CA 2016 Rheology

Rheology
Theory and Applications
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Course Outline
Basics in Rheology Theory Oscillation

TA Rheometers Linear Viscoelasticity
Instrumentation Setting up Oscillation Tests
Choosing a Geometry Transient Testing
Calibrations Applications of Rheology
Flow Tests Polymers
Viscosity Structured Fluids
Setting up Flow Tests Advanced Accessories
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Basics in Rheology Theory
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Rheology: An Introduction
Rheology: The study of

stress-deformation relationships
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Rheology: An Introduction
Rheology is the science of flow and deformation

of matter
The word ‘Rheology’ was coined in the 1920s by
Professor E C Bingham at Lafayette College in Indiana
Flow is a special case of deformation
The relationship between stress and deformation
is a property of the material

= Viscosity
= Modulus
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Simple Steady Shear Flow
Top plate Area = A

x(t) Velocity = V0
Force = F
y Bottom Plate
y
Velocity = 0
x
F
Shear Stress, Pascals σ=
A
x(t ) σ
Shear Strain, % γ= η= Viscosity, Pa⋅s
y γ&
γ
Shear Rate, sec-1 γ& =
t
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Torsion Flow in Parallel Plates
Ω
r θ
Stress (σ
σ) " = $#% × M
r = plate radius
h = distance between plates
M = torque (µN.m)
Strain (γγ) = × θ
θ
θ = Angular motor deflection (radians)

Ω= Motor angular velocity (rad/s) Strain rate ( ) = × Ω
Ω
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TA Instruments Rheometers
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Rotational Rheometers at TA
ARES G2 DHR
Controlled Strain Controlled Stress

Dual Head Single Head
SMT CMT
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Rotational Rheometer Designs
Dual head or SMT Single head or CMT

Separate motor & transducer Combined motor & transducer
Displacement
Measured Transducer Sensor
Torque
(Stress) Measured Strain
or Rotation
Non-Contact
Drag Cup
Motor
Applied
Torque
Sample (Stress)
Applied
Strain or Direct Drive Static Plate
Plate
Rotation Motor
Note: With computer feedback, DHR and AR can work in controlled strain/shear
rate, and ARES can work in controlled stress.
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What does a Rheometer do?
Rheometer – an instrument that measures both viscosity and

viscoelasticity of fluids, semi-solids and solids
It can provide information about the material’s:

Viscosity - defined as a material’s resistance to deformation and
is a function of shear rate or stress, with time and temperature
dependence
Viscoelasticity – is a property of a material that exhibits both

viscous and elastic character. Measurements of G’, G”, tan δ with
respect to time, temperature, frequency and stress/strain are
important for characterization.
A Rheometer works simply by relating a materials property from how hard it’s
being pushed, to how far it moves
by commanding torque (stress) and measuring angular displacement (strain)

by commanding angular displacement (strain) and measuring torque (stress)
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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:
1. Torque (Force)
2. Angular Displacement
3. Angular Velocity
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Torque Shear Stress
In a rheometer, the stress is calculated from the

torque.
The formula for stress is: σ = Μ × Kσ

Where σ = Stress (Pa or Dyne/cm2)
Μ = torque in N.m or gm.cm
Kσ = Stress Constant
The stress constant, Kσ, is a geometry dependent factor
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Angular Displacement Shear Strain
In a SMT Rheometer, the angular displacement

is directly applied by a motor.
The formula for strain is: γ = Kγ × θ

%γ = γ × 100
where γ = Strain
Kγ = Strain Constant
θ = Angular motor deflection (radians)
The strain constant, Kγ, is a geometry dependent factor
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Equation for Modulus
Describe
In Spec Correctly
σ M ⋅ Kσ
G= =
γ θ ⋅ Kγ
Geometric
Rheological Constitutive Raw rheometer
Parameter Equation Specifications
Shape
Constants
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.
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Angular Velocity Shear Rate
In a SMT rheometer, the angular speed is directly

controlled by the motor).
The formula for shear rate is:
= &' × Ω
where = Shear rate
Kγ = Strain Constant
Ω = Motor angular velocity in rad/sec
The strain constant, Kγ, is a geometry dependent factor
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Equation for Viscosity
Describe
In Spec Correctly
σ M ⋅ Kσ
η= =
γ& Ω ⋅ K γ
Geometric
Parameter Equation Specifications
Shape
Constants
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.
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Discovery Hybrid Rheometer Specifications
Specification HR-3 HR-2 HR-1

Bearing Type, Thrust Magnetic Magnetic Magnetic
Bearing Type, Radial Porous Carbon Porous Carbon Porous Carbon
Motor Design
Minimum Torque (nN.m) Oscillation
Drag Cup
0.5
Drag Cup
2
Drag Cup
10 HR-2
HR-3
Minimum Torque (nN.m) Steady 5 10 20 HR-1
Shear
Maximum Torque (mN.m) 200 200 150
Torque Resolution (nN.m) 0.05 0.1 0.1
Minimum Frequency (Hz) 1.0E-07 1.0E-07 1.0E-07
Maximum Frequency (Hz) 100 100 100
Minimum Angular Velocity (rad/s) 0 0 0
Maximum Angular Velocity (rad/s) 300 300 300
Displacement Transducer Optical Optical Optical
encoder encoder encoder
Optical Encoder Dual Reader Standard N/A N/A
Displacement Resolution (nrad) 2 10 10
Step Time, Strain (ms) 15 15 15
Step Time, Rate (ms) 5 5 5
DHR - DMA mode (optional)
Normal/Axial Force Transducer FRT FRT FRT
Motor Control FRT
Maximum Normal Force (N) 50 50 50
Minimum Force (N) Oscillation 0.1
Normal Force Sensitivity (N) 0.005 0.005 0.01 Maximum Axial Force (N) 50
Minimum Displacement (µm) 1.0
Normal Force Resolution (mN) 0.5 0.5 1 Oscillation
Maximum Displacement (µm) 100
Oscillation
Displacement Resolution (nm) 10
Axial Frequency Range (Hz) 1 x 10-5 to 16
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ARES-G2 Rheometer Specifications
Force/Torque Rebalance Transducer (Sample Stress)

Transducer Type Force/Torque
Rebalance
Transducer Torque Motor Brushless DC
Transducer Normal/Axial Motor Brushless DC
Minimum Torque (µN.m) Oscillation 0.05
Minimum Torque (µN.m) Steady Shear 0.1
Maximum Torque (mN.m) 200
Torque Resolution (nN.m) 1
Transducer Normal/Axial Force Range (N) 0.001 to 20
Transducer Bearing Groove Compensated
Air
Driver Motor (Sample Deformation)

Maximum Motor Torque (mN.m) 800 Orthogonal Superposition (OSP) and
Motor Design Brushless DC DMA modes
Motor Bearing Jeweled Air, Sapphire Motor Control FRT
Displacement Control/ Sensing Optical Encoder
Strain Resolution (µrad) 0.04 Minimum Transducer Force (N) 0.001
Oscillation
Minimum Angular Displacement (µrad) 1
Maximum Transducer Force 20
Oscillation
(N)
Maximum Angular Displacement (µrad) Unlimited
Minimum Displacement (µm) 0.5
Steady Shear Oscillation
Angular Velocity Range (rad/s) 1x 10-6 to 300 Maximum Displacement (µm) 50
Angular Frequency Range (rad/s) 1x 10-7 to 628 Oscillation
Step Change, Velocity (ms) 5 Displacement Resolution (nm) 10
Step Change, Strain (ms) 10 Axial Frequency Range (Hz) 1 x 10-5 to 16
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Geometry Options
Concentric Cone and Parallel Torsion

Cylinders Plate Plate Rectangular
Very Low Very Low Very Low

to Medium Solids
to High Viscosity
Viscosity Viscosity to Soft Solids
Water to Steel
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Choosing a Geometry Size
Assess the ‘viscosity’ of your sample

When a variety of cones and plates are available, select diameter
appropriate for viscosity of sample
Low viscosity (milk) - 60mm geometry
Medium viscosity (honey) - 40mm geometry
High viscosity (caramel) – 20 or 25mm geometry
Examine data in terms of absolute instrument variables
torque/displacement/speed and modify geometry choice to move
into optimum working range
You may need to reconsider your selection after the first run!
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Parallel Plate
Strain Constant: &' = ,+

(to convert angular velocity, rad/sec, to shear rate,
1/sec, at the edge or angular displacement, radians,
to shear strain (unitless) at the edge. The radius, r,
and the gap, h, are expressed in meters)
Gap (h) Stress Constant: &( = *+) %

Diameter (2⋅⋅r)
(to convert torque, N⋅m, to shear stress at the
edge, Pa, for Newtonian fluids. The radius, r, is
expressed in meters)
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When to use Parallel Plates
Low/Medium/High Viscosity Samples with long relaxation time

Liquids Temperature Ramps/ Sweeps
Soft Solids/Gels Materials that may slip
Thermosetting materials Crosshatched or Sandblasted plates
Samples with large particles
Small sample volume
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Plate Diameters
Shear Stress
20 mm
40 mm
60 mm
2
As diameter decreases, shear stress increases "=- )
/0
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Plate Gaps
Shear
Rate
2 mm Increases
1 mm
0.5 mm
0
As gap height decreases, shear rate increases = Ω
ℎ
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Effective Shear Rate varies across a Parallel Plate
For a given angle of deformation, there is a greater arc of

deformation at the edge of the plate than at the center
34 dx increases further from the center,

= h stays constant
ℎ
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Shear Rate is Normalized across a Cone
The cone shape produces a smaller gap height closer to inside,

so the shear on the sample is constant
34
= h increases proportionally to dx, γ is uniform
ℎ
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Cone and Plate
Strain Constant: &' = 65

(to convert angular velocity, rad/sec, to shear rate.
1/sec, or angular displacement, radians, to shear strain,
which is unit less. The angle, β, is expressed in radians)
7
Stress Constant: &( = )*+ %
(to convert torque, N⋅m, to shear stress, Pa.

The radius, r, is expressed in meters)
Diameter (2⋅⋅r)
Truncation (gap)
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When to use Cone and Plate
Very Low to High Viscosity Liquids

High Shear Rate measurements
Normal Stress Growth
Unfilled Samples
Isothermal Tests
Small Sample Volume
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Cone Diameters
Shear Stress
20 mm
40 mm
60 mm
3
As diameter decreases, shear stress increases "=-
2/0 7
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Cone Angles
Shear Rate
Increases
2°
1°
0.5 °
1
As cone angle decreases, shear rate increases = Ω
:
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Limitations of Cone and Plate
Typical Truncation Heights:

1° degree ~ 20 - 30 microns
2° degrees ~ 60 microns
4° degrees ~ 120 microns
Cone & Plate Truncation Height = Gap
Gap must be > or = 10 [particle size]!!
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Correct Sample Loading
× Under Filled sample:

Lower torque contribution
× Over Filled sample:

Additional stress from
drag along the edges
Correct Filling
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Concentric Cylinder
01) + 02)
Strain Constant: &' =
02) 01)
(to convert angular velocity, rad/sec, to shear rate,
1/sec, or angular displacement, radians, to shear
strain (unit less). The radii, r1 (inner) and r2 (outer),
are expressed in meters)
) ) *
01 + 02
Stress Constant: &( = 5
;*< 02) 01)
(to convert torque, N⋅m, to shear stress, Pa. The bob
length, l, and the radius, r, are expressed in meters)
*Note including end correction factor. See TRIOS Help TAINSTRUMENTS.COM

Double Wall
Use for very low viscosity systems (<1 mPas)
r1
r2
h
r3
r4
01) + 02)
Strain Constant: &' =
02) − 01)
+5# ?+)#
Stress Constant: &( = ;*,∙+ # + # ?+ #
) 5 7
ARES Gap Settings: standard operating gap DW = 3.4 mm

narrow operating gap DW = 2.0 mm
Use equation Gap > 3 × (R2 –R1)
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When to Use Concentric Cylinders
Low to Medium Viscosity Liquids

Unstable Dispersions and Slurries
Minimize Effects of Evaporation
Weakly Structured Samples (Vane)
High Shear Rates
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Peltier Concentric Cylinders
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Torsion Rectangular
A
&' =
G )
B 1 − 0.378 H w = Width
l = Length
3 + 5.J t = Thickness
H
&I =
K ∙ A)
Advantages: Disadvantages:
High modulus samples No pure Torsion mode for

Small temperature high strains
gradient
Simple to prepare
Torsion cylindrical also available

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Torsion and DMA Measurements
Torsion and DMA geometries allow solid samples to be

characterized in a temperature controlled environment
Torsion measures G’, G”, and Tan δ

DMA measures E’, E”, and Tan δ
ARES G2 DMA is standard function (50 µm amplitude)
DMA is an optional DHR function (100 µm amplitude)
Rectangular and DMA 3-point bending and tension

cylindrical torsion (cantilever not shown)
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Geometry Overview
Geometry Application Advantage Disadvantage
Cone/plate fluids, melts true viscosities temperature ramp difficult

viscosity > 10mPas
Parallel Plate fluids, melts easy handling, shear gradient across

viscosity > 10mPas temperature ramp sample
Couette low viscosity samples high shear rate large sample volume
< 10 mPas
Double Wall Couette very low viscosity high shear rate cleaning difficult
samples < 1mPas
Torsion Rectangular solid polymers, glassy to rubbery Limited by sample stiffness

composites state
Limited by sample stiffness

Solid polymers, films, Glassy to rubbery
DMA (Oscillation and
Composites state
stress/strain)
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Rheometer Calibrations and
Performance Verification
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DHR – Calibration Options
Instrument Calibrations
Inertia (Service)
Rotational Mapping
Geometry Calibrations:
Inertia
Friction
Gap Temperature
Compensation
Rotational Mapping
Details in Appendix #4
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ARES-G2 – Calibration Options
Transducer
Temperature Offsets
Phase Angle (Service)
Measure Gap Temperature
Compensation
Compliance and Inertia (from table)
Gap Temperature Compensation
Details in Appendix #4
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Verify Rheometer Performance
Rheometers are calibrated from the factory and again at

installation.
TA recommends routine validation or confidence checks
using standard oils or Polydimethylsiloxane (PDMS).
PDMS is verified using a 25 mm parallel plate.

Oscillation - Frequency Sweep: 1 to 100 rad/s with 5% strain at 30°C
Verify modulus and frequency values at crossover
Standard silicone oils can be verified using cone, plate or

concentric cylinder configurations.
Flow – Ramp: 0 to 88 Pa at 25°C using a 60 mm 2° cone
Service performs this test at installation
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PDMS Frequency Sweep Results
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Load Standard Oil
Set Peltier temperature to 25°C and

equilibrate.
Zero the geometry gap
Load sample
Be careful not to introduce air bubbles!
Set the gap to the trim gap
Lock the head and trim with non-absorbent

tool
Important to allow time for temperature equilibration.
Go to geometry gap and initiate the

experiment.
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Flow Ramp – Standard Oil (Service Test)
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Setting up Rheological Experiments
Flow Tests
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Viscosity: Definition
Viscosity is…
“lack of slipperiness”
synonymous with internal friction
resistance to flow
The Units of Viscosity are …

SI unit is the Pascal.second (Pa.s)
cgs unit is the Poise
10 Poise = 1 Pa.s
1 cP (centipoise) = 1 mPa.s (millipascal second)
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Equation for Viscosity
Describe
In Spec Correctly
σ M ⋅ Kσ
η= =
γ& Ω ⋅ K γ
Geometric
Parameter Equation
Shape
Specifications
Constants
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Typical Viscosity Values (Pa-s)
Asphalt Binder -------------- 100,000

Polymer Melt ---------------- 1,000
Molasses --------------------- 100
Liquid Honey ---------------- 10 Need for
Glycerol ---------------------- 1 Log scale
Olive Oil ---------------------- 0.01
Water ------------------------- 0.001
Air ----------------------------- 0.00001
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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
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Characteristic Diagrams for Newtonian Fluids
Ideal Yield Stress

(Bingham Yield)
η, Pa.s
σ, Pa
γ ,1/s or σ, Pa
γ ,1/s
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Characteristic Diagrams for Shear Thinning Fluids
105 105
103 103
η, Pa.s
η, Pa.s
101 101
10-1 10-1
10-6 10-4 10-2 100 102 104 10-1 10-0 10-1 102 103
,1/s σ, Pa
105
Ideal Yield Stress
Another name for a shear thinning
103 (Bingham plastic)
σ, Pa
fluid is a pseudo-plastic
101
10-1
10-6 10-4 10-2 100 102 104
γ ,1/s
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Characteristic Diagrams for Shear Thickening Fluids
Dilatant material resists

deformation more than in
proportion to the applied
Log η, Pa.s
force (shear-thickening)
Cornstarch in water or sand

on the beach are actually
dilatant fluids, since they do
not show the time-
dependent, shear-induced
change required in order to
Log , 1/s be labeled rheopectic
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Non-Newtonian, Time Dependent Fluids
Rheopectic materials
become more viscous
Rheopectic with increasing time of
applied force
Higher concentration
Viscosity
latex dispersions and

Shear Rate = Constant plastisol paste materials
exhibit rheopectic
behavior
Thixotropic Thixotropic materials
become more fluid with
increasing time of applied
force
time
Coatings and inks can
display thixotropy when
sheared due to structure
breakdown
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Flow Experiments
Flow Experiments
Constant shear rate/stress (or Peak hold)
Continuous stress/rate ramp and down
Stepped flow (or Flow sweep)
Steady state flow
Flow temperature ramp
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Constant Shear Rate/Stress
Stress /Rate
Constant rate vs. time
Constant stress vs. time
USES
Single point testing
Scope the time for steady state under certain rate
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Constant Shear Rate/Stress
3.500 4.000
Hand Wash Rate 1/s
3.500
3.000
3.000
2.500
2.500
shear stress (Pa)
viscosity (Pa.s)
2.000
2.000
1.500
Viscosity at 1 1/s is 2.8 Pa⋅s 1.500
1.000
1.000
0.5000
0.5000
0 0
0 5.0000 10.000 15.000 20.000 25.000 30.000
time (s)
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Continuous Ramp
Deformation
Stress is applied to
material at a constant
m =Stress rate rate. Resultant strain
(Pa/min) is monitored with time.
time (min)
USES
Yield stress
Scouting Viscosity Run
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Stress Ramp: Flow Media Dispersion
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Thixotropic Loop - Continuous Ramp Up and Down
Deformation
Stress is first increased,
then decreased, at a
σ
constant rate. Resultant
strain is monitored with
time
time.
USES
“Pseudo-thixotropy” from Hysteresis loop
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Up & Down Flow Curves - 2 Repeats
Run in Stress Control TA Instruments

500.0
400.0
shear stress (Pa)
300.0
Red: First cycle
Blue: Second cycle
200.0
FORDB3.04F-Up step
FORDB3.04F-Down step
FORDB3.05F-Up step
100.0 FORDB3.05F-Down step
0
0 0.1000 0.2000 0.3000 0.4000 0.5000
shear rate (1/s)
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Stepped or Steady-State Flow
Deformation
σ
Data point saved
Stress is applied to sample.
or Viscosity measurement is taken
when material has reached steady
state flow. The stress is
increased(logarithmically) and the
time process is repeated yielding a
viscosity flow curve.
Delay time
σ USES
or
Steady State Flow Viscosity Flow Curves

γ or σ = Constant Yield Stress Measurements
time
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Stepped or Steady-State Flow
A series of logarithmic stress steps allowed to reach steady state, each

one giving a single viscosity data point:
Data at each
Shear Rate
Shear
Thinning
Region
Viscosity
Time
Shear Rate, 1/s

η = σ / (d γ/dt)
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DHR and ARES G2: Steady State Flow
Control variables:
Shear rate
Velocity
Torque
Shear stress
Steady state algorithm
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Flow Sweeps- Water-Based Paint with Solvent Trap
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Comparison of Cough Syrups
0.8000 Sample 1-Flow step

Sample 2-Flow step
0.7000
Which material would do a better job

0.6000
coating your throat?
viscosity (Pa.s)
0.5000
0.4000
0.3000
0.2000
0.1000
0
0.1000 1.000 10.00 100.0 1000
shear rate (1/s)
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Comparison of Two Latex Paints
10000
A.01F-Flow step
B.01F-Flow step
Low shear rates B>A
1000
viscosity (Pa.s)
100.0
10.00
Medium shear rates A>B
1.000
High shear rates B>A

0.1000
1.000E-4 1.000E-3 0.01000 0.1000 1.000 10.00 100.0 1000
shear rate (1/s)
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Flow Temperature Ramp
Hold the rate or stress

X X X X constant whilst
ramping the
temperature.
time (min)
USES
Measure the viscosity change vs. temperature
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Viscosity: Temperature Dependence
Notice a nearly 2 decade decrease in viscosity. This displays the importance of

thermal equilibration of the sample prior to testing.
i.e. Conditioning Step or equilibration time for 3 to 5 min
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Flow Testing Considerations
Small gaps give high shear rates

Be careful with small gaps:
Gap errors (gap temperature compensation) and shear
heating can cause large errors in data.
Recommended gap is between 0.5 to 2.0 mm.
Secondary flows can cause increase in viscosity curve
Be careful with data interpretation at low shear rates
Surface tension can affect measured viscosity, especially
with aqueous materials
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Water at 25°C – Secondary Flow
Surface tension at low torques
Secondary flows at high shear rates
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Wall Slip
Wall slip can manifest as “apparent double yielding”

Can be tested by running the same test at different gaps
For samples that don’t slip, the results will be independent of the gap
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Shear Thinning or Sample Instability?
When Stress Decreases with

Shear Rate, it indicates that
sample is leaving the gap
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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
η (γ ) ≡ η (ω )
& *
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Viscoelasticity
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Elastic Behavior of an Ideal Solid
Hooke’s Law of Elasticity: Stress = Modulus ⋅ Strain
γ1 γ2 γ3
3
Stress (σ)
2 E
1 2 3
Strain (ɣ)
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Elastic Behavior of an Ideal Solid
Hooke’s Law of Elasticity: Stress = Modulus ⋅ Strain
E > E > E
"
L= γ1 γ2 γ3

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Viscous Behavior of an Ideal Liquid
Newton’s Law: stress

= coefficient of viscosity ⋅ shear rate
η
Stress (σ)
" = η ∙
Shear Rate (ɣ)
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Viscous Behavior of an Ideal Liquid
Newton’s Law: stress= coefficient of viscosity ⋅ shear rate "

η=

η < η < η
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Viscoelastic Behavior
σ = E*ε + η*dε/dt
Kelvin-Voigt Model (Creep) Maxwell Model (Stress Relaxation)
L1
L2
Viscoelastic Materials: Force

depends on both Deformation and
Rate of Deformation and vice versa.
Viscoelasticity Defined
Range of Material Behavior

Liquid Like---------- Solid Like
Ideal Fluid ----- Most Materials -----Ideal Solid
Purely Viscous ----- Viscoelastic ----- Purely Elastic
Viscoelasticity: Having both viscous

and elastic properties
Materials behave in the linear manner, as described by Hooke and
Newton, only on a small scale in stress or deformation.
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Pitch Drop Experiment
Long deformation time: pitch behaves

like a highly viscous liquid
9th drop fell July 2013
Short deformation time: pitch behaves
like a solid
Started in 1927 by Thomas Parnell in Queensland, Australia

http://www.theatlantic.com/technology/archive/2013/07/the-3-most-exciting-words-in-science-right-now-the-pitch-dropped/277919/
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Time-Dependent Viscoelastic Behavior
T is short [< 1s] T is long [24 hours]
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Time-Dependent Viscoelastic Behavior
Silly Putties have different characteristic relaxation times

Dynamic (oscillatory) testing can measure time-dependent
viscoelastic properties more efficiently by varying frequency
(deformation time)
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Viscoelasticity, Deborah Number
Old Testament Prophetess who said (Judges 5:5):

"The Mountains ‘Flowed’ before the Lord"
Everything Flows if you wait long enough!
Deborah Number, De - The ratio of a characteristic

relaxation time of a material (τ) to a characteristic time of
the relevant deformation process (T).
De = τ/T
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Deborah Number
Hookean elastic solid - τ is infinite

Newtonian Viscous Liquid - τ is zero
Polymer melts processing - τ 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
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Time and Temperature Relationship
(E' or G') (E' or G')

(E" or G") (E" or G")
log Frequency Temperature
log Time log Time
TAINSTRUMENTS.COM
Linear Viscoelasticity Region (LVR) Defined
"If the deformation is small, or applied sufficiently slowly,

the molecular arrangements are never far from
equilibrium.
The mechanical response is then just a reflection of

dynamic processes at the molecular level which go on
constantly, even for a system at equilibrium.
This is the domain of LINEAR VISCOELASTICITY.
The magnitudes of stress and strain are related

linearly, and the behavior for any liquid is completely
described by a single function of time."
Mark, J., et. al., Physical Properties of Polymers, American Chemical Society, 1984, p. 102.
TAINSTRUMENTS.COM
Importance of LVR
E’ (or G’), E” (or G”), tan δ, η*

Measuring linear viscoelastic properties helps us bridge the gap
between molecular structure and product performance
TAINSTRUMENTS.COM
Oscillatory Tests
TAINSTRUMENTS.COM
Understanding Oscillation Experiments
Define Oscillation Testing
Approach to Oscillation Experimentation

Stress and Strain Sweep
Time Sweep
Frequency Sweep
Temperature Ramp
Temperature Sweep (TTS)
TAINSTRUMENTS.COM
What is Oscillation?
Phase angle δ
Strain, ε
Stress, σ*
Dynamic stress applied sinusoidally

User-defined Stress or Strain amplitude and frequency
TAINSTRUMENTS.COM
Frequency Defined
Time to complete one oscillation

Frequency is the inverse of time
Units
Angular Frequency = radians/second
Frequency = cycles/second (Hz)
Rheologist must think in terms of rad/s.
1 Hz = 6.28 rad/s
TAINSTRUMENTS.COM
Frequency
ω = 6.28 rad/s
ω = 12.560rad/s
0 0 0 0
Time = 1sec ω = 50 rad/s
TAINSTRUMENTS.COM
Amplitude: Strain or Stress
Strain and stress are calculated from peak amplitude in the

displacement and torque waves, respectively.
0 0 0 0
Time = 1sec
TAINSTRUMENTS.COM
Dynamic Mechanical Testing
Deformation
An oscillatory (sinusoidal)
deformation (stress or strain)
is applied to a sample.
Response
The material response
(strain or stress) is measured.
The phase angle δ, or phase

shift, between the deformation Phase angle δ
and response is measured.
TAINSTRUMENTS.COM
Dynamic Testing: Response for Classical Extremes
Purely Elastic Response Purely Viscous Response

(Hookean Solid) (Newtonian Liquid)
δ = 0° δ = 90°
Strain Strain
Stress Stress
TAINSTRUMENTS.COM
Dynamic Testing: Viscoelastic Material Response
Phase angle 0°< δ < 90°
Strain
Stress
TAINSTRUMENTS.COM
Viscoelastic Parameters: Complex, Elastic, & Viscous Stress
The stress in a dynamic experiment is referred to as the

complex stress σ*
The complex stress can be separated into two components:
1) An elastic stress in phase with the strain. σ' = σ*cosδ δ
σ' is the degree to which material behaves like an elastic solid.
2) A viscous stress in phase with the strain rate. σ" = σ*sinδ δ
σ" is the degree to which material behaves like an ideal liquid.
Phase angle δ
Complex Stress, σ* σ* = σ' + iσ
σ"
Complex number: 4 + NO = 4) + O)
The material functions can be described in

Strain, ε terms of complex variables having both real and
imaginary parts. Thus, using the relationship:
TAINSTRUMENTS.COM
Viscoelastic Parameters
The Modulus: Measure of ∗ ∗

materials overall resistance to G = ST
deformation.
The Elastic (Storage) Modulus:
Q ∗
Measure of elasticity of material. G = ST
cos δ
The ability of the material to store
energy.
The Viscous (loss) Modulus:
" ∗
The ability of the material to G = ST
sin δ
dissipate energy. Energy lost as
heat.
Tan Delta:
Y"
Measure of material damping -
such as vibration or sound
tan δ = YQ
damping.
TAINSTRUMENTS.COM
Storage and Loss of a Viscoelastic Material
RUBBER BALL X LOSS

(G”)
TENNIS
BALL X
STORAGE
(G’)
G*
Dynamic measurement G"
represented as a vector
Phase angle δ
G'
TAINSTRUMENTS.COM
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:
η* = η’ + i η”
or
η* = G*/ω
Note: frequency must be in rad/sec!
TAINSTRUMENTS.COM
Dynamic Rheological Parameters
Parameter Shear Elongation Units
Strain γ = γ0 sin(ωt) ε = ε0 sin(ωt) ---
Stress σ = σ0sin(ωt + δ) τ = τ0sin(ωt + δ) Pa
Storage Modulus
G’ = (σ0/γ0)cosδ E’ = (τ0/ε0)cosδ Pa
(Elasticity)
Loss Modulus
G” = (σ0/γ0)sinδ E” = (τ0/ε0)sinδ Pa
(Viscous Nature)
Tan δ G”/G’ E”/E’ ---
Complex Modulus G* = (G’2+G”2)0.5 E* = (E’2+E”2)0.5 Pa
Complex Viscosity η* = G*/ω ηE* = E*/ω Pa·sec
Cox-Merz Rule for Linear Polymers: η*(ω) = η( ) @ = ω
TAINSTRUMENTS.COM
Understanding Oscillation Experiments
Define Oscillation Testing
Approach to Oscillation Experimentation

1. Stress and Strain Sweep
2. Time Sweep
3. Frequency Sweep
4. Temperature Ramp
5. Temperature Sweep (TTS)
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Dynamic Strain or Stress Sweep
Stress or strain
The material response to

increasing deformation
amplitude (strain or
stress) is monitored at a
constant frequency and
Time temperature.
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
TAINSTRUMENTS.COM
Dynamic Strain Sweep: Material Response
Linear Region:
Modulus
Non-linear Region:
independent
of strain
Modulus is a function of strain
G'
Stress
Constant γc = Critical Strain

Slope
Strain (amplitude)
TAINSTRUMENTS.COM
Temperature Dependence of LVR
In general, the LVR is shortest when the sample is in its

most solid form.
Solid
G’
Liquid
% strain
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Frequency Dependence of LVR
LVR decreases with increasing frequency

Modulus increases with increasing frequency
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SAOS versus LAOS Waveforms
Linear response to a sinusoidal excitation

is sinusoidal and represented by the
fundamental in the frequency domain
Nonlinear response to a sinusoidal

excitation is not sinusoidal and
represented in the frequency domain by
the fundamental and the harmonics
TAINSTRUMENTS.COM
LAOS: Analysis of Higher Harmonics
SAOS γ(t) = γ0 sin(ωt)
τ(t) = τ0 sin(ωt+δ)
LAOS γ(t) = γ0 sin(ωt)

Fourier Series expansion:
τ(t) = τ1 sin(ω1t+ϕ1) + τ3 sin(3ω1t+ϕ3) +
τ5 sin(5ω1t+ϕ5) + ...
∞
= Σ τ sin(nω +ϕ )
n=1
n 1 n
odd
Lissajous plot: Stress vs. Strain (shown)
or stress vs. Shear rate
TAINSTRUMENTS.COM
Dynamic Time Sweep
Stress or strain
The material response

is monitored at a
constant frequency,
amplitude and
temperature.
Time
USES
Time dependent Thixotropy
Cure Studies
Stability against thermal degradation
Solvent evaporation/drying
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Importance of Time Sweep
Important, but often overlooked

Visually observe the sample
Determines if properties are changing over the time of
testing
Complex Fluids or Dispersions
Preshear or effects of loading
Drying or volatilization (use solvent trap)
Thixotropic or Rheopectic
Polymers
Degradation (inert purge)
Crosslinking
TAINSTRUMENTS.COM
Time Sweep on PEEK Melt - Thermal Stability
2000G time sweep at 400°C
105
Under N2 Under air
104
)
]
a
( P
[
"
G
103
)
]
a
P
[
(
'
G
102
101
0.0 10.0 20.0 30.0 40.0 50.0 60.0
time [min]
TAINSTRUMENTS.COM
Time Sweep on Latex
100.0 Structural Recovery after Preshear
80.00
G' (Pa)
60.00
40.00
20.00
0 0
25.00 50.00 75.00 100.0 125.0 150.0 175.0 200.0 225.0
time (s)
TAINSTRUMENTS.COM
Importance of Waiting for Structure Rebuild
Delay after pre-shear = 150 sec

Sample “A” time sweep
100.0
Delay after pre-shear = 0 sec
100.0
G' (Pa)
Pre-shear conditions:
100 1/s for 30 seconds
10.00 10.00
0 25.00 50.00 75.00 100.0 125.0 150.0 175.0 0.1000 1.000 10.00 100.0
time (s) osc. stress (Pa)
End of LVR is indicative of “Yield” or “Strength of Structure”

Useful for Stability predictions (stability as defined by yield)
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Solvent Trap System for Effective Evaporation Control
Solvent trap cover picks up heat from Peltier Plate to insure uniform temperature
Solvent in
Solvent Trap Cover Well
Peltier
Plate
Sample
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Cure of a "5 Minute" Epoxy
TA Instruments
1000000 G' 1000000
5 min
100000 100000
10000 G" 10000

G' (Pa)
G'' (Pa)
1000 1000
Gel Point: G' = G"
t = 330 s
100.0 100.0
10.00 10.00
1.000 1.000
0 200.0 400.0 600.0 800.0 1000 1200
time (s)
TAINSTRUMENTS.COM
Frequency Sweep
The material response to

increasing frequency (rate of
deformation) is monitored at
Amplitude
a constant amplitude (strain

or stress) and temperature.
Time
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)
TAINSTRUMENTS.COM
Frequency Sweep: Material Response
Transition
Rubbery Region
Terminal Plateau
Region Region
Glassy Region
1
2 Storage Modulus (E' or G')
Loss Modulus (E" or G")
log Frequency (rad/s or Hz)
TAINSTRUMENTS.COM
Frequency Sweep- Time Dependent Viscoelastic Properties
Frequency of modulus
crossover correlates
with Relaxation Time
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Cox-Merz Example - LDPE at 190°C
η (γ& ) ≡ η * (ω )
Flow instability

LDPE Freq sweep 2mm gap – Cox Merz

LDPE shear rate 1mm gap
LDPE Shear rate 2 mm gap
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Importance of Frequency Sweeps
High and low rate (short and long time) properties

Viscosity Information - Zero Shear Viscosity, shear
thinning
Elasticity (reversible deformation) in materials
MW & MWD differences polymer melts and solutions
Finding yield in gelled dispersions
Can extend time or frequency range with TTS
3.4
G'  Mw 
η0 ≈ M 3.4
w and J e = 2
≈  
( G" )  M z 
TAINSTRUMENTS.COM
Frequency in DHR Rheometer
DHR has a combined motor and transducer design.

In an DHR 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.
TAINSTRUMENTS.COM
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
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Inertial Effects in Oscillation for DHR
Inertia consideration
Viscosity limitations with frequency
Minimize inertia by using low mass geometries
Monitor inertia using Raw Phase in degree
When Raw Phase is greater than:
150°° degrees for AR series
175°° degrees for DHR series
This indicates that the system inertia is dominating the
measurement signal. Data may not be valid
Raw Phase × Inertia Correction = delta
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Access to raw phase angle
DHR Correction for Inertia only available with TA
Instruments Rheometers!
Waveforms at high frequencies
Inertial effects at
high frequencies
Negligible correction at low frequencies
TAINSTRUMENTS.COM
Frequency Sweeps in ARES-G2
ARES-G2 has a separate motor and transducer

design.
In an ARES-G2, the motor applies the deformation
independent of the torque measurement on the transducer.
The moment of inertia required to move the motor is
decoupled from the torque measurements.
This means the motor inertia does not contribute to the test
results.
Benefits of ARES-G2:
System inertia free
Capable of running low viscosity samples up to high
frequency
TAINSTRUMENTS.COM
ARES-G2 Closed-Loop Control
FRT
Deflection FRT null Position
Purest
Measurement !
Torque to drive FRT
To maintain Zero
Position = Sample
Torque
Motor
Inertia Target
NOT Part of Measured Strain
Measurement Motor
Displacement Or
Speed
Motor torque and

sample torque are Torque to
separated. drive motor
to desired displacement
TAINSTRUMENTS.COM
Dynamic 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
Temperature (°C)
intervals. time between
data points
m = ramp rate
(°C/min)
Denotes Oscillatory
Measurement
time (min)
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Temperature Sweep (or Step) - Single /Multi-Frequency
A step and hold temperature Soak

profile is applied. The Time
material response is Step Size

monitored at one, or over a
range of frequencies, at Oscillatory
Measurement
constant amplitude of
deformation.
– No thermal lag Time
Soak
Time
Oscillatory
Step Size Measurement
Time
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Dynamic Temperature Ramp or Sweep: Material Response
Glassy Region
Transition
Region Rubbery Plateau
Region Terminal Region
log E' (G') and E" (G")
Storage Modulus (E' or G')

Loss Modulus (E" or G")
Temperature
TAINSTRUMENTS.COM
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
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Acrylonitrile Butadiene Styrene (ABS)
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DHR: Axial Force Control
It is important to setup normal force control during any temperature

change testing or curing testing
Some general suggestions for normal force control
For torsion testing, set normal force in tension: 1-2N ± 0.5-1.0N
For curing or any parallel plate testing, set normal force in
compression: 0 ± 0.5N
TAINSTRUMENTS.COM
Using Axial Force Control in a Thermosetting Material
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TA Tech Tip – Axial Force Control
Videos available at www.tainstruments.com under the Videos tab or on the TA

tech tip channel of YouTube™ (https://www.youtube.com/user/TATechTips)
TAINSTRUMENTS.COM
Cure or Thermoset Materials
Cures are perhaps the most challenging experiments to conduct on

rheometers as they challenge all instrument specifications both high
and low.
The change in modulus as a sample cures can be as large as 7-8
decades and change can occur very rapidly.
AR, DHR, and ARES instruments have ways of trying to cope with
such large swings in modulus
AR: Non-iterative sampling (w/ Axial force control)
DHR: Non-iterative sampling (w/ Axial force control) and
Auto-strain (w/ Axial force active) in TRIOS v3.2 or higher
ARES: Auto-strain (w/ Axial force or auto-tension active)
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Thermosetting Polymers
Material fully cured
At start of test have a material that starts as Maximum h or G’ reached
liquid, paste, pressed power Pellet, or prepreg
η
or
G’
Crosslinking
reaction causes
h and G’ to increase
Temp As the temp increases Material hits minimum viscosity which depends on
the viscosity of resin Max temperature, frequency, ramp rate and may depend
decreases on strain or stress amplitude
Time
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DHR and AR: Data Collection Options
Non-Iterative Sampling – motor

torque is adjusted based on
previous stress value and predicts
new value required to obtain the
target strain (good for rapid
measurements)
Precision Sampling – motor torque

is adjusted at the end of an
oscillation cycle in order to reach
commanded strain
Continuous Oscillation (direct

strain)* – motor torque is adjusted
during the oscillation cycle to apply
the commanded strain
*Continuous oscillation only available with DHR-2 and DHR-3

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Continuous Oscillation on Single Head Rheometer
Continuous oscillation (or direct strain control): incremental approach

controls the strain and hits the target during a single cycle
Non-iterative: uses the settings entered for the first data point and then uses
previous cycle
Precision: iterates using the initial settings entered for each data point
θ(t+1)1
θ(t)1
Μ(t+1)1
Μ(t)1
Point 1
or cycle
TAINSTRUMENTS.COM
DHR and AR: Non-iterative Sampling
η
or
G’
Torque
Strain
Concern: How high does strain go at minimum

Temp viscosity. Does higher strain inhibit the cure
(break structure that begins to form as material
crosslinks). Does this affect time to minimum
viscosity or gel time?
Time
TAINSTRUMENTS.COM
ARES, ARES-G2 and DHR: Auto-Strain
Torque Upper torque limit
Strain
η
or
G’
Temp Lower
torque limit
Time
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Axial Force Control and Auto-strain
ARES-G2 DHR
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Using Auto Strain in a Temperature Ramp- Up
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Using Auto Strain in a Temperature Ramp- Down
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Thermoset Testing Considerations
Strain
Depends on sample
Verify the LVR in the cured state ( e.g. 0.05%)
Normal force control or auto-tension
Requires active to adjust for sample shrinkage and/or thermal
expansion in parallel plates
Temperature
Isothermal
Fast ramp + isotherm: the fastest ramp rate
Continuous ramp rate: 3 – 5 °C/min.
Frequency
Typically 1Hz (6.28 rad/s), 10 rad/s or higher
TAINSTRUMENTS.COM
Transient Tests
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Stress Relaxation Experiment
Strain is applied to sample instantaneously

(in principle) and held constant with time.
Stress is monitored as a function of time σ(t).
DHR and AR
Response time dependent on feedback loop
Strain
0
time
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0
time
Response of Classical Extremes
Hookean Solid Newtonian Fluid
stress for t>0 is 0

stress for
t>0
is constant
0 0
time time
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Response of ViscoElastic Material
Stress decreases with time

starting at some high value
and decreasing to zero.
0
time
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) = σ(t)/γγ
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Stress Relaxation: Material Response
Glassy Region
Transition
Region Rubbery Terminal
Plateau Region
Region
log time
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Stress Relaxation on PDMS
1.00E5
10000
1000
100
10
1
0.01 0.1 1 10 100
time (s)
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Determining 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.
γ = Kγ × θ (%γ = γ × 100)
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Stress Relaxation and Linear Region
Stress Relaxation of PDMS, Overlay

105
G(t)
200% strain
50% strain
10% strain
104
G(t) ( )
[Pa]
103
2
10
200% strain is outside the linear region

1
10
0.0 5.0 10.0 15.0 20.0 25.0 30.0
time [s]
TAINSTRUMENTS.COM
Creep Recovery Experiment
Stress is applied to sample instantaneously, t1, and held

constant for a specific period of time. The strain is
monitored as a function of time (γ(t) or ε(t))
The stress is reduced to zero, t2, and the strain is
monitored as a function of time (γ(t) or ε(t))
Native mode on AR (<1 msec)
Stress
t1 time t2
TAINSTRUMENTS.COM
t1 time t2
Response of Classical Extremes
Stain for t>t1 is constant Stain rate for t>t1 is constant

Strain for t >t2 is 0 Strain for t>t1 increase with time
Strain rate for t >t2 is 0
t1 time t2 t1 time t2
TAINSTRUMENTS.COM
Creep: Material Response
Rubbery
log Creep Compliance, Jc
Plateau
Region
Transition
Region
Glassy Region
Terminal Region
log time
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Creep Recovery: Response of Viscoelastic
Material
Creep σ > 0
σ/η
t1 t2
time
Strain rate decreases

with time in the creep
zone, until finally
reaching a steady state.
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Creep Recovery: Response of Viscoelastic
Material
Creep σ > 0 Recovery σ = 0 (after steady state)
σ/η
Recoverable
Strain
Unrecoverable
Strain
t1 t2
time
Strain rate decreases In the recovery zone, the viscoelastic

with time in the creep fluid recoils, eventually reaching a
zone, until finally equilibrium at some small total strain
reaching a steady state. relative to the strain at unloading.
TAINSTRUMENTS.COM
Creep σ > 0 Recovery σ = 0 (after steady state)
σ/η
Less Elastic
More Elastic
Creep Zone Recovery Zone
t1 t2
time
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Creep Recovery : Creep and Recoverable Compliance
more elastic
1/η
Je
Creep Zone Je = Equilibrium recoverable compliance
Jr(t)
J(t)
Recovery Zone
time time
Creep Compliance Recoverable Compliance
^() γ\ − γ t
J t = J t =
σ
a
The material property obtained from Where γu = Strain at unloading
Creep experiments: γ(t) = time dependent
Compliance = 1/Modulus (in a sense) recoverable strain
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Viscoelastic Ringing – DHR or AR
• The ringing oscillations can be rather short-lived and may not be apparent unless using log time scale.
• The sudden acceleration, together with the measurement system’s inertia, causes a strain overshoot. For
viscoelastic materials, this can result in viscoelastic ringing, where the material undergoes a damped
oscillation just like a bowl of Jell-o when bumped.
Creep ringing in rheometry or how to deal with oft-discarded data in step stress tests!
RH Ewoldt, GH McKinley - Rheol. Bull, 2007
TAINSTRUMENTS.COM
ARES-G2 Stress Control Loop
Inner
Motor Position Loop
σcmd(t) ∆σ(t) θ(t) θ(t)
PID motor
integrator
σ(t)
FRT sample
Linear response Material response
Stress is controlled by closing the loop around the sample

requires optimization of control PID parameters
Pretest to determine material’s response and PID Constants
TAINSTRUMENTS.COM
Programming Creep on an ARES-G2
Set up a pre-test and get the sample information into the loop
Stress Control Pre-test: frequency sweep within LVR
TAINSTRUMENTS.COM
ARES-G2 Stress Control Pretest
Pretest Frequency Sweep from 2 to 200 rad/s data analyzed in

software to optimize Motor loop control PID constants
LDPE melt
Freq. Sweep
T = 190°C
TAINSTRUMENTS.COM
Creep on HDPE Melt
3.5000
HDPE Creep Recovery at 200°C
3.0000
2.5000
2.0000
% strain
1.5000
1.0000
0.50000
0
0 2000.000 4000.000 6000.000 8000.000 10000.000
time global (s)
TAINSTRUMENTS.COM
Determining Stress For Creep Experiment
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.
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.
σ = Kσ x Μ
TAINSTRUMENTS.COM
Applications of Rheology
Polymers
TAINSTRUMENTS.COM
Purpose of a Rheological Measurement
Three main reasons for rheological testing:

Characterization
MW, MWD, formulation, state of flocculation, etc.
Process performance
Extrusion, blow molding, pumping, leveling, etc.
Product performance
Strength, use temperature, dimensional stability, settling
stability, etc.
TAINSTRUMENTS.COM
Polymer Testing and Rheology
Molecular Structure
MW and MWD
Chain Branching and Cross-linking
Interaction of Fillers with Matrix Polymer
Single or Multi-Phase Structure
Viscoelastic Properties
As a function of:
Strain Rate(frequency)
Strain Amplitude
Temperature
Processability & Product Performance
TAINSTRUMENTS.COM
Rheology Applications in Polymers
Material Property
Composites, Thermosets Viscosity, Gelation, Rate of Cure, Effect of
Fillers and Additives
Cured Laminates Glass Transition, Modulus Damping, impact
resistance, Creep, Stress Relaxation, Fiber
orientation, Thermal Stability
Thermoplastics Blends, Processing effects, stability of

molded parts, chemical effects
Elastomers Curing Characteristics, effect of fillers,

recovery after deformation
Coating, Adhesives Damping, correlations, rate of degree of
cure, glass transition temperature, modulus
TAINSTRUMENTS.COM
Most Common Experiments on Polymers
Oscillation/Dynamic
Time Sweep
Degradation studies, stability for subsequent testing
Strain Sweep – Find LVER
Frequency Sweep – G’, G”, η*
Sensitive to MW/MWD differences melt flow can not see
Temperature Ramp/Temperature Step
Transitions, viscosity changes
TTS Studies
Flow/Steady Shear
Viscosity vs. Shear Rate Plots
Find Zero Shear Viscosity
Low shear information is sensitive to MW/MWD differences melt flow
can not see
Creep and Recovery
Creep Compliance/Recoverable Compliance
Very sensitive to long chain tails
TAINSTRUMENTS.COM
Polymer Melt Thermal Stability
Polyester Temperature stability

275
Determines if properties
Temperature stability are changing over the
good
poor
time of testing
5
10 250
Degradation
Temperature T [°C]
Modulus G' [Pa]
Molecular weight
225 building
Crosslinking
4
200
10
175
-2 0 2 4 6 8 10 12 14 16 18
Time t [min]
Important, but often overlooked!
TAINSTRUMENTS.COM
Idealized Flow Curve – Polymer Melts
Power Law Region
First Newtonian Plateau

η0 = Zero Shear Viscosity
η0 = K x MW 3.4
Extend Range
log η
with Time-
Temperature
Superposition (TTS)
Measure in Flow Mode & Cox-Merz
Extend Range Second Newtonian

with Oscillation Plateau
& Cox-Merz
Molecular Structure Compression Molding Extrusion Blow and Injection Molding
1.00E-5 1.00E-4 1.00E-3 0.0100 0.100 1.00 10.00 100.00 1000.00 1.00E4 1.00E5
shear rate (1/s)

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Melt Rheology: MW Effect on Zero Shear Viscosity
Sensitive to Molecular Weight, MW

For Low MW (no Entanglements) η0 is proportional to MW
For MW > Critical MWc, η0 is proportional to MW3.4
log ηo
3.4
MWc
η0 = K⋅⋅Mw η0 = K⋅⋅Mw 3.4

log MW
Ref. Graessley, Physical Properties of Polymers, ACS, c 1984.
TAINSTRUMENTS.COM
Influence of MW on Viscosity
The zero shear viscosity increases with increasing molecular weight.

TTS is applied to obtain the extended frequency range.
7
10 The high frequency
SBR Mw [g/mol]
130 000 behavior
10
6
230 000 (slope -1) is
320 000 independent of the
Viscosity η* [Pa s]
430 000 molecular weight

5
10
Zero Shear Viscosityηo [Pa s]
4
10 Zero Shear
Viscosity
6
10
3
10 Slope 3.08 +/- 0.39
5
10
100000
2
10 Molecilar weight M w [Daltons]
-4 -3 -2 -1 0 1 2 3 4 5
10 10 10 10 10 10 10 10 10 10
Frequency ω aT [rad/s]
TAINSTRUMENTS.COM
Influence of MWD on Viscosity
A Polymer with a broad MWD exhibits non-Newtonian flow

at a lower rate of shear than a polymer with the same η0,
but has a narrow MWD.
Narrow MWD
Broad MWD
Log Shear Rate (1/s)

TAINSTRUMENTS.COM
Influence of MW on G‘ and G“
The G‘ and G‘‘ curves are shifted to lower frequency

with increasing molecular weight.
6
10
5
10
Modulus G', G'' [Pa]
4
10
SBR M w [g/mol]
3 G' 130 000
10 G'' 130 000
G' 430 000
2 G'' 430 000
10 G' 230 000
G'' 230 000
1
10
-4 -3 -2 -1 0 1 2 3 4 5
10 10 10 10 10 10 10 10 10 10
Freq ω [rad/s]
TAINSTRUMENTS.COM
Influence of MWD on G‘ and G“
6
10
Modulus G', G'' [Pa]
5
10
The maximum in G‘‘ is a good
indicator of the broadness of the
4
10 distribution
SBR polymer melt
G' 310 000 broad
3 G" 310 000 broad
10 G' 320 000 narrow
G" 320 000 narrow
Narrow
-3 -2 -1 0 1 2 3 4
10 10 10 10 10 10 10 10 Broad
Frequency ωaT [rad/s]
Higher crossover frequency : lower Mw

Higher crossover Modulus: narrower MWD
(note also the slope of G” at low
frequencies – narrow MWD steeper slope)
TAINSTRUMENTS.COM
High MW Contributions
400,000 g/mol PS 400,000 g/mol PS

400,000 g/mol PS
+ 1% 12,000,000 g/mol + 4% 12,000,000 g/mol
Macosko, TA Instruments Users’ Meeting, 2015 TAINSTRUMENTS.COM

Importance of Verifying Thermal Stability
Good thermal stability

one crossover point,
η* plateaus at low ω
Poor thermal stability

multiple crossover points
η* continues to increase
over time
Time Sweep can verify if
the sample is unstable
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Surface Defects during Pipe Extrusion
HDPE pipe surface defects
o Surface roughness
T = 220 C
5 5
correlates with G‘ or
10 10
elasticity → broader
Complex viscosity η* [Pa s]

MWD or tiny
amounts of a high
Modulus G' [Pa]
MW component
4 4
10 10
G' rough surface

3 G' smooth surface 3
10 10
η* rough surface
η* smooth surface
0.1 1 10 100
Frequency ω [rad/s]
Blue-labled sample shows a rough surface after extrusion

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Tack and Peel of Adhesives
Tack and Peel performance of a PSA
Bond strength is
obained from peel good tack and peel
(fast) and tack Bad tack and peel
Storage Modulus G' [Pa]

(slow) tests
4
10
It can be related to
the viscoelastic
properties at peel
different
frequencies 3
10
tack
0.1 1 10
Frequency ω [rad/s]
Tack and peel have to be balanced for an ideal adhesive

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Dried Adhesives- Tack Test
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Creep and Recovery with Increasing Stress
LDPE Melt creep recovery
Recoverable Compliance Jr(t) [1/Pa]

-1 -1
10 LDPE Melt 10
Non linear effects
10 Pa o
T=140 C can be detected in
50 Pa
100 Pa slope 1 recovery before
Compliance J(t) [1/Pa]
-2 -2
10 10
500 Pa they are seen in the
1000 Pa increasing creep (viscosity
5000 Pa stress dominates)
-3 -3
10 10
-4 -4
10 10
-5 -5
10 10
0.1 1 10 100 1000
Time t [s]
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Effect of Filler on Melt Viscosity
Neat and Filled LDPE
10
7
o
Fillers increase the
Temperature 180 C melt viscosity
LDPE filled
6
10 LDPE neat
Due to inter-particle
Viscosity η(γ) [Pa s]
5
interactions, the
10
. non-Newtonian
4
range is extended to
10 low shear rates and
the zero shear
3
10 viscosity increases
dramatically
2
10
1E-5 1E-4 1E-3 0.01 0.1 1 10 100 1000 10000
.
Shear rate γ [1/s]
The material has a yield, when rate and viscosity are

inverse proportional at low rate.
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Extensional Viscosity Measurements
Fix drum connected to transducer
Rotating drum connected to the motor:

rotates around its axis
rotates around axis of fixed drum
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Why is Elongation Viscosity Important?
Application to processing: many processing flows are

elongation flows - testing as close as possible to
processing conditions (spinning, coating, spraying)
Relation to material structure: non linear elongation

flow is more sensitive for some structure elements
than shear flows (branching, polymer architecture)
Testing of constitutive equations: elongation results in

addition to shear data provide a more general picture
for developing material equations
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LLDPE (Low branching)
106
105
104
)
]
s
-
a
LLDPE, T = 130 o C
( P
e [
η
0 . 01 s -1
0.
103
0 . 1 s -1
0.
1 s -1
102 3 s -1
10 s -1
[Steady Shear Viscosity * 3]
101
10-2 10-1 100 101 102 103
Warning: Overlay units don't match timee [s]
TAINSTRUMENTS.COM
LDPE (High branching)
106
105
LDPE, T 150 o C
104
)
]
s 0.
0 . 003 s - 1
0.
0 . 01 s - 1
-
a
( P
e [
0.
0 . 03 s - 1
η
103
0.
0.1 s- 1
0.
0.3 s- 1
1 s-1
102 3 s-1
10 s - 1
30 s - 1
[ Steady Shear Viscosity * 3]
101
10-2 10-1 100 101 102 103
Warning: Overlay units don't match, Frequency timee [s]
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Thermosetting Polymers
Thermosetting polymers are perhaps the

most challenging samples to analyze on
rheometers as they challenge all instrument
specifications both high and low.
The change in modulus as a sample cures

can be as large as 7-8 decades and
change can occur very rapidly.
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Thermosets Analysis
Monitor the curing process

Viscosity change as function of time or temperature
Gel time or temperature
Test methods for monitoring curing
Temperature ramp
Isothermal time sweep
Combination profile to mimic process
Analyze cured material’s mechanical properties (G’,
G”, tan δ , Tg etc.)
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Structural Development During Curing
Gel point
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At the Gel Point
Molecular weight Mw goes to infinity

System loses solubility
Zero shear viscosity goes to infinity
Equilibrium Modulus is zero and starts to rise
to a finite number beyond the gel point
Note: For most applications, gel point can be

considered as when G’ = G” and tan δ = 1
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Curing Analysis: Isothermal Curing
TA Instruments
1000000 G' 1000000
5 min
100000 100000
10000 G" 10000

G' (Pa)
G'' (Pa)
1000 1000
Gel Point: G' = G"
t = 330 s
100.0 100.0
10.00 10.00
1.000 1.000
0 200.0 400.0 600.0 800.0 1000 1200
time (s)
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Thermoset Using a Temperature Ramp
Surface Master 905
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At the Gel Point Continued…
• The process of viscosity increasing takes place in two

stages: the gelation process (frequency independent) and
vitrification (related to the network Tg relative to cure
temperature and is frequency dependent).
• When you look at an isothermal cure at a constant
frequency the modulus crossover point has both the
information of gelation and vitrification.
To avoid this, run multiple isothermal runs at different
frequencies and plot the cross over in tan delta. This is the
frequency independent gel point.
Alternatively, use a single mutliwave test
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Gel Point using Tan Delta
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Isothermal Curing
130°C
140°C 135°C 120°C
125°C
145°C
G’ (MPa)
Tire Compound:
Effect of Curing Temperature
Time (min)
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UV Light Guide Curing Accessory
Collimated light and mirror assembly insure uniform irradiance

Maximum intensity at plate 300 mW/cm2
Broad range spectrum with main peak at 365 nm
Cover with nitrogen purge ports
Optional disposable acrylic plates
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UV Cure Profile Changes with Temperature
up to 50 points
per second
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Polymer Structure-Property Characterization
Glass transition
Secondary transitions
Crystallinity
Molecular weight/cross-linking
Phase separation (polymer blends, copolymers,...)
Composites
Aging (physical and chemical)
Curing of networks
Orientation
Effect of additives
Reference: Turi, Edith, A, Thermal Characterization of Polymeric Materials, Second Edition, Volume I., Academic Press, Brooklyn, New
York, P. 489.
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How to Measure Glass Transition
G' Onset: Occurs at lowest temperature - Relates to

mechanical failure
G" Peak: Occurs at middle temperature - more closely

related to the physical property changes attributed to the
glass transition in plastics. It reflects molecular processes -
agrees with the idea of Tg as the temperature at the onset
of segmental motion.
tan δ Peak: Occurs at highest temperature - used
historically in literature - a good measure of the "leatherlike"
midpoint between the glassy and rubbery states - height
and shape change systematically with amorphous content.
Reference: Turi, Edith, A, Thermal Characterization of Polymeric Materials, Second Edition, Volume I., Academic Press, Brooklyn, New York, P. 980.
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Pasta Cooked in Torsion Immersion
Allows samples to be
Addition of Water
characterized while fully 1.000E10 100.0
immersed in a temperature
controlled fluid using Peltier Isotherm with 90.0
Concentric Cylinder Jacket water at 22 °C
1.000E9
Isotherm
Track changes in mechanical with water
80.0
properties such as swelling or at 95 °C
plasticizing
70.0
1.000E8
temperature (°C)
G’G'(Pa)
(Pa)
Temperature 60.0
ramp to 95 °C
1.000E7
50.0
40.0
1.000E6
30.0
1.000E5 20.0
0 10.0 20.0 30.0 40.0 50.0 60.0
time global (min)
time (min)
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Testing Solids on a Rheometer
Torsion and DMA geometries allow solid samples to be

characterized in a temperature controlled environment
– DMA functionality is standard with ARES G2 and optional DHR
E = 2G(1 + ν) ν : Poisson’s ratio

Modulus: G’, G”, G* Modulus: E’, E”, E*
Rectangular and DMA 3-point bending and tension

cylindrical torsion (Cantilever not shown)
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Glass Transition- ABS
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The Glass & Secondary Transitions
Glass Transition - Cooperative motion among a large number of

chain segments, including those from neighboring polymer chains
Secondary Transitions
Local main-chain motion - intramolecular rotational motion of
main chain segments four to six atoms in length
Side group motion with some cooperative motion from the main
chain
Internal motion within a side group without interference from
side group
Motion of or within a small molecule or diluent dissolved in the
polymer (e.g. plasticizer)
Reference: Turi, Edith, A, Thermal Characterization of Polymeric Materials, Second Edition, Volume I.,
Academic Press, Brooklyn, New York, P. 487.
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Polycarbonate in Torsion
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Crystallinity, Molecular Weight, and Crosslinking
Increasing
Crystallinity
log Modulus
Amorphous Crystalline
3 decade drop Cross-linked

in modulus at Tg
Increasing MW
Tm
Temperature
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Applications of Rheology
Structured Fluids
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Structured Fluids
Multiphase systems consisting of a dispersed phase

(solid, fluid, gas) in surrounding fluid phase
Examples are: Properties:

Paints Yield Stress
Coatings Non-Newtonian
Inks Viscous Behavior
Personal Care Products Thixotropy
Cosmetics Elasticity
Foods
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Idealized Flow Curve
What shear rate?
4) Chewing, swallowing 8) Spraying and brushing

1) Sedimentation
5) Dip coating 9) Rubbing
2) Leveling, Sagging
6) Mixing, stirring 10) Milling pigments
3) Draining under gravity
log η
7) Pipe flow 11) High Speed coating
4
5
6 8 9
1 2 3 7 10 11
1.00E-5 1.00E-4 1.00E-3 0.0100 0.100 1.00 10.00 100.00 1000.00 1.00E4 1.00E5 1.00E6
shear rate (1/s)

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General Viscosity Curve for Suspensions
This viscosity is often called

the Zero Shear Viscosity, η0,
or the Newtonian Viscosity
First
Newtonian
Plateau Possible
log η Increase in
Second Viscosity
Power-Law Newtonian
Shear Thinning Plateau
σ ∝ m or, equivalently, η ∝ m-1

m is usually 0.15 to 0.6
log
Reference:Barnes, H.A., Hutton, J.F., and Walters, K., An Introduction to Rheology,
Elsevier Science B.V., 1989. ISBN 0-444-87469-0
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Reason for Shape of General Flow Curve
Brownian diffusion
randomizes
Shear field aligns

particles along
Turbulent flow pushes
log η streamlines
particles out of
alignment, destroying
order and causing
increase in viscosity
(shear thickening)
Shear thinning Shear thickening
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Closing the Gap
Linear or Exponential speed profile after reaching ‘Closure Distance’

Normal Force set not to exceed a certain value after reaching the user
defined ‘Closure Distance’
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Comparison of Linear and Exponential Closing
250
Exponential Close
200
G' (Pa)
150
Fast Linear Close
100
50
0
0 200 400 600 800 1000
Time (s)
Lowering the gap can introduce shear, breaking down weakly structured samples
Reducing the gap closure speed can minimize this effect
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Using Pre-Shearing
Monitor the viscosity signal during the pre-shear to

determine if the rate and duration are appropriate
If the viscosity is increasing during the pre-shear, the sample is
rebuilding. The pre-shear should be higher than the shear
introduced during loading to erase sample loading history
The viscosity should decrease and then level off
Typical Pre-Shear: 1- 100 sec-1, 30-60 seconds
Use an amplitude sweep to determine what strain to use
for time sweep
A high strain will break down the sample, and not allow rebuilding
A low strain will give a weak signal
Based on the Time Sweep, determine an appropriate
equilibration time for that sample
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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.)
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Structured Fluid: Pre-testing
1. 2. 3.
Three consecutive time sweeps:

Time sweep within LVR (check if loading destroyed structure)
Time sweep at large strain
Time sweep back to LVR (check structure rebuild)
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Time Sweeps- Hand Cream
Storage Application At Rest
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Yield Stress
Structured fluids exhibit yield-like behavior, changing from ‘solid-like’ to

readily flowing fluid when a critical stress is exceeded. Rheological
modifiers are often used to control the yield behavior of fluids.
There are multiple methods to measure Yield stress. The apparent

yield stress measured is not a single value, as it will vary depending
on experimental conditions.
Why modify the yield behavior?

to avoid sedimentation and increase the shelf live
to reduce flow under gravity
to stabilize a fluid against vibration
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Yield Stress in a Flow Stress Ramp
Stress is ramped linearly from 0 to a value above Yield Stress and the stress at
viscosity maximum can be recorded as Yield Stress
The measured yield value will depend on the rate at which the stress is increased.
The faster the rate of stress increase, the higher the measured yield value
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Yield Stress in a Flow Stress Ramp
Yield Stress
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Yield Stress: Flow Sweep Down - Rate Control
When the Yield Stress is small, a flow rate sweep from high
to low shear rate is preferred
Eliminates start-up effects for
more accurate measurements
slope: -0.995
Initial high shear rate acts as a
pre-shear, erasing loading effects
Steady State sensing allows the

sample time to rebuild
The plateau in shear stress is a

measure of the yield stress.
At the plateau, Viscosity vs.

Shear Rate will have a slope of -1
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Yield: Stress/Strain Sweep Method
1000 Perform strain or stress

Sun Block Lotion
sweep in oscillation
Yield stress is the on set of

G’ curve. It is the critical
G' (Pa)
stress at which irreversible

Onset point
osc. stress: 1.477 Pa
G': 346.6 Pa
plastic deformation occurs.
End condition: Finished normally
100.0
0.01000 0.1000 1.000 10.00
osc. stress (Pa)
Yield stress of a sun block lotion
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Viscosity Ranges of Paints/Coatings
Low shear viscosity 10-3 to 1 s-1

leveling, sagging, sedimentation
Medium shear viscosity10-103 s-1

mixing, pumping and pouring
High shear viscosity 103 - 106 s-1

brushing, rolling spraying
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Viscosity Ranges of Paints/Coatings
10
4 At Rest Processing Performance
3
10
LSV MSV HSV
2
10
Roling
Viscosity h [Pas]
1
Brushing
10 Spraying
0
10
Mixing
-1
10 Leveling Pumping
Sagging Consistency
-2
10
Sedimentation Appearence
-3
10
0.1 1 10 100 1000 10000 100000
shear rate g [1/s]
The two coatings show the same consistency after formulation,

but they exhibit very different application performance
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Thixotropy
The thixotropy characterizes the time dependence of

reversible structure changes in complex fluids. The
control of thixotropy is important to control:
process conditions for example to avoid structure build up in pipes
at low pumping rates i.e. rest periods, etc....
sagging and leveling and the related gloss of paints and coatings,
etc..
Sag Leveling
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Thixotropic Loop Test
Stress is ramped up linearly,

and then back down, over the
same duration
In a thixotropic material, there will be a hysterisis between the two curves
The further the up ramp and down ramp curves differ, the larger the area
between the curves, the higher the thixotropy of the material.
See also AAN 016 – Structured Fluids
TAINSTRUMENTS.COM
Structure Recovery
after preshear η*
Structure build up
Modulus G', G'' [Pa]; Viscosity η* [Pas]

G'
G''
Pre-shear the sample 2
10
G'oo
to break down
structure. Then
monitor the increase
of the modulus or
complex viscosity as Frequency 1Hz
G'o strain 2%
function of time. -1
preshear 10s at 60 s
0 20 40 60 80 100 120
time t min]
b Q A = b′d + (b′e − b′d )(1 − f G/I ) τ = characteristic recovery time
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Time Sweep after Pre-Shearing
b Q A = b′d + (b′e − b′d )(1 − f G/I )

a = G’ at time zero (t0)
b = G’ at infinite time (t∞)
c = characteristic recovery time (τ)
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Thixotropic Index & Recovery Time
The non-sagging formula (with additive) has both a shorter recovery

time and a higher final recovered viscosity (or storage modulus), and
the recovery parameter takes both of these into account to predict
significantly better sag resistance.
The ratio η(∞) /t, is the recovery parameter (a true thixotropic index),
and has been found to correlate well to thixotropy-related properties
such as sag resistance and air entrainment.
Rheology in coatings, principles and methods

RR Eley - Encyclopedia of Analytical Chemistry, 2000 - Wiley Online Library
TAINSTRUMENTS.COM
Case Study of 4 Paints
100.0
Paint A
10.00
Paint B
viscosity (Pa.s)
Paint C
1.000 Paint D
0.1000
0.01000 0.1000 1.000 10.00 100.0
shear rate (1/s)
TAINSTRUMENTS.COM
120.0
Thixotropy (Pa/s):
Paint A = 657.0
Paint B = 436.5
100.0
Paint C = 254.0
Paint D = 120.3
80.00
Paint A
shear stress (Pa)
60.00
Paint B
40.00
Paint C
20.00
Paint D
0
0 10.00 20.00 30.00 40.00 50.00 60.00 70.00 80.00 90.00 100.0
shear rate (1/s)
TAINSTRUMENTS.COM
15.00
Paint A
12.50
10.00
G' (Pa)
7.500
5.000 Paint B
2.500
Paint C
Paint D
0
0 100.0 200.0 300.0 400.0 500.0 600.0 700.0 800.0 900.0
time (s)
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Paint A Paint B
Paint C Paint D
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Antiperspirant/Deodorant
Roll-ons: Rheology and end-use performance

The viscosity has to be balanced to provide the correct viscosity at a
given shear rate
viscosity
storage
application
shear rate
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Antiperspirant/Deodorant
Sticks: Rheology and process performance
use small particles to reduce sedimentation speed
add rheological modifier like clay to stabilize the suspension

and keep the particles in suspension
1E+08
x x x x x x
x
1E+07 x The temperature
x
Modulus G' [Pa]
1E+06 x dependence of the

modulus governs the
1E+05
x behavior during the
1E+04 x application to the skin
1E+03
0 10 20 30 40 50 60 70
Temperature [C]
TAINSTRUMENTS.COM
Elasticity: Oscillation Frequency Sweep
Cosmetic lotion
Many dispersion exhibit
2.0
solid like behavior at rest
Modulus G', G'' [Pa]; Viscosity η* [Pa s]
3
10
1.5
The frequency
1.0
dependence and the
absolute value of tan δ
tan δ
2
10 0.5
correlate with long time
0.0 stability
complex viscosity
G' -0.5
1
10 G''
tan δ
-1.0
0.1 1 10 100
frequency ω [rad/s]
Note: strain amplitude has to be in the linear region
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Foam Handwash Strain Sweep: Din vs Vane Rotor
DIN Vane
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TRIOS Help Menu
Browse the contents list or

search using the search tab.
Access to Getting Started

Guides also found through
the help menu.
TAINSTRUMENTS.COM
Instructional Videos
From www.tainstruments.com click on Videos, Support or Training
Select Videos for TA Tech Tips, Webinars and Quick Start Courses
See also: https://www.youtube.com/user/TATechTips
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Instructional Video Resources
Quickstart e-Training Courses Strategies for Better Data - Rheology
TAINSTRUMENTS.COM
Need Assistance?
Check the online manuals and error help.

Contact the TA Instruments Hotline
Phone: 302-427-4070 M-F 8-4:30 EST
Select Thermal , Rheology or Microcalorimetry Support
Email: [email protected] or
[email protected] or
[email protected]
Call your local Technical or Service Representative
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For instructional videos go to: www.youtube.com/user/TATechTips
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Thank You
The World Leader in Thermal Analysis,

Rheology, and Microcalorimetry
TAINSTRUMENTS.COM
Appendix 1: Time Temperature
Superposition (TTS)
TAINSTRUMENTS.COM
Time and Temperature Relationship
(E' or G') (E' or G')

(E" or G") (E" or G")
log Frequency Temperature

Linear viscoelastic properties are both time-dependent and
temperature-dependent
Some materials show a time dependence that is proportional to the
temperature dependence
Decreasing temperature has the same effect on viscoelastic
properties as increasing the frequency
For such materials, changes in temperature can be used to “re-scale”
time, and predict behavior over time scales not easily measured
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Time Temperature Superpositioning Benefits
TTS can be used to extend the frequency beyond the

instrument’s range
Creep TTS or Stress Relaxation TTS can predict
behavior over longer times than can be practically
measured
Can be applied to amorphous, non modified polymers
Material must be thermo-rheological simple
One in which all relaxations times shift with the same shift factor aT
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When Not to Use TTS
If crystallinity is present, especially if any melting

occurs in the temperature range of interest
The structure changes with temperature
Cross linking, decomposition, etc.
Material is a block copolymer (TTS may work within a limited
temperature range)
Material is a composite of different polymers
Viscoelastic mechanisms other than configuration changes of the
polymer backbone
e.g. side-group motions, especially near the Tg
Dilute polymer solutions
Dispersions (wide frequency range)
Sol-gel transition
TAINSTRUMENTS.COM
Guidelines for TTS
Decide first on the Reference Temperature: T0. What is the

use temperature?
If you want to obtain information at higher frequencies or

shorter times, you will need to conduct frequency (stress
relaxation or creep) scans at temperatures lower than T0.
If you want to obtain information at lower frequencies or

longer times, you will need to test at temperatures higher
than T0.
Good idea to scan material over temperature range at

single frequency to get an idea of modulus-temperature
and transition behavior.
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TTS Shifting
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TTS Shifting
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TTS Shifting
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TTS Shifting
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TTS Shifting
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TTS Shifting
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TTS Shifting
aT=140
aT=150
aT=160
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Shift Factors aT vs Temperature
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Shift Factors: WLF Equation
Master Curves can be generated using shift factors

derived from the Williams, Landel, Ferry (WLF)
equation
log aT= -c1(T-T0)/c2+(T-T0)
aT = temperature shift factor
T0 = reference temperature
c1 and c2 = constants from curve fitting
Generally, c1=17.44 & c2=51.6 when T0 = Tg
TAINSTRUMENTS.COM
When not to use the WLF Equation
Sometimes you shouldn’t use the WLF equation (even if it

appears to work)
If T > Tg+100°C
If T < Tg and polymer is not elastomeric
If temperature range is small, then c1 & c2 cannot be calculated
precisely
In these cases, the Arrhenius form is usually better

ln aT = (Ea/R)(1/T-1/T0)
aT = temperature shift factor

Ea = Apparent activation energy
T0 = reference temperature
T = absolute temperature
R = gas constant
Ea = activation energy
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Verify Data for TTS
Polystryene
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Verify Data for TTS
Polystryene
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References for TTS
1) Ward, I.M. and Hadley, D.W., "Mechanical Properties of Solid Polymers",

Wiley, 1993, Chapter 6.
2) Ferry, J.D., "Viscoelastic Properties of Polymers", Wiley, 1970, Chapter 11.
3) Plazek, D.J., "Oh, Thermorheological Simplicity, wherefore art thou?"

Journal of Rheology, vol 40, 1996, p987.
4) Lesueur, D., Gerard, J-F., Claudy, P., Letoffe, J-M. and Planche, D., "A
structure related model to describe asphalt linear viscoelasticity", Journal of
Rheology, vol 40, 1996, p813.
TAINSTRUMENTS.COM
Appendix 2: Software Screen Shots
TRIOS
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DHR Peak Hold: Constant Shear Rate vs. Time
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ARES-G2: Stress Growth Test (Step Rate)
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Continuous Ramp
Control variables:
Shear rate
Velocity
Torque
Shear stress
Thixotropic loop be done by adding another ramp step
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Thixotropic loop
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ARES G2: Stress Ramp: Stress Control Pre-test
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ARES G2: Stress Ramp (Thixotropic Loop)
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DHR and ARES G2: Steady State Flow
Control variables:
Shear rate
Velocity
Torque
Shear stress
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DHR and ARES G2: Flow Temp Ramp
To minimize thermal
lag, the ramp rate
should be slow.
1-5°C/min.
Control variables:
Shear rate
Velocity
Torque
Shear stress
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DHR: Strain/Stress Sweeps
Control variables:
Osc torque
Osc stress
Displacement
% strain
Strain
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ARES G2: Strain Sweep
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DHR: Time Sweep
Pre-shear can be setup

by adding a
“conditioning” step before
the time sweep.
The strain needs to be in the LVR
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ARES G2: Time Sweep
Pre-shear step
Structure Recovery
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Fast Data Sampling Option in Time Sweep
Strain control mode Stress control mode
Fast data acquisition is used for monitoring fast changing

reactions such as UV initiated curing
The sampling rate for this mode is twice the functional oscillation
frequency up to 25Hz.
The fastest sampling rate is 50 points /sec.
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Frequency Sweep
Control variables:
Osc torque
Osc stress
Displacement
% strain
Strain
Common frequency range: 0.1 – 100 rad/s.

Low frequency takes long time
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
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ARES G2:Frequency Sweep (Strain Control)
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DHR: Temperature Sweep
Control variables:
Osc torque
Osc stress
Displacement
% strain
Strain
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DHR: Temperature Ramp
To minimize thermal
lag, recommend
using slow ramp rate
e.g. 1-5°C/min.
The strain needs Control variables:

to be in the LVR Osc torque
Osc stress
Displacement
% strain
Strain
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DHR: Axial Force Control

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ARES G2: Temp Step
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ARES G2: Temp Ramp
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ARES G2: Axial force control and auto-strain
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DHR: Stress Relaxation
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ARES G2: Stress Relaxation
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DHR: Creep Recovery
Creep Recovery
Rule of thumb: recovery time is 2-3 times longer than creep time
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ARES G2: Creep
Requires measured
modulus to start feed
back loop
Motor and transducer work in a feedback loop
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Programming Creep on a ARES G2
Set up a pre-test and get the sample information into the loop
Stress Control Pre-test: frequency sweep within LVR
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ARES G2: Creep - Recovery
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Appendix 3: Software Screen Shots
Rheology Advantage
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AR: Peak Hold
Control variables:
Shear rate
Velocity
Torque
Shear stress
Multiple rate can be done by adding more peak hold steps
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AR: Continuous Ramp
Control variables:
Shear rate
Velocity
Torque
Shear stress
Thixotropic loop be done by adding another ramp step

Or go through the template
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AR: Continuous Ramp
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AR: Stepped Flow
Control variables:
Shear rate
Velocity
Torque
Shear stress
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AR: Steady State Flow
Control variables:
Shear rate
Velocity
Torque
Shear stress
During the test, the dependent 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 dependent variable is recorded over the Sample period.
When consecutive average values (Consecutive within tolerance) are within the
Percentage 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.
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AR: Flow Temp Ramp
To minimize thermal
lag, the ramp rate
should be slow.
1-5°C/min.
Control variables:
Shear rate
Velocity
Torque
Shear stress
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AR: Stress Sweep
Variables:
Stress
Torque
For running an unknown sample, it is recommended to sweep torque instead of

stress. Because stress is geometry dependent
The starting torque can be from the lowest of the instrument specification
The maximum torque is sample dependent. You can setup a high number and
manually stop the test when it gets outside the LVR.
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AR: Time Sweep
Control variables:
Osc torque
Osc stress
Displacement
% strain
Strain
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AR: 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.)
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AR: Frequency Sweep
Control variables:
Osc torque
Osc stress
Displacement
% strain
Strain
Common frequency range: 0.1 – 100 rad/s.

Low frequency takes long time
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
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AR: Temp Sweep
Control variables:
Osc torque
Osc stress
Displacement
% strain
Strain
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AR: Temp Ramp
To minimize thermal
lag, recommend
using slow ramp rate
e.g. 1-5°C/min.
Control variables:
Osc torque
Osc stress
Displacement
% strain
Strain
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AR: Normal Force Control
During a test
Before starting a test

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AR: Stress Relaxation
Motor and transducer work in a feedback loop
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AR: Creep Recovery
Rule of thumb: recovery time is 2-3 times longer than creep time
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AR : Steady State Algorithm Creep
Default
values
shown
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.
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Appendix 4: Rheometer Calibrations
DHR and AR
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DHR – Calibration Options
Inertia (Service)
Rotational Mapping
Oscillation Mapping (recommended for interfacial measurements)
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DHR – Inertia Calibration
Go to the Calibration tab and select Instrument

Make sure there is no geometry installed and then click calibrate
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DHR – Geometry Calibration
Inertia
Friction
Gap Temperature
Compensation
Rotational Mapping
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TA Tech Tip – Geometry Calibrations
Videos available at www.tainstruments.com under the Videos tab or on the TA tech

tip channel of YouTube™ (http://www.youtube.com/user/TATechTips)
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Rheometer Calibrations
ARES-G2
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ARES-G2 – Calibration Options
Temperature Offsets
Phase Angle (Service)
Measure Gap Temperature
Compensation
Transducer
Compliance and Inertia (from table)
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ARES-G2 – Transducer Calibration
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ARES-G2 – Geometry Calibration

Enter manually or run calibration
Compliance and Inertia

(from table in Help menu)
Geometry Constants
Calculated based on dimensions
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Geometry Inertia & Compliance- Help Menu
What if the online table does not list a compliance value for my specific geometry?
Use the compliance value for a geometry of the same/similar dimension, type, and
material.
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ARES-G2 - Gap Temperature Compensation
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General Rheometer Maintenance
Air Supply
Dry particulate-free air (dew point -40 °C)
Check filters/regulators on a periodic basis to ensure proper
pressure, free of moisture/oil/dirt buildup.
If air must be turned off, then make sure that the bearing lock is
fastened
NOTE: Do not rotate drive-shaft if air supply is OFF!
Location
Isolate the instrument from vibrations with a marble table or
Sorbathane pads.
Drafts from fume hoods or HVAC systems and vibrations from
adjacent equipment can contribute noise to measurements,
particularly in the low torque regime. Use a Draft Shield to
isolate instrument from drafts.
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General Rheometer Maintenance - Peltier
Circulator Maintenance
Proper operation of a fluid circulator is vital for correct
and efficient operation of Peltier-based temperature
control devices.
Check fluid levels and add anti-fungal additive regularly.

Note: if operating circulator below 5°C then it is
recommended to fill the circulator with a mixture or
material with a lower freezing point than water to
prevent permanent circulator damage.
Example: add ~20% v/v ethanol to water
Keep it clean!
Flush and clean circulator, Peltier system, and tubing at
first sight of contamination.
When not in use, it is strongly recommended to

deactivate the Peltier device and turn off the circulator.
TAINSTRUMENTS.COM
Geometry Information – Estimated Min and Max Shear Rates
Sample Max Shear Rate Min Shear Rate

Geometry Diameter (mm) Degree Gap (micron)
Volume (mL) (approx) 1/s (approx) 1/s
0 1000 0.05 1.20E+03 4.00E-07
0 500 0.03
0.5 18 1.17E-03
8 1 28 2.34E-03
2 52 4.68E-03
4 104 9.37E-03
0 1000 0.31 3.00E+03 1.00E-06
0.5 18 0.02 3.44E+04 1.15E-05
20 1 28 0.04 1.72E+04 5.73E-06
2 52 0.07 8.60E+03 2.87E-06
4 104 0.15 4.30E+03 1.43E-06
0 1000 0.49 3.75E+03 1.25E-06
Parallel Plate 0.5 18 0.04
and Cone and 25 1 28 0.07
Plate 2 52 0.14
4 104 0.29
0 1000 1.26 6.00E+03 2.00E-06
0.5 18 0.15 3.44E+04 1.15E-05
40 1 28 0.29 1.72E+04 5.73E-06
2 52 0.59 8.60E+03 2.87E-06
4 104 1.17 4.30E+03 1.43E-06
0 1000 2.83 9.00E+03 3.00E-06
0 500 1.41
0.5 18 0.49 3.44E+04 1.15E-05
60 1 28 0.99 1.72E+04 5.73E-06
2 52 1.97 8.60E+03 2.87E-06
4 104 3.95 4.30E+03 1.43E-06
Conical Din Rotor 19.6 4.36E+03 1.45E-06
Recessed End 6.65 4.36E+03 1.45E-06
Concentric
Double Wall 11.65 1.59E+04 5.31E-06
Cylinder
Pressure Cell 9.5
Standard Vane 28.72
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Basic Parameters and Units
Stress = Force /Area [Pa, or dyne/cm2 ]

σ = shear stress
Strain = Geometric Shape Change [no units]
γ = shear strain
Strain Rate or Shear Rate = Velocity Gradient [1/s]
γ = shear strain rate
Modulus = Stress / Strain [Pa or dyne/cm2 ]
G = Shear Modulus
Compliance = Strain / Stress [1/Pa or cm2/dyne]
Typically denoted by J
Viscosity = Stress /Strain Rate [Pa·s or Poise]
Denoted by η
S.I. units 10 = c.g.s. units
X
TAINSTRUMENTS.COM
Common Symbols used in Rheology
Greek Latin
aT: Temperature shift factor
γ (gamma): Shear Strain
B: Bulk Creep Compliance
(gamma dot): Shear Rate
D: Tensile Compliance
δ (delta): Phase Angle
E: Young’s (Tensile) Modulus
ε (epsilon): Elongational Strain
E’: Tensile Storage Modulus
f (epsilon dot): Elongational Strain Rate
E”: Tensile Loss Modulus
η (eta): Shear Viscosity
G: Shear Modulus
ηE (eta E): Elongational Viscosity
G’: Shear Storage Modulus
η* (eta star): Complex Viscosity
G”: Shear Loss Modulus
µ (mu): Microns
E* or G*: Complex Modulus
ν (nu): Frequency (Hz)
J: Shear Compliance
ρ (rho): Density
K: Bulk Modulus (or also Stiffness)
σ (sigma): Shear Stress
N1: Normal Force in Steady Flow
τ (tau): Elongational Stress
T: Temperature
ω (omega): Angular Frequency (rad/sec)
Tg: Glass Transition Temperature
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Sample Preparation
Polymers
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Know Your Sample – Polymers
Polymer samples come in different forms (e.g. powder, flakes,

pellets) and can be sensitive to environmental conditions
Careful sample preparation techniques are required to prepare
good test specimens for reproducible testing
Molding a sample
Handling powders, flakes
Controling the environment
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Molding Polymer Pellets
The best approach is to mold a sample plate (50x50 mm2 or 100x100 mm2)
Molding temperature: 10 - 20°C > than test temperature
Apply pressure: 8 – 12,000 lbs
Keep at elevated temperature long enough to let the sample relax
Cool down slowly under pressure to avoid orientations
Punch out a sample disk (8 or 25 mm)
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Molding Powders and Flakes
Before molding at high temperature, the sample has to be compacted

cold to reduce the volume
The compacted samples are transferred to the mold
Follow steps from the molding pellets procedure
Note: Sample may need to be stabilized or dried to avoid degradation
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Preparing Semi-solid Samples
Cut rectangular sheets of prepreg or adhesive (30x30mm)

Alternate direction of layer approx. 5 layer on top of each other
(remove release paper from PSA)
Compress the stack of sample layers in a press (4 – 5000 lbs)
Punch out 25 mm disks
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Controlling Environmental Conditions During Sample Prep
Polypropylene and Polyolefines in general tend

to degrade fast – need to be stabilized by
adding antioxidents
Moisture sensitive materials such as
polyamides and polyester require drying in
vacuum or at temperatures around 80°C.
Materials such as Polystyrene or Polymethyl-
methacrylate (PMMA) also absorb moisture. In
the melt phase, the gas separates into bubbles
and the sample foams
Pre-drying in vacuum is essential prior to
Vacuum oven
testing
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Loading a Molded Disk
Geometry gap and Trim gap icons
Set Environmental
System to test
temperature
Load molded disk

onto lower plate
Close the oven and Monitor Axial or After sample Close the oven and
bring the upper Normal force relaxes, open the adjust gap to
plate to the trim during this oven and trim geometry/test gap
gap position period excess sample
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Loading Polymer Pellet Samples
Set Environmental
System to test
temperature
Mount melt ring

onto the lower plate
and load pellets
Bring the upper After few minutes, After sample Close the oven and
plate close to top of open the oven, relaxes, open the adjust gap to
melt ring and close remove melt ring oven and trim geometry/test gap
the oven and go to trim gap excess sample
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Sample Preparation
Structured Fluids
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Know Your Sample – Structured Fluids
Structured fluids can range in consistency from low viscosity (e.g. milk)
to high viscosity, pasty materials (e.g. tooth paste)
Structured materials are very sensitive to mechnical and
environmental conditions
Be aware of largest particle size in sample and choose the geometry
appropriately (cone vs parallel plate vs vane geometry)
Samples can also be time dependent – how you treat the sample
(handling, loading, pre-conditioning) may affect test results!
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Handling Low Viscosity Fluids
Fluid samples which pour freely are relatively easy to handle prior to loading
Keep the container closed to avoid evaporation of solvent or continuous phase
Shake or stir sample to remove concentration gradients in suspensions
Adequate shelf temperature may be necessary to avoid phase separation in
emulsions
Never return used sample into original flask to avoid contamination
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Loading Low Viscosity Fluids
Deposit fluid in the middle of the plate

Set a motor velocity of ~ 1 rad/s and move to geometry gap
Add additional material along the sides of the geometry – capillary forces will
draw the sample between the gap
When finished, click on the “Stop Motor” button
NOTE: If the sample is a structured fluid, setting a motor velocity will introduce
shear history onto the sample and can destroy the sample structure!
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Handling Paste/Slurry & Gel Materials
The structure of high viscosity pastes and slurries may change with time
Food samples, like dough, can change continuously
The test samples need to be prepared carefully and consistently for
each experiment to obtain reproducibility
Slurries that may settle can gradually build a cake – these samples
have to be tested before sedimentation
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Loading Pastes and Slurries
Scoop up the paste with a spatula and deposit it at the center of the lower plate
For less viscous materials, a syringe with a cut-off tip can be used
Load ~ 10-20 excess material to ensure complete sample filling
Set the gap to the trim gap and use exponential gap closure profile to minimize
shear in the sample
Lock the bearing, trim excess material and set final gap
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Handling Gels
Gels, especially chemical gels, may change irreversibly when large deformations
are applied (for example, while loading)
Prepare (formulate) the sample in the final shape required for the measurement
so it can be loaded without deforming (cut, punch, …)
Alternatively, prepare the sample in situ – on the rheometer systemic rheology
Take care to avoid introducing air bubbles!
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Rheology

Theory and Applications

Basics in Rheology Theory Oscillation

Rheology: The study of

Rheology is the science of flow and deformation

Top plate Area = A

Controlled Strain Controlled Stress

Dual head or SMT Single head or CMT

Rheometer – an instrument that measures both viscosity and

It can provide information about the material’s:

Viscoelasticity – is a property of a material that exhibits both

by commanding torque (stress) and measuring angular displacement (strain)

From the definition of rheology,

the science of flow and deformation of matter

Fundamentally a rotational rheometer will apply or

In a rheometer, the stress is calculated from the

The formula for stress is: σ = Μ × Kσ

The stress constant, Kσ, is a geometry dependent factor

In a SMT Rheometer, the angular displacement

The formula for strain is: γ = Kγ × θ

The strain constant, Kγ, is a geometry dependent factor

In a SMT rheometer, the angular speed is directly

The formula for shear rate is:

The strain constant, Kγ, is a geometry dependent factor

Specification HR-3 HR-2 HR-1

Force/Torque Rebalance Transducer (Sample Stress)

Driver Motor (Sample Deformation)

Concentric Cone and Parallel Torsion

Very Low Very Low Very Low

Assess the ‘viscosity’ of your sample

Strain Constant: &' = ,+

Gap (h) Stress Constant: &( = *+) %

Low/Medium/High Viscosity Samples with long relaxation time

For a given angle of deformation, there is a greater arc of

34 dx increases further from the center,

The cone shape produces a smaller gap height closer to inside,

Strain Constant: &' = 65

(to convert torque, N⋅m, to shear stress, Pa.

Very Low to High Viscosity Liquids

Typical Truncation Heights:

Cone & Plate Truncation Height = Gap

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

× Under Filled sample:

× Over Filled sample:

*Note including end correction factor. See TRIOS Help TAINSTRUMENTS.COM

ARES Gap Settings: standard operating gap DW = 3.4 mm

Low to Medium Viscosity Liquids

High modulus samples No pure Torsion mode for

Torsion cylindrical also available

Torsion and DMA geometries allow solid samples to be

Torsion measures G’, G”, and Tan δ

Rectangular and DMA 3-point bending and tension

Geometry Application Advantage Disadvantage

Cone/plate fluids, melts true viscosities temperature ramp difficult

Parallel Plate fluids, melts easy handling, shear gradient across

Torsion Rectangular solid polymers, glassy to rubbery Limited by sample stiffness

Limited by sample stiffness

Rheometers are calibrated from the factory and again at

PDMS is verified using a 25 mm parallel plate.

The Modulus: Measure of ∗ ∗