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Rheology

Rheology
• It is a Greek work coined by Scientist Eugen C.
Bingham.
• It is combination of two words: rheo means to flow
and logy means to study.
• Definition:
– Rheology is defined as science of study of flow of liquid
or soft solids or in some cases solids.
Fundamentals of Rheology
• Consider a block of liquid consisting a parallel
plate similar to deck of cards as shown in
diagram.
• A bottom layer is fixed while a top layer is
moved at constant velocity
• A
Application of Rheology in Pharmacy
• Standards of liquid

• For manufacturing of dosage form

• Handling of drugs for administration

• As a quality control tool

• Determination of molecular weight


Fundamentals of Rheology
• Now consider that a constant force is applied
on the top layer of liquid block.
• As the top layer moves, the layers below top
layer will also move.
• The velocity of these layers will be directly
proportional to the distance from bottom layer.
Fundamentals of Rheology
• The difference in velocity (dv) between two
planes of liquid will depend upon distance
between them (dr).
Shearing stress
• The force per unit area applied on liquid is
called as shearing stress.
• F=FI/A
Rate of Shear
• The difference in velocity of two layers (dv/dr) is called as
velocity gradient or Rate of shear (G) or shear rate.
• Rate of shear (G) : The rate of change of stress is called as the
rate of shear.
• G=dv/dr
Newton’s law of Flow
• Newton was the first to study flow of liquids in quantitative
way.
• He recognized that higher the viscosity of liquids greater will
the force per unit area required to move top layer.
• Hence

FI/A = η dv/dr
Newton’s law of Flow

F=ηG
Where F= force per unit are i.e. shearing stress
η = Viscosity
G = rate of shear or shear rate
This is Newton’s law for flow of liquid and the liquid which
follow this law are called as Newtonian System and the systems
which does not follow this law are called as non-Newtonian
system.
Viscosity (η)
• Viscosity of any liquid is defined as it is internal resistance of
liquid to flow.
• Viscosity id inverse of fluidity (φ) which is ability to flow.

• Viscosity is given in the units as poise and centipoise.

• 1 cp =0.01 poise

• Viscosity is dependent on temperature and hence fluidity also


depends on temperature.
• As temperature increases viscosity decreases.
Newton’s law of Flow
• When we plot graph of rate of shear versus shear stress then following
type of graph is observed in case of Newtonian Systems. Such graphs are
called as Rheograms.
Non- Newtonian Systems.
• These are the materials which does not follow Newton’s law of flow.
• In these kinds systems rate of shear is not directly proportional to the shear stress.

• In Newtonian fluids viscosity always remains constant. It does not change with change in
shear stress.
• But in case of non-Newtonian fluids there are changes in viscosity as shear stress
changes.
• Hence shear stress and rate of shear are not proportional to each other.
• There are three types of non- Newtonian systems
– Plastic

– Pseudoplastic

– Dilatant
Plastic flow
• The rheogram of plastic flow is given in above graph.

• The curve does not pass through the origin.

• The substance initially behaves like elastic body, the rate of shear is not

proportional to the shear stress.

• After application of more shear stress, rate of shear becomes proportional to the

shear stress.

• This linear proportion when extrapolated on x axis, it intersect at some point called

as yield value (f).

• Hence plastic flow resembles to Newtonian flow after yield value.


Plastic flow

Yield value
Plastic flow
• Plastic flow is associated with presence of flocculated particles in concentrated

suspension, butter, certain ointments, pastes and gel.

• Floccules are interconnected with each other due to aggregation.

• This structure is maintained when system is at rest.

• When shear stress is applied initially, this structure does not break.

• But as the shear stress increases beyond yield value,

(F-f) this structure breaks and the material starts to flow and act as Newtonian

system.

• Material that follow plastic flow are called as Bingham systems.


Plastic flow
• The quantitative behavior of Bingham systems is
expressed by Bingham equation.

U= F-f/G
where
U= plastic viscosity.
F= Shear stress
f= yield value
G= rate of shear
Pseudoplastic Flow
• These kind of systems are also called as Shear
thinning system.
• As the shear stress increases viscosity decrease and
hence there is less change in rate of shear.
• When rheogram of Pseudoplastic is plotted following
type of graph is obtained.
Pseudoplastic Flow
Pseudoplastic Flow
• The consistency curve for Pseudoplastic flow begins at origin.

• But as the shear stress increases, rate of shear does not

increases proportionally.

• Pseudoplatic flow can be found in emulasions, suspensions etc..

• Pseudoplastic material is also called as shear thinning material.

• Viscosity decreases as shear stress is increased.


Pseudoplastic Flow
•Pseudoplastic flow rheogram can be expressed by following exponential formula.

FN= ηIG
Where N= number given to the exponent

ηI = Viscosity coefficient

G= Rate of shear

In case of Pseudoplastic flow N is higher than 1 and increases when fluid becomes

more non-Newtonian.
Pseudoplastic Flow
• Taking log of above equation
N log F = log ηI + log G
On rearranging above equation
log G = N log F - log ηI
This is simplified equation for Pseudoplastic
flow.
Dilatant Fluid
Measurement of Viscosity
• Ostwald Viscometer
Ostwald Viscometer
• Used to determine viscosity of Newtonian liquids.
• Principle: When liquid flows due to gravity, the time required to
flow between two marks (A and B) through a vertical capillary
tube is determined.
• The time of flow of test liquid is then compared with the time
required for a liquid of known viscosity (usually water).
• The viscosity of unknown liquid can be determined by using
equation
Ostwald Viscometer
Derivation
• Derivation of above equation is based on Poiseuille’s law.
Derivation
• For the given Ostwald Viscometer the radius,
volume and length remains constant can be
denoted by k.
• Hence above equation can be written as
η = KtΔP
The pressure head ΔP depends on the density of
liquid. (ρ)
hence η = Kt ρ
• For first liquid equation can be written as
• η1 = Kt1ρ1
• For second liquid equation can be written as
• η2 = Kt2ρ2
• By comparing above two equation we can get
Falling Sphere Viscometer
Falling Sphere Viscometer
• The apparatus consists of a glass tube positioned vertically.
• A constant temperature jacket with provision for water circulation is arranged
around the glass tube.
• The test liquid is placed in glass chamber.
• A steel ball is dropped into the liquid and allowed to reach equilibrium with
surrounding temp.
• The tube is with the jacket is then inverted due to which ball comes at the top of
glass tube.
• The time taken for the ball to fall between two marks is accurately recorded
• The process is repeated several times to get concurrent result.
Falling Sphere Viscometer
• The viscosity of Newtonian system can be
calculated from below equation.
Cup and Bob Viscometer
Cup and Bob Viscometer
• In this type of viscometer the sample is placed in between gap of cup and
bob.

• The bob is immersed in sample up to particular height.

• Now either the cup is rotated or bob is rotated.

• Due to this rotation, viscous drag is produced which is then measured by


using spring or sensor as a torque.

• Depending upon whether cup or bob is rotated there are two types of
models of cup and bob viscometer.
Cup and Bob Viscometer
1. Revolving cup type: Couette type: MacMichel viscometer

2. Revolving bob type: Searle type: Stromer viscometer.

The number of revolution represent the rate of shear and torque represent shear stress.

From above data following equation is used to calculate viscosity.

η= kv (w/v)
Where
η= apparent viscosity
w= shearing stress (weight on bob)
v= rate of shear (rpm)
kv= Constant for the instrument
Cup and Bob Viscometer
• The popular viscometer based on Searle principle is the Stromer
instrument.
• In this type the sample is placed between cup and bob and allowed to
reach temperature equilibrium.
• A time required for the bob to make 100 revolution is then recorded.
• The weight on bob is then increased and same procedure is repeated.
• In this way, a rheogram can be constructed by plotting rpm (rate of shear)
versus weight (shear stress).
Plug Flow
• One of the disadvantage of cup and bob viscometer is plug flow.

• In this type of viscometer the sample is placed in between cup and bob

and either one is rotated.

• The amount of stress exerted on liquid which is near the wall of bob is

more as compared to liquid which is far from wall of bob forming a solid

plug.

• Different kind of stress is being exerted on different parts of liquid and

hence readings may not represent stress on entire system.


Cone and Plate viscometer
Cone and Plate viscometer
• The sample is placed at the centre of plate, which is then raised into a

position under the cone.

• Then cone is driven by variable speed motor and sample is sheared

between narrow gap of stationary plate and rotating cone.

• The rate of shear in rpm is increased or decreased by a selector dial and

viscous traction or torque produced on cone is then recorded on the

indicator scale.

• Then a graph of rpm (rate of shear) versus scale reading (shearing stress)

can be constructed.
Cone and Plate viscometer
• For Newtonian System viscosity can be
estimated by equation,
η= C (T/v)
Where C= instrument constant
T= Torque reading
v= speed of the cone.
Cone and Plate viscometer
• For plastic flow equation can be modified as

U= Cf (T-Tf/v)
where Tf is the shearing stress at
extrapolated on x axis.
Cone and Plate viscometer
• It has several advantages over cup and bob
viscometer like
– There is no formation of plug flow
– Sample required is very small
– Cleaning is very easy
– Less time is required for temperature equilibrium.
Bulge type loop:
• Some of the dispersions in pharmacy produce a complex
thixotropic curves when shear stress in increased a particular
point, then decreased and corresponding rate of shear is
recorded.
• A concentrated aqueous bentonite Gel, 10% and 15% by
weight produces a characteristic bulge in upcurve.
• This type of upcurve is obtained because of formation house
of card structure of bentonite crystals causing swelling of
bentonite magmas.
• Because of this bulge type curve is
obtained.
Complex thixotropic curve
• Bulge type loop:
Spur type thixotropic curve
• In more complex structure, more complex
rheogram is obtained like in procaine penicillin
G gel for IM injection.
• The spur value represent a sharp point of
structure breakdown.
Spur type thixotropic curve
Pharmaceutical Application of Rheology
Pharmaceutical Application of Rheology
6. Rheological properties of creams and ointments are
assessed time to time during their shelf life in order to
ensure their stability.

7. The property of Dilatant material can be utilized for


formulation of in-situ gelling type of dosage form.

8. Syringability of viscous material can be improved by


formulation of shear thinning systems.