Pharmaceutics B

(1103213)

Rheology 2
Dr. Zahid Hussain (PhD)
Office : M23-143
Email : zhussain@sharjah.ac.ae
Phone : +971504081850
 Learning objectives

At the end, students should be able to understand;

 Non-Newtonian systems

1. Plastic flow

2. Pseudoplastic flow

3. Dilatant flow

 Thixotropy, Rheopexy, Anti-Thixotropy

 Non-Newtonian Systems

• The majority of liquid pharmaceutical products do not follow

Newton’s law of flow (i.e. viscosity varies with shear rate or
shearing stress). These systems are referred to as Non-
Newtonian systems.

• Non-Newtonian behavior is generally exhibited by

heterogeneous dispersions such as colloidal dispersions,
emulsions, suspensions, creams, gels and ointments.
Types of Non-Newtonian Behavior

1. Plastic Flow
2. Pseudoplastic Flow
3. Dilatant Flow

 Time dependant behaviour

• Thixotropy & Rheopexy
• Anti-thixotropy
Non-Newtonian Behavior
 Non-Newtonian Behavior

Viscosity of Non-Newtonians systems changes with shear.

1. Plastic Flow
 Plastic Flow

• A system that does not begin to flow until the shearing stress
exceeded from a certain value (referred to as yield value).

• At shearing stresses below the yield value, the substance acts

as an elastic material (does not flow).

• Flow curves for plastic systems do not pass through the origin,
but rather intersect the shearing stress axis at a particular point
referred to as the yield value (f).

• Materials exhibiting plastic flow are known as Bingham bodies.

Rheogram of Plastic Flow

Yield value (f)

 Plastic Flow
• The slope of the rheogram is termed as mobility, analogous to fluidity in
Newtonian systems, and its reciprocal is known as the plastic viscosity (U).
• During flow, the viscosity decreases (mobility increases) with increasing
shearing stress until a minimum viscosity is reached.

Yield value (f)

Example: Concentrated flocculated suspensions

(Ketchup).
 Plastic Flow
• A plastic system resembles a Newtonian system at shear stresses
above the yield value.

Slope of the linear part is

termed mobility.
1/slope is the Plastic viscosity
(U).
 Mechanism of Plastic Flow
Below the yield value Above the yield value

At rest Sheared

Flocculated particles; Deflocculated particles;

increased void volume; vehicle is released resulting in
vehicle entrapped in voids resulting in a drop in viscosity
relatively high viscosity
 Mechanism of Plastic Flow
• Plastic flow is associated with the presence of flocculated
particles in concentrated suspensions which results in the
formation of a continuous structure throughout the system.
• A yield value is required to break the contacts between the
adjacent particles (due to van der Waals forces) to make the
fluid flow.
• The yield value is an indication of flocculation, the more
flocculated the suspension, the higher will be the yield value.
• Once the yield value has been exceeded, any further increase
in shearing stress (i.e. F-f) brings about a directly proportional
increase in the rate of shear (G).
 Plastic Flow
The equation describing plastic flow is:

F f
 
U
G
Where:
U = plastic viscosity (poise)
f = is the yield value, or intercept on the shearing stress axis in
dynes/cm2
F= shearing stress (dynes/cm2)
G= rate of shear (sec-1)
 Example
A plastic material was found to have a yield value of 5200
dynes/cm2. At shearing stresses above the yield value, F was
found to increase linearly with G. If the rate of shear was 150
sec-1 when F was 8000 dynes/cm2, calculate the U (plastic
viscosity) of the sample.

Solution:
U = (8000  5200)/150
= 2800/150
= 18.67 poise
2. Pseudoplastic Flow
 Pseudoplastic Systems
• Many liquid pharmaceutical products which contain polymers
(as excipients or carriers) such as suspensions and colloidal
dispersions exhibit pseudoplastic flow.
• Pseudoplastic systems become more fluid when shaken or
stirred faster, e.g., suspensions.
• Paint also exhibits Pseudoplastic flow.
 Polymers
• Polymeric dispersions exhibit pseudoplastic flow.
• Polymers are widely used in pharmaceuticals.
• They are used to form carriers in drug delivery.
• They are prime component in dermatologic and ophthalmic
products such as gels.
• They can also be used as stabilizers and viscosity-modifiers.
• Polymers of the same brand such as Poloxamers are present
in the market in different molecular weight.
• The rheological behavior of the polymer depends on the
molecular weight.
 Rheogram of Pseudoplastic Flow
• The consistency curve begins at the origin.
• There is no yield value as in plastic flow.
• No part of the curve is linear, therefore, the viscosity of a
pseudoplastic material cannot be expressed by any single value.

Shear thinning system

  with  F

Example: polymer solutions/dispersions

 Pseudoplastic Flow
 The viscosity of a pseudoplastic substance decreases with
increasing shearing stress or rate of shear.
 Pseudoplastic materials are frequently referred to as “shear-
thinning systems”.
 No single viscosity can be obtained for a pseudoplastic
system since viscosity keeps changing by changing the
shearing stress.
 The most satisfactory representation for a pseudoplastic
material, however, is probably a graphic plot of the entire
consistency curve or rheogram.
Shear thinning in polymeric systems

Under shearing stress, the entangled polymer chains become disentangled

and aligned, causing Shear Thinning and a reduction in viscosity.
 Shear thinning in particulate dispersions

At Rest (high ) Under Shear (low )

Under shearing stress, the aggregated particles become separate, causing

Shear Thinning and a reduction in viscosity.
Mechanism of Pseudoplastic Flow
 The curved rheogram for pseudoplastic materials results from
a shearing action on long-chain molecules such as polymers or
aggregated particles.
 As shearing stress is increased, entangled polymers become
disentangled and they align their long axes in the direction of
flow.
 This orientation reduces internal resistance of the material and
allows a greater rate of shear at each successive shearing
stress.
 In addition, some solvent molecules associated with polymers
may also get released resulting in further lowering of apparent
viscosity.
 Comparison

• Newtonian systems are completely described by

viscosity ().
• Plastic systems are adequately described by yield
value (f) and plastic viscosity (U).

• Comparison between different pseudoplastic systems

is more difficult, and usually the whole rheogram is
used for comparison purpose.
3. Dilatant Flow
 Dilatant Flow

• Certain suspensions having high concentration (50% or

more) of small deflocculated particles exhibit an increase in
resistance to flow with an increase in shearing stress.

• Such systems actually dilate (increase volume) when sheared

and hence are termed as dilatant systems.

• Dilatant flow is the inverse of Pseudoplastic flow (shear-

thickening systems).
 Rheogram of Dilatant Flow

  with  F Shear thickening systems

Example: Concentrated
deflocculated suspension (e.g.,
starch suspension in water)
Dilatant Flow
A possible cause of dilatant flow
At rest Sheared

Close-packed particles; Flocculation of particles;

minimum void volume; increased void volume;
sufficient vehicle; relatively low vehicle entrapped in voids;
viscosity relatively high viscosity
 A possible cause of dilatant flow

At rest Sheared

• At rest, particles are closely packed with minimal voids. The amount of
vehicle in the suspension is sufficient to fill voids and permits particles to
move relative to one another at low rates of shear (can be poured from a
bottle).
• As shear stress is increased, the bulk of the system expands or dilates
and the particles undergo flocculation.
• Such an arrangement leads to a significant increase in inter-particle void
volume that entrap vehicle resulting in an apparent high viscosity.
 Mechanism of Dilatant Flow

• The amount of vehicle remains

constant but becomes insufficient
to fill the voids between particles,
which results in increasing
resistance to flow because
particles are no longer completely
wetted by the vehicle.
• Eventually the suspension will set
up as a firm paste if shearing
continues.
 Precautions
• Dilatant behavior cautions that appropriate
measures must be taken during the
processing of dilatant materials.
• Conventionally, processing of dispersions
containing solid particles is facilitated by
the use of high-speed mixers, blenders, or
mills.
• Although this is advantageous with all
other rheologic systems, dilatant materials
may solidify under these conditions of high
shear, thereby overloading and damaging
of processing equipment may happen.
Rheology Summary
Practice Questions
 Question 1
The following rheogram represents which one of the following
systems?

Shearing stress
A. Plastic systems
B. Pseudoplastic systems
C. Dilatant systems
D. Newtonian systems

Rate of shear
 Question 2
The following rheogram represents which one of the following
systems?

Rate of shear
A. Concentrated flocculated suspensions
B. Concentrated deflocculated suspensions
C. Polymeric dispersions
D. Glycerin
Shearing stress
 Question 3
The following figure represents which one of the following
systems?

viscosity ()
A. Plastic systems
B. Pseudoplastic systems Shear Rate (G)
C. Dilatant systems
D. Newtonian systems
E. A & B
Time-dependent behavior
 Thixotropy
 Thixotropic materials are the plastic or pseudoplastic materials
that gain back their viscosity when you stop shearing but they
take some time to do so (i.e. they do not regain their viscosity
immediately after releasing the shearing stress).
 Thixotropy is defined as “an isothermal and comparatively
slower recovery (return back to its original state) on standing of
a material of which consistency (viscosity) was lost through the
shearing stress”.
 Thixotropy can be applied only to shear-thinning systems
(pseudoplastic and plastic).
 Thixotropy
• If the rheogram shows a hysteresis loop, that is, the curve obtained on
increasing the shearing stress is not superimposable with the curve
obtained on decreasing the shearing stress then the system is called
thixotropic system.
• The hysteresis loop is formed by the up- and down-curves of the rheogram.
• The down-curve is displaced relative to the up-curve.

Hysteresis loop
 Hysteresis loop
 The area of hysteresis loop can be
used to measure thixotropic
breakdown.
 It may be obtained readily by means
of a planimeter or other suitable
techniques.
 Smaller the hysteresis loop (area
between the up- and down-curves)
the faster the material regains its
viscosity when shearing stress is
released.
Time dependent behavior (Thixotropy)
• If the down-curve is displaced to the left of the up-curve, it shows that
material has lower consistency (viscosity) at any one shearing stress on
the down-curve compared to up-curve.
• This indicates a breakdown of structure that does not reform immediately
when shearing stress is removed or reduced (slow recovery – recovery
takes time).
Thixotropy
 Mechanism of Thixotropy
• Thixotropic materials exhibit inter-molecular (or inter-
particles) interactions

Shearing

At rest

Under shear, viscosity drops and the material moves from a ‘gel’ state into a
‘sol’ state. At rest the ‘gel’ state reforms.
 Thixotropy (Gel-Sol-Gel)

Viscosity-time curve

Viscosity
() Gel state

Sol state
G = constant G=0

Time
Remove shear

Gel-sol-Gel
 Importance of Thixotropy
• Thixotropic materials, like polymers, are very useful to include
in various pharmaceutical preparations such as suspensions.
• At rest, suspension gain high viscosity which prevents
particles sedimentation. But when shearing stress applied
(patient shake the bottle before use), viscosity drops so patient
can easily pour liquid from the bottle.
• After stopping shaking, suspension takes some time to regain
its viscosity which allows patient enough time to take the dose.
• After using the suspension, the viscosity will increase again to
prevent sedimentation.
 Importance of Thixotropy

Stability of dispersions:
When dispersing a drug in a liquid vehicle (water), drug has a
tendency to settle in the bottle, leading to uneven doses. However,
thixotropic behaviour prevents sedimentation of drugs and hence
improve stability of pharmaceutical dispersions.
 Rheopexy
 It is sometimes possible to accelerate solidification (gelling) of a
thixotropic sol by gentle and regular movement such as swirling the
material in a beaker. This phenomena is known as rheopexy.
 The gentle motion assists the particles in making contact or
polymers to entangle with each other, but at the same time, this low
shearing stress is insufficient to cause shear-thinning.
 Anti-thixotropy
• At any one rate of shear, consistency (viscosity) is
greater on the down-curve than the up-curve.

• This phenomenon is therefore associated with dilatant

systems.
Anti-Thixotropy for dilatant system

gel

sol
sol

At any one rate of shear, the consistency (viscosity) of the down-curve is

higher than that of the up-curve.
 Reference/Recommended Books

1. Howard C. Ansel & Shelly J. Stockton. Pharmaceutical calculations, 15th

edition, Lippincott Williams and Wilkins, Baltimore, MD (2017).
2. Ansel’s Pharmaceutical Dosage Forms and Drug Delivery Systems. Ed. L.
V. Allen & H. C. Ansel, 10th Edition, 2011, Pub. Lippincott Williams and
Wilkins, Baltimore. ISBN: 9781451188769.