Blood Diseases Hemoglobin/Hematocrit Value

Polycythemia
Dengue fever

Sickle Cell Anemia

Malaria

The hematocrit, also known as packed cell

volume (PCV) or erythrocyte volume fraction
(EVF), is the volume percentage (%) of red blood Hematocrit measure of % RBC
cells in blood. It is normally 45% for men and 40% Males: 47% 5%
for women. It is considered an integral part of a Females: 42% 5%
person's complete blood count results, along with
hemoglobin concentration, white blood cell count,
and platelet count.

Rule of 3's: Hgb should be 3 times the

Hematocrit (Hct) (i.e. Hgb of 9 gm/dl should
make Hct 27%). The Hgb should increase 1
gm/dl & 3% Hct for each unit of PRBC's if you
need a transfusion.
1
Introduction To Rheology

Santanu Dhara

School of Medical Science and Technology

Indian Institute of Technology
Kharagpur-721302

2
 Definition of Rheology

Rheology is the science of flow and

deformation of matter
We use rheology to study flow behavior of
ceramics loaded slurries for preparation,
casting and gelling.

3
Flow and Deformation Parameters:
Shear Stress, Shear Strain, & Shear Rate

Stress: Force per unit area.

Symbol: Units: Pa (SI) or dyn/cm (cgs)

Shear Strain: Relative deformation in shear.

Symbol: Units: None

Shear Rate: Change of shear strain per unit time.

Symbol: Units: s-1

4
 Range of Rheological Material
Behavior
Rheology: The study of flow and
deformation of matter.

Range of material behavior

Solid Like ---------Liquid Like
Ideal Solid-------------Ideal Fluid

Classical Extremes
5
 Classical Extremes: Elasticity

1678: Robert Hooke develops his

True Theory of Elasticity
The power of any spring is in the same
proportion with the tension therof.
Hookes Law: = G or (stress = G x strain)
where G is the RIGIDITY MODULUS
Hookes law describes ideal mechanical behavior using a
constitutive equation in which stress and strain are related through
a proportionality constant called the modulus G. If you double the
stress, you double the strain.
6
 Classical Extremes: Viscosity

1687: Isaac Newton addresses liquids and steady simple

shearing flow in his Principia

The resistance which arises from the lack of slipperiness of

the parts of the liquid, other things being equal, is
proportional to the velocity with which the parts of the liquid
are separated from one another.
Newtons Law: =
where is the Coefficient of Viscosity
Newtonss law describes idea flow behavior using a constitutive
equation in which stress and rate of strain are related through a
proportionality constant called the viscosity. If you double the stress, you
double the shear rate. 7
Viscosity and Steady
Shear Testing

8
Viscosity: Definition

Viscosity is . . . .
lack of slipperiness.
synonymous with internal friction.
resistance to flow.

A measure of the resistance of flow due to internal

friction when one layer of fluid is caused to move in
relationship to another layer.
9
 Viscosity: Units

The Units of Viscosity are . . . . .

SI unit is the Pascal.second (Pa.s)
cgs unit is the Poise
Poise is > Pa.s by a factor of 10
.
10 Poise =1 Pa s
1 cP (centipoise) = 1 m Pa.s (mili-pascal-second)

10
Typical Viscosities (Pa.s)

Asphalt Binder --------------- 100,000

Polymer Melt ----------------- 1,000
Molasses ---------------------- 100
Liquid Honey ----------------- 10
Glycerol ----------------------- 1
Olive Oil ----------------------- 0.01
Water -------------------------- 0.001
Air ------------------------------- 0.00001

11
Typical Shear Rates (1/s)

Sedimentation 10-4
Molecular Structure
Leveling/Sagging 10-3 to 100
Compression Molding
Pouring 100 to 101
Extrusion
Pumping 101 to 103

Blow Molding
Rubbing 103 to 104
Injection Molding
Spraying 105
Bearing lubrication 106 12
Variables that Affect Viscosity

Shear Rate
Time of Shearing
Temperature
Pressure

13
Newtonian Vs. Non-Newtonian Behavior

Strict definition of Newtonian Behavior

is only stress generated in simple shear flow (no normal stress
difference).
Shear viscosity does not vary with shear rate.
is constant with time of shearing.
in fluid falls immediately to zero when shearing is stopped. When
sheared again, the is as was previously measured (regardless of
delay between measurements).
measured in different types of deformation are in proportion to
one another.
measured in uniaxial extension is three times shear (Troutons
Ratio)

A Liquid showing any deviation from

Newtonian is said to be non-Newtonian
14
Characteristic Diagrams for Newtonian Fluids
, Pa

, Pa.s
,1/s ,1/s

15
Non-Newtonian Fluids

Non-Newtonian Time Independent Liquids, = ( )

Viscosity of fluid is dependent on shear rate but
independent of the time of shearing. The viscosity
is presented at a specific shear rate and referred
to as the apparent viscosity, shear viscosity or
shear dependent viscosity.

Non-Newtonian Time Dependent Liquids, = (,t)

Viscosity of fluid is dependent on shear rate and
the time during which shear rate is applied.
16
Non-Newtonian, Time Independent Fluids

Shear-Thinning
A decrease in viscosity with increasing shear
rate. Also referred to as Pseudoplasticity.

Shear-Thickening
An increase in viscosity with increasing shear
rate. Also referred to as Dilatancy.

17
Characteristic Diagrams for Shear Thinning Fluids

105 105

103
, Pa.s

103

, Pa.s
101 101

10-1 10-1
10-6 10-4 10-2 100 102 104 10-6 10-4 10-2 100 102 104

,1/s , Pa
105

103
, Pa

101

10-1
10-6 10-4 10-2 100 102 104
,1/s 18
Shear Thinning Behavior

Shear thinning behavior is often a result of:

Orientation of non-sherical particles in the direction of
flow. An example of this phenomenon is the pumping of
fiber slurries.
Orientation of polymer chains in the direction of flow and
breaking of polymer chains during flow. An example is
polymer melt extrusion
Deformation of spherical droplets to elliptical droplets in
an emulsion. An industrial application where this
phenomenon can occur is in the production of low fat
margarine.
Breaking of particle aggregates in suspensions. An
example would be stiring paint.
19
Non-Newtonian, Time Dependent Fluids

Thixotropy
A decrease in apparent viscosity with time under
constant shear rate or shear stress, followed by a
gradual recovery, when the stress or shear rate is
removed.
Rheopexy
An increase in apparent viscosity with time under
constant shear rate or shear stress, followed by a
gradual recovery when the stress or shear rate is
removed. Also called Anti-thixotropy or negative
thixotropy.
Reference:Barnes, H.A., Hutton, J.F., and Walters, K., An Introduction to Rheology,
Elsevier Science B.V., 1989. ISBN 0-444-87469-0 20
Non-Newtonian, Time Dependent
Fluids

Shear Rate = Constant

Viscosity

Rheopectic

Thixotropic

time

21
 Linearity vs. Non-Linearity

Hookes and Newtons laws are linear

laws. They assume direct proportionality
between stress and strain, or shear rate
no matter what the stress.
Most materials we work with obey these
laws over a limited range of stresses.
Beyond this limited range a material
behaves non-linearly.
22
Newtonian and Non-Newtonian
Behavior of Fluids
Newtonian Region
Non-Newtonian Region
Independent of
= f()

23
 Linear and Non-Linear Stress-
Strain Behavior of Solids
1000 100.0
Linear Region Non-Linear Region
G is constant G = f()

100.0

osc. stress
(Pa)
G'

(Pa)
10.00

1.000 0.01000
0.010000 0.10000 1.0000 10.000 100.00 1000.0 24
% strain
Types Of Flow

"Yield"
Bingham

Plastic

Shear Thinning
Pseudoplastic
Yield y Newtonian
Stress Dilatant

Shear Thickening

25
Model Fitting

Newtonian

Pseudoplastic

Dilatant

Bingham

Casson

Herschel-Bulkley

26
 Steady Shear Test Modes

Stepped Ramp - Equilibrium Flow

Continuous Ramp

Temperature Ramp

27
Stress Ramp Test - Continuous Ramp

Deformation
Stress (Pa)

Stress is applied to
material at a constant
m =Stress rate rate. Resultant strain is
(Pa/min) monitored with time.

time (min.)

USES
Yieldstress
Scouting Viscosity Run

28
Idealized Full Flow Curve

(1) (1) Sedimentation

Asphalt Binder
(2) (2) Leveling
Molasse (3) Pouring
s (4) Pumping
Glycerol (3) (5) Rubbing
Log

(6) Spraying
Castor Oil
(4) (5) (6)
Olive Oil

Water

10 E - 6 10 E 1 10 E 4
.
Log

29
Viscosity: Temperature dependence

30
 Type of Viscometer
Ostwald viscometers named after Wilhelm Ostwald or
glass capillary viscometers. Another type is the
Ubbelohde viscometer.

They basically consist of a glass tube in the shape of a U

held vertically in a controlled temperature bath.
In one arm of the U is a vertical section of precise narrow
bore (the capillary). Above this is a bulb, there is another
bulb lower down in the other arm.
In use, liquid is drawn into the upper bulb by suction, then
allowed to flow down through the capillary into the lower
bulb.
Two marks (one above and one below the upper bulb)
indicate a known volume. The time taken for the level of the
liquid to pass between these marks is proportional to the
kinematic viscosity.
Most commercial units are provided with a conversion
factor, or can be calibrated by a fluid of known properties
31
 Rotary Viscometer - Spring

Brookfield

Fungilab viscoelite

Air bearing (Graphite bearing)

Bohlin Rheometers and Viscometers

TA instrument

32
CSL2

Air Bearing & Motor

2
CSL 100
Optical Encoder
Rheometer

Measuring System

Temperature Control Cell

Autogap Set

33
Cross-Section CSL
Draw
Optical Rod
Encoder
Air
Bearing

Controlled
Measurement Torque
Geometry Motor

Peltier Temperature
Control Plate
Micrometer
Wheel

Pneumatic
Auto Gap Set
Ram
Motor
34
Cross-Section of CSL Drive

Air Bearing Optical Encoder

Air
Jet

Air
Jet

Non-Contact Motor

Drag
Cup
35
Controlled Stress Schematic

Ball Slide

Column

Draw Rod
Rheometer Head

AR 1000 air bearing

drag-cup motor
Geometry

optical encoder

Normal Force Sample Plate

Transducer Peltier (optional)

blank (optional)
(optional)

Rheometer Base

auto gap set motor

AGS encoder

communication ports

36
AR 1000: Rheometer Head Schematic

Optical Encoder

Upper Radial Bearing

Thrust Bearing

Drag Cup

Drag-cup Motor

Lower Radial Bearing Motor Housing

37
 Parallel Plate

R
Strain Constant: K =
H
3 * Gc
Stress Constant: K = (R/10)3

Variable Gap (Sample Thickness)

500 to 2000 microns recommended.
Assortment of Plate Diameters (2 cm, 4 cm, and 6 cm
Standard)
Easy to load. Able to use with a wide range of viscosities.
Velocity gradient from center to edge of plate during steady
shear testing. 38
Plate Gaps and Diameters

Shear Stress

2cm

4cm

6cm

Decreases
Gap 0
Increases
Shear Rate Infinity

39
Gap Choice for Parallel Plate Geometry

Set gap to be at least 10 x particle or droplet

size [consider extremes of size distribution]
Minimum gap should be 1000 microns

1) Set Gap & Trim Edge 2) Close 10 - 50

microns

Plate & Plate Plate & Plate

40
Cone Angles and Diameters

Shear Stress

2cm

4cm

6cm

Decreases
Angle
Increases
Shear Rate

41
Limitations of Cone & Plate for Dispersions -
Fixed Gap!

Truncation Heights:
1 degree ~ 20 - 30 microns
2 degrees ~ 60 microns
4 degrees ~ 120 microns

Cone & Plate Truncation Height = Gap

Gap must be > or = 10 [particle size]!! 42

Concentric Cylinder

2
Strain Constant: K =
1-(R1/R2)2
1,000
Stress Constant: K = 2L(R )2
1

Large surface area to obtain low stress measurements.

Possibility of shear history effects from loading.

Good for testing suspensions with limited stability. 43

Solvent Trap System

Reduces errors due to solvent evaporation

Available for cones, plates, and concentric
cylinders

44
Edge Effects

Under Filling

Over Filling

Correct Filling

45
Rheology of
Dispersions

46
 Dispersion -
Definition
DEFINITION: Discrete particles randomly
distributed in a fluid medium. Dispersions can be
broken into three categories

Suspensions - solid particles in a liquid medium.

Emulsions - liquid droplets in a liquid medium.
Foam - a gas in a liquid medium.

Reference:Macosko, C.W., Rheology: Principles, Measurements, and Applications,

VCH Publishers Inc., 1994. ISBN 1-56081-579-5
47
 Dispersion

Particle,
Number, Size,
+ Droplet, or
Air Bubble
Shape, Density

Modify
Surface

-
Liquid
Medium

Continuous
Phase, c 48
 Factors Influencing Rheology of
Dispersions
High volume fractions, Particle size Particle size distribution

Vs

Electrostatic interactions Particle shape Steric Hindrance

+ + + +
------
+ + + +

49
 Concentration of Particles

Rheology depends greatly on the

hydrodynamic
forces that act on the surface of particles
(aggregates) regardless of the density.

Need to define concentration of suspension

in terms of phase volume or volume-per-
volume fraction as opposed to weight-per-
weight fraction which is often used as a
measure of concentration. 50
Reference:Barnes, H.A., Hutton, J.F., and Walters, K., An Introduction to Rheology,
Elsevier Science B.V., 1989. ISBN 0-444-87469-0
 Forces Acting on Particles
Arise from interaction between particles and result in overall
repulsion or attraction between particles.
Repulsion
Like electrostatic charges.
Entropic repulsion of polymeric or surfactant material on the
surface of the particle.
Net repulsive Forces Particles remain separate (dispersed or
deflocculated).
Attraction
London - Van der Walls attraction between particles.
Electrostatic attraction between unlike charges on different parts
of a particle (edge/face attraction between clay particles).
Net attractive forces Particles flocculate.

51
Reference:Barnes, H.A., Hutton, J.F., and Walters, K., An Introduction to Rheology,
Elsevier Science B.V., 1989. ISBN 0-444-87469-0
Forces Between Particles

In most dispersions, particles are kept apart (in suspension) by

modifying the surface of the particle.

Van der Waals Forces

lead to particle clumping
Want to prevent particles
from clumping

There are generally two ways to modify the the surface

of a particle to maintain a stable dispersion
Electrostatics forces
Steric forces
52
Mechanism of stabilization of the colloidal particle
in suspending medium
UT = UA + (URe + URs )

Where URe and URs are the

energy term due to
electrostatic repulsion and
steric stabilization

The repulsive force should be

predominant over Vander Walls
force of attraction

For electro statically stabilized slurry, the zeta

potential of the suspended powder should be
higher than 25 mV
53
 Different State of Dispersion of Slurry
Dispersed State
-150 Nontouching Particle
Flocced State Coagulated State
Touching & Cohesive Network Nontouching & Cohesive
Particle Network Particle Network

Hydration Layer
Repulsion+ Van der Waals
Primary Attraction
Maximum

0 Interparticle Spacing Interparticle Spacing

0
Interparticle Spacing

Shallow Hydration
Van der Waals Attraction Van der Waals Minimum
Attraction +
Electrostatic Repulsion
(a) Deep Primary Minimum (b) Deep Primary Minimum (c) Deep Primary Minimum
+150

Flocculated Slurry
Dispersed Slurry
Coagulated Slurry 54
 Slurry Characteristics

Forming of dense, defect free ceramic components via

gelcasting requires use of highly loaded slurries.

In addition to high solids loading, gelcasting slurries

must be stable, Shear thinning

Yield stress 50 Pa
Viscosity 2 Pa.s at the shear rate 10 s-1 55
 Dispersion Stability

Two ways dispersed particles are stabilized.

Electrostatically
The existence of a net charge which causes particles
to repel one another.
Sterically by absorption of polymer molecules on the
particles.
film of absorbed surfactant which which prevents
the particles from adhering to one another may be
sufficient to keep dispersed particles in suspension.

Ref: Rohn, C.L.,The Rheology of Coatings and Dispersions,

Journal of Water Borne Coatings, Au gust, 1987. 56
 Electrostatic Forces on Particles
Electrostatic Repulsion
- - - -
- - - - - - -
- - - - -
- - - -
- - - -
-
- -- - - - - - Pseudo-Structure
- - - - -
- -- - - -
- - - - - - -
- - - - -
- - - -
- - - -
- - -- - - - - -
- - -- - - -
57
Steric Hindrance of Particles

Adsorbed Polymer

Non-interacting

Bridging Floc

58
 Concentrated
Suspensions
In concentrated suspensions, particles may link to build a three-
dimensional network structure which extends through the whole
system.
This structure in a suspension is a result of particle-particle
interactions. These particle-particle interactions cause deviation
from Newtonian behavior in a suspension.
We need to recognize that the rheology of suspensions is measured
macroscopically but the rheology depends very much on
microscopic considerations. Measuring these particle-particle
interactions or structure will yield valuable information about the
microstructure of the suspension.
Reference: Sato, T., Rheology of Suspensions, Journal of Coatings
59
Technology,
Vol. 67, No. 847, August 1995.
Particle-Particle Interactions
Cause Structure

60
 The Maximum Packing Fraction, m

The maximum packing fraction m is the volume

fraction of particles at which a three-dimensional
continuous contacting network is formed.

At m the suspension is jammed up and flow is

impossible.

At m the suspension the viscosity goes to infinity.

m ranges form 0.5 to 0.75. (FCC m = 0.74)

61
 The Maximum Packing Fraction, m
Packing Fraction: The ratio of the total volume of a set of
objects packed into a space to the volume of that space.

m depends on particle arrangement, particle size

distribution, and particle shape.
Broader particle size distributions tend to have higher m.
the suspension is jammed up and flow is impossible.
Non-spherical particles have lower m (poor space fitting).
Particle flocculation leads to a low m (in general flocs are
not close packed).
Good to normalize concentration as the ration /m.
62
 Limited Cases for the Viscosity Flow
Curve for Suspensions

Yield stress develops below which there

is no real macroscopic flow

Low shear viscosity limit often

disappears with higher concentration

log

log
63
 Ink Flow Curves: vs. Shear
Stress
Yield stress develops below which there
1000000 is no real macroscopic flow

100000
Low shear viscosity limit often
disappears with higher concentration
viscosity (Pa.

10000

1000

100.0
s)

10.00

1.000

0.1000
1.000 10.00 100.0 1000
64
shear stress (Pa)
 Ink Flow Curve: vs. Shear
Stress
1000000
Yield Stress
100000

10000
viscosity (Pa.

1000

100.0
4 decade drop in

10.00
s)

1.000

0.1000
0.1000 1.000 10.00 100.0 1000
shear stress (Pa) 65
"Yield" Curve for Grease
400 Pa 600 Pa
1.0E8

1.0E7 800 Pa

1.0E6

1.0E5
viscosity (Pa.

Six Decade
1.0E4
Drop in
1.0E3
s)

1.0E2

10.00

1.0
100.0 1000 10000
66
shear stress (Pa)
The yield strength or yield point of a material of a material is
defined in engineering of a material is defined in engineering and
materials science of a material is defined in engineering and
materials science as the stress of a material is defined in
engineering and materials science as the stress at which a material
begins to deform plastically of a material is defined in
engineering and materials science as the stress at which a material
begins to deform plastically. Prior to the yield point the material
will deform elastically and will return to its original shape when
the applied stress is removed. Once the yield point is passed some
fraction of the deformation will be permanent and non-reversible.
How do you measure?

67
 Yield Stress of Alumina-Zirconia Suspensions

The yield stress of concentrated suspensions of alumina, zirconia, and mixed

alumina-zirconia powders was measured by the vane technique as a function of
solids loading, relative amounts of alumina and zirconia, and pH. At the isoelectric
point (IEP), the yield stress varied as the fourth power of the solids loading.

Vijay Ramakrishnan, Pradip S. G. Malghan using Vane geometry.

68
J. Am. Ceram. Soc, 1996.
Ink Flow Curves: vs. Shear
Rate

=
10
.5
Pa

=
11
.5
Pa

69
 Concentrated Suspensions
Exhibit Elasticity
Concentrated suspensions typically show some degree of
elasticity. If the material has a yield stress then it behaves
as an elastic gel under small stresses or strains.

The storage modulus, G, is a measure of the elasticity of

the material and is a direct measure of the particle-
particle interactions. Hence, G is a measure of the
structural characteristics of a material.

We can therefore use Dynamic Mechanical Testing to

characterize the structure of a concentrated suspension.
The mechanical response is extremely sensitive to the
amplitude of the applied deformation, or .
70
Gel Structure in Suspensions

71
 Gel Structure in Suspensions

Unbroken Gel Structure

Broken
Structure begins
Structure
to Breakdown

Increasing Amplitude
of Shear Deformation 72
Stability is Related to Structure
in Inks

73
 Time-Dependent Gellation

Break Structure Gel Structure

under high shear rebuilds with
time

Time

74
 Optimization of the dispersant

Darvan DBAC

The optimized dispersant amounts - 4.6 mg and 1.9 mg

Darvan and DBAC respectively per gm of alumina
powder
55 vol% alumina loading slurry showed shear thinning
75
behaviour
 Effect of nature and dispersant amount on non-Newtonian index
Slurry Zeta Potential (mV)

The zeta potential values were

maximum for optimum Darvan 821 A DBAC

amount of dispersant
3.2 mg 4.6 mg 6.3 mg 1.4 mg 1.9 mg 4.2 mg
The zeta potential value was
high enough to stabilize the
Fresh -64.4 -73.6 -69.1 -35.3 -63.4 -52.2
slurry
Aged -68.8 -77.9 -74.5 -21.8 -65.8 -78.2

All slurries were pseudoplastic in nature (n <1)

The non-Newtonian index n as a function of

dispersant amount

All slurries had n values in the range of 0.11 to 0.33.

n was maximum for the optimum amount of

dispersant. 76
 Comparison of the two dispersants

Darvan DBAC

For the same percent mole fraction below optimum, the increase in viscosity was
sharper for DBAC slurries as compared to the Darvan slurries. This was because the
carboxylic group of Darvan is 15 times that of DBAC and the ability of Darvan to
provide steric hindrance.

Sharper rise in viscosity was observed for similar percent mole fraction above the
optimum in case of Darvan in comparison to DBAC due to tangling and double layer
compression 77
 Aging Behaviour of the slurries
Darvan DBAC

Among all Darvan and DBAC based slurries, the ones with below optimum
amount of dispersant exhibited significant change in viscosity as a result of
both static and dynamic aging treatments.
Slurries with optimum and above optimum amounts of the two dispersants
exhibited much lesser change in viscosity as a result of static or dynamic
78
aging treatments. J. Am. Ceram. Soc, 2005
Bacterial Aging

79
 Hysteresis behaviour

Hysteresis was maximum for less than optimum amount of the

dispersants and minimum for optimum amount of the dispersants.
For more than optimum amount of dispersant, hysteresis was
observed for Darvan based slurries due to tangling of long chain
dispersant while for DBAC based slurries no hysteresis was observed.80
 Darvan

DBAC

Thixotropic behavior of aged slurries followed similar trends as exhibited by the changes
in viscosity. Slurries that experienced an increase in viscosity also showed pronounced
thixotropic behavior following aging. 81
 Summary of the Aging of gelcasting
slurries:
55 vol% alumina loading slurries were shear thinning in
behaviour
The slurries with optimum amount dispersants were most stable
due to maximum zeta potential values thus viscosity was
minimum.
At optimum level of dispersant the n values were maximum.
The hysteresis behaviour was minimum with optimum level of
dispersants.
Hysteresis of aged slurries was similar to aging behaviour of
slurries
82
 Below optimum amount of dispersant exhibited significant change in
viscosity as a result of both static and dynamic aging treatments.

During static aging treatments, the formation of inter-particle network

was responsible for the observed increase in viscosity.

Roll mixing of slurries (dynamic aging) led to a decrease in viscosity

for Darvan based slurries, similar change in viscosity was not observed
for DBAC based slurries.

Rather an increase in viscosity was observed for DBAC based slurries,

most likely due to bio-degradation of DBAC during the dynamic aging
period at below optimum level of dispersant.

It was concluded that in general dispersant addition above the

optimum level may be tolerable but care must be taken to not let the
dispersant addition be below the optimum.

83
 Different terms related to Rheology:
Shear Stress
Slippage
Shear strain or Strain rate
Different geometry
Viscosity
Solvent trap
Yield Stress
Thixotropy
Newtonian
Rheopexy
Non-Newtonian
Shear Thinning (Pseudoplastic)
Non-Newtonian Index
Shear thickening (Dilatant)
Consistency factor
Instantaneous viscosity
Pseudoplastic
Apparent Viscosity
Plastic
Aging
Bingham
Structure of material
Power law, Casson,
Herchele Buckley and other different models

84
Linear Viscoelasticity

85
Viscoelasticity Defined

Range of Material Behavior

Solid Like ---------- Liquid Like
Ideal Solid ----- Most Materials ----- Ideal Fluid
Purely Elastic ----- Viscoelastic ----- Purely Viscous

Viscoelasticity: Having both viscous

and elastic properties
86
Linear Viscoelasticity Defined

"If the deformation is small, or applied sufficiently slowly,

the molecular arrangements are never far from
equilibrium. The mechanical response is then just a
reflection of dynamic processes at the molecular level
which go on constantly, even for a system at equilibrium.
this is the domain of LINEAR VISCOELASTICITY. The
magnitudes of stress and strain are related linearly,
and the behavior for any liquid is completely described by
a single function of time." (Written by Bill Graessley,
Princeton University)
Reference: Mark, J.,et.al., Physical Properties of Polymers, American Chemical Society, 1984, p. 102.
87
Response for Classical Extremes

Spring Dashpot Purely Viscous

Purely Elastic
Response Response

Hookean Solid Newtonian

= G Liquid
=
In the case of the classical extremes, all that matters is
the values of stress, strain, strain rate. The response is
independent of the loading.
88
Time-Dependent Viscoelastic Behavior:
Solid and Liquid Properties of "Silly Putty"

T is short [< 1s] T is long [24 hours]

Deborah Number [De] = / 89

Dynamic Mechanical
Analysis
OR
Oscillatory Testing

90
Dynamic Mechanical Testing

Deformation
An oscillatory (sinusoidal)
deformation (stress or strain)
is applied to a sample.
Response
The material response
(strain or stress) is measured.

The phase angle , or phase

shift, between the deformation Phase angle
and response is measured.

91
Dynamic Mechanical Testing
Response for Classical Extremes

Purely Viscous
Purely Elastic Response Response
(Hookean Solid) (Newtonian Liquid)
= 90
= 0

Stress Stress

Strain Strain

92
Dynamic Mechanical Testing Viscoelastic
Material Response

Phase angle 0 < < 90

Strain

Stress

93
 Viscoelastic property of a slurry or gel

The viscoelastic property is characterized using

sinusoidal applied shear stress,
= o sin t
shear stress, o, shear stress amplitude,
94
angular velocity and t time.
The resulting deformation () developed in the
slurry can be represented by
= o sin (t + )
o strain amplitude and phase displacement angle
between applied stress and resulting deformation.

= 90o indicates purely viscous behaviour when

stress is out of phase with strain
= 0o indicates a purely elastic behaviour when
stress and strain are in phase
= 45o indicates a purely viscoelastic character of
the slurry 95
The complex modulus G* is defined as
| G* | = | o | / | o |
The complex modulus is divided into elastic storage modulus (G) and viscous
loss modulus (G) as follows

G = G* cos

G = G* sin

The storage modulus (G) is a measure of energy stored elastically, while

the loss modulus (G) is a measure of the energy dissipated as heat during
flow in the system after a shear perturbation. The loss tangent (tan ) can
be obtained from the ratio of loss modulus and storage modulus i.e., tan =
G/G.
Most of the slurries are non-Newtonian and exhibit both viscous flow and
elastic behaviour, which can be characterized by the above measurements.
The viscoelastic measurements can also be used for studying gelation
kinetics or coagulation with change in ionic strength in the slurries. 96
Complex Stress, *
DMA Viscoelastic Parameters:
The Complex, Elastic, & Viscous Stress
The stress in a dynamic experiment is referred to as the
complex stress *
The complex stress can be separated into two components:
1) An elastic stress in phase with the strain. ' = *cos
' is the degree to which material behaves like an elastic solid.
2) A viscous stress in phase with the strain rate. " = *sin
" is the degree to which material behaves like an ideal liquid.

Phase angle

* = ' + i"

Strain, 97
DMA Viscoelastic Parameters

The Complex Modulus: Measure of

materials overall resistance to G* = Stress*/Strain
deformation. G* = G + iG
The Elastic (Storage) Modulus:
Measure of elasticity of material. The G' = (stress*/strain)cos
ability of the material to store energy.

The Viscous (loss) Modulus:

The ability of the material to dissipate G" = (stress*/strain)sin
energy. Energy lost as heat.

Tan Delta:
Measure of material damping - such
as vibration or sound damping. Tan = G"/G'
98
DMA Viscoelastic Parameters: Damping, tan

G*
Dynamic measurement G"
represented as a vector
Phase angle
It can be seen here that
G* = (G2 +G2)1/2 G
' ratio of the
The tangent of the phase angle is the
loss modulus to the storage modulus.
tan = G"/G'
"TAN DELTA" (tan ) is a measure of the
damping ability of the material.
99
 Gel point !!!

Cross-over point of G' and G is the

gel point over time and temperature.

100
Application:

Viscoelastic behaviour of the slurry

Gelation Kinetics
Structure of the slurry

101
 How to measure gelation kinetics?
Oscillation behaviour of the sample is examined to
understand gelation kinetics by studying different
parameters such as elastic modulus (G), viscous
modulus (G) and phase angle () at different conditions.

For carrying out measurement of gelation kinetics, the

following steps are performed-

1. The first step is to find out the constant values of %strain

and frequency where the strain (deformation) is
proportional to the stress, and G and G are
independent of the measuring conditions (stress, strain,
and frequency). Thus linear viscoelastic behaviour of the
slurry against time sweep measurement.
102
 How to find out linear visco-elastic region?

1. Amplitude sweep measurement of G & G vs. strain (0.001 to 100

according to material) at constant frequency (1 Hz and constant
temperature). Look at the linear region in the plot of G & G vs. strain.
Find out the value of % strain in the 2/3 of the linear region.
2. G & G vs. frequency sweep (1 to 100 Hz) measurement at constant %
strain (selected from 2/3 of the linear region from above). Find out the
value of frequency in the 2/3 of the linear region.
3. Now, measure G & G vs. time sweep at constant %strain and frequency.
This measurement will be a linear plot as %strain and frequency are within
the limit of elastic deformation zone.
4. Plot of G & G vs. time & or temperature soon after addition of cross
linking agent will be resulted in change in phase deference delta and
increase in storage modulus and reduction in loss modulus. At delta=0
degree, gelation is complete.

103
First, amplitude sweeps were performed at 1 Hz on 0.5 wt% chitosan solution.
The amplitude sweeps showed G and G to be strain independent at
deformations between 0.001 and 10. Based on this result of amplitude sweep, a
value of 1.5% strain was chosen in the linear regime for frequency sweep
measurement. From frequency sweep measurement at constant 1.5% strain, a
value of 2 Hz was chosen in the linear regime. Time sweep and temperature
sweep measurement were carried out to examine gelation behaviour of the 0.5
wt% aqueous chitosan solution at constant strain of 1.5% and 2 Hz frequency.
Time sweep measurement showed linear viscoelastic region at applied strain and
frequency with comparable magnitude of G and G values. This result indicates
that 0.5 wt% aqueous chitosan has almost 50-50 solid liquid behaviour. When the
same experiment was carried out with temperature sweep measurement (Fig.3), it
was observed that both elastic modulus (G) and viscous modulus (G) are going
up after 50o C temperature and phase angle also started going down and finally
become almost zero degree. The magnitude of increase in G was relatively
higher than G due to temperature assisted gelation of chitoan-DHF system. After
completion of the measurement, it was observed that the chitosan sample
becomes brown film due to gelation reaction.

104
Fig. 3 Gelation behaviour of 0.5 wt% aqueous chitosan solution is plotted against temperature at
constant strain of 1.5% and 2 Hz frequency.

105
Fig. 4 Elastic modulus (G) as function of temperature for 2.0 and 0.5 wt% aqueous chitosan solution at
constant strain of 1.5% and 2 Hz frequency.

106
Fig. 7 Gelation behaviour of slurry composition B (see Table 1) is plotted against temperature
measurement at constant 3% strain and 5 Hz frequency.

107
Fig. 8 Change in elastic modulus (G) of different slurry compositions (see Table 1) is plotted
against temperature at constant 3 % strain and 5 Hz frequency.

108
Fig. 9 Change in viscous modulus (G) of different slurry compositions (see Table 1) is
plotted against temperature at constant 3 % strain and 5 Hz frequency.

109
Fig. 10 Change in phase angle () of different slurry compositions (table 1) is plotted against
temperature at constant 3 % strain and 5 Hz frequency.

110
 Gelcasting of polymerizable MAM-MBAM based slurry

The grinding media was removed and the slurries were well deaired
Prior to mold filling, initiator Ammonium per sulphate (APS) and
catalyst Tetra methyl ethylene diamine (TEMED) were added and mixed
Slurries were poured into metal or plastic molds coated with white
petroleum jelly
The molds containing the slurries were kept in an oven preheated to 50oC
for gel formation.

The parts were removed from the mold soon after gelling before any significant
drying could occur

111
 Gelation behaviour of 55 volume % alumina slurrries

Temperature Induced Gelation

Room Temperature Gelation

Measurement conditions
Frequency: 1 Hz
Strain: 1 % 112
 Environment friendly process for shaping of ceramics

Homogenize extracted egg white

Prepare egg white-water premix, add antifoaming agent (1-octanol)
Add dispersant, powder and mill for 24 hours
Filter the slurry to separate the media, roll mix for an hour and idle for 30
minutes
Cast in molds and place in oven or water bath preheated to 80oC

Temperature induced gelation of a

slurry with 30 volume % ceramic
and 50 % binder in premix

S. Dhara and P. Bhargava, J. Am.

Ceram. Soc., 84 [12] 3048-50 (2001) 113
At Frequency: 1 Hz, Strain: 1 %
 Rheological Characteristics of Egg White based Slurry
35 vol% powder

For same binder water ratio, viscosity of the slurry increased with the
increase in solids loading
For a fixed solids loading slurry, the viscosity rapidly increased with the
increase of binder percent
Maximum solids loading achieved was 55 volume% with 20 volume % or
less binder in the premix 114
Rheology of the slurry using different slurry compositions

The green bodies were produced using these slurry

115
 Setting of as cast foam
Setting of foams soon after casting is essential to retain the foam microstructure
Setting of the cast foams was carried out by drop wise
addition of nitric acid

Change in viscoelastic behaviour of At frequency of 1 Hz and 0.01% strain

slurry after foaming
Gelation behaviour of foams was confirmed by viscoelastic
116
measurement before and after addition of acid
 Viscosity control and its influence on total porosity

Viscosity of the slurries can be tailored by binder volume percent in

the premix and ceramic powder loading

Viscosity exerts a strong influence on foaming behaviour of the

slurries and thus total porosity of the samples

117
J. Am. Ceram. Soc, under revision
 Temperature Induced Gelation Behaviour

Viscoelastic property of foamed Temperature induced gelation at 50oC

slurry is measured at constant
frequency of 1 Hz Measured at constant frequency of 1 Hz
and 1% strain
118
 References:
Presentation of TA instrument for
Rheology of fluid.
J. Am. Ceram. Soc., 71[12]1062-70
91988).
Principles of Ceramics Processing- J.S.
Reed
J. Am. Ceram. Soc, 81[3]549-56, 1998.
Uematsu Keizu et. al.
PhD Thesis by S. Dhara
119
A VISCOSITY PRIMER: VISCOSITY DEFINITIONS

Viscosity Definition: A measure of the resistance of flow due to internal

friction when one layer of fluid is caused to move in relationship to
another layer. The Poise represents absolute viscosity, the tangential
force per unit area of either of two horizontal planes at unit distance
apart, the space between being filled with the substance. A liquid with an
absolute viscosity of one Poise requires a force of one dyne to maintain
a velocity differential of one centimeter per second over a surface one
centimeter square. When the ratio of shearing stress to the rate of shear
is constant, as is the case with water and thin motor oils, the fluid is
called a Newtonian fluid. In the case of non-Newtonian fluids, the ratio
varies with the shearing stress, and viscosities of such fluids are called
apparent viscosities. In the new SI system, it is proposed that values for
the Poise be stated as Pascal seconds, the conversion factor being 1
Poise equal to 1 10-1 Pas. A common measurement unit is the
milliPascal second (mPas). Conversion factors are as follows:
1 centipoise (cP) = 0.01 poise (P)
1 Pas = 10 P
1 cP = 0.001 Pas = 1 mPas
1 Pas = 1000 cP 120
Absolute Viscosity
Definition: The tangential force per unit area of two parallel planes at
unit distance apart when the space between them is filled with a fluid
and one plane moves with unit velocity in its own plane relative to the
other. Also known as coefficient of viscosity.

Apparent Viscosity
Definition: The value obtained by applying the instrumental equations
used in obtaining the viscosity of a Newtonian fluid to viscometer
measurements of a non-Newtonian fluid.

Dilute Solution Viscosity

Definition: The viscosity of a dilute solution of a polymer, measured
under prescribed conditions, is an indication of the molecular weight of
the polymer and can be used to calculate the degree of
polymerization.

121
Intrinsic Viscosity ([])
Definition: The ratio of a solutions specific viscosity to the concentration of the
solute, extrapolated to zero concentration. Intrinsic viscosity reflects the capability of
a polymer in solution to enhance the viscosity of the solution. The viscosity behavior
of macromolecular substances in solution is one of the most frequently used
approaches for characterization.
The intrinsic viscosity number is defined as the limiting value of the specific
viscosity/concentration ratio at zero concentration. Intrinsic viscosity is determined
by measuring the relative viscosity at several different concentrations and then
extrapolating the specific viscosity to zero concentration. The variation of the
viscosity number with concentration depends on the type of molecule as well as the
solvent. In general, the intrinsic viscosity of linear macromolecular substances is
related to the molecular weight or degree of polymerization. With linear
macromolecules, viscosity number measurements can provide a method for the
rapid determination of molecular weight when the relationship between viscosity and
molecular weight has been established. Intrinsic viscosity is calculated by
determining the reduced viscosity (sp/c) and extrapolating to infinite dilution.
Huggins equation
[] = limred
c0
Craemer equation
[] = liminh
122
c0