Rheology

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Unit-II

Rheology
rheo – to flow
logos – science
ology – the study of
Rheology is the science that concerns with the flow of
liquids and the deformation of solids.
Importance in several dosage forms, simple liquids, gels,
ointments, creams and pastes.
(i) Manufacture of dosage forms: Materials undergo
processes such as mixing, flowing through pipes, filling into
the containers etc. Flow related changes influence the
selection of mixing equipment.
(ii) Handling of drugs for administration : The syringibility of
the medicines, the pouring of the liquids from containers,
extrusion of ointment from tubes, all depend on the changes
in flow behavior of dosage forms.
Viscosity:
✔ Flow property of a liquid is expressed in terms of viscosity.
✔ Viscosity is an index of resistance of a liquid to flow.
Consider a block of liquid consisting of parallel layers of
molecules similar to a deck of cards

When pressure is applied horizontally on the top layer 'A',


the liquid begins to flow.
Thus, liquids resist the flow and this resistance is
estimated and expressed as viscosity.
Flow of liquid through a pipe

Shear Stress:
Force per unit area which is applied to bring the flow.
Rate of shear:
Change in velocity with infinitesimal change in distance.

The higher the viscosity the higher the force per unit area
required to produce a certain rate of shear.
Coefficient of viscosity is defined as the force per unit area
required to maintain unit difference in velocity between two
parallel layers in the liquid, one centimeter apart.
Units: Poise, Centipoise

Fluidity:
This term fluidity, Ø, is used to denote the reciprocal of
viscosity.
Kinematic viscosity- It is defined as viscosity divided by
density of the liquid.

Units- stokes (s), centistokes (c)

Relative viscosity : Ratio of viscosity of the dispersion to


that of the solvent.
,

Specific viscosity: This term is defined as the relative


increase in the viscosity of the dispersion over the solvent.
Reduced viscosity: Ratio of specific viscosity to the
concentration.

Intrinsic viscosity: The reduced viscosity is determined at


various concentrations of a substance and the results are
plotted. Extrapolation to C=0 to get the intercept which is
termed as Intrinsic viscosity.

Factors influencing the viscosity


Intrinsic Factors Extrinsic Factors
• Molecular Weight • Pressure
• Shape • Temperature
• Added Substances
Newtonian flow: Liquids that obey Newton's law of flow
are called as Newtonian fluids.

Shear stress-shear rate relationship is normally represented


in the form of a curve namely rheogram or consistency curve

Ex.
Water
Solutions of syrups
Glycerin
Very dilute Colloidal solution
Chloroform
Non-Newtonian flow:
(i) Plastic flow
(ii) Pseudoplastic flow
(iii) Dilatant flow
Plastic flow
• Material behaves like an elastic body and fails to flow
when less amount of stress is applied.
• Further increase in shear stress leads to non-linear
increase in shear rate which progressively gets linearized.
• After extrapolation the linear portion intersects the X axis
at a point called yield value.
• Plastic flow resembles the Newtonian flow above the yield
value.
Materials that follow the plastic flow are called as Bingham
bodies.

Plastic Viscosity (U)


F- shear stress
f- yield value
G- rate of shear
Pseudoplastic flow

• As the shear stress increases progressively, shear rate also


increases but the trend is not linear.
• Viscosity of a pseudoplastic system can not be expressed
by a single value.
• Ex. Tragacanth in water, Sodium alginate in water,
Methylcellulose in water
• This stress induced orientation reduces the internal
resistance of the material.
• In addition the solvent molecules which were earlier
associated with the polymer molecules will also be
released.
The greater the value of N above unity, the greater the
pseudoplastic behavior of the material.

Dilatant flow

The system exhibits enhanced resistance to flow with


increasing rate of shear.
When sheared, these systems increase their volume and
hence, are called as dilatant (shear thickening systems
because of increased apparent viscosity at higher rates of
shear).

Examples:
• Suspensions containing high concentration of solids (>50
percent) of small, deflocculated particles
• Suspension of starch in water
• Inorganic pigments in water
e.g. Kaolin 12% in water
Zinc oxide 30 % in water
Allows the particles to move Particles are not wetted,
relative to one another. develop resistance to flow.
Thixotropy-
• Shear thinning system
• When agitated and kept aside are expected to return to its
original state of fluidity
• Takes longer time to recover compared to time taken for
agitation
Thixotropy is defined as an isothermal and comparatively slow
recovery, on standing of a material, of a consistency, lost
through shearing.
Thixotropic behavior-
Negative Thixotropy-
• Upon shaking, the system behaves like a gel and imparts
greater suspendability.
• Antithixotropy or negative thixotropy represents an increase
in consistency on the down curve. Eg. Magnesia Magma
• Thixotropy is a desirable property for emulsions,
suspensions and creams.
• Greater the thixotropy, higher the stability.
• During storage high consistency will extend the settling
while with shaking it will convert into sol form which will be
easy to pour from the container.
Determination of flow properties-
Capillary viscometer-
• Ostwald viscometer to determine the viscosity of Newtonian
liquids.
• When a liquid flows by gravity, the time required for the liquid
to pass between two marks through a vertical capillary tube
is determined.
• The time of flow of the liquid under test is compared with the
time required for a liquid of known viscosity (usually water).
• The viscosity of the unknown liquid can be determined by
using following equation;
https://www.youtube.com/watch?v=I0aYfmbGmSA
Falling sphere viscometer-
• The apparatus consists of a glass tube positioned vertically
• Constant temperature jacket around the tube
• The test liquid is placed inside the glass tube

https://www.youtube.com/watch?v=BBe8hvqii60
• Glass or steel ball is dropped
• t is the time interval for the ball to fall between the two points
• Sb and Sf are the specific gravities of the ball and text fluid
• B is a constant
Cup and Bob viscometer-
• Multipoint viscometer belongs to the category of rotational
viscometer
Principle-
• The sample is placed in the cup and the bob is placed in the
cup up to an appropriate height.
• The sample is accommodated between the gap of cup and
bob.
• Now, either the cup or bob is made to rotate and the torque
resulting from the viscous drag is measured by a spring or
sensor in the drive of the bob.
• The number of revolutions (rpm) and the torque represent the
rate of shear and shearing stress, respectively.
• Eg. Stormer viscometer
• Equation to calculate the apparent viscosity-
Plug Flow-
• Stress difference between sample at the inner wall of the
cup and at the wall of the bob
• Material at the inner wall of the cup remain as a solid plug
Can be minimized by;
(i) using the largest bob possible in order to reduce the gap
(ii) increasing the speed of rotation of the bob so that the
stress at outer wall of the cup is above the yield value and the
system undergoes laminar flow
Cone and plate-
Sample is sheared in the narrow gape between the stationary
plate and rotating cone.
Advantages-
• The rate of shear is constant throughout the sample; plug
flow not observed.
• Sample required is small
• Cleaning and filling is easy
• Less time is required for temperature equilibration
Viscosity-
Newtonian Fluid Plastic material

η and U - viscosity and plastic viscosity


C and Cf - instrument constant
T and Tf – Torque (shearing stress) and yield value
V- Speed of the cone (Rate of shear)

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