PHCT 202: Physical

Pharmacy

Rheology and Viscosity

 Outline
Introduction
Definition of some terms
Rheology
Viscosity
• Kinematic viscosity
• Dynamic viscosity
Newtonian systems
• Newton’s law of fluidity
Non-Newtonian systems
• Plastic systems
• Pseudoplastic systems
• Dilatant systems
Determination of viscosity; Choice of viscometer
• Capillary (Ostwald) viscometer
• Falling-sphere viscometer
• Cup-and-Bob Viscometer
INTRODUCTION
Definition of some terms
• Viscosity
• Kinematic viscosity
• Shear stress
• Shear rate
• Fluidity
• Dilatancy
• Plasticity
• Pseudoplasticity
• Yield value
• Shear thinning
• Shear thickening
• Viscoelasticity
• Thixotrophy
Rheology is the scientific study of the flow and deformation of materials,
particularly non-Newtonian fluids and soft matter. It involves understanding how
materials respond to stress, strain, and other forces, and how their properties
change over time.

Viscosity (ƞ) is defined as the resistance provided to a layer of liquid when it

moves over another layer of liquid. It is the resistance to motion exhibited by most
fluids, and it arises when there is relative movement between fluid layers.

It quantifies the hindrance to flow resulting from internal friction between these
layers as they traverse one another during fluid motion.

Alternatively, viscosity can be described as a measure of a fluid’s thickness or its

impeding nature for objects passing through.
Fluids with high viscosity impede motion due to robust intermolecular interactions,
generating significant internal friction that hinders the movement of layers. In
contrast, fluids with low viscosity flow effortlessly, as their molecular composition
produces minimal friction during motion.
While gases also possess viscosity, it is less perceptible in everyday experiences.

Viscosity is calculated using the relationship

ƞ=

Where
Ƞ = viscosity
F = Shear stress
G = Rate of shear
Factors affecting viscosity

These are factors that can cause changes in viscosities of liquids and are classified
as either intrinsic or extrinsic factors.

 Intrinsic factors
• Molecular weight and shape
• Intermolecular forces

 Extrinsic factors
• Pressure
• Addition of electrolytes
• Temperature
Viscosity Types

There are two ways to measure the viscosity of fluids vis:

 Kinematic Viscosity
 Dynamic Viscosity (Absolute Viscosity)
Kinematic Viscosity is a measure of a fluid's internal resistance to flow under
gravitational forces. It is determined by measuring the time in seconds, required for
a fixed volume of fluid to flow a known distance by gravity through a capillary within
a calibrated viscometer at a closely controlled temperature.

The kinematic viscosity [m2/s] is the ratio between the dynamic viscosity [Pa. s = 1
kg/m·s] and the density of a fluid [kg/m3] at the same temperature.

Kinematic Viscosity is represented by the Greek letter 'ν' (nu) and is measured in
Stokes (St), with 1 St = 1 cm²/s = 10−4 m2/s.

The formula for calculating kinematic viscosity is: ν = μ/ρ , where 'μ’ (mu)
represents dynamic viscosity and 'ρ' (rho) is the fluid's density.
Dynamic viscosity gives an overview of the force needed to make the fluid flow
at a certain rate and is commonly measured using instruments called rotational
viscometers.

The dynamic viscosity formula is represented as η= T/γ ​, where η (eta) is the dynamic
viscosity, T is the shearing stress, and γ (gamma) is the shear rate.

The SI units for dynamic viscosity are expressed as Pa·s (Pascal-seconds) or Ns/m²
(Newton-seconds per square meter).
 Differences Between Kinematic And Dynamic Viscosity
Properties Kinematic Viscosity Dynamic Viscosity
Also known as Diffusivity of momentum Absolute Viscosity
Inertia as well as viscous The viscous force of the
Represents
force fluid
Symbol ν μ
The ratio of dynamic The ratio of shear stress to
Ratio
viscosity to density shear strain
When inertia, as well as When viscous force is
Used
viscous force, is dominant dominant
Density Dependent Independent
Unit m2/s Ns/m2
Newton’s Law of Viscosity

The shear stress in flowing fluid is directly proportional to the rate of shear

FαG

F=ƞG

Where
F = Shear stress
G = Rate of shear
Ƞ = coefficient of viscosity

When data are plotted by taking F on x-axis and G on y-axis, a flow curve
referred to as Rheogram or consistency curve, is obtained.
 Liquid
Systems and
Types of Flow

Non Liquid systems

Newtonian Newtonian

Types of flow
Plastic Pseudoplastic Dilatant
Newtonian Flow

How do Newton's laws apply to fluid dynamics?

Newton's laws apply to fluid dynamics by describing the motion and forces acting on
fluids.

In fluid dynamics, Newton's first law states that a fluid at rest will remain at rest
unless acted upon by an external force, while a fluid in motion will continue to move at
a constant velocity in a straight line unless acted upon by an external force. This law
is important in understanding the behaviour of fluids in static and dynamic situations.

Newton's second law states that the rate of change of momentum of a body is equal
to the force applied. This implies that the force acting on an object (fluid in this case),
is equal to its mass multiplied by its acceleration. In fluid dynamics, this law is used to
calculate the forces acting on a fluid element as it moves through a fluid, taking into
account factors such as pressure, viscosity, and turbulence.
Newton's third law states that, for every action there is an equal and opposite
reaction, and this applies to fluid dynamics in the form of fluid pressure. When a
fluid is forced to move in a certain direction, it exerts an equal and opposite force
on the object causing the movement.
Newtonian Fluids

The fluid whose viscosity remains constant is

known as the Newtonian fluid. These fluids are
independent of the amount of shear stress
applied to them with respect to time. The
relationship between the viscosity and shear
stress of these fluids is linear.

Examples of Newtonian Fluids

•Water
•Alcohol
•Mineral oil
•Gasoline
Rheogram
Non-Newtonian Fluids

• The fluids whose viscosity change when shear stress is applied are known as Non-
Newtonian fluids. These are systems or liquids that do not follow the Newton’s Law of
Viscosity.
• Non-Newtonian flow is observed in complex heterogeneous systems in which the
relationship between shear stress (F) and the rate of shear (G) is nonlinear.
• Most liquids in pharmacies are non-Newtonian systems e.g. emulsions, creams,
suspensions, ointments.

Examples of Non-Newtonian Fluids

• Toothpaste
• Ketchup
• custard
• Cosmetics
• Paint
• molten polymers
• melted butter
Effect of time of shear stress application on flow of Non Newtonian Systems

 Time independent flow

• Plastic flow
• Pseuodoplastic flow
• Dilatant flow

 Time dependent systems

• Thixotrophy
• Rheopexy
Plastic flow

Plastic flow describes a system in which no

flow occurs until shear stress (F) reaches a
critical transition point (yield value)
- At stresses below the yield value, the
system acts like a elastic material
- At stresses above the yield value, the
relationship between shear stress and rate
of shear becomes linear

The plastic flow curve does not pass through

the origin and it intersects the shearing stress
axis (or will if the straight part of the curve is
extrapolated to the axis) at the yield value.
Rheogram
Formula for determining plastic flow

U=F-

Where
U = plastic viscosity
= yield value
F = shearing stress
= rate of shear

Examples of plastic fluids:

•quark
•tomato paste
•tooth paste
•hand cream
•some ketchups
•grease
Pseudoplastic Flow

The curve for a pseudoplastic material

(otherwise called shear thinning material)
begins at the origin (or at least approaches
it at low rates of shear). As the shear stress
increases, the shear rate also increases,
but not linear.

• The curved rheogram for pseudoplastic

materials is due to shearing action on the
long chain molecules of materials such as
linear polymers.

Rheogram
Aqueous solutions of polymers (polysaccharides) are a good example of systems
with pseudoplastic flow
- At rest polymers within the solution become coiled up in their globular form
- When shear stress (e.g. agitation or shaking) is applied, the polymer chains
untangle.
- With increased agitation, the polymers align themselves in the direction of flow
Example of materials that display pseudoplastic flow include suspensions,
emulsions, dispersion of polymers as seen in

•paints
•Shampoos
•slurries
•fruit juice concentrates
•ketchup
Dilatant Flow

The viscosity of these fluids increases when shear

stress is applied and thus often called “shear thickening
systems”.

Certain suspensions with a high percentage of

dispersed solids (about 50% or more) exhibit an
increase in resistance to flow with increasing rates of
shear. Such systems actually increase in volume when
sheared and are termed dilatant.
When the stress is removed, a dilatant system returns
to its original state of fluidity

Quicksand, corn flour with water, putty are examples of Rheogram

dilatant fluids.
Thixotrophy and Rheopexy
When left to rest, Newtonian systems will revert
back to their original form. That is, they have
identical downward curves.

When left to rest, non-Newtonian systems do

slowly revert back to something close to their
original form, but they do not have identical
downward curves. This phenomenon is known as
thixotropy

Thixotropy can be defined as an isothermal and

comparatively slow recovery, on standing of a
material, of a consistency lost through shearing.
Thixotropy is characterised by the progressive decrease in viscosity with time for a
constant applied shear stress, followed by a gradual recovery when the stress is
removed. Clear examples of thixotropic fluids from practice are ketchup, toothpaste,
margarine or shaving cream.

Many gels and colloids are thixotropic materials, exhibiting a stable form at rest but
becoming fluid when agitated. Some thixotropic fluids return to a gel state almost
instantly, such as ketchup, and are called pseudoplastic fluids. Others such as
yogurt take much longer and can become nearly solid.

Rheopectic fluids: The viscosity of these fluids increases when shear stress is
applied along with time. They are similar to dilatant fluids, however, these fluids are
time-dependent. After releasing the forces, it decreases again. Cream and gypsum
paste are examples of rheopectic fluids.
 THIXOTROPHY
Gel-Sol-Gel)

At rest
(High viscosity)
Multipoint contacts Gel state

On shear
(Low viscosity)
Contacts break down Sol state

Set aside
(High viscosity)

Particle contacts re-established Gel state

When is thixotropy useful?

 Shear thinning is useful for suspension/creams

• Increased viscosity at rest → Increased stability
• Thinning with agitation → easy administration

 For pharmaceuticals like suspensions and emulsions that require agitation prior
to administration, thixotropy is useful as the delay in reversion to original
viscosity ensure product is administered before it thickens up again

 Intramuscular depot injection

• High shear stress through the needle → thinning allows easy admin.
• At relative rest in muscle →viscous depot which can release the drug slowly
over a long period of time
• If the suspension was not thixotropic it could be too thin in the muscle to
form a depot
Determination of Viscosity

Viscometer

Single point Multi-point

Ostwald/Capillary Falling Sphere Cup and Bob Cone and Plate

Ostwald/Capillary Viscometer
Operational Procedure

• Fill the viscometer with the liquid being examined

through left arm of tube to slightly above the bubble
using a pipette

• Suck the liquid (through right arm of tube) to above

start mark and allow it to flow downward.

• Note the time of flow for liquid from start to stop

mark.

• Determine the viscosity using formula where

viscosity of water.
Falling Sphere Viscometer
Rate (speed) at which ball with particular density and
Falling sphere viscometer
diameter falls is inversely proportional to viscosity of
liquid.

Operational Procedure

• The sample & ball are placed in the inner glass tube &
allowed to reach temperature equilibrium with the
water in the surrounding constant temperature
jacket.

• The tube & jacket are then inverted, which effectively

places the ball at the top of the inner glass tube.

• The time for the ball to fall between two marks is

accurately measured & repeated several times.
Cup and Bob viscometer

This is a multipoint viscometer and belongs to the

category of rotational viscometers.

Operational Procedure

• The test sample is placed in space between cup

and bob up-to an appropriate height and
allowed to reach temperature equilibrium and
then sheared by rotating cup.

• Viscous drag on bob due to sample causes it to turn

and the resultant torque is proportional to viscosity
of sample and this is measured by a spring or sensor
in the drive of the bob.
Cone and plate Viscometer

Operational Procedure

The sample is placed at the center of the plate,

which is raised into position under the cone.

The cone is driven by variable speed motor and

sample is sheared in the narrow gap between
stationary plate and rotating cone.

Rate of shear in rpm is increased & decreased by

selector dial and viscous traction or torque
(shearing stress) produced on the cone is
measured by a selector dial.
Brookfield viscometer, a rotational viscometer, basically
consists of two parts - a head unit with a motor and a spindle Brookfield Viscometer
that is driven by the motor.

Operational Procedure
Suspension of the sample is made and an appropriate
spindle is selected and immersed in the test material.
The viscosity is determined by measuring the resistance of a
spindle rotating in the sample.
Pharmaceutical Applications of Rheology

• Rheology has wide application in manufacturing of dosage forms & handling of drugs
for administration. Formulation of emulsions, cosmetic creams, ophthalmic
preparations, pastes, lotions, suspensions, suppositories, ointments and tablet
coating.

• Fluidity of solutions for injection and passage of the liquid through a syringe needle

• In mixing and flow of materials, their packaging into the containers. Extrusion of a
paste from a tube .

• Mixing process affect the viscosity of formulation - For shear-thickening system, high
viscosity can have a significant effect on the content uniformity of drug.

• The settling and aggregation of solid particles in suspensions are viscosity-dependent.

Emulsion consistency and stability is viscosity-dependent