give the plastic viscosities U, and U, respectively. The rate at which thixotropy is disrupted is calculated as follows,

Rate of

shear G)
(sec")
b- 1/U

Shearing stress (F) (dynes/cm)

Measurement of Thixotropy at Ipcreasing Shear Rate
ates
for
Figure: Graph 2[Plastic viscosity ofbA curve(U1)-Plasticviscosity of Bc curve(U2)]
=

breakdown (M) Rate ofshear for curve Be(v2)

Coefficient of thixotropic log
Rate ofshear for curve bA(v,)

M==20-U (units of M= dynes.sec/cm)

21os
M = U - U 2

V2 sic breakdown coefficient

coefficient (Mis
breakdown (M) is not constant. This is because M depends
s

thixotropic
the value of
Demerit of this that
on rates of shear.
book is
CRIMINAL act.Anyonefound guiltyis LIABLE toface LEGAL proceedings.
a
CRIMINAL

omig
ofthis
 Fnysi

2.16 (Unit-I1)
Applications of Thixotropy VIScOMETERS
sphere
viscomer
neter.
5. workingoffalling

Thixotropic phenomena increases the the April-18, (R16), 09 m[5]

the formulation. consistency of Q9.
Discuss

2. It finds
of doses.
application in dispensing and administration or
viscometer,
sphere
on
falling
3. It improves the physical stability of dosage forms. Write a
note
May-17, (R15), a1(h) mta]
example increase in For
of the suspensions. thixotropy increases the stability or
4. Gve examples
Due to viscometers?

thixotropy,
spur value is seen in case o multipoint
intramuscular depots of procaine
penicillin gel. This
What are May-16, (R13), a1(h) ma]
phenomena prolongs the action of drug in blood.
or
Antithixotropy/Negative Thixotropy viscometers are suitable for
It differs from type of
thixotropy in the following aspects, What
viscosity of non-Newtonian
. m e a s u r e m e n t of
The downward curve shows increase in suitable explanations.
viscosity. systems? Justify with
. The downward curve is towards
theright graph.
side ofthe Multipoint Viscometers, Rotational
Refer Only Topics:
Example : Rheological analysis of magnesia magma Viscometers) t eeTa
depicted antithixotropic nature.
May-16, (R13), a8(b) m[5]

B or
C

Rate of Write the principle and working of Brookefield

shear(G) viscometer.
(sec
(Refer Only Topic: Brookefield Viscometer)
Answer: May-15, (R13), Q8 m[41
Shearing stress (F)
(dynes/cm?) Classification of Viscometers
Figure: Graph of Magnesia Magma The different equipiments used to determine
include.
viscosity
When magnesia magma is subjected to increasing
and decreasing rates of shear (G). it exhibits thickening. 1. Single Point Viscometers
At the fourth stage D, no further thickening was seen as
there was no increase in viscosity and moreover the upward These viscometers work at a single rate of shear i.e.,
curve superimposed on the downward curve.
The point D is of the line
a
Single point on the rheogram. Extrapolation
referred to as the equilibrium state (i.e., gel-like). through this point to the origin
(a) Under normal storage conditions, the antithixotropic rheogram. These instruments are useful gives a complete
material comprises of abundant individual particles viscosity of Newtonian systems as in for measuring the
and these the rate of shear
and small flocs. The system exhibits low viscosity. shearing stress are directly
(b) Application of shear increases the interparticle (a) Ostwald's proportional. They incude.
collisions and thus interparticle bonding which results
(b) Falling
(Capillary) viscometer
in the formation of few large flocs. The system now ball (sphere)
exists in sol state.
2.
Multipoint-Viscometers viscometer. Viscometers
(Rotational)
Removal of stress results in the breakdown of large
(c) Single point
flocs to give rise to individual particles and small flocs. thixotropic viscometer
at materials as it fails to adequately character
Negative thixotropy is seen in flocculated solids varying rates
of shear cannot assess their
having a concentration range of l-10%, whereas in dilatant single point viscometer and stress.
This behaviou
the volume of solids is greater
than 50%.
viscometer. necessitated limitationpoint
systems,
sheat and These viscometers the use of
provide complete work at differentmuu
rates of
Rheopexy
It is a process by
which certain thixotropic substance systems. Multipoint rheogram
more when they are stirre
rapidly whe Newtonian systems viscometers are for non-Newo tonian

change
to
shaken or tapped.
gel form
maintained. The provided app
viscous drag on themain principle that the rat of
to also
applicable
ear is
in water.
is to be body present involved is the
sn of
Example:
Gypsum

WARNING:Xerox/Photocopying ofthis INAL act.

determined. in the exeru
They include, fluid whose viscosity
Anyone found
guilty is LIABIE
(a) Cup and bob (Unit-11) 2.17
viscometer viscometer/Concentric cylinder Where,
() Couette type
of viscometer (E.g : MacMichael- P, Density ofliquid
viscometer)
(i) Searle type of PDensity of water
viscometer
viscometer, Brookefield (E.g: Stormer
viscometer) The value of h is same in both cases since equal
b) Cone and plate viscometer. volumes of both liquids are taken, and therefore they stand
1 Ostwald's (Capillary) Viscometer at the same height. Hence,

Principle
. (7)
It is commonly used Pa2
to determine the
aNewtonian system. Ostwald's viscometer viscosity of Procedure
is based on
Poiseuille's law which relates the rate of flow of a Ostwald's viscométer is used for measuring the
through capillary tube with the coefficient of liquid
viscosity of viscosity of Newtonian liquids. Initially the viscometer is
the liquid and is expressed by the
following equation, thoroughly cleaned with chromic acid mixture and dried. A
nPr
known volume of water usually 10-25 ml depending upon
the capacity of the bulb A' is pipetted into bulb 'B'. It
81 .(1)
then sucked into bulb A' with the help of a rubber tube
is
Where,
attached to end 'C" till it rises to mark 'M. The time taken
n =
Coefficient of viscosity (poise) by water to flow through the capillary tube DE is noted by
P Hydrostatic (driving) pressure (dynes/cm?) means of a stop watch. Let the time bet. The viscometer is
r=Radius of the narrow tube (cm) drid and the same volume of liquid under examination is
taken into bulb B, so that the pressure head remains same.
t Time (seconds)
The process is repeated as before and let the time of flow
V= Volume of the liquid (ml) be t,. If the densities of water (p,) and that of the liquid
(p,)
I = Length of the narrow tube (cm) are known then the viscosity of the unknown liquid can be
As P hpg .. (2) easily calculated using the formula given below,

Where,
h Height of the column
Px
Rubber tube
P-Density ofthe liquid -Pipetted
Substituting equation (2) in equation (1) M
npg)
hpg)rt
8/7
(Poiseuille's equation) . (3)

determine the viscosity of Bulb

The usual procedure is to
water at different
a liquid with reference to the viscosity of
relative viscosity. The method Capillary
emperatures. This is termed a[ region Bulb

nvolves measuring the time of flow of

equal volumes of
examination through the same
water and the liquid under ofthe same volume
times offlow
capillary. Ifr, and , are the and n, are their
and water respectively, and n,
iquid then
Spective coefficients of viscosity,
hp gT . . (4)
Figure: Ostwald's /Capillary Viscometer
Viscosity of any liquid (M,)- 8M

(5). Ostwald's viscometer can also be used to determine

the kinematic
Viscosity of water (n,) 8 viscosity of the sample. The procedure
(5), involved in determining the kinematic viscosity is similar to
by equation
Dividing equation (4) that already discussed. It should be recalled that
kinematic
viscosity is given by the equation
Relative viscosity ,
8V7 .(6) Kinematic viscosity =
hpg x ho,gtr P
8V
o o k is a CRIMINAL act.AnyoneToundguity is LIABLE to face LEGAL Droceedine
 Physical

2.18 (Unit-I1)
Substituting equation (7) in the above equation,

P Pa2

2 sample.
P:
-

2
x
Kinematic viscosity dependent upon
the densityofthe
is not
From the above equation, it can be inferred that kinematic viscosity
fiuid in the
Demerit
fill accurate
amount of the
difficult to
Ostwald's viscometer is not suitable for viscous liquids as it is
viscometer.
Applications iP 1Or 11quid
evaluation prescribed by
Mea viscometer is an official method of
parafhn,
or
or
VIscoSity by
Ostwald's
dextran 40 injection and light liquid paraffin which is used as a vehicle TOr splay
colloids
dilute suspensions,
evaluation of emulsions,
LsO
s e d as a quality control measure during formulation

etc.

2. Falling Ball (Sphere) Viscometer

Principle
fiow.
Falling sphere viscometer works on the principle of Stoke's law of viscous
(8)
S=6Tnn
Where,
f=Viscous downward force
n = Coefficient of viscosity

=Radius of the sphere

v =Velocity with which the sphere is travelling

We know, f=mg
i.e., Force = Mass x Acceleration due to gravity.

R t as the sphere is falling vertically through the liquid, the resultant downward force (f) becomes as,
fm-m,)g ... (9)
Where,
m= Mass of the spher
m= Mass of the liquid displaced.
When the sphere attains a constant velocity (called terminal velocity) as it falls through the
(equation (8)) acting on it equals
the downward force (equation (9) liquid, the upward force
We know,
Mass Volume x Density
Mass of the sphere = Volume of thessphere x Density of the sphere

m, xP
(m,)TDensity of the liquid (o.) . (10)
liquid
Mass ofthe
and (11)
(11) in equation (9),
equatic .. (11)
equations
(10) and
Substituting

-4/3
r'p,Je

S= (4/3 r'p,
is a C L act. Anyone found guilty . (12)
ofthisbook
WARNING:
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sLIABLE to face LEGAL
pro
proceerinns
 and Deformation of Solids
enogyand

At equilibrium,
Upward force= Downward (Unit-I 2.19
6 amv=(4/3 Tr Ps-4/3Tr p,)e force
(From equations (8) and
6 Tmrv =4/3 tr (12))
9 7mrv2 t(P,-P)g (P,-PJs
9nv=2r(P,-P,)8
9v
Bv knowing all the above parameters, n can be
calculated.
Sample tube-
Steel ball

Constant
temperature
jacket

Figure: Falling Ball/Sphere Viscometer

trocedure
In the falling ball viscosity method, a column ofliquid about 40 cm high is taken in a thermostatic vertical tube,
Hich is having a cross section of at least 10 times that ofthe spherical bal. Two borizontal marks are engraved on the
a distance ofabout 10 cm from the top and bottom,respectivelyofthe liquid column. The spherical ball s inserted
t e centre of the tube from the top. The time taken by the spherical ball to traverse the distance between the two marks
viscosities of two liquids, measured with the same sphere and
OICd. Stoke's law can be used to determine the relative
and filled to the same height in each case
Ps-P,)

2 (Ps, P,)
streamine iow only. Hence, this method is useful for liquids having
for liquids exhibiting
toke's law holds good
high viscosities. Cylinder
Viscometer

its into the outer cylinder (Bob resembles

pCup and Bob
Viscometer/Concentric
outer cylinder. The bob fits.
forms the to be analyzed.
consists of a cup which with the substance
is filled
Tepparatus two cylinders
between the
ylinder). The s p a c e

Cup/Outer
cylinder
Bob/Inner
Substance to
cylinder
be analysed

Viscometer
Bob
and
Cup
Figure:
found guilty is LIABLE to face LEGAL proceedings.
otis
CRIMINAL act Anyone
a
 Physa
m e a s u r e d
b ne angular
which
is
2.20 (Unit-I) inner
cylinder,
d i v i d e d
as,
or further

Torque (force) is created rotation of the oute

cylinder
is
due to
outer
a p p a r a t u s

deflection Q. Based of the

the rotation of drag of the
he analyzin
cylinder,
on

Couete Tvpe of Viscometer

outer and inner
i n f i u e n c e
of
v i s c o u s
anat

the
due to s u b s t a n c e .

This cylinder)
only,
apparatus involves rotation of the cup (outer cy l
cup (outer ofthe
analyzing

Sample onto the bob. The torque created is related to the viscosity
E.g: MacMichael viscometer.
Searle Type of Viscometer
ns apparatus involves the rotation of the bob (inner cylinder) o
E.gs: 1. Stormer viscometer
2. Brookefield viscometer.
Stormer Viscometer
Revolution Winding
counter spool
-Pulley
EF
Hanger

Weights
Rotating Stand
bob
Sample to be- Cup
analysed
Clamp
Water bath-
Heating
coils

Base of
the stand

Figure: Stormer Viscometer

This apparatus is used to determine the Tundamental
properties of
thixotropy etc.).
rheology (i.e., yield value, plastic viscosity
The sample to be analyzed is placed berween tne two Cyunders and maintained at an equilibrium
added
are onto the hanger and
Simultaneousiyminute temperature. Weigns
roaons or the bob are recorded for a certain time
htained is plotted by taking
revolutions per pm) vs addition of period. The dala
nd the weights added into dynes/cm). nis appararus is used to weights (rpm values are converted to sec
than 20 çentipoise (cps) only. determine the viscosity of the
substances mo
Viscosity (n) = Instrument Constant (K ) x Weight in grams (w)
T.p.m(v)
Weight in
Plastic Viscosity (U)= Instrument Constant (K) x n (w) Weight of
yield value (w,)
Brookefield Viscometer
T.p.mv)
Brookefield viscon is a highly sensitive isensitive
instrument used for the
determination of complete data oe
rheological datalogical
of measurement
the
industry for the ev. evaluation of
of viscosit, Newtonianof non-Newtonian viscosity offuids
and non
and
e m e n t .of
fuids and
an
also
for

the
pharmaceutica.

dosage
fotms. a
Searn
It is Searle
type of
of
viscosity
rotati suspensions and also liquids. It is
commo oh
used in

harmaceutical
ha
A
measured
ity
quantity of
of
fuid.pe
rotational
fuid to be analyzed is
viscometer in
which
for the
quality contro
revolving.
placed in the cup the cup is
is
this ibook is a
offthis IMINAL act. and the bob
is
stationary acaP
Xerox/Photocopying

Anyone found guilty is immersed in

Care

N I N G :

llon
 nd eronmation ot
gheologya Solids
a be taken such that the bob (Unit-1) 2.21
does not touch the
spindle driven
with a driven by a calibr
calibrated ch bottom or the sides of the cup. The upper, end of the bob is attached
beryllium copper spring mounted cup. 1he
areavailabie and tne process of upp indles of various
and error basis. Upon rotating theselection of the spindle and its rotational speed
on a
motor snan
is completely
sIZes
the trial
the fluid 1s sheared between the spindle a definite constant speed, the bob
at based u
outer moves the procesS
drag on the
bob that accounts for the surface of the bob and the inner surface of the TIU
the spindle also rotates along with the production of torque by the spring. The
cup. This resuns f
bob. When the pointer attached upp
at tne
rotating dialI ((scale) is
stopped. The pointer then markstorque is produced, the pointer is
the displacement clamped or as and he
The torque produced 1s disp of spindle (spindle lag) on the scale as .
proportional to the viscous drag on the bob, hence the viscosity of the
torque is the measure of the
shearing stress. process fuid 1.e, une
The spindle size and its rotational
speed when multiplied by the scale reading (0),
of fluid in centipoise. The degree of gives the value for the viscosty
rotational speeds. thixotropy of the fluid may be obtained by
taking the measurements at varying
Note:
When no sample is present in the cup and the bob is rotated, the pointer marks "0' on the scale, even upon
increasing or decreasing the rotational speeds.
2. When a rheogram in plotted for a
thixotropic liquid by taking rotational speed
upward curve is obtained upon increasing the rotàtional speed of spindle and
of spindle (rpm) on
downward
an
curve is obtained upon y-axis,
decreasing the rotational speed of the spindle.

50 Downwardcurve

40
30 premdn Amo
20

10
X

40 50 60 70 80
10 20 30
Scale reading (0)
Vs 0
Figure: Rheogram of rpm
Rotating shaft

>Pointer

5 70 65
454015
6058 50/4

uli
80

Speed reguator

105 110 s10 15

Rotating dial (scale)

Rotating bob

Process fhuid

Stationary cup

Figure: Brookefield Viscometer

 Physical Phar.

2.22 Unit-)
Merits of Cup and Bob
Viscometer
1. Easy to operate.
2. Gives quick results.
5. Highly sensitive measuring system.
4. Instantly responds to changes in viscosity. as
non-Newtonian
uids
fluic can
Newtonian
as well
the
5.
Since the rate
ofshear is constant for both the cup and the bob,
be evaluated.
rotational speeds of the spindle.
6. changing the
Shear dependant behaviour offluids can be determined by
be accurately detert
can
y I low, medium as well as highly viscous fluids
teel.
of stainicso
8. Easy to clean, since major portion of the instrument is made up
Demerits of Cup and Bob Viscometer
1. Varying shearing stress is seen between the two cylinders.
L.
Development of heat of friction at high shear rates.
3. Large amounts of the analyzing substance should be used (around 20-50 ml.
. Maintenance of the equipment is difñcult.
between the cup and the bob and made
5.
: in viscometer, when the sample is placed in the gap
cup and bob
occurs because the stress exerted
stress across it. This probably
tO
rotate, the sample experiences different amounts of at the inner wall of the cup. Hence,
the reading
near the wall of the bob is relatively higher than the stress exerted
does not give a true indication of the stress exerted on entire sample.
Plug flow is not desirable during rheologic evaluation of dispersion systems. It can be reduced by,
Increasing the speed of rotation of the bob. This leads to higher stress at outer wall of the cup. As a result, the
system follows laminar flow.
ii) Using a large bob so as to minimize the gap between cup and the bob.
Cone and Plate Viscometer
Ferranti-Shirley viscometer

Principle
The cone and plate viscometer is a precisetorque meter which measures the resistance to rotation offered by the
fluid present between the cone and the stationary plate.

Cone (Rotating)
Plate (Stationary)
Sample (at the
center of the
plate)
Figure: Cone and Plate
Viscometer
The apparatus consists ofa stationary plate which isflat and circular. A rotatin
the centre.
The The sample under analysis is placed at the centre of the plate and rate of shear (F)
placed
is increased
above theand
plate
decreased.
towards
is measured and a graphical plot of rate of shear (Feor
The torque obtained rpm vs
obtained.
shearing stress (G) or scale reading
Viscosity for Newtonian liquid (h)
=
Instrumental constant ( Torque reading (T)
Speed of the cone in
r.p.m (v)
Torque
viscosity of Bingham
bodies (U) =

Instrumental constant (C) x reading (T) Torque at

Speed of the shearing stress (T)
Plastic
ham bodies ()
=
Instrumental nstant (C) x
cone in
rpm (v)
Yield
value of
Bingham
Torque at shearing
stress (T)
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ofthis bookis a CRIMINAL found guilty is LIABLE to
face LEGAL
procee dings.
 t and Deformation of Solids
Meris

Plugflow
fow is not seen as rate of (Unit-I 2.28
shear (F) is
Easy to clean, fill and maintain. constant throughout the
Temperature stability is seen.
analyzing sample.
The sample to be analyzed is used in
smaller quantities (around 0.1
oplications
-

0.2 ml).
Cone and plate viscometer is used in the
metals. evaluation of biologie
logical fluids and thick film coatings containing precious
is also used for
determining
Discuss the working of cupabsolute
010.
and bob
viscosity of liquids.
viscomete. April-18, (R16), Q9 m[5]
or
ud brti o
Explain determination of viscosity using
cup and bob method. May-17, (R15), a8(a) m[5]
Ansver

For answer refer Page No. 2.19, Q9,

Topic: Cup and Bob
4.Explain determination of viscosity using cone and Viscometer/Concentric Cylinder Viscometer.
plate. May-17, (R15), Q9(a) m[5]
or
Write principle and working of cone and plate viscometer.
Answer: May-15 (R13), Q8 m[4]
For answer refer Page No. 2.22, Q9, Topic: Cone and Plate Viscometer.

DEFORMATION OF SOLIDS
6.1 Plastic and Elastic Deformations
12. Mention the forces experienced by solid particles. Add a note on their deformations.

Answer:
V When force is applied on solid material the changes that takes place in it has been explained below.

The Deformation
solid body, it undergoes a definite change in its geometry. This change is
When opposing forces are applied on to a
The strain is referred to the relative amount of deformation that is
BoVemed by the nature of the opposing force applied.
UCed by the opposing forces on a solid body.
strains on a solid body are demonstrated by the following diagrams.
The common forms of
-D
- D-
Original shape- Shape after
applying strain
H
Shape after
applying strain

-Original shape
(ii) Compressional Strain
() Tensile Strain

(iii) S h e a r S t r a i n

LIABLEto face LEGAL proceedinas.

kis aCRIMINAL act.Anyoe10und guity is
 Physical Pharmaceutica-
2.24 (Unit-I)
Where, H, Initial =

length
H
Length obtained after applying strain
=

D.= Initial breadth

D Breadth obtained after
applying strain
---
Original shape-shape after applying strain
= Represents the directions of opposing forces applied
Example
in length (AH). The initial length
s
subjected to compression at hoth ends: it results in reduction by the original length
ofsolid body wasy
divided
The ofthe solid body
be defined the change in length
of the body. It may be may as
o
represented as,
Strain (Z)= Keduction in length of solid body(AH)u
Initial length of solid body (Ho)
Stress 'o' is defined as, the force per unit area on a body that tends to cause it to derOrm.
o mulaen
Stress (o)= Force( Area (4)
2. The Compression
1. When a mass of powder is subjected to external mechanical forces, it results in reduction in its bulk volume.
2. When the powder is compressed by loading, it causes the powder particles to exhibit a close repacking. This is
the initial mechanism of volume reduction in most cases. Further, the packing of powdered particles is carried
out with more difficulty. Further, the compression leads to deformation of particles.
3. When the load is removed from the powdered mass, it leads to the deformation of the particles, which is
spontaneously reversible. This is referred to as elastic phenomena (i.e., it shows the property of rubber). ct
Example: The acetyl salicylic acid and microcrystalline cellulose shows this elastic deformation
properties.
4. (a) In some powdered solids, if loads are applied above their elastic limit or yielding point, it results in
defofmation such that upon removal of the loads, the deformation is not reversible
Ch) In such cases, the reduction in bulk volume is because of
immediately.
plastic deformation and due to the particles
viscous/streamline/laminarflow. This plastic.behaviour is shown
in those
powdered materials whose shear
strength is less than tensile strength (1.e., shear strength < tensile strength). When shear strength is greater
than tensile strength, the powdered particles get
iractured, thus
fe called brittle fracture. Brittle fracture is observed in hard occupying the air spaces. This
phepomenon
and brittle particles. (Example: Sucrose)
(c) It is predisposed that the
powderca matera undergoes deformation in particular
acture. The process where the
particles of
powdered
a
way based on its
(irrespective of large particles) is called 'microsquashing material may exhibit plastic deformatio
5. effects
A studyasOIand
u when the load is increased. The deformation effects involve p
breaking
s in detemination
and then development
of different

new bonds' among the powdered particles. This results in con.

n.
6. The roll compaction or extrusion processes, where high compressive
may takes place. force is
utilized, the following proces es
(a) Elastic deformation

When the stress applied on the material does

not exceed
elastic deformation.
its elastic limit
(b) Plastic deformation
or
yield oint, it
poi is termed
as

on the solid particle

stress applied
Once the exceeds yield
deformation
which 1s an irreversible process point or elastic
limit,iitt is termed as plastic
is a CRIMIN
X e r o x / P h o t o c o p y i n g
ofthis kbook act.
Anyone found guilty is
LIABLE ta fan
WARNING:
 Rheology and Deformation of Solids
The elastic and (Unit-11) 2.25
plastic deformation of particles is
strain curve. studied with the help of the following graph depicting stress-

Plastic

Yield point
deformation

onsera uoyeojop
Energy stored as strain within the particle
Figure: Graph Representing Stress and Strain
7. The plastic deformation is
is never in
dependent time and occurs at various
on
rates. Hence, the powdered mass of tablet
equilibrium
state of stress-strain. In other words, as
the
rate at which load is applièd and removed is critical. " deformation process is time dependent, the
6.2 Heckel Equation/Plot
Q13. Write short notes on Heckel plot.
Answer:
Since the beginning of history of pharmacy, oral route of drug administration has been
ease of administration and
patient compliance. Among all the available oral dosage forms, tabletspopularly practised due to
are manufactured on
scale basis due to their simple
manufacturing processes, as they can be easily prepared out of granules, large
through compression process. The quality of powder and its cómpressibility plays an powders and pellets
There are several compression important role in tablet preparation.
is useful for those
techniques among which direct compression is the simplest and easier
process. This
powders which exhibit good flow property, high compactibility and less segregation property. process
Till now several powder compression models have been
developed by several prominent workers to explain
compression parameters. The first attempt was made by Walker, where he explained relationship between
powder
and pressure
applied to produce powder bed or tablet. However, his theory was not taken.into consideration dueporosity
of mathematical explanation to support the theory. Later Heckel in 1961 proposed a theory on powder compression lack
to

with mathematical explanation. Though his theory was criticized along

initially, it is now mostly accepted one not only due to
simple mathematical calculations but also due to its easy differentiation between plastic and brittle materials.
Heckel plot explains the relationship between densification of powder and the pressure exerted over it. It also states
that the forceor pressure applied on
powder during compression exhibits
first-order kinetics.
The equation is mathematically represented as,
+A

Where,
D Relative density of tablet
P Pressure applied
K Slope
A Densification at low pressure by interparticulate movement.
 2.26 (Unit-11)

Phase-IPhase-11 Phase-Ill

In

P applied
Plot
Illustration of Heckel's ess of compression,
Figure: Graphical initial p r o c e s s
in the
In the above graph, phase-I represents particle rearrangement and fragmentation
ation.
phase-ll represents plastic deformation, whereas phase-IlI represents elastic dero
transitional state
or powder into tablets.
the
Leuenberger further improvised Heckel plot which describes
It is and
mathematically represented as,

le.---P)n
Where,
-Pressure
p Relative density
P.-Critical density
According to Heckel plot, Hersey and Rees as well as York and Pipel categorized
based on their behaviour towards compression. powder into three types (A, B and C)
Type-A
With the increase in pressure of
compression, powdered
Solid
deformation. Materials belonging to this type have less elastic limit. particles shows linear
graph which represents plastic
E.g: Sodium Chloride (NaCI).

P applied

gure: Graphical
stration of Type-A
Type-B
initially exhibitaa curve
Materials
The solid powdered particles curved region
plastic ow. This type of
flow
linear straight
line representing
behaviour iswhich
shownindicates
E.g: Lactose. by
toughparticle fragmentation followed bya
materials
WARNING:Xerox/Photocopying
ofthisbook
is a CRIMIN
NAL act.
Anyone found
fOtii
with high elastio
guilty is IIAnL
 P applied

Figure: Graph Illustrating Type-B Materials

Type-C
Materials of this type initially shows elevated linear
graph which gradually flattens with an increase in the pressure
applied. This is due to the absence of
rearrangement phase or phase-I.

in -D

P applied

Figure: Graphical Illustration of Type-C Materials