Rheology

Dr. BUYINZA NICHOLASKabali

B.Pharm, MPharm Pharmaceutics fellow
Introduction
• Rheology is the scientific study of deformation &
flow properties of matter.
• Rheology can be applied to solids, liquid & gaseous
states of matter.

From rheological perspective:

• Solids- completely resistant to deformation.
• Liquids- less resistant
• Gases- completely nonresistant
Key
• Viscosity is a measure of resistance to flow or
thickness.
• Elasticity refers to stickiness.
• Elasticity is a property of solid materials while
viscosity is a property of liquid materials.

• Viscoelasticity is a phenomenon observed in

materials that exhibit both elastic behavior &
viscous flow.
Categories of fluid systems and
flow patterns
a) Newtonian systems-
• exhibit Newtonian flow

b) Non-Newtonian systems
1. Plastic flow
2. Pseudoplastic flow
3. Dilatant flow
a) Newtonian systems.
 NEWTONIAN SYSTEMS (1)
• As shown in fig.1, application of a horizontal force (F)
over area (A) is known as shear stress.
• Newton proposed that velocity (dv) of the material over
a small distance (dx) that it travels is directly
proportional to shear stress.
 F/A ∝ dv/dx
 F/A = ηdv/dx
• η is coefficient of viscosity of Newtonian fluid.

• Change in velocity over distance is known as rate of

shear.
• The reciprocal of viscosity is fluidity (∅) or ∅ = 1/ η
• The slope of this line yields fluidity or 1/ η.
Viscosity types of viscosity
• Dynamic viscosity the constant of proportionality is
the coefficient of dynamic viscosity, more usually
referred to simply as the viscosity
• Note that rate of flow was directly related to the
applied stress according to newton

• Kinematic viscosity: Kinematic viscosity is defined

as dynamic viscosity divided by density of the
substance:
• K = η/ρ
Linear relationship btn rate of shear & shear stress in a
Newtonian fluid.
a) Newtonian systems
• Newton’s law of viscosity describes a linear
relationship btn shear stress (σ) & shear rate (γ) of
a fluid subject to mechanical stress

Newtonian fluids:
• Obey Newton’s law of viscosity.
• Viscosity is independent of shear rate
• Examples
• Acetone, Ethanol, Water, olive oil, castor oil
Units
• Units of shear stress = F/A = dynes/cm2
• Units of rate of shear = (cm/s)/cm =1/S
orS-1
• Units of viscosity

• More convenient units of viscosity is a

poise (ps).
 Determination of Newtonian
viscosity
a) Ostwald U-tube viscometer
• introduce the liquid into the viscometer up
to mark G through arm V using a pipette
long enough to prevent wetting the sides of
the tube.

• clamp the viscometer vertically in a

constant-temp water bath & allow to reach
required temp.
• Adjust liquid level in tube W until the
meniscus is just above mark E.
• Record time for meniscus to fall btn marks E
and F
.

Ostwald U-tube
viscometer
Calculation of viscosity from capillary
viscometers
• Poiseuille's law states that for a liquid flowing through a
capillary tube;  r 4
tP

8 LV

• Where:
• r is the radius of the capillary
• t is the time of flow
• P is the pressure difference across ends of the tube
• L is the length of the capillary
 r4
•
 KtP
V is the volume ofKliquid.

8 LV

1 K ' t1 1 1 K ' t1 1

• Viscosity of twoliquids can be compared
K ' t 
 2 K ' t2  2 2 2 2

1 t
 1
2 t2

• For kinematic viscosity,

 b) Falling-sphere viscometer
place liquid in a fall tube which clamped
vertically in a constant-temp bath & allow to
reach required temp.
introduce a steel sphere into the fall tube.
monitor passage of the sphere by means of a
telescope & the time it takes to fall btn marks
uniform terminal velocity, u of a sphere of
A and B is recorded
density ρs & diameter d falling through a
liquid of viscosity, η & density ρ is given
l 3
3 du  d g (  s  l )
by: 6

 d 2 g (  s  l )
Rearranging gives: 
18u

 d 2 g (  s  l )
For kinematic viscosity:  
18 l u
b) Non-Newtonian Systems
• Viscosity is dependent on shear
• shear stress & shear rate is non-linear, & can even
be time dependant
• Flow is not described by a single constant value of
viscosity.

• Non-Newtonian behavior is exhibited by majority of

pharmaceutical products like colloidal solutions,
emulsions, liquid suspensions and ointments.
1) Plastic (or Bingham) flow
• No flow occurs in response to shear until a transition
point called yield value is reached (f)
• yield value is: minimum shear stress required by a
system be4 it deforms & begins to flow. It is therefore
a measure of minimum stress required to induce flow.

• After yield value, the relationship btn shear stress &

shear rate becomes linear.
• Slope of the linear portion is used to calculate plastic
viscosity value.
Plastic flow
rheogram
• The plastic flow curve
does not pass through
the origin & it
intersects the shearing
stress axis (or will if
the straight part of the
curve is extrapolated
to the axis) at a
particular point
referred to as yield
value. (f)
Plastic flow
• Observed in suspensions, gels & creams.

Applications of yield value:

• For a suspension measures how many times a bottle
needs 2 be shaken be4 product flows.
• For ointments & creams, it measures the force
required to spread material on the skin.
If yield value is:
• High- product will not rub easily
• very low- product will run.
2. Pseudoplastic flow
• Pseudoplastic curve begins at the origin. No part of
the curve is linear, viscosity of a pseudoplastic
material cannot be expressed by any single value.

• The viscosity of a pseudoplastic substance ↓with ↑

rate of shear

• Such systems exhibit (shear thinning)

Pseudoplastic flow cont…
• As shearing stress ↑, normally disarranged
molecules begin to align their long axes in the
direction of flow, ↓ internal resistance of the
material and allows a greater rate of shear at each
successive shearing stress

• Examples are liquid dispersions of natural and

synthetic gums (e.g., tragacanth, sodium alginate,
methylcellulose, and sodium carboxymethyl
cellulose)
3. Dilatant flow
• A.k.a shear-thickening systems.
• Viscosity ↑ with ↑ in shear rate. materials ↑ in
volume during shearing hence reducing increasing
viscosity.

• less common than plastic or pseudoplastic flow but

may be exhibited by dispersions containing a high
concentration (≥50%) of small, deflocculated
particles.
Explanation for dilatant flow
• At low shear particles are closely packed with minimal
interparticle volume (voids). the vehicle is sufficient to
fill the voids. this fluid can adequately lubricate the
relative movement of the particles.

• At high shear, the bulk of the system expands or dilates.

particles take on an open form of packing leading to a
significant ↑ in interparticle void volume. at some point,
the amount of vehicle becomes insufficient to fill ↑voids
btn particles. resistance to flow ↑ b’se particles are no
longer completely wetted, or lubricated, by the vehicle.
Eventually, the suspension will set up as a firm paste.
Conti…
• When the stress is removed, a dilatant system
returns to its original state of fluidity.

• Dilatant materials may solidify under conditions of

high shear, overloading and damaging processing
equipment.
 summary

Newtonian fluid

Dilatant fluid
(shear thickening)

Pseudoplastic fluid
shear rate (shear thinning)

Bingham plastic

shear stress
Viscosity vs shear stress
Newtonian fluids:
• exhibit constant viscosity independent of stress.

Non-Newtonian fluids: viscosity can change when

under force to either more liquid (pseudo plastic)
also called shear thinning or more solid (dilatant)
also called shear thickening.
• In shear thinning- viscosity reduces with stress.
• Shear thickening- viscosity increases with stress.
Graph describes the
relationship.
Thixotropy
• defined as a comparatively slow recovery of
material structure on standing that was lost by
shear thinning (applies to pseudo-plastic)

• Thixotropic systems are composed of particles that

interact by secondary bonds to produce a loose
three-dimensional structure, so that the material is
gel-like when unsheared.

• When the shear stress is removed the structure

tends to reform but the process is not immediate.
Upward& downward shear rate curves for
pseudoplastic system exhibiting thixotropic behavior.
Determination of viscosity of non-newtonian systems

Rotational viscometers
• These instruments rely on the viscous drag exerted on a body when it
is rotated in the fluid to determine the viscosity of the fluid.

Examples include:
1. Concentric cylinders
2. Cone plate

• The major advantage of such instruments is that wide ranges of

shear rate can be achieved, and often a programme of shear rates
can be produced automatically.
1. Concentric cylinder viscometers
• Consists of two coaxial cylinders of different
diameters, the outer (cup) containing the fluid &
inner cylinder (bob). Outer cylinder is rotated &
viscous drag exerted by fluid is transmitted to the
inner cylinder as a torque. The stress on this inner
cylinder is indicated by the angular deflection, θ.

• Torque, T, can be calculated from:

C is the torsional constant of the wire.
C T
Concentric cylinder viscometers

• viscosity is then given by:

 1 1 
 2  2 T
 r1 r2 

4 h
• where
• r1 = radius of inner cylinder
• r2 = radius of outer cylinder
• h = height of inner cylinder
• ω = angular velocity of
outer cylinder.

Concentric cylinder geometry

Concentric cylinder viscometers
• Advantages:
• Useful for Newtonian and non-Newtonian fluids.
• Wide ranges of shear rate can be achieved by
varying the diameters of the cylinders.

• Disadvantages:
• Frictional heating can be a problem at high shear
rates hence temperature control is essential
• Filling and cleaning are often difficult when the
gap is small
 2) Cone-plate viscometers
•.
is composed of a flat circular plate with a wide-angle cone
placed centrally above it. tip of the cone just touches the
plate & the sample is loaded into the included gap. If the
plate is rotated the cone will be caused to rotate against a
torsion wire. viscosity is given by:

3T

2 r 
3

where
ω = angular velocity of the plate
T = torque
r= radius of the cone
α = angle between the cone & the Cone-plate geometry
plate.
 End
Any Questions??