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Reference Manual

Rheology of Fluids Using the


AR2000ex Advanced Rheometer
System
Section 1: Theory of Rheology

Part 1: Introduction and General
Theory of Rheology

Part 2: Viscometric Theory

Part 3: Viscoelastic Theory
Section 1: Theory of Rheology

Part 1: Introduction and General
Theory of Rheology


Definition
Rheology is defined as the study of the flow and
deformation of matter. The word was coined in the
1920s by Professor E.C. Bingham at Lafayette
College in Indiana.
Flow How liquids behave or respond to stress
We refer to this as a Viscous response
Deformation How solids behave or respond to
stress
We refer to this as an Elastic response

Two Important Material Laws
1. Newtons Law of Viscosity (for Fluids)
Equation: o = q *
o = Shear Stress, a Force Parameter
= Shear Rate, a Velocity Parameter
q = Viscosity of the fluid. Viscosity is a material
property. For simple, Newtonian fluids, the symbol for
viscosity is often .
2. Hookes Law of Elasticity (for Solids)
Equation: o = G *
o = Shear Stress, a Force Parameter
= Shear Strain, a Deformation Parameter
G = Modulus of the solid, which is a material property.




In tensor form,
o = q

In tensor form,
o = G
Constitutive Relations
Modulus
Strain
Stress
=
ity Vis
rate Shear
Stress
cos =
Strain, =
x(t)
y
0

Modulus G =
t

t =
F
A
y
0

x(t)
u
V
y
x
A
z
Shear deformation

.
=
A
At
Shear Deformation
Viscosity q =
t

.
Rheometric Testing
Two general classifications of testing
Viscometric: various test methods in which the material
is sheared continuously in order to observe the response of
a fully-developed flow field to changes in shear rate, shear
stress, temperature or time
specialized Transient testing
a subset of viscometric testing in which stress or shear
rate is applied to the sample and no limitation is
applied to the resultant deformation. However, in
transient testing we are primarily concerned with the
time dependent response to very basic changes in
stress or strain
Creep/Creep Recovery
Stress Relaxation


Oscillatory or Dynamic
Third specialized mode
Transient: a subset of viscometric testing in which
stress or shear rate is applied to the sample and no
limitation is applied to the resultant deformation.
However, in transient testing we are primarily concerned
Creep/Creep Recovery
Stress Relaxation
Rheometric Testing (contd)
Two general classifications of testing
Oscillatory or Dynamic Testing modes
This range of testing capability is what separates our type
of rheometers from simple viscometers and is the primary
reason for their existence
Dynamic testing is more of a perturbation technique in
which typically low levels of stress/strain are applied
using a frequency-based control of rate. This technique
allows the isolation of the elastic and viscous components
of the complete viscoelastic response of the fluid to be
evaluated.
This technique is more sensitive to wide ranges in
morphology and molecular-level differences in materials
than any other single analytical technique
Section 1: Theory of Rheology


Part 2: Viscometric Theory


Steady Simple Shear Flow (Fluid Flow)
Top Plate Velocity = V
0
; Area = A; Force = F
Bottom Plate
Velocity = 0
x
y
H
v
x
= (y/H)*V
0

= dv
x
/dy = V
0
/H
.
o = F/A
q = o/
.
Shear Rate, sec
-1

Shear Stress, Pascals
Viscosity, Pa-sec
This is obtained from solving the equation of
motion using the boundary conditions at y = 0
(v
x
=0) and y = H (v
x
=V
0
). See next page.
These are the fundamental flow parameters. Shear rate is always a
change in velocity with respect to distance.
Viscosity: Units
The Units of Viscosity are . . . . .
SI (International) unit is the Pascal
.
second (Pa
.
s)
c-g-s unit is the Poise
Conversion: 10 Poise =1 Pa
.
s
1 cP (centipoise) = 1 m Pa
.
s (milli-pascal-second)
Typical Viscosity Values (Pa-s)
Asphalt Binder..
Polymer Melt
Molasses ..
Liquid Honey
Glycerol
Olive Oil
Water
Air .
100,000
1,000
100
10
1
0.01
0.001
0.00001
The range of viscosity values one encounters
suggests the use of logarithmic scales when
plotting data.
Viscous Behavior
Ideal Liquid

1687: Isaac Newton addresses liquids and steady shearing flow in 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.


Dashpot:
Mechanical Analogue of
Viscous Response
Newtons Law of Viscosity
Newtons Law: stress = (coefficient of viscosity) shear-rate
q o

=
Viscosity is affected by the following:
Material
Molecular Weight
Molecular Weight Distribution, Branching
Temperature
Concentration
Particle Size
Particle Size Distribution
Newtonian and Non-Newtonian Fluids
Newtonian Fluids - constant proportionality between shear
stress and shear-rate

Non-Newtonian Fluids - Viscosity is time or shear rate
dependent
Time :
At constant shear-rate, if viscosity
Decreases with time Thixotropy
Increases with time - Rheopexy
Shear-rate :
Shear - thinning
Shear - thickening
General Flow Classifications
Time
V
i
s
c
o
s
i
t
y

(
P
a
-
s
e
c
)
Rheopectic
Stable
Thixotropic
Shear Rate (1/sec)
S
h
e
a
r

S
t
r
e
s
s

(
P
a
)
Dilatant
Newtonian
Pseudoplastic
Some dough-like materials
exhibit rheopecticity when
processed.
Coatings and inks can
display thixotropy when
sheared due to structure
breakdown.
An example of dilatancy is
wet sand on the beach.
Most materials used
industrially are
pseudoplastic.
o
,

P
a

,1/s or o, Pa
q
,

P
a
.
s

,1/s
Ideal Yield Stress
(Bingham Yield)
Characteristic Diagrams for Newtonian Fluids
Characteristic Diagrams for Shear Thinning Fluids
,1/s
10
5


10
3

10
1


10
-1
10
-6
10
-4
10
-2
10
0
10
2
10
4
o
,

P
a
Ideal Yield Stress
(Bingham plastic)
10
5


10
3

10
1


10
-1
10
-6
10
-4
10
-2
10
0
10
2
10
4
q
,

P
a
.
s

,1/s
10
5


10
3

10
1


10
-1
10
-1
10
-0
10
-1
10
2
10
3
q
,

P
a
.
s

o, Pa
Characteristic Diagrams for Shear Thickening
L
o
g

q
,

P
a
.
s

Log ,1/s
Non-Newtonian, Time Dependent Fluids
time
V
i
s
c
o
s
i
t
y

Thixotropic
Rheopectic
Shear Rate = Constant
Typical Flow Curve, showing Different Flow Regimes
Log Shear Rate (1/s)
L
o
g

V
i
s
c
o
s
i
t
y

(
P
a
-
s
e
c
)

Newtonian Region:
Viscosity is essentially
constant.
This viscosity is often
called the Zero Shear
Viscosity, q
0
, or the
Newtonian Viscosity.
For undiluted polymers,
q
0
= K M
w
3.4
when M
w
>
M
e
, the molecular weight
between entanglements.
Transition Region to non-
Newtonian behavior
Power Law Region:
o
m
or,
equivalently, q
m-1

m is usually 0.15 to 0.6
Second Newtonian Region:
Viscosity is essentially
constant again.


Structure Breakdown under Shear:

Increasing Time at Rest
Correlations of Shear Rates with Various Processes
1
1) Sedimentation
2) Leveling, Sagging
3) Draining under gravity
4) Chewing and swallowing
5) Dip coating
6) Mixing and stirring
7) Pipe flow
8) Spraying and brushing
9) Rubbing
10) Milling pigments in fluid
base
11) High Speed coating



2 3
6
5
8 9
1.00 1.00E-5 1.00E-4 1.00E-3 0.0100 0.100
shear rate (1/s)
10.00 100.00 1000.00 1.00E4 1.00E5
l
o
g

q

1.00E6
11 7
4
10
Section 1: Theory of Rheology


Part 3: Viscoelastic Theory
Viscous and Elastic Responses
Most materials behave such that they have a combination of
viscous and elastic responses under stress or deformation.
Materials behave in the linear manner, as described by
Hooke and Newton, only in rare cases where the
morphology is simple, or when the deformation or shear
stress is on a small scale.
Most Materials
Ideal Solid Ideal Liquid
Viscoelasticity: the Deborah Number
Deborah was an Old Testament Prophetess
who said :
"The Mountains Flow before the Lord"

She was the first rheologist -- Everything
Flows if you wait long enough!
Deborah Number, De - The ratio of a
characteristic relaxation time of a material (t)
to a characteristic time of the relevant
deformation process ( T ).

De = t/T
Deborah Number
Hookean elastic solid - t is infinite
Newtonian Viscous Liquid - t is zero
Polymer melts processing - t may be a few seconds
High De Solid-like behavior
Low De Liquid-like behavior
IMPLICATION: Material can appear solid-like because
1) it has a very long characteristic relaxation time or
2) the relevant deformation process is very fast
Elastic Behavior
Ideal Solid

1678: Robert Hooke develop his True Theory of Elasticity

The power of any spring is in the same proportion with the
tension thereof.

o = G
Hookes Law of Elasticity
Hookes Law: Stress = Modulus Strain
Spring:
Mechanical Analogue of
Elastic Response
Simple Shear Deformation (Solids and/or Oscillation)
Top Plate Displacement = X
0
; Area = A; Force = F
Bottom Plate
Displacement = 0
x
y
H
x = (y/H)*X
0

= dx
x
/dy = X
0
/H
o = F/A
G = o/
Shear Strain, unitless
Shear Stress, Pascals
Modulus, Pa
These are the fundamental deformation parameters. Shear strain is
always a change in displacement with respect to distance.
Remember Liquid Flow Behavior?
0 1 2 3
F
Move piston through
dashpot
Force (F) depends on
velocity (v) and vice
versa.
Force is independent of
position (x) (within
reason)
For simple fluids, F v
1
; F = F(x)
x
Heres Viscoelasticity (Solid+Liquid)
F
F
Viscoelastic Materials:
Force depends on
both Deformation and
Rate of Deformation
and vice versa.
The material exhibits
behavior lying in
between classic fluid
and classic solid
behavior
Maxwell Model
Kelvin (Voigt) Model
Time-Dependent Viscoelastic Behavior
T is short [< 1s] T is long [24 hours]
Deborah Number [De] = t / T
Viscoelastic Modeling for Transient Testing
F
Maxwell Model
The Maxwell model is useful for illustrating stress
relaxation behavior.

For 1 element:
G(t) = G
i
exp(-t/t
i
)
Where G(t) is the modulus at time, t,
following a strain imposition at t = 0.
G
i
is the spring constant; q = viscosity
t
i
is the Relaxation Time = q
i
/G
i
Log time (sec)
L
o
g

G
(
t
)

(
P
a
)
For N elements in Parallel:
G(t) = EG
i
exp(-t/t
i
)
i = 1
N
1-element stress
relaxation curve
Integral Form:
G(t) = G
e
+ }Hexp(-t/t
i
)dln(t)

-
Storage and Loss for a Viscoelastic Material
TENNIS
BALL
STORAGE
(G)
LOSS
(G)
SUPER
BALL
STORAGE
(G)
LOSS
(G)
Viscoelastic Test Methods: Oscillation
Dynamic or Oscillatory Testing
Oscillatory Stress or Strain sweeps to determine
Linear Viscoelastic Region
Yield Stress
Frequency sweeps to evaluate rate response
characteristics
Time sweeps to determine kinetic events, such as
reactions, curing, stability, or structure
buildup/breakdown
Temperature ramps or sweeps to determine
mechanical properties and transition temperatures
SINUSOIDAL DEFORMATION FOR DYNAMIC TESTING
Time
R
e
s
p
o
n
s
e
,

S
t
r
a
i
n
90
o

o
o

STRAIN
ELASTIC
RESPONSE
VISCOUS
RESPONSE
VISCOELASTIC
RESPONSE
Polymers and many suspensions, emulsions
and solutions are viscoelastic materials.
Both components viscosity and elasticity
are important.
Viscoelastic Parameters
The Elastic (Storage) Modulus:
Measure of elasticity of material.
The ability of the material to store
energy.
G' = (stress*/strain)coso
= stress/strain
G" = (stress*/strain)sino
= stress/strain

The Viscous (loss) Modulus:
The ability of the material to
dissipate energy. Energy lost as
heat.
The Complex Modulus: Measure
of materials overall resistance to
deformation.
G* = Stress*/Strain
G* = G + iG
Tan o = G"/G'
Tan Delta:
Measure of material damping - such
as vibration or sound damping.
Gel Structure in Suspensions
Unbroken Gel
Structure
Increasing Oscillation Amplitude/Magnitude
In Shear Deformation
Structure begins
to Breakdown
Broken
Structure
Dynamic Stress (Amplitude) Sweeps for Yield
Determination (Structure Break-Down)
100.0 0.1000 1.000 10.00
osc. stress (Pa)
10000
10.00
100.0
1000
G
' (P
a
)
Ink Samples: Oscillation Stress Sweeps @ 6.28 rad/s
Dynamic Rheological Parameters
Parameter Shear Elongation Units
Strain =
0
sin(t) =
0
sin(t) ---
Stress o = o
0
sin(t + ) t = t
0
sin(t + ) Pa
Storage Modulus
(Elasticity)
G = (o
0
/
0
)cos E = (t
0
/
0
)cos Pa
Loss Modulus
(Viscous Nature)
G = (o
0
/
0
)sin E = (t
0
/
0
)sin Pa
Tan G/G E/E ---
Complex Modulus G* = (G
2
+G
2
)
0.5
E* = (E
2
+E
2
)
0.5
Pa
Complex Viscosity q* = G*/ q
E
* = E*/ Pa-sec
Cox-Merz Rule for Linear Polymers: q*() = q() @ =
. .
Section 2: Rheometer Basics

Rheometer construction
Geometry selection
Basic operational principles
The AR2000ex Rheometer
Applied
Strain or
Rotation
Measured
Torque
(Stress)
Direct
Drive
Motor
Transducer
Separate motor &
transducer

Combined motor &
transducer
Displacement
Sensor
Measures Strain
(angular rotation)
and rate of
rotation
(Shear Rate)
Non-Contact
Drag Cup
Motor
Applied
Torque
(Stress)
Static Plate
AR2000ex
Controlled Stress/Strain
CMT
Combined Motor-Transducer
Five Important Rheometer Specifications
Torque range
This specification is the most practically important specification for daily use of the
rheometer. You cannot expect to get accurate of precise data below the minimum torque
specification of the rheometer.
Angular Resolution
This specification may be important when working with very stiff solid samples, as it relates
to how small of a strain can be properly measured or controlled by the rheometer
Angular Velocity Range
For fluids, the minimum angular velocity relates to the lowest controllable shear rate, when
operating in rate controlled mode. When operating in stress controlled mode, the rate is
measured passively and can achieve rates on the order of 1e
-8
1/s

Frequency Range
Specified frequency range of stress rheometers (like the AR2000ex) may not be useable on
all samples. The inertia effect of the motor on the resolution of phase angle will be
compromised at higher frequencies, especially at low viscosities. The AR2000ex allows
you to observer the raw phase angle if this number exceeds 160 degrees, the inertial effect
is probably not correctable anymore and the data should be suspect.
Normal Force
The first normal stress difference (N1) can be very important information in the analysis of
viscoelastic fluids --- however, very few applied fluids labs use this function and it tends to
be more academic/research in nature. The N1 is directly related to extensional viscosity
behavior.

Specification
TA
AR1500ex
TA
AR2000ex
TA
AR G2
Min. Torque [N.m]:
Oscillation
Flow

0.1
0.1

0.03
0.1

0.003
0.01
Max. Torque [N.m] 150 200 200
Min. Frequency [Hz] 1.00e-06 1.00e-07 1.00e-07
Max. Frequency [Hz] 100 100 100
Min. Ang. Velocity CS [rad/s] 0 0 0
Min. Ang. Velocity CR [rad/s] 1.00e-07 1.00e-08 1.00e-09
Max. Ang. Velocity CS [rad/s] 300 300 300
Displacement resolution [Rad] 0.04 0.04 0.025
Air bearing type Porous carbon Porous carbon Magnetic
Normal force transducer N/a Wheatstone bridge
in base
Wheatstone bridge
in base
Min. Normal Force [N] N/a 0.005 0.005
Max. Normal Force [N] N/a 50 50
AR-Series Instrument Specifications
What does a Rheometer do?

Rheometer an instrument that measures both viscosity
and viscoelasticity of fluids, semi-solids and solids

It provides information about the materials:
Viscosity function of shear rate or stress, time &
temperature dependence
Viscoelastic properties (G, G, tan o) with respect to
time, temperature, frequency & stress/strain
Transient response (relaxation modulus, creep
compliance, creep recovery)
How do Rheometers work?
From the definition of rheology,

the science of flow and deformation of matter
or
the study of stress (Force / Area) deformation
(Strain or Strain rate) relationships.

Fundamentally a rotational rheometer will apply or
measure the following:
1. Torque (Angular Force)
2. Angular Displacement
3. Angular Velocity
1. Torque
Torque M is a measure of how much a force F acting
on an object causes that object to rotate.
The object rotates about an axis, called the pivot point,
labeled 'O'.
The distance from the pivot point to the point where the
force acts is called the moment arm, and is denoted by
'r'.
M = r x F sin(u)
= r x F, for u = 90
r
F
Torque Shear Stress
In a rheometer, the stress is calculated from
the torque.
The formula for stress is: o = K
o
x M
Where o = Stress (Pa or Dyne/cm
2
)
K
o
= Stress Constant
M = torque in mNm or gm
.
cm

The stress constant, K
o
, is a geometry
dependent factor.
2. Angular Displacement
Angular displacement is the angle (distance) that a
rotating body goes through

s = r u

Where: s is the arc-length
r is the radius of the circle
is the central angle (in
radian) swept out by the arc
Multiply the angle in degrees by
t/180

to determine radians

Multiply the angle in radian by
180/t to determine degrees
r
s
u
Angular Displacement Shear Strain
In a SMT Rheometer the angular displacement is directly
applied by a motor.

The formula for strain is: = K

x u (% = *100)
where = Strain
K

= Strain Constant
u = Angular motor deflection (radians)

The strain constant, K

, is a geometry dependent factor.



3. Angular Velocity
Strain Rate = Change of strain per unit time of
measurement

F
s2
s1
s = r u
Angular Velocity Shear Rate
In a SMT rheometer, the angular speed is directly
controlled by the motor).
The formula for shear rate is:



where = Shear rate
K

= Strain Constant
O = Motor angular velocity in rad/sec.

The strain constant, K

, is a geometry dependent factor.



O = x K

Modes of Deformation
Bending
Compressive
Rectangular
Torsion
Tensile
DMA
Rheology
Torsional
Shear
Strain, =
x(t)
y
0

Modulus G =
t

t =
F
A
y
0

x(t)
u
V
y
x
A
z
Shear deformation

.
=
A
At
Shear Deformation
Viscosity q =
t

.
Equation for Modulus
Raw rheometer
Specifications
Geometric
Shape
Constants
Constitutive
Equation
G
K x
K x M
= =

o
u

o
Rheological
Parameter
In Spec
Describe
Correctly
Equation for Viscosity
q

o
= =
O

K x
K x M
Raw rheometer
Specifications
Geometric
Shape
Constants
Constitutive
Equation
Rheological
Parameter
In Spec
Describe
Correctly
Ranges of Rheometers and DMAs
Loss Modulus (E" or G")
Storage Modulus (E' or
G')
Temperature
Range of AR/ARES Rheometer
Range of DMA/RSA
Some Viscoelastic
Liquid
Characterization
Possible with
Shear Sandwich
Temperature Control Systems: Fluids
AR: 40 C 200 C
Peltier Plate Peltier Concentric cylinder
AR: -20 C 150 C
Rheological Testing
Basic Rheological Approach
1. Apply Stress/Torque/Force and
measure resulting Deformation
and/or Deformation Rate
(Controlled Force, Controlled
Stress)


2. Control Deformation and/or
Deformation Rate and measure
Force needed (Controlled
Strain or Shear Rate)
Displacement
Sensor
Measured Strain
or Rotation
Non-Contact
Drag Cup
Motor
Applied
Torque
(Stress)
Stationary
Plate
Typical Geometries for Rheological Testing in Shear
Parallel
Plate
Cone and
Plate
Concentric
Cylinders
Torsion
Rectangular
Very Low
to Medium
Viscosity
Low
to High
Viscosity
Low
Viscosity
to Soft Solids
Very Soft to Very
Rigid Solids
The equation of motion and other relationships have been used to determine the appropriate
equations to convert machine parameters (torque, angular velocity, and angular displacement) to
rheological parameters.
Concentric Cylinder
Features:
Good for testing suspensions with
limited stability
Good for testing samples with large particle
size
Suitable for low viscosity fluids
Shear Rate and Shear Stress are reasonably
constant with small gaps.
Strain Constant: K

=
2
1-(R
1
/R
2
)
2
Stress Constant: K
o
=
1
2tL(R
1
)
2
R1 = Inner Radius
R2 = Outer Radius
L = Cylinder immersed height
Cone and Plate
Strain Constant: K

=
1
|
Stress Constant: K
o
=
3
2tR
3
Features:
Shear Stress and Shear Rate are constant
throughout the gap.
Suitable for low to medium viscosity fluids
Can be used to determine Normal Stress
Differences (see next page.)
R = Plate Radius
| = Cone Angle
(radians)
Note: If there are particles
in the fluid, they should be
<10% of the truncation
gap.
Cone and Plate - Normal Forces
Normal Stress Difference:
In steady flow, viscoelastic fluids can exert a
force that tries to separate the cone and the
plate.
A parameter to measure this is the Normal
Stress Difference, N1, which equals
o
xx
- o
yy
from the Stress Tensor.
N1 = 2F/(tR
2
), where F is the measured
force.
+
1
= N1/
2
This is the primary normal stress
coefficient.
Few people use this feature, but it is
available.

Parallel Plate Geometry
Strain Constant: K

=
R
H
Stress Constant: K
o
=
2
tR
3
Features:
Shear Stress and Shear Rate or Strain are at
maximum values at the edge of the
geometry, 0 along the vertical axis.
Suitable for low to medium viscosity fluids
One can adjust gap to appropriate value.
R = Plate Radius
H = Gap Height
(r) =
R
(r/R), so (R) =
R
and (0) = 0
o(r) = (M/(2tR
3
))(3 + (dlnM/dln
R
))(r/R)
Parallel Plate Geometry Part 2


For Newtonian fluids,
o(r) = (2M/(tR
3
))(r/R)
o(R) = (2M/tR
3
)
For all fluids,
o(R) = o(R)
apparent
(3+dlnM/dln
R
)/4
If one is comparing 2 materials, the stress correction is usually not employed.
If one wants to compare parallel plate data with cone-and-plate data, the
stress correction should be performed.
This is not an issue with solids testing in transient or dynamic testing.


Geometry Considerations for Cones
Angle
Shear Rate
Decreases
Increases
At the same
torque level,
Shear Stress
goes as the 3
power of plate
diameter.
20mm
40mm
60mm
At the same angular
velocity, the shear rate
varies as the 1 power of
the cone angle.
Geometry Considerations for Plates
20mm
40mm
60mm
At the same
torque level,
Shear Stress
goes as the 3
power of plate
diameter.
Gap
Decreases
Increases
Shear Rate
At the same angular
velocity, the shear rate
varies as the 1 power of
the gap height.
Double Wall
Strain Constant: K

=
Stress Constant: K
o
=


1/((R2/R1)
2
-1)
+1/(1-(R3/R4)
2
)
1/(2pL(R2
2
+R3
2
))
Use for very low viscosity systems (<1 mPas)
R1
R2
R3
R4
AR Series Peltier Concentric Cylinders
Torsion Rectangular
K

= T/L(1-0.378(T/W)
2
)
K
t
= (3 +1.8/W)/(WT
2
)
W = Width
L = Length
T = Thickness
Advantages:

high modulus samples
small temperature gradient
simple to prepare

Disadvantages:

no pure Torsion mode for
high strains
Section 3: Applied Rheology

Viscometric Testing Methods
Oscillation Testing Methods
Transient Testing Methods
Setting up Rheological Experiments

1. Viscometric Tests
Typical Test Methods: Viscometry
Steady
Shear Rate sweeps most common
Shear Stress sweeps to get Yield Stress
Time sweeps at constant shear rate or shear stress to
determine stability
Up/down Shear Rate ramps
Temperature ramps and constant shear rate to
determine critical temperature response of materials
Transient
Stress Relaxation
Creep/Creep Recovery
AR Rheometer and Flow Testing
The AR2000ex rheometer can do steady shear viscosity
measurements in two ways.
Controlled Stress or CS Mode
The torque is applied to the sample via the drag
cup motor and the angular displacement is
measured as a function of time via the optical
encoder.
Controlled Rate or CR Mode
The angular velocity is controlled and the torque
required to measure the speed is recorded.
AR Rheometer and Flow Testing
CR (Controlled Rate) angular velocity
specifications are different then CS (Controlled
Stress) angular velocity specifications
Example using AR2000ex
Angular Velocity CR Mode: 1E-8 to 300 rad/s
Angular Velocity CS Mode: 0 to 300 rad/s
Flow Experiments
Flow Experiments
Peak Hold
Constant shear rate/stress
Continuous stress/rate ramp
Stepped flow
Steady state flow
Temperature ramp
Peak Hold (Constant Shear Rate/Stress)
time (min.)
Constant rate vs. time

Constant stress vs. time
USES
Observation of time-based stability
Single point testing (viscosity at specific rate/stress and temperature)
Scope the time for steady state under certain rate
Peak Hold at 1 s
-1
shear rate (Emulsion)
0 5.0000 10.000 15.000 20.000 25.000 30.000
time (s)
0
0.5000
1.000
1.500
2.000
2.500
3.000
3.500
s
h
e
a
r

s
t
r
e
s
s

(
P
a
)
0
0.5000
1.000
1.500
2.000
2.500
3.000
3.500
4.000
v
i
s
c
o
s
i
t
y

(
P
a
.
s
)
Hand Wash Rate 1/s
Steady-State Viscosity
at 1 s
-1
= 2.8 Pa-s
Note the stress overshoot
and gradual relaxation to
steady state viscosity. This
is typical of viscoelastic
fluids.
AR2000ex: Peak Hold
Control variables:
Shear rate
Velocity
Torque
Shear stress
Multiple rates can be done by adding more peak hold steps
Continuous Ramp
Stress is applied to
material at a constant
rate. Resultant strain is
monitored with time.
time (min.)
m =Stress rate
(Pa/min)
Deformation
USES
Yield stress
Scouting (quick) Viscosity Run
Reproducing or performing Thix-Loop test
Thixotropic Loop Continuous Ramp Up and Down
Deformation
o
time
Stress is applied to
material at a constant
rate. Resultant strain is
monitored with time.
USES
Pseudo-thixotropy from Hysteresis loop
Old-fashioned test favored by users of simple viscometers,
especially common in the paints and coatings industries
0.5000 0 0.1000 0.2000 0.3000 0.4000
shear rate (1/s)
500.0
0
100.0
200.0
300.0
400.0
s
h
e
a
r

s
t
r
e
s
s

(
P
a
)
TA Instruments
FORDB3.04F-Up step
FORDB3.04F-Down step
FORDB3.05F-Up step
FORDB3.05F-Down step
Up & Down Flow Curves - 2 Repeats
Extrapolate for
Traditional Yield Stress
run in Stress Control
Red: First cycle
Blue: Second cycle
AR2000ex: Continuous Ramp
Control variables:
Shear rate
Velocity
Torque
Shear stress
Thixotropic loop be done by adding another ramp step (to zero)
Or go through the template
AR2000ex: Continuous Ramp (Thix Loop Template)
Stepped or Steady-State Flow
Deformation
time
Denotes
Measurement
Delay time
Steady State Flow

or o = Constant
time
l
Stress is applied to sample.
Viscosity measurement is taken
when material has reached steady
state flow. The stress is
increased(logarithmically) and the
process is repeated yielding a
viscosity flow curve.

USES
Viscosity Flow Curves
Yield Stress Measurements
o
or


o
or


Steady State Flow
1.000E-41.000E-3 0.01000 0.1000 1.000 10.00 100.0 1000 10000
shear rate (1/s)
0.01000
0.1000
1.000
10.00
100.0
1000
10000
1.000E5
v
i
s
c
o
s
i
t
y

(
P
a
.
s
)
Carreau
a: zero-rate viscosity: 39470 Pa.s
b: infinite-rate viscosity: 0.09264 Pa.s
c: consistency: 7383 s
d: rate index: 0.8587
standard error: 9.179
thixotropy: 0 Pa/s
normalised thixotropy: 0 1/s
End condition: Finished normally
Hand Cream
hand cream cone-0001f, Steady state flow step
hand cream cone-0001f, Steady state flow step - Carreau
AR2000ex: Steady State Flow
During the test, the dependant variable (speed in controlled stress mode or torque
in controlled shear rate mode) is monitored with time to determine when stability
has been reached.
An average value for the dependant variable is recorded over the Sample period.
When consecutive average values (Consecutive within tolerance) are within the
tolerance specified here, the data is accepted.
The software will also accept the point at the end of the Maximum point time,
should the data still not be at a steady state value.
Control variables:
Shear rate
Velocity
Torque
Shear stress
Steady state algorithm
Shear Rate Sweep
Examples
Melt Strength
Leveling
0.1 1 10 100 1000
Shear Rate (1/sec)
V
i
s
c
o
s
i
t
y

(
P
a
-
s
e
c
)
Broad Distribution
Narrow Distribution
Example
Processability
This illustrates why it is
important to characterize
material over a range of
shear rates, not just a
single point.
Steady Stress Sweep for Yield Stress
1000 0.1000 1.000 10.00 100.0
shear stress (Pa)
1000000
0.1000
1.000
10.00
100.0
1000
10000
100000
v
i
s
c
o
s
i
t
y

(
P
a
.
s
)

4 decade drop in q
Yield Stress
Yield stress is
important for
materials like
toothpaste,
mayonnaise, slurries,
shampoos, and a
variety of materials.
AR2000ex: Stepped Flow
Control variables:
Shear rate
Velocity
Torque
Shear stress
A series of logarithmic stress steps allowed to reach
steady state, each one giving a single viscosity data point:
Shear
Thinning
Region
Shear Rate, 1/s
V
i
s
c
o
s
i
t
y

Shear Rate
Time
q = o / /
(d dt)
Stepped or Steady-State Flow

Flow Temperature Ramp
Hold the rate or stress
constant whilst ramping
the temperature.
time (min.)
USES
Measure the viscosity change vs. temperature
X X X X
Viscosity: Temperature Dependence
100.0 20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0
temperature (Deg C)
10000
10.00
100.0
1000
v
i
s
c
o
s
i
t
y

(
P
a
.
s
)
Therefore, one must ensure thermal equilibration of the sample prior to testing,
i.e. Conditioning Step : equilibration time = 5 minutes
AR2000ex: Flow Temp Ramp
Control variables:
Shear rate
Velocity
Torque
Shear stress
To minimize thermal
lag, the ramp rate
should be slow.
1-5C/min.
Temperature Sweeps for Structure Buildup
25.0 50.0 75.0 100.0 125.0 150.0 175.0 200.0 225.0
temperature (F)
0
5.000E-3
0.01000
0.01500
0.02000
0.02500
0.03000
v
i
s
c
o
s
i
t
y

(
p
o
i
s
e
)
0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
t
i
m
e

(
m
i
n
)
Milk Mix: 20 F/min Temperature Ramp with Parallel Plates
Onset point
temperature: 189.0 F
viscosity: 6.841E-3 poise
Flow Testing Considerations
Small gaps give high shear rates
Be careful with small gaps. Shear heating can
cause large errors in data. Recommended gaps
are 0.5 to 2.0 mm.

Secondary flows can cause increase in viscosity
curve this secondary flow is the result of
instabilities in the flow field at higher shear rates

Instrument Artifact: Secondary flow
10000 1.000 10.00 100.0 1000
shear rate (1/s)
1.200E-3
0
2.000E-4
4.000E-4
6.000E-4
8.000E-4
1.000E-3
v
i
s
c
o
s
i
t
y

(
P
a
.
s
)

water at 20C
Other Flow Testing Considerations
Edge Failure Sample leaves gap because of normal
forces
Look at stress vs. shear rate curve stress should
not decrease with increasing shear rate this
indicates sample is leaving gap
Possible Solutions:
use a smaller gap or smaller angle so that you get
the same shear rate at a lower angular velocity
if appropriate (i.e. Polymer melts) make use of
Cox Merz Rule
( ) ( ) e q q
*

Example of Cox-Merz Rule


1000 1.000E-3 0.01000 0.1000 1.000 10.00 100.0
shear rate (1/s)
10000
100.0
1000
v
i
s
c
o
s
i
t
y

(
P
a
.
s
)

Linear Polyethylene Flow Data
Linear Polyethylene Oscillation Data [Cox Merz]
Flow instability
Complete Flow Curves for Polystyrene Melts
10
100
1000
10000
100000
0.1 1 10 100 1000 10000
Shear Rate (sec
-1
)
V
i
s
c
o
s
i
t
y

(
P
a
-
s
e
c
)
242,000
217,000
179,000
117,000
48,500
Narrow MWD Polystyrenes
Zero shear viscosities
depend on Mw.
Higher Mw material exits
the Newtonian region at
lower shear rates.
Power law slope is
independent of Mw.
Some Models for Flow Behavior
Model Equation
Newtonian o = q
0

Bingham o = o
0
+ q
0

Casson o
1/2
= o
0
1/2
+ q
0
1/2

1/2
Power Law o = K
c
Herschel Bulkley o = o
0
+ K
c
Sisko q = q

+ K
n-1
Williamson q = q
0
/(1+(/
0
)
c
)
Cross (q-q

)/(q
0
-q

) = 1/(1+(/
0
)
d
)
Ellis (q-q

)/(q
0
-q

) = 1/(1+(o/o
0
)
d
)
Carreau (q-q

)/(q
0
-q

) = 1/(1+(/
0
)
2
)
d/2










Setting up Rheological Experiments

3. Transient Tests
Transient Test Methods
Steady
Shear Rate sweeps most common
Shear Stress sweeps to get Yield Stress
Time sweeps at constant shear rate or shear stress to
determine stability
Up/down Shear Rate ramps
Temperature ramps and constant shear rate to determine
critical temperature response of materials
Transient
Stress Relaxation
Creep/Creep Recovery
Viscoelastic Modeling for Transient Testing
F
Maxwell Model
The Maxwell model is useful for illustrating stress
relaxation behavior.

For 1 element:
G(t) = G
i
exp(-t/t
i
)
Where G(t) is the modulus at time, t,
following a strain imposition at t = 0.
G
i
is the spring constant; q = viscosity
t
i
is the Relaxation Time = q
i
/G
i
Log time (sec)
L
o
g

G
(
t
)

(
P
a
)
For N elements in Parallel:
G(t) = EG
i
exp(-t/t
i
)
i = 1
N
1-element stress
relaxation curve
Integral Form:
G(t) = G
e
+ }Hexp(-t/t
i
)dln(t)

-
Stress Relaxation (Solid-like Modelling)
Rubbery
Plateau
Region
Transition
Region
Glassy Region
Log time
MW has practically
no effect on the
modulus in the
Glassy Region
Low
MW
Med.
MW
High
MW
Broad
Molecular
Weight
Distribution
Crosslinked
Stress Relaxation
10
0
10
1
10
2
10
3
10
7
10
8
10
9
time [s]


G
(
t
)

(
)








[
P
a
]
Stress Relaxation of Soy Flour, Overlay
G(t)
T=20C
T=30C
T=40C
T=50C
Test material is
deformed
instantaneously
and held at a
constant strain.
Stress is
monitored as a
function of time.
One typically
plots the
modulus, G(t) as
a function of
time.
Viscoelastic Modeling for Transient Testing
Kelvin Model
The Kelvin model is useful for illustrating creep
behavior.

For 1 element:
J(t) = J
i
(1-exp(-t/t
i
))
Where J(t) is the compliance at time, t,
following a stress imposition at t = 0.
J
i
is the reciprocal of G
i
, the spring
constant; q = viscosity
t
i
is the Relaxation Time = q
i
/G
i
For N elements in Series:
J(t) = J
0
+
EJ
i
(1-exp(-t/t
i
) + t/q
i = 1
N
1-element creep/
recovery curves
Integral Form:
J(t) = Jg + }L(1-exp(-t/t
i
))dln(t)
+ t/q

-
F
Kelvin (Voigt) Model
Time (sec)
C
o
m
p
l
i
a
n
c
e

(
1
/
P
a
)
Creep Testing (Fluid-Like Modelling)
Reference: Mark, J., et.al., Physical Properties of Polymers ,American Chemical Society, 1984, p. 102.
Creep o> 0
time
t
1
t
2
Recoverable
Strain
Recovery o = 0 (after steady state)
o/q
Strain rate decreases
with time in the creep
zone, until finally
reaching steady state.
In the recovery zone, the
viscoelastic fluid recoils,
eventually reaching an
equilibrium value.
Instantaneous
stress (o) is
applied at t = 0.
Strain ((t)) is
monitored as a
function of time.
One typically
plots the
Compliance, (J(t)
= (t)/o), or Strain
((t)) as a
function of time
Creep is
usually followed
by creep
recovery.
Creep/Creep Recovery
0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0
time global (min)
0
2.5000E-4
5.0000E-4
7.5000E-4
1.0000E-3
1.2500E-3
1.5000E-3
s
t
r
a
i
n
0
3.0000E-4
c
o
m
p
l
i
a
n
c
e

J
(
t
)

(
1
/
P
a
)
Creep
Recovery
The useful parameters for
creep are
J
e
0
, which is the intercept of
the line that describes the creep
in the steady state flow region
and
q, which is inversely related to
the slope of the line
The software provides a best
fit for the model, J(t) = EJ
i
(1-exp(-
t/t
i
))+t/q
The J(t) or (t) values at
particular times are useful as
well.
Line tangent to
curve in steady
flow region. Horizontal line drawn from
intercept of steady state
tangent line. This is the
theoretical limit of recovery.
For some systems,
J
e
0
(M
z
/M
w
)
2
Setting up Rheological Experiments

2. Oscillatory Tests
Understanding Oscillation Experiments
Define Oscillation Testing
Oscillation and the Linear Viscoelastic Region
Approach to Oscillation Experimentation
Stress and Strain Sweep
Time Sweep
Frequency Sweep
Temperature Ramp
Temperature Sweep (TTS)
Stress, o*
Strain, c
Phase angle o
Dynamic stress applied using a sinusoidal control model
User-defined Stress or Strain amplitude and frequency
What is Oscillation?
Frequency Defined
Time to complete one oscillation
Frequency is the inverse of time
Units
Angular Frequency = rad/s
Frequency = Hz = cycles/second
Rheologist must think in terms of rad/s.
1 Hz = 6.28 rad/s
Frequency
0 0 0 0
Time
e = __1___rad/s
e = ___8__rad/s
e = ___2__rad/s
Amplitude: Strain or Stress
0 0 0 0
Time = 1sec
Strain and stress are calculated from peak amplitude in the
displacement and torque waves, respectively.
Phase Angle
The measured shift between the input wave and
the output wave is called Phase angle
-1.5
0
1.5
0 6.3
Angle
Stimulus (stress or strain)
Response (strain or stress)
phase angle, o
Phase Angle
Stress
Strain
o = 90
Purely Elastic Response
(Hookean Solid)
Purely Viscous Response
(Newtonian Liquid)
Stress
o = 0
Phase angle 0 < o < 90

Stress

Strain
Visco-Elastic Response
Strain
Viscoelastic Parameters
Complex, Elastic, & Viscous Stress
The stress in a dynamic experiment is referred to as the complex
stress o*
Phase angle o
Complex Stress, o*
Strain, c
o* = o' + io"
The complex stress can be separated into two components:
1) An elastic stress in phase with the strain. o' = o* coso
o' is the degree to which material behaves like an elastic solid.
2) A viscous stress in phase with the strain rate. o" = o* sino
o" is the degree to which material behaves like an ideal liquid.
Viscoelastic Parameters
The Elastic (Storage) Modulus:
Measure of elasticity of material.
The ability of the material to store
energy.
G' = (stress*/strain)coso
= stress/strain
G" = (stress*/strain)sino
= stress/strain

The Viscous (loss) Modulus:
The ability of the material to
dissipate energy. Energy lost as
heat.
The Complex Modulus: Measure
of materials overall resistance to
deformation.
G* = Stress*/Strain
G* = G + iG
Tan o = G"/G'
Tan Delta:
Measure of material damping - such
as vibration or sound damping.
Storage and Loss for a Viscoelastic Material
TENNIS
BALL
STORAGE
(G)
LOSS
(G)
SUPER
BALL
STORAGE
(G)
LOSS
(G)
Complex Viscosity
The viscosity measured in an oscillatory experiment is a
Complex Viscosity much the way the modulus can be
expressed as the complex modulus. The complex viscosity
contains an elastic component and a term similar to the
steady state viscosity.

The Complex viscosity is defined as:

q* = q - iq
or
q* = G*/e

Note: frequency must be in rad/sec!

Define Linear Viscoelastic Region (LVR)
Concept of Linear Viscoelastic Region

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.
Importance of LVR
G,G, tan o, q*
Measuring linear viscoelastic properties helps us bridge the
gap between molecular structure and product performance.
Linear Viscoelastic Region (LVR)
Non-Linear Region
G = f()
Linear Region
G is constant
o
G
1000.0 0.010000 0.10000 1.0000 10.000 100.00
% strain
1000
1.000
10.00
100.0
100.0
0.01000
o
s
c
.

s
t
r
e
s
s

(
P
a
)

End of LVR or
Critical Strain
c

Dynamic Rheological Parameters
Parameter Shear Elongation Units
Strain =
0
sin(t) =
0
sin(t) ---
Stress o = o
0
sin(t + ) t = t
0
sin(t + ) Pa
Storage Modulus
(Elasticity)
G = (o
0
/
0
)cos E = (t
0
/
0
)cos Pa
Loss Modulus
(Viscous Nature)
G = (o
0
/
0
)sin E = (t
0
/
0
)sin Pa
Tan G/G E/E ---
Complex Modulus G* = (G
2
+G
2
)
0.5
E* = (E
2
+E
2
)
0.5
Pa
Complex Viscosity q* = G*/ q
E
* = E*/ Pa-sec
Cox-Merz Rule for Linear Polymers: q*() = q() @ =
. .
Typical Test Methods: Oscillation
Dynamic or Oscillatory Testing
Oscillatory Stress or Strain sweeps to determine
Linear Viscoelastic Region
Yield Stress
Frequency sweeps to evaluate rate response
characteristics
Time sweeps to determine kinetic events, such as
reactions, curing, stability, or structure
buildup/breakdown
Temperature ramps or sweeps to determine
mechanical properties and transition temperatures
Approach to Linear Viscoelastic Sample Characterization
LVR Characterization
Determine LVR
Oscillation Strain Sweep
Sample is Stable
No or ??

Yes
Determine Stability
Time Sweep
Thixotropy

Volatilization

Degradation
Choose
Parameters
Run Test
Choose
Parameters
Run Test
Examine Data
Define LVR
Examine Data
Sample is Stable
Yes No
Determine
Why
Preshear
& Delay
Solvent Trap
or
Pressure Cell
Purge Gas
or
Decrease
Temp.
Take Corrective
Action
Additional
Testing
-Freq Swp
-Temp
Swp
-TTS
Understanding Oscillation Experiments
Define Oscillation Testing
Oscillation and the Linear Viscoelastic Region
Approach to Oscillation Experimentation
Stress and Strain Sweep
Time Sweep
Frequency Sweep
Temperature Ramp
Temperature Sweep (TTS)
Dynamic Strain or Stress Sweep
The material response
to increasing
deformation amplitude
(strain or stress) is
monitored at a constant
frequency and
temperature.
time

S
t
r
e
s
s

o
r

s
t
r
a
i
n

Main use is to determine LVR
All subsequent tests require an amplitude found in the
LVR
Tests assumes sample is stable
If not stable use Time Sweep to determine stability
Linear Viscoelasticity (Oscillation Strain Sweep)
Non-Linear Region
G = f() Linear Region:
Osc Stress is linear
with Strain.
G, G are constant.
o
G
1000.0 0.010000 0.10000 1.0000 10.000 100.00
% strain
1000
1.000
10.00
100.0
100.0
0.01000
o
s
c
.

s
t
r
e
s
s

(
P
a
)

End of LVR or
Critical Strain
c

It is preferable to perform testing in the linear region because you are measuring
intrinsic properties of the material, not material that has been altered.
Temperature Dependence of LVR
In general, the LVR is shortest when the sample is in
its most solid form.





% strain
G


Solid
Liquid
1000.0
Frequency Dependence of LVR
0.010000 0.10000 1.0000 10.000 100.00
% strain
100.0
0.1000
1.000
10.00
G
'

(
P
a
)

End of
LVR
20
rad/s
2 rad/s
0.05 rad/s
Strain Sweep on Polymer Solution at Several Frequencies.
AR2000ex: Oscillation Strain or Stress Sweep
Recommend range:
Polymer melts: 0.1-100%
Dispersions: lowest-10%
AR2000ex: Strain Sweep Options
The default is Continuous oscillation. Good for most tests.
Fast oscillation is only for fast curing reactions such as UV
curing.
For general curing or rigid solid sample testing, it is
recommended to use Non-iterative sampling
Get definition from the fly help
Click fly help, then click
on the following page
AR2000ex: OscillationStress Sweep
The range is
sample
dependent
Structure in Suspensions
Unbroken Gel
Structure
Increasing Amplitude/Magnitude
of Shear Deformation
Structure begins
to Breakdown
Broken
Structure
The Strength of a Suspensions Structure
We plot the Gversus the stress. The range stresses over which G is
independent of the applied stress is called the linear viscoelastic region. Over
the linear region the materials structure is unbroken. The end of the linear
region is called the critical stress, o
c.
Above o
c
the structure of the material is
broken. The higher the o
c
, the stronger the strength of the structure. o
c
is also a
measure of the apparent yield stress of the material.
Sun Tan Lotion Dynamic Stress Sweep
o
c
Linear Region
Unbroken
Structure
1000 1.000E-3 0.01000 0.1000 1.000 10.00 100.0
osc. stress (Pa)
1000
0.1000
1.000
10.00
100.0
G
' (P
a)
Dynamic Stress Sweeps for Yield Determination
100.0 0.1000 1.000 10.00
osc. stress (Pa)
10000
10.00
100.0
1000
G
' (P
a
)
Ink Samples: Oscillation Stress Sweeps @ 6.28 rad/s
Oscillation Time Sweep (Time Ramp)
Time
Deformation
The material response
is monitored at a
constant frequency,
amplitude and
temperature.
USES
Time dependent Thixotropy
Cure Studies
Stability against thermal degradation
Solvent evaporation/drying
Importance of Time Sweep
Important, but often overlooked
Determines if properties are changing over the time of
testing
Complex Fluids or Dispersions
Drying or volatilization
Thixotropic
Rheopectic
Polymers
Degradation
Molecular weight building
Crosslinking

Importance of Waiting for Structure Rebuild
175.0 0 25.00 50.00 75.00 100.0 125.0 150.0
time (s)
100.0
10.00
G
'

(
P
a
)

Sample A time sweep
100.0 0.1000 1.000 10.00
osc. stress (Pa)
100.0
10.00
Delay after pre-shear = 0 seconds
Delay after pre-shear = 150 seconds
Pre-shear conditions:
100 1/s for 30 seconds
End of LVR is indicative of Yield or Strength of Structure
Useful for Stability predictions (stability as defined by yield)
Cure of a "5 minute" Epoxy
1200 0 200.0 400.0 600.0 800.0 1000
time (s)
1000000
1.000
10.00
100.0
1000
10000
100000
G
'

(
P
a
)
1000000
1.000
10.00
100.0
1000
10000
100000
G
'
'

(
P
a
)
TA Instruments
Gel Point - G' = G"
T = 330 s
5
mins.
G'
G"
145C
140C
135C
130C
125C
120C
Time (min)
Tire Compound:
Effect of Curing Temperature
Oscillation Time Sweep: Isothermal Curing
AR2000ex: Oscillation Time Sweep
Control variables:
Osc torque
Osc stress
Displacement
% strain
Strain
AR2000ex: Pre-shear Conditions
The goal for pre-shear is to remove the sample history at loading
For high viscosity sample, use low rate (10 1/s) and long time (2 min.)
For low viscosity sample, use high rate (100 1/s) and short time (1 min.)
Time Sweeps for Structure Buildup
225.0
0
25.00 50.00 75.00 100.0 125.0 150.0 175.0 200.0
time (s)
100.0
0
20.00
40.00
60.00
80.00
G
'

(
P
a
)

Structural Recovery after Preshear of a Latex
This is a useful test for monitoring structure
buildup of a material that has been pre-
sheared to remove all structure.
25C
Pre-shear at
100 sec
-1
for
30 seconds.
6.28 rad/sec
1% Strain
Oscillation Time Sweeps for Structure Buildup
0 500.00 1000.0 1500.0 2000.0 2500.0 3000.0 3500.0 4000.0
time (sec)
1.000
10.000
100.000
1000.000
10000.000
1.00E5
n
s
t
a
r

(
c
P
)
99.4
99.6
99.8
100.0
100.2
100.4
100.6
t
e
m
p
e
r
a
t
u
r
e

(

F
)
Skim Milk Curd Time: Dynamic Time Sweep Using Vaned Rotor
Mean: 3.255 cP
Oscillation Frequency Sweep
The material response to
increasing frequency
(rate of deformation) is
monitored at a constant
amplitude (strain or
stress) and temperature.
Time
A
m
p
l
i
t
u
d
e
Strain should be in LVR
Sample should be stable
Remember Frequency is 1/time so low
frequencies will take a long time to collect
data i.e. 0.001Hz is 1000 sec (over 16 min)
Importance of Frequency Sweeps
High and Low Rate (short and long time) modulus
properties.
Viscosity Information - Zero Shear Viscosity, shear
thinning
Elasticity (reversible deformation) in materials
MW & MWD differences Polymer Melts and
Polymer solutions.
Finding Yield in gelled dispersions
Can extend time or frequency range with TTS

4 . 3
2
e
4 . 3
0
) " (
'
and
|
|
.
|

\
|
~ = ~
z
w
w
M
M
G
G
J M q
Influence of MWD on G and G
The G, G cross-over point
can indicate the molecular
weight distribution, e.g.,
PDI 1/G
c
broad
narrow
The maximum in G can be an
indicator of the molecular
weight distribution
10
-3
10
-2
10
-1
10
0
10
1
10
2
10
3
10
4
10
3
10
4
10
5
10
6
M
o
d
u
l
u
s

G
'
,

G
'
'

[
P
a
]
Frequency a
T
[rad/s]
SBR polymer melt
G' 310 000 broad
G" 310 000 broad
G' 320 000 narrow
G" 320 000 narrow
10
-3
10
-2
10
-1
10
0
10
1
10
2
10
3
10
4
0.0
5.0x10
4
1.0x10
5
1.5x10
5
2.0x10
5
SBR G'' 320 000
SBR G'' 310 000 (broad)
M
o
d
u
l
u
s

G
'
'

[
P
a
]
Frequency a
T
[rad/s]
AR2000ex: Oscillation Frequency Sweep
Control variables:
Osc torque
Osc stress
Displacement
% strain
Strain
As long as in the LVR, the test frequency can be set either from
high to low, or low to high
The benefit doing the test from high to low
Being able to see the initial data points earlier
0.1000 1.000 10.00 100.0
ang. frequency (rad/s)
100.0
1000
10000
1.000E5
G
'

(
P
a
)
100.0
1000
10000
1.000E5
G
'
'

(
P
a
)
100.0
1000
10000
1.000E5
|
n
*
|

(
P
a
.
s
)
At high frequencies, the elastic
properties dominate.
At low frequencies, the viscous
properties dominate.
Oscillation Frequency Sweep on PDMS (Silly Putty)
Frequency in AR Rheometer
AR has a combined motor and transducer design.
In an AR rheometer, the applied motor torque and the
measured amplitude are coupled.
The moment of inertia required to move the motor and
geometry (system inertia) is coupled with the angular
displacement measurements.
This means that BOTH the system inertia and the
sample contributes to the measured signal.
Inertial Effects
What is Inertia?

Definition: That property of matter which
manifests itself as a resistance to any change in
momentum of a body
Instrument has inertia
Sample has inertia
Inertial Effects in Oscillation for AR
AR consideration
Viscosity limitations with frequency
Minimize inertia by using low mass geometries
Monitor inertia using Raw Phase in degree
When Raw Phase is grater than 150 degree. This
indicates that the system inertia is dominating the
measurement signal. Data may not be valid

raw phase * Inertia Correction = delta
AR Correction for Inertia
100.0 0.01000 0.1000 1.000 10.00
frequency (Hz)
1.000E6
1000
10000
1.000E5
G
' (Pa)
70.00
0
10.00
20.00
30.00
40.00
50.00
60.00
d e l t a ( d e g r e e s )
1.000E6
1000
10000
1.000E5
G
'' (Pa)
70.00
0
10.00
20.00
30.00
40.00
50.00
60.00
r a w p h a s e ( d e g r e e s )
Pdms-ar-04o
Increasing correction at higher frequencies
Negligible correction at low frequencies
Oscillation Temperature Ramp
A linear heating rate
is applied. The
material response is
monitored at a
constant frequency
and constant
amplitude of
deformation. Data is
taken at user defined
time intervals.
time (min)
Denotes Oscillatory
Measurement
time between
data points
m = ramp rate
(C/min)
Oscillation Temperature Sweep (Step & Hold)
Time
Soak Time Step
Size
Denotes Oscillatory
Measurement
A step and hold
temperature
profile is applied.
The material
response is
monitored at one,
or over a range of
frequencies, at
constant
amplitude of
deformation.
Advantage over Temp Ramp no thermal lag.
Why look at temperature dependence?
Solid in torsion rectangular
Look at Tg, secondary transitions and study
structure-property relationships of finished
product.
Themosetting polymers
Follow curing reactions
Polymer melts and other liquids
Measure temperature dependence of viscoelastic
properties
AR2000ex: Temperature Sweep
Control variables:
Osc torque
Osc stress
Displacement
% strain
Strain
AR2000ex: Temperature Ramp
Control variables:
Osc torque
Osc stress
Displacement
% strain
Strain
To minimize thermal
lag, recommend
using slow ramp rate
e.g. 1-5C/min.
Temperature Ramp Curing
0 5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0
time global (min)
1.000
10.00
100.0
1000
10000
1.000E5
1.000E6
1.000E7
G
'

(
P
a
)
20.0
40.0
60.0
80.0
100.0
120.0
140.0
t
e
m
p
e
r
a
t
u
r
e

(

C
)
1.000
10.00
100.0
1000
10000
1.000E5
1.000E6
1.000E7
G
'
'

(
P
a
)
PVC Dispersion Resin Curing
G cross-over point
Cross-over points: 1
time global: 15.3 min
G': 5.353 Pa
End condition: Finished normally
Curing at Different Ramp Rate
0.0
10.0 20.0 30.0 40.0 50.0
60.0
10
1
10
2
10
3
10
4
10
5
10
6
time [min]


G
*

(
)







[
P
a
]
Filled Epoxy Curing
G*
Epoxy Curing at 3C/min
Epoxy Curing at 5C/min
Epoxy Curing at 10C/min
Temperature Ramp +Isothermal Curing

0.0

10.0

20.0

30.0

40.0

50.0

60.0

70.0

80.0

90.0

100.0

10

-1

10

0

10

1

10

2

10

3

10

4

10

5

10

6

10

7

20.0

40.0

60.0

80.0

100.0

120.0

140.0

160.0

time [min]



G
'

(

)








[
P
a
]



G
"

(

)








[
P
a
]



T
e
m
p

(

)











[

C
]

Epoxy Resin Curing
G' / G" Crossover Point:(39.364,181.27)
Setting up Rheological Experiments

3. Transient Tests
Stress Relaxation Experiment
Strain is applied to sample instantaneously
and held constant with time.
Stress is monitored as a function of time o(t)
AR
Response time dependant on feedback loop
(<60 msec on AR2000)
time
S
t
r
a
i
n

0
Stress Relaxation Experiment
Response of Classical Extremes
time
0
time
0
stress for
t>0
is constant
time
0
stress for t>0 is 0
Hookean Solid
Newtonian Fluid
Stress Relaxation Experiment (contd)
Response of Material

For small deformations (strains within the linear region)
the ratio of stress to strain is a function of time only.

This function is a material property known as the
STRESS RELAXATION MODULUS, G(t)
G(t) = o(t)/
Stress decreases with time
starting at some high value
and decreasing to zero.
Log time 0
Stress Relaxation on PDMS (Silly Putty)
100 0.01 0.1 1 10
time (s)
1.00E5
1
10
100
1000
10000
AR2000ex: Stress Relaxation
Motor and transducer work in a feedback loop
Determining Proper Strain For Stress Relaxation
Research Approach, such as generation of a family of
curves for TTS, then the strain should be in the linear
viscoelastic region. The stress relaxation modulus will be
independent of applied strain (or will superimpose) in the
linear region.
Application Approach, mimic real application. Then the
question is "what is the range of strain that I can apply on
the sample?" This is found by knowing the Strain range the
geometry can apply.
The software will calculated this for you.
= K

x u (% = *100)
Stress Relaxation and Linear Region
0.0
5.0 10.0 15.0 20.0 25.0
30.0
10
1
10
2
10
3
10
4
10
5
time [s]


G
(
t
)

(
)





[
P
a
]
Stress Relaxation of PDMS, Overlay
G(t)
200% strain
50% strain
10% strain
200% strain is outside the linear region
Creep & Recovery Experiment
S
t
r
e
s
s

time
t
1
t
2
Creep: Stress is applied to sample instantaneously at
t
1
, and held constant for a specific period of time. The
strain is monitored as a function of time (t).
Recovery: The stress is reduced to zero at t
2
, and the
strain is monitored as a function of time (t).
Native mode on AR (<1 msec)
Creep / Recovery Experiment
Response of Classical Extremes
Stain for t>t1 is
constant
Strain for t >t2 is 0
time time
Stain rate for t>t1 is constant
Strain for t>t1 increase with
time
Strain rate for t >t2 is 0
t
1
t
2
t
2
t
1
time t
2
t
1
Creep Recovery Experiment: Viscoelastic Material
Reference: Mark, J., et.al., Physical Properties of Polymers ,American Chemical Society, 1984, p. 102.
Creep o> 0
time
t
1
t
2
Recoverable
Strain
Recovery o = 0 (after steady state)
o/q
Strain rate decreases
with time in the creep
zone, until finally
reaching a steady state.
In the recovery zone, the viscoelastic
fluid recoils, eventually reaching a
equilibrium at some small total strain
relative to the strain at unloading.
Creep / Recovery Experiment
The material property obtained from Creep experiments:
Compliance (= 1/Modulus in sense)
J
(
t
)

1/q
time
Creep Zone
J
r
(
t
)

time
Recovery Zone
Creep Compliance Recoverable Compliance
J
e
0

more elastic
J
r
(t) = {
u
(t)} / o

J(t) = (t)/o
J
e
0

AR2000ex: Creep Recovery
Rule of thumb: recovery time is 2-3 times longer than creep time
AR2000ex : Steady State Algorithm Creep
During the test, the angular velocity is monitored with
time to determine when stability has been reached.
An average value for the angular velocity is recorded
over the Sample period.
When consecutive average values (Consecutive within
tolerance) are within the tolerance specified here, the
data is accepted.
Default
values
shown
Determining Proper Stress For Creep Experiment
Application Approach - If you are doing creep on a solid,
you want to know the dimension change with time under a
specified stress and temperature, then the questions is "what
is the max/min stress that I can apply to the sample?". This is
found by knowing the Stress range the geometry can apply.
The software will calculated this for you.
Research Approach - If you are doing creep on a polymer
melt, and are interested in viscoelastic information (creep and
recoverable compliance), then you need to conduct the test at
a stress within the linear viscoelastic region of the material.
o = K
o
x M
Creep Testing and Linear Region
250.0 0 50.00 100.0 150.0 200.0
time (s)
100.0
1.0E-3
0.010
0.10
1.0
10.0
c
o
m
p
l
i
a
n
c
e

(
m
^
2
/
N
)

Stress = 0.3, 0.4 & 0.5 Pa
Chocolate Milk creep test
0.5 Pa is outside the linear region
Solid Polymers/Composites
Testing Solids on Rheometer
Torsion Rectangular
Deformation mode: torsion
Samples: soft to rigid solid
Dimension: rectangular
Modulus: G, G, G*

E = 2G(1 + v)
v : Poissons ratio
AR2000ex: Normal Force Control
It is important to setup normal force control during any temperature
change testing or curing testing, or for any solid torsion testing
Some general suggestions for normal force control
For torsion testing, set normal force in tension:
Typical settings = 0.5 - 2N with tolerance of 0.1 - 1.0N

Before starting a test
During a test