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
= Strain Constant
O = Motor angular velocity in rad/sec.
The strain constant, 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
NonContact
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 coneandplate 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(10.378(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: 1E8 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 timebased 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
SteadyState Viscosity
at 1 s
1
= 2.8 Pas
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 ThixLoop 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
Pseudothixotropy from Hysteresis loop
Oldfashioned 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
FORDB3.04FUp step
FORDB3.04FDown step
FORDB3.05FUp step
FORDB3.05FDown 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 SteadyState 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
1.000E41.000E3 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: zerorate viscosity: 39470 Pa.s
b: infiniterate 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 cone0001f, Steady state flow step
hand cream cone0001f, 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 SteadyState 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.
15C/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
5.000E3
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: 6.841E3 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)
1.200E3
0
2.000E4
4.000E4
6.000E4
8.000E4
1.000E3
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
*
1/2
Power Law o = K
c
Herschel Bulkley o = o
0
+ K
c
Sisko q = q
+ K
n1
Williamson q = q
0
/(1+(/
0
)
c
)
Cross (qq
)/(q
0
q
) = 1/(1+(/
0
)
d
)
Ellis (qq
)/(q
0
q
) = 1/(1+(o/o
0
)
d
)
Carreau (qq
)/(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
1element stress
relaxation curve
Integral Form:
G(t) = G
e
+ }Hexp(t/t
i
)dln(t)

Stress Relaxation (Solidlike 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
(1exp(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
(1exp(t/t
i
) + t/q
i = 1
N
1element creep/
recovery curves
Integral Form:
J(t) = Jg + }L(1exp(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 (FluidLike 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
2.5000E4
5.0000E4
7.5000E4
1.0000E3
1.2500E3
1.5000E3
s
t
r
a
i
n
0
3.0000E4
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
(1exp(
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
Userdefined 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
ViscoElastic 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)
NonLinear 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*/ Pasec
CoxMerz 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)
NonLinear 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: 0.1100%
Dispersions: lowest10%
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 Noniterative 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 1.000E3 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 preshear = 0 seconds
Delay after preshear = 150 seconds
Preshear 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: Preshear Conditions
The goal for preshear 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
Preshear 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 crossover 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 )
Pdmsar04o
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
structureproperty 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. 15C/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 crossover point
Crossover 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 23 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
1.0E3
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
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