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ƒ Basics in Rheology Theory ƒ Oscillation

ƒ TA Rheometers ƒ Linear Viscoelasticity
ƒ Instrumentation ƒ Setting up Oscillation Tests
ƒ Choosing a Geometry ƒ Transient Testing
ƒ Calibrations ƒ Applications of Rheology
ƒ Flow Tests ƒ Polymers
ƒ Viscosity ƒ Structured Fluids
ƒ Setting up Flow Tests ƒ Advanced Accessories

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Rheology: The study of

stress-deformation relationships

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ƒ Rheology is the science of flow and deformation

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

ୗ୲୰ୣୱୱ ౏౪౨౛౩౩
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ൌ ‘†—Ž—•

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Top plate Area = A

x(t) Velocity = V0
Force = F

y Bottom Plate
y
Velocity = 0
x
F
Shear Stress, Pascals σ=
A

γ=
x(t ) σ
Shear Strain, % η= Viscosity, Pa⋅s
y γ

γ
Shear Rate, sec-1 γ =
t

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Ω
r θ

σ)
Stress (σ ߪ ൌ  ഏೝమయ ൈM
r = plate radius
h = distance between plates
M = torque (μN.m)
Strain (γγ) ߛ ൌ  ೓ೝ ൈθ
θ
θ = Angular motor deflection (radians)
ೝ
Ω= Motor angular velocity (rad/s) Strain rate (ߛሶ ) ߛሶ ൌ  ೓
ൈΩ
Ω

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ARES G2 DHR

Controlled Strain Controlled Stress

Dual Head Single Head
SMT CMT
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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 ^ƚĂƚŝĐWůĂƚĞ
Static 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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ƒ Rheometer – an instrument that measures both viscosity and

viscoelasticity of fluids, semi-solids and solids

ƒ It can provide information about the material’s:

ƒ Viscosity - defined as a material’s resistance to deformation and
is a function of shear rate or stress, with time and temperature
dependence

ƒ 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.

ƒ A Rheometer works simply by relating a materials property from how hard it’s
being pushed, to how far it moves

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

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

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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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ƒ In a rheometer, the stress is calculated from the

torque.

ƒ The formula for stress is: σ сΜ п <σ

Where σ = Stress (Pa or Dyne/cm2)
Μ = torque in N.m or gm.cm
<σ = Stress Constant

ƒ The stress constant, <σ, is a geometry dependent factor

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ƒ In a SMT Rheometer, the angular displacement

is directly applied by a motor.

ƒ The formula for strain is: γ с<γ п θ

йγ сγ п ϭϬϬ
where γ = Strain
<γ = Strain Constant
θ = Angular motor deflection (radians)

ƒ The strain constant, <γ, is a geometry dependent factor

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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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ƒ In a SMT rheometer, the angular speed is directly

controlled by the motor).

ƒ The formula for shear rate is:

ߛሶ  ൌ  ‫ܭ‬ఊ ൈ :
where ߛሶ = Shear rate
<γ = Strain Constant
Ω = Motor angular velocity in rad/sec

ƒ The strain constant, <γ, is a geometry dependent factor

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Describe
In Spec Correctly

σ M ⋅ Kσ
η= =
γ Ω ⋅ K γ
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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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 ,ZͲϮ
,ZͲϯ
Minimum Torque (nN.m) Steady 5 10 20 ,ZͲϭ
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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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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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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ƒ Assess the ‘viscosity’ of your sample

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

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Strain Constant: ‫ܭ‬ఊ ൌ  ௛௥

(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)

'ĂƉ;ŚͿ Stress Constant: ‫ܭ‬ఙ ൌ  గ௥ଶ య

ŝĂŵĞƚĞƌ;Ϯ⋅⋅ƌͿ
(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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ƒ Low/Medium/High Viscosity ƒ Samples with long relaxation time

Liquids ƒ Temperature Ramps/ Sweeps
ƒ Soft Solids/Gels ƒ Materials that may slip
ƒ Thermosetting materials ƒ Crosshatched or Sandblasted plates
ƒ Samples with large particles
ƒ Small sample volume

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Shear Stress

20 mm

40 mm

60 mm

ʹ
As diameter decreases, shear stress increases ߪൌ‫ ܯ‬ଶ
ߨ‫ݎ‬
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Shear
Rate
2 mm Increases

1 mm

0.5 mm

‫ݎ‬
As gap height decreases, shear rate increases ߛሶ ൌ ȳ
݄
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ƒ For a given angle of deformation, there is a greater arc of

deformation at the edge of the plate than at the center

݀‫ݔ‬ dx increases further from the center,

ߛൌ
݄ h stays constant

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

so the shear on the sample is constant

݀‫ݔ‬
ߛൌ h increases proportionally to dx, γ is uniform
݄

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Strain Constant: ‫ܭ‬ఊ ൌ  ఉଵ

(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)

ଷ
Stress Constant: ‫ܭ‬ఙ ൌ  ଶగ௥ య

(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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ƒ Very Low to High Viscosity Liquids

ƒ High Shear Rate measurements
ƒ Normal Stress Growth
ƒ Unfilled Samples
ƒ Isothermal Tests
ƒ Small Sample Volume

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Shear Stress

20 mm

40 mm

60 mm

͵
As diameter decreases, shear stress increases ߪൌ‫ܯ‬
ʹߨ‫ ݎ‬ଷ
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Shear Rate
Increases

2°

1°

0.5 °

ͳ
As cone angle decreases, shear rate increases ߛሶ ൌ ȳ
ߚ
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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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× Under Filled sample:

Lower torque contribution

× Over Filled sample:

Additional stress from
drag along the edges

9 Correct Filling

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‫ͳݎ‬ଶ ൅ ‫ʹݎ‬ଶ
Strain Constant: ‫ܭ‬ఊ ൌ
‫ʹݎ‬ଶ ‫ͳݎ‬ଶ
(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)

ଶ ଶ *
‫ ͳݎ‬൅ ‫ʹ ݎ‬
Stress Constant: ‫ܭ‬ఙ ൌ  ଵ 
ସగ௟ ‫ʹݎ‬ଶ ‫ͳݎ‬ଶ
(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

'RXEOH:DOO
ƒ Use for very low viscosity systems (<1 mPas)

r1
r2
h
r3
r4

‫ͳݎ‬ଶ ൅ ‫ʹݎ‬ଶ
Strain Constant: ‫ܭ‬ఊ ൌ
‫ʹݎ‬ଶ െ‫ͳݎ‬ଶ
௥ଵమ ା௥ଶమ
Stress Constant: ‫ܭ‬ఙ ൌ  ସగ௛ή௥ మ ௥ మ ା௥ మ
ଶ ଵ ଷ

ARES Gap Settings: standard operating gap DW = 3.4 mm

narrow operating gap DW = 2.0 mm
Use equation Gap > 3 × (R2 –R1)
TAINSTRUMENTS.COM
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ƒ Low to Medium Viscosity Liquids

ƒ Unstable Dispersions and Slurries
ƒ Minimize Effects of Evaporation
ƒ Weakly Structured Samples (Vane)
ƒ High Shear Rates

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‫ݐ‬
‫ܭ‬ఊ ൌ
௧ ଶ
݈ ͳ െ ͲǤ͵͹ͺ ௪ w = Width
l = Length
͵ ൅ ଵǤ଼ t = Thickness
௪
‫ܭ‬ఛ ൌ
‫ ݓ‬ή ‫ݐ‬ଶ

Advantages: Disadvantages:

ƒ High modulus samples ƒ No pure Torsion mode for

ƒ Small temperature high strains
gradient
ƒ Simple to prepare

Torsion cylindrical also available

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ƒ Torsion and DMA geometries allow solid samples to be

characterized in a temperature controlled environment

ƒ Torsion measures G’, G”, and Tan δ

ƒ DMA measures E’, E”, and Tan δ
ƒ ARES G2 DMA is standard function (50 μm amplitude)
ƒ 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 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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ƒ Instrument Calibrations
ƒ Inertia (Service)
ƒ Rotational Mapping

ƒ Geometry Calibrations:
ƒ Inertia
ƒ Friction
ƒ Gap Temperature
Compensation
ƒ Rotational Mapping

ƒ Details in Appendix #4

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ƒ Instrument Calibrations
ƒ Transducer
ƒ Temperature Offsets
ƒ Phase Angle (Service)
ƒ Measure Gap Temperature
Compensation

ƒ Geometry Calibrations:
ƒ Compliance and Inertia (from table)
ƒ Gap Temperature Compensation

ƒ Details in Appendix #4

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ƒ Rheometers are calibrated from the factory and again at

installation.
ƒ TA recommends routine validation or confidence checks
using standard oils or Polydimethylsiloxane (PDMS).

ƒ PDMS is verified using a 25 mm parallel plate.

ƒ Oscillation - Frequency Sweep: 1 to 100 rad/s with 5% strain at 30°C
ƒ Verify modulus and frequency values at crossover

ƒ Standard silicone oils can be verified using cone, plate or

concentric cylinder configurations.
ƒ Flow – Ramp: 0 to 88 Pa at 25°C using a 60 mm 2° cone
ƒ Service performs this test at installation

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ƒ Set Peltier temperature to 25°C and

equilibrate.
ƒ Zero the geometry gap

ƒ Load sample
ƒ Be careful not to introduce air bubbles!

ƒ Set the gap to the trim gap

ƒ Lock the head and trim with non-absorbent

tool
ƒ Important to allow time for temperature equilibration.

ƒ Go to geometry gap and initiate the

experiment.

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ƒ Viscosity is…
ƒ “lack of slipperiness”
ƒ synonymous with internal friction
ƒ resistance to flow

ƒ The Units of Viscosity are …

ƒ SI unit is the Pascal.second (Pa.s)
ƒ cgs unit is the Poise
ƒ 10 Poise = 1 Pa.s
ƒ 1 cP (centipoise) = 1 mPa.s (millipascal second)

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Describe
In Spec Correctly

σ M ⋅ Kσ
η= =
γ Ω ⋅ K γ
Geometric
Rheological Constitutive Raw rheometer
Parameter Equation
Shape
Specifications
Constants

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

6 Polymer Melt ---------------- 1,000
6 Molasses --------------------- 100
6 Liquid Honey ---------------- 10 Need for
6 Glycerol ---------------------- 1 Log scale
6 Olive Oil ---------------------- 0.01
6 Water ------------------------- 0.001
6 Air ----------------------------- 0.00001

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ƒ Newtonian Fluids - constant proportionality between

shear stress and shear-rate

ƒ Non-Newtonian Fluids - Viscosity is time or shear rate

dependent
ƒ Time:
ƒ At constant shear-rate, if viscosity
ƒ Decreases with time – Thixotropy
ƒ Increases with time - Rheopexy
ƒ Shear-rate:
ƒ Shear - thinning
ƒ Shear - thickening

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Ideal Yield Stress

(Bingham Yield)

η, Pa.s
σ, Pa

γ ,1/s or σ, Pa
γ ,1/s

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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
,GHDO<LHOG6WUHVV
%LQJKDPSODVWLF
ƒ Another name for a shear thinning
103
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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ƒ Dilatant material resists

deformation more than in
proportion to the applied
Log η, Pa.s

force (shear-thickening)

ƒ 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 ߛሶ , 1/s be labeled rheopectic

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ƒ Rheopectic materials
become more viscous
Rheopectic with increasing time of
applied force
ƒ Higher concentration
Viscosity

latex dispersions and

Shear Rate = Constant plastisol paste materials
exhibit rheopectic
behavior
Thixotropic ƒ Thixotropic materials
become more fluid with
increasing time of applied
force
time
ƒ Coatings and inks can
display thixotropy when
sheared due to structure
breakdown

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ƒ Flow Experiments
ƒ Constant shear rate/stress (or Peak hold)
ƒ Continuous stress/rate ramp and down
ƒ Stepped flow (or Flow sweep)
ƒ Steady state flow
ƒ Flow temperature ramp

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Stress /Rate

ƒ Constant rate vs. time

ƒ Constant stress vs. time

USES
ƒ Single point testing
ƒ Scope the time for steady state under certain rate

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

time (min)

USES
ƒ Yield stress
ƒ Scouting Viscosity Run

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Deformation
ƒ Stress is first increased,
then decreased, at a
σ
constant rate. Resultant
strain is monitored with
time
time.

USES
ƒ “Pseudo-thixotropy” from Hysteresis loop

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Run in Stress Control TA Instruments

500.0

400.0
shear stress (Pa)

300.0
ZĞĚ͗&ŝƌƐƚĐLJĐůĞ
ůƵĞ͗^ĞĐŽŶĚĐLJĐůĞ
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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Deformation

σ
Data point saved
ƒ Stress is applied to sample.
Žƌ Viscosity measurement is taken
ߛሶ 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
Žƌ
ߛሶ
Steady State Flow ƒ Viscosity Flow Curves
γ or σ = Constant ƒ Yield Stress Measurements

time

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ƒ 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)

TAINSTRUMENTS.COM
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Control variables:
ƒ Shear rate
ƒ Velocity
ƒ Torque
ƒ Shear stress

Steady state algorithm

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0.8000 ^ĂŵƉůĞϭͲ&ůŽǁƐƚĞƉ
^ĂŵƉůĞϮͲ&ůŽǁƐƚĞƉ

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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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)

TAINSTRUMENTS.COM
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ƒ Hold the rate or stress

y y y y constant whilst
ramping the
temperature.

time (min)

USES
ƒ Measure the viscosity change vs. temperature

TAINSTRUMENTS.COM
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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

TAINSTRUMENTS.COM
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ƒ Small gaps give high shear rates

ƒ Be careful with small gaps:
ƒ Gap errors (gap temperature compensation) and shear
heating can cause large errors in data.
ƒ Recommended gap is between 0.5 to 2.0 mm.
ƒ Secondary flows can cause increase in viscosity curve
ƒ Be careful with data interpretation at low shear rates
ƒ Surface tension can affect measured viscosity, especially
with aqueous materials

TAINSTRUMENTS.COM
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Surface tension at low torques

Secondary flows at high shear rates

TAINSTRUMENTS.COM
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ƒ Wall slip can manifest as “apparent double yielding”

ƒ Can be tested by running the same test at different gaps
ƒ For samples that don’t slip, the results will be independent of the gap

TAINSTRUMENTS.COM
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When Stress Decreases with

Shear Rate, it indicates that
sample is leaving the gap

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ƒ Edge Failure – Sample leaves gap because of normal

forces
ƒ Look at stress vs. shear rate curve – stress should not
decrease with increasing shear rate – this indicates sample
is leaving gap
ƒ Possible Solutions:
ƒ use a smaller gap or smaller angle so that you get the same
shear rate at a lower angular velocity
ƒ if appropriate (i.e. Polymer melts) make use of Cox Merz
Rule

η (γ ) ≡ η (ω )
 *

TAINSTRUMENTS.COM
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TAINSTRUMENTS.COM
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Hooke’s Law of Elasticity: Stress = Modulus ⋅ Strain

γ1 γ2 γ3

3
^ƚƌĞƐƐ;ʍͿ

2 

1 2 3
^ƚƌĂŝŶ;࠹Ϳ
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Hooke’s Law of Elasticity: Stress = Modulus ⋅ Strain

E > E > E

ߪ
‫ܧ‬ൌ γ1 γ2 γ3
ߛ

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Newton’s Law: stress

= coefficient of viscosity ⋅ shear rate
Ș
^ƚƌĞƐƐ;ʍͿ

ߪ ൌ K ή  ߛሶ

^ŚĞĂƌZĂƚĞ;࠹Ϳ

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Newton’s Law: stress= coefficient of viscosity ⋅ shear rate ߪ

Ʉൌ
ߛሶ
Ș < Ș < Ș

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L1
L2

sŝƐĐŽĞůĂƐƚŝĐDĂƚĞƌŝĂůƐ͗&ŽƌĐĞ
ĚĞƉĞŶĚƐŽŶďŽƚŚĞĨŽƌŵĂƚŝŽŶĂŶĚ
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 9LVFRHODVWLFLW\'HILQHG

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
ƒ Materials behave in the linear manner, as described by Hooke and
Newton, only on a small scale in stress or deformation.

TAINSTRUMENTS.COM
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ƒ Long deformation time: pitch behaves

like a highly viscous liquid
ƒ 9th drop fell July 2013
ƒ Short deformation time: pitch behaves
like a solid

Started in 1927 by Thomas Parnell in Queensland, Australia

ŚƚƚƉ͗ͬͬǁǁǁ͘ƚŚĞĂƚůĂŶƚŝĐ͘ĐŽŵͬƚĞĐŚŶŽůŽŐLJͬĂƌĐŚŝǀĞͬϮϬϭϯͬϬϳͬƚŚĞͲϯͲŵŽƐƚͲĞdžĐŝƚŝŶŐͲǁŽƌĚƐͲŝŶͲƐĐŝĞŶĐĞͲƌŝŐŚƚͲŶŽǁͲƚŚĞͲƉŝƚĐŚͲĚƌŽƉƉĞĚͬϮϳϳϵϭϵͬ

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

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ƒ Silly Putties have different characteristic relaxation times

ƒ Dynamic (oscillatory) testing can measure time-dependent
viscoelastic properties more efficiently by varying frequency
(deformation time)

TAINSTRUMENTS.COM
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ƒ Old Testament Prophetess who said (Judges 5:5):

"The Mountains ‘Flowed’ before the Lord"

ƒ Everything Flows if you wait long enough!

ƒ Deborah Number, De - The ratio of a characteristic

relaxation time of a material (τ) to a characteristic time of
the relevant deformation process (T).

Ğсτͬd

TAINSTRUMENTS.COM
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ƒ Hookean elastic solid - IJ is infinite

ƒ Newtonian Viscous Liquid - IJ is zero
ƒ Polymer melts processing - IJ 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

TAINSTRUMENTS.COM
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(E' or G') (E' or G')

(E" or G") (E" or G")

log Frequency Temperature

log Time log Time

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"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
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͛;Žƌ'͛Ϳ͕͟;Žƌ'͟Ϳ͕ƚĂŶδ͕ηΎ
Measuring linear viscoelastic properties helps us bridge the gap
between molecular structure and product performance

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2VFLOODWRU\7HVWV

TAINSTRUMENTS.COM
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ƒ Define Oscillation Testing

ƒ Approach to Oscillation Experimentation

ƒ Stress and Strain Sweep
ƒ Time Sweep
ƒ Frequency Sweep
ƒ Temperature Ramp
ƒ Temperature Sweep (TTS)

TAINSTRUMENTS.COM
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Phase angle δ
Strain, ε

Stress, σΎ

Dynamic stress applied sinusoidally

User-defined Stress or Strain amplitude and frequency

TAINSTRUMENTS.COM
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ƒ Time to complete one oscillation

ƒ Frequency is the inverse of time
ƒ Units
ƒ Angular Frequency = radians/second
ƒ Frequency = cycles/second (Hz)
ƒ Rheologist must think in terms of rad/s.
ƒ 1 Hz = 6.28 rad/s

TAINSTRUMENTS.COM
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ω = 6.28 rad/s

ω = 12.560rad/s
0 0 0 0

dŝŵĞсϭƐĞĐ ω = 50 rad/s

TAINSTRUMENTS.COM
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ƒ Strain and stress are calculated from peak amplitude in the

displacement and torque waves, respectively.

0 0 0 0

dŝŵĞсϭƐĞĐ

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

ƒ The phase angle δ, or phase

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

TAINSTRUMENTS.COM
 '\QDPLF7HVWLQJ5HVSRQVHIRU&ODVVLFDO([WUHPHV

Purely Elastic Response Purely Viscous Response

(Hookean Solid) (Newtonian Liquid)
δ сϬ° δ сϵϬ°

Strain Strain

Stress Stress

TAINSTRUMENTS.COM
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Phase angle 0°< δ < 90°

Strain

Stress

TAINSTRUMENTS.COM
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ƒ The stress in a dynamic experiment is referred to as the

complex stress σ*
ƒ 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: ‫ ݔ‬൅ ݅‫ ݕ‬ൌ ‫ݔ‬ଶ ൅ ‫ݕ‬ଶ

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
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The Modulus: Measure of ‫כ‬ ୗ୲୰ୣୱୱ‫כ‬

materials overall resistance to
ൌ ୗ୲୰ୟ୧୬
deformation.
The Elastic (Storage) Modulus:
ᇱ ୗ୲୰ୣୱୱ‫כ‬
Measure of elasticity of material.
ൌ ୗ୲୰ୟ୧୬
…‘• Ɂ
The ability of the material to store
energy.
The Viscous (loss) Modulus:
̶ ୗ୲୰ୣୱୱ‫כ‬
The ability of the material to
ൌ ୗ୲୰ୟ୧୬
•‹ Ɂ
dissipate energy. Energy lost as
heat.
Tan Delta:
ୋ̶
Measure of material damping -
such as vibration or sound
–ƒ Ɂ ൌ ୋᇱ
damping.

TAINSTRUMENTS.COM
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RUBBER BALL y LOSS

(G”)
TENNIS
BALL y
STORAGE
(G’)

G*
Dynamic measurement G"
represented as a vector
Phase angle δ
G'
TAINSTRUMENTS.COM
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ƒ 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.

ƒ The Complex viscosity is defined as:

Ș* = Ș’ + i Ș”
or
Ș* = G*/Ȧ

Note: frequency must be in rad/sec!

TAINSTRUMENTS.COM
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Parameter Shear Elongation Units

Strain ɶ сɶϬƐŝŶ;ʘƚͿ ɸ сɸϬ ƐŝŶ;ʘƚͿ ---

Stress σ сσϬƐŝŶ;ʘƚнɷͿ τ сτϬƐŝŶ;ʘƚнɷͿ Pa

Storage Modulus
'͛с;σϬͬɶϬͿĐŽƐɷ ͛с;τϬͬɸϬͿĐŽƐɷ Pa
(Elasticity)

Loss Modulus
'͟с;σϬͬɶϬͿƐŝŶɷ ͟с;τϬͬɸϬͿƐŝŶɷ Pa
(Viscous Nature)

Tan į 'ͬ͟'͛ ͬ͛͟ ---

Complex Modulus 'Ύ с;'͛Ϯн'͟ϮͿϬ͘ϱ Ύ с;͛Ϯн͟ϮͿϬ͘ϱ Pa

Complex Viscosity ηΎ с'Ύͬʘ ηΎ сΎͬʘ Pa·sec

Cox-Merz Rule for Linear Polymers: η*(Ȧ) = η(ߛሶ ) @ ߛሶ = Ȧ

TAINSTRUMENTS.COM
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ƒ Define Oscillation Testing

ƒApproach to Oscillation Experimentation

1. Stress and Strain Sweep
2. Time Sweep
3. Frequency Sweep
4. Temperature Ramp
5. Temperature Sweep (TTS)

TAINSTRUMENTS.COM
'\QDPLF6WUDLQRU6WUHVV6ZHHS
Stress or strain

ƒ The material response to

increasing deformation
amplitude (strain or
stress) is monitored at a
constant frequency and
Time temperature.

ƒ Main use is to determine LVR

ƒ All subsequent tests require an amplitude found in the LVR
ƒ Tests assumes sample is stable
ƒ If not stable use Time Sweep to determine stability

TAINSTRUMENTS.COM
'\QDPLF6WUDLQ6ZHHS0DWHULDO5HVSRQVH

Linear Region:
Modulus
Non-linear Region:
independent
of strain
Modulus is a function of strain

G'

Stress

Constant
Slope
γĐ сCritical Strain

Strain (amplitude)
TAINSTRUMENTS.COM
7HPSHUDWXUH'HSHQGHQFHRI/95

ƒ In general, the LVR is shortest when the sample is in its

most solid form.

Solid
G’

Liquid

% strain

TAINSTRUMENTS.COM
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ƒ LVR decreases with increasing frequency

ƒ Modulus increases with increasing frequency

TAINSTRUMENTS.COM
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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
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^K^ γ(t) = γ0 sin(ωt)

τ(t) = τ0 sin(ωt+δ)

>K^ 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
'\QDPLF7LPH6ZHHS
Stress or strain

ƒ The material response

is monitored at a
constant frequency,
amplitude and
temperature.
Time

USES
ƒ Time dependent Thixotropy
ƒ Cure Studies
ƒ Stability against thermal degradation
ƒ Solvent evaporation/drying

TAINSTRUMENTS.COM
,PSRUWDQFHRI7LPH6ZHHS

ƒ Important, but often overlooked

ƒVisually observe the sample
ƒ Determines if properties are changing over the time of
testing
ƒ Complex Fluids or Dispersions
ƒ Preshear or effects of loading
ƒ Drying or volatilization (use solvent trap)
ƒ Thixotropic or Rheopectic
ƒ Polymers
ƒ Degradation (inert purge)
ƒ Crosslinking

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Under N2 Under air




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ϭϬϬ͘Ϭ Structural Recovery after Preshear

ϴϬ͘ϬϬ
G' (Pa)

ϲϬ͘ϬϬ

ϰϬ͘ϬϬ

ϮϬ͘ϬϬ

Ϭ 0
Ϯϱ͘ϬϬ ϱϬ͘ϬϬ ϳϱ͘ϬϬ ϭϬϬ͘Ϭ ϭϮϱ͘Ϭ ϭϱϬ͘Ϭ ϭϳϱ͘Ϭ ϮϬϬ͘Ϭ ϮϮϱ͘Ϭ

time (s)

TAINSTRUMENTS.COM
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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)

ƒ End of LVR is indicative of “Yield” or “Strength of Structure”

ƒ Useful for Stability predictions (stability as defined by yield)

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Solvent trap cover picks up heat from Peltier Plate to insure uniform temperature

^ŽůǀĞŶƚŝŶ
^ŽůǀĞŶƚdƌĂƉŽǀĞƌ tĞůů

WĞůƚŝĞƌ
WůĂƚĞ
^ĂŵƉůĞ

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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
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ƒ The material response to

increasing frequency (rate of
deformation) is monitored at
ŵƉůŝƚƵĚĞ

a constant amplitude (strain

or stress) and temperature.

dŝŵĞ

ƒ Strain should be in LVR

ƒ Sample should be stable
ƒ 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
)UHTXHQF\6ZHHS0DWHULDO5HVSRQVH

Transition
Rubbery Region
Terminal Plateau
Region Region

Glassy Region

1
2 Storage Modulus (E' or G')
>ŽƐƐDŽĚƵůƵƐ;ΗŽƌ'ΗͿ

log Frequency (rad/s or Hz)

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Frequency of modulus
crossover correlates
with Relaxation Time

TAINSTRUMENTS.COM
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η (γ ) ≡ η * (ω )

Flow instability
Z

LDPE Freq sweep 2mm gap – Cox Merz

LDPE shear rate 1mm gap
LDPE Shear rate 2 mm gap

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,PSRUWDQFHRI)UHTXHQF\6ZHHSV

ƒ High and low rate (short and long time) properties

ƒ Viscosity Information - Zero Shear Viscosity, shear
thinning
ƒ Elasticity (reversible deformation) in materials
ƒ MW & MWD differences polymer melts and solutions
ƒ Finding yield in gelled dispersions
ƒ Can extend time or frequency range with TTS

3.4
G' § Mw ·
η0 ≈ M 3.4
w and J e = 2
≈ ¨¨ ¸¸
( G" ) © M z ¹

TAINSTRUMENTS.COM
)UHTXHQF\LQ'+55KHRPHWHU

ƒ DHR has a combined motor and transducer design.

ƒ In an DHR rheometer, the applied motor torque and
the measured amplitude are coupled.
ƒ The moment of inertia required to move the motor and
geometry (system inertia) is coupled with the angular
displacement measurements.
ƒ This means that BOTH the system inertia and the
sample contributes to the measured signal.

TAINSTRUMENTS.COM
,QHUWLDO(IIHFWV

ƒ What is Inertia?
ƒ Definition: That property of matter which manifests
itself as a resistance to any change in momentum of a
body
ƒ Instrument has inertia
ƒ Sample has inertia

TAINSTRUMENTS.COM
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ƒ Inertia consideration
ƒ Viscosity limitations with frequency
ƒ Minimize inertia by using low mass geometries
ƒ Monitor inertia using Raw Phase in degree
ƒ When Raw Phase is greater than:
ƒ 150°° degrees for AR series
ƒ 175°° degrees for DHR series
ƒ This indicates that the system inertia is dominating the
measurement signal. Data may not be valid

Raw Phase × Inertia Correction = delta

TAINSTRUMENTS.COM
 Access to raw phase angle
'+5&RUUHFWLRQIRU,QHUWLD only available with TA
Instruments Rheometers!

Waveforms at high frequencies

Inertial effects at
high frequencies

Negligible correction at low frequencies

TAINSTRUMENTS.COM
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ƒ ARES-G2 has a separate motor and transducer

design.
ƒ In an ARES-G2, the motor applies the deformation
independent of the torque measurement on the transducer.
ƒ The moment of inertia required to move the motor is
decoupled from the torque measurements.
ƒ This means the motor inertia does not contribute to the test
results.
ƒ Benefits of ARES-G2:
ƒ System inertia free
ƒ Capable of running low viscosity samples up to high
frequency

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$5(6*&ORVHG/RRS&RQWURO

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

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'\QDPLF7HPSHUDWXUH5DPS

ƒ 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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ƒ 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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'\QDPLF7HPSHUDWXUH5DPSRU6ZHHS0DWHULDO5HVSRQVH

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")

dĞŵƉĞƌĂƚƵƌĞ
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ƒ Solid in torsion rectangular

ƒ Look at Tg, secondary transitions and study structure-
property relationships of finished product.
ƒ Themosetting polymers
ƒ Follow curing reactions
ƒ Polymer melts and other liquids
ƒ Measure temperature dependence of viscoelastic
properties

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ƒ It is important to setup normal force control during any temperature

change testing or curing testing
ƒ Some general suggestions for normal force control
ƒ For torsion testing, set normal force in tension: 1-2N ± 0.5-1.0N
ƒ For curing or any parallel plate testing, set normal force in
compression: 0 ± 0.5N

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ƒ Videos available at www.tainstruments.com under the Videos tab or on the TA

tech tip channel of YouTube™ (ŚƚƚƉƐ͗ͬͬǁǁǁ͘LJŽƵƚƵďĞ͘ĐŽŵͬƵƐĞƌͬddĞĐŚdŝƉƐ)

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ƒ Cures are perhaps the most challenging experiments to conduct on

rheometers as they challenge all instrument specifications both high
and low.
ƒ The change in modulus as a sample cures can be as large as 7-8
decades and change can occur very rapidly.
ƒ AR, DHR, and ARES instruments have ways of trying to cope with
such large swings in modulus
ƒ AR: Non-iterative sampling (w/ Axial force control)
ƒ DHR: Non-iterative sampling (w/ Axial force control) and
Auto-strain (w/ Axial force active) in TRIOS v3.2 or higher
ƒ ARES: Auto-strain (w/ Axial force or auto-tension active)

TAINSTRUMENTS.COM
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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
Žƌ
'͛

Crosslinking
reaction causes
h and G’ to increase

dĞŵƉ 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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ƒNon-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)

ƒPrecision Sampling – motor torque

is adjusted at the end of an
oscillation cycle in order to reach
commanded strain

ƒContinuous 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 (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

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η
Žƌ
'͛

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

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Torque Upper torque limit

Strain

η
Žƌ
'͛

Temp Lower
torque limit

Time

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ARES-G2 DHR

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ƒ Strain
ƒ Depends on sample
ƒ Verify the LVR in the cured state ( e.g. 0.05%)
ƒ Normal force control or auto-tension
ƒ Requires active to adjust for sample shrinkage and/or thermal
expansion in parallel plates
ƒ Temperature
ƒ Isothermal
ƒ Fast ramp + isotherm: the fastest ramp rate
ƒ Continuous ramp rate: 3 – 5 °C/min.
ƒ Frequency
ƒ Typically 1Hz (6.28 rad/s), 10 rad/s or higher

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ƒ Strain is applied to sample instantaneously

(in principle) and held constant with time.
ƒ Stress is monitored as a function of time σ(t).
ƒ DHR and AR
ƒ Response time dependent on feedback loop
Strain

Ϭ
time

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Ϭ
time
Response of Classical Extremes

Hookean Solid Newtonian Fluid

stress for t>0 is 0

stress for
t>0
is constant
Ϭ Ϭ
time time
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Response of ViscoElastic Material

Stress decreases with time

starting at some high value
and decreasing to zero.
Ϭ
time

ƒ For small deformations (strains within the linear region)

the ratio of stress to strain is a function of time only.

ƒ This function is a material property known as the

STRESS RELAXATION MODULUS, G(t)
G(t) = σ(t)/γγ

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Glassy Region
Transition
Region Rubbery Terminal
Plateau Region
Region

log time

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ϭ͘ϬϬϱ

ϭϬϬϬϬ

ϭϬϬϬ

ϭϬϬ

ϭϬ

ϭ
Ϭ͘Ϭϭ Ϭ͘ϭ ϭ ϭϬ ϭϬϬ
time (s)

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ƒ 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.

ƒ 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.
ƒ The software will calculated this for you.

γ с<γ п θ ;йγ с γ п ϭϬϬͿ

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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]

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ƒ 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))
ƒ The stress is reduced to zero, t2, and the strain is
monitored as a function of time (γ(t) or ε(t))
ƒ Native mode on AR (<1 msec)
Stress

t1 time t2

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t1 time t2
Response of Classical Extremes

ƒ Stain for t>t1 is constant ƒ Stain rate for t>t1 is constant

ƒ Strain for t >t2 is 0 ƒ Strain for t>t1 increase with time
ƒ Strain rate for t >t2 is 0

t1 time t2 t1 time t2
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Rubbery
log Creep Compliance, Jc

Plateau
Region

Transition
Region

Glassy Region
Terminal Region

ůŽŐƚŝŵĞ

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ƌĞĞƉσ хϬ

σ/η

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ƌĞĂĐŚŝŶŐĂƐƚĞĂĚLJƐƚĂƚĞ͘

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ƌĞĞƉσ хϬ ZĞĐŽǀĞƌLJσ сϬ;ĂĨƚĞƌƐƚĞĂĚLJƐƚĂƚĞͿ

σ/η
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hŶƌĞĐŽǀĞƌĂďůĞ
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njŽŶĞ͕ƵŶƚŝůĨŝŶĂůůLJ ĞƋƵŝůŝďƌŝƵŵĂƚƐŽŵĞƐŵĂůůƚŽƚĂůƐƚƌĂŝŶ
ƌĞĂĐŚŝŶŐĂƐƚĞĂĚLJƐƚĂƚĞ͘ ƌĞůĂƚŝǀĞƚŽƚŚĞƐƚƌĂŝŶĂƚƵŶůŽĂĚŝŶŐ͘

DĂƌŬ͕:͕͘Ğƚ͘Ăů͕͘WŚLJƐŝĐĂůWƌŽƉĞƌƚŝĞƐŽĨWŽůLJŵĞƌƐ͕ŵĞƌŝĐĂŶŚĞŵŝĐĂů^ŽĐŝĞƚLJ͕ϭϵϴϰ͕Ɖ͘ϭϬϮ͘

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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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more elastic
ϭͬη
:Ğ
Creep Zone Je = Equilibrium recoverable compliance

:ƌ;ƚͿ
:;ƚͿ

Recovery Zone
time time
Creep Compliance Recoverable Compliance
ஓሺ୲ሻ ɀ୳ െ ɀ –
– ൌ ୰ – ൌ 
ɐ
஢
The material property obtained from Where γu = Strain at unloading
Creep experiments: γ(t) = time dependent
Compliance = 1/Modulus (in a sense) recoverable strain

Mark, J., et. al., Physical Properties of Polymers, American Chemical Society, 1984, p. 102.

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• 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

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/ŶŶĞƌ
DŽƚŽƌWŽƐŝƚŝŽŶ>ŽŽƉ
σĐŵĚ;ƚͿ Δσ;ƚͿ θ;ƚͿ θ;ƚͿ
W/ ŵŽƚŽƌ
ŝŶƚĞŐƌĂƚŽƌ
σ;ƚͿ
&Zd ƐĂŵƉůĞ
>ŝŶĞĂƌƌĞƐƉŽŶƐĞ DĂƚĞƌŝĂůƌĞƐƉŽŶƐĞ

ƒ Stress is controlled by closing the loop around the sample Æ

requires optimization of control PID parameters
ƒ Pretest to determine material’s response and PID Constants

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ƒ Set up a pre-test and get the sample information into the loop
ƒ Stress Control Pre-test: frequency sweep within LVR

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Pretest Æ Frequency Sweep from 2 to 200 rad/s Æ data analyzed in

software to optimize Motor loop control PID constants

LDPE melt
Freq. Sweep
T = 190°C

TAINSTRUMENTS.COM
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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)

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ƒ 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.
ƒ 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.
ƒ The software will calculated this for you.

σ = Kσ x Μ

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Three main reasons for rheological testing:

ƒ Characterization
MW, MWD, formulation, state of flocculation, etc.
ƒ Process performance
Extrusion, blow molding, pumping, leveling, etc.
ƒ Product performance
Strength, use temperature, dimensional stability, settling
stability, etc.

TAINSTRUMENTS.COM
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Molecular Structure
ƒ MW and MWD
ƒ Chain Branching and Cross-linking
ƒ Interaction of Fillers with Matrix Polymer
ƒ Single or Multi-Phase Structure
Viscoelastic Properties
As a function of:
ƒ Strain Rate(frequency)
ƒ Strain Amplitude
ƒ Temperature
Processability & Product Performance

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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
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ƒ Oscillation/Dynamic
ƒ Time Sweep
ƒ Degradation studies, stability for subsequent testing
ƒ Strain Sweep – Find LVER
ƒ Frequency Sweep – G’, G”, η*
ƒ Sensitive to MW/MWD differences melt flow can not see
ƒ Temperature Ramp/Temperature Step
ƒ Transitions, viscosity changes
ƒ TTS Studies
ƒ Flow/Steady Shear
ƒ Viscosity vs. Shear Rate Plots
ƒ Find Zero Shear Viscosity
ƒ Low shear information is sensitive to MW/MWD differences melt flow
can not see
ƒ Creep and Recovery
ƒ Creep Compliance/Recoverable Compliance
ƒ Very sensitive to long chain tails

TAINSTRUMENTS.COM
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Polyester Temperature stability

275
Determines if properties
Temperature stability are changing over the
good
poor
time of testing
5
10 250
ƒ Degradation

Temperature T [°C]
Modulus G' [Pa]

ƒ Molecular weight
225 building
ƒ Crosslinking

4
200
10

175
-2 0 2 4 6 8 10 12 14 16 18
Time t [min]

Important, but often overlooked!

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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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ƒ Sensitive to Molecular Weight, MW

ƒ For Low MW (no Entanglements) η0 is proportional to MW
ƒ For MW > Critical MWc, η0 is proportional to MW3.4

log ηo
3.4
MWc

η0 с<⋅⋅Dǁ η0 с<⋅⋅Dǁ ϯ͘ϰ

log MW

Ref. Graessley, Physical Properties of Polymers, ACS, c 1984.

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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]

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ƒ 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)

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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]
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6
10
Modulus G', G'' [Pa]

5
10
ƒ 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
EĂƌƌŽǁ
-3 -2 -1 0 1 2 3 4
10 10 10 10 10 10 10 10 ƌŽĂĚ
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)

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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

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ƒ Good thermal stability

ƒ one crossover point,
ƒ Ș* plateaus at low Ȧ

ƒ Poor thermal stability

ƒ multiple crossover points
ƒ Ș* continues to increase
over time
ƒ Time Sweep can verify if
the sample is unstable

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HDPE pipe surface defects

o ƒ 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 performance of a PSA

ƒ 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
ƒ 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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LDPE Melt creep recovery

Recoverable Compliance Jr(t) [1/Pa]

-1 -1
10 LDPE Melt 10
ƒ 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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Neat and Filled LDPE

10
7
o
ƒ &ŝůůĞƌƐŝŶĐƌĞĂƐĞƚŚĞ
Temperature 180 C ŵĞůƚǀŝƐĐŽƐŝƚLJ
LDPE filled
6
10 LDPE neat
ƒ ƵĞƚŽŝŶƚĞƌͲƉĂƌƚŝĐůĞ
Viscosity η(γ) [Pa s]

5
ŝŶƚĞƌĂĐƚŝŽŶƐ͕ƚŚĞ
10
. ŶŽŶͲEĞǁƚŽŶŝĂŶ
4
ƌĂŶŐĞŝƐĞdžƚĞŶĚĞĚƚŽ
10 ůŽǁƐŚĞĂƌƌĂƚĞƐĂŶĚ
ƚŚĞnjĞƌŽƐŚĞĂƌ
3
10 ǀŝƐĐŽƐŝƚLJŝŶĐƌĞĂƐĞƐ
ĚƌĂŵĂƚŝĐĂůůLJ
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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Fix drum connected to transducer

Rotating drum connected to the motor:

ƒ rotates around its axis
ƒ rotates around axis of fixed drum
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ƒ Application to processing: many processing flows are

elongation flows - testing as close as possible to
processing conditions (spinning, coating, spraying)

ƒ Relation to material structure: non linear elongation

flow is more sensitive for some structure elements
than shear flows (branching, polymer architecture)

ƒ Testing of constitutive equations: elongation results in

addition to shear data provide a more general picture
for developing material equations

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ƒ Thermosetting polymers are perhaps the

most challenging samples to analyze on
rheometers as they challenge all instrument
specifications both high and low.

ƒ 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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ƒ Monitor the curing process

ƒViscosity change as function of time or temperature
ƒ Gel time or temperature
ƒ Test methods for monitoring curing
ƒTemperature ramp
ƒIsothermal time sweep
ƒCombination profile to mimic process
ƒ Analyze cured material’s mechanical properties (G’,
G”, tan δ , Tg etc.)

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ƒ Molecular weight Mw goes to infinity

ƒ System loses solubility
ƒ Zero shear viscosity goes to infinity
ƒ 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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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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• 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.
ƒ 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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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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ƒ Collimated light and mirror assembly insure uniform irradiance

ƒ Maximum intensity at plate 300 mW/cm2
ƒ Broad range spectrum with main peak at 365 nm
ƒ Cover with nitrogen purge ports
ƒ Optional disposable acrylic plates
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ƉĞƌƐĞĐŽŶĚ

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ƒ Glass transition
ƒ Secondary transitions
ƒ Crystallinity
ƒ Molecular weight/cross-linking
ƒ Phase separation (polymer blends, copolymers,...)
ƒ Composites
ƒ Aging (physical and chemical)
ƒ Curing of networks
ƒ Orientation
ƒ 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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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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ƒ 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
Isotherm
ƒ
1.000E9
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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ƒ 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

сϮ';ϭнʆͿ ʆ ͗WŽŝƐƐŽŶ͛ƐƌĂƚŝŽ
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 - Cooperative motion among a large number of

chain segments, including those from neighboring polymer chains

Secondary Transitions
ƒ Local main-chain motion - intramolecular rotational motion of
main chain segments four to six atoms in length
ƒ Side group motion with some cooperative motion from the main
chain
ƒ Internal motion within a side group without interference from
side group
ƒ 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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Increasing
Crystallinity
log Modulus

Amorphous Crystalline

3 decade drop Cross-linked

in modulus at Tg

Increasing MW
Tm

Temperature

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ƒ Multiphase systems consisting of a dispersed phase

(solid, fluid, gas) in surrounding fluid phase

ƒExamples are: ƒ Properties:

ƒ Paints ƒ Yield Stress
ƒ Coatings ƒ Non-Newtonian
ƒ Inks Viscous Behavior
ƒ Personal Care Products ƒ Thixotropy
ƒ Cosmetics ƒ Elasticity
ƒ Foods

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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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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 ∝ ߛሶ m or, equivalently, η ∝ ߛሶ m-1

m is usually 0.15 to 0.6

log ߛሶ
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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Brownian diffusion
randomizes

Shear field aligns

particles along
ůŽŐ η streamlines Turbulent flow pushes
particles out of
alignment, destroying
order and causing
increase in viscosity
(shear thickening)

Shear thinning Shear thickening

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ƒLinear or Exponential speed profile after reaching ‘Closure Distance’

ƒNormal Force set not to exceed a certain value after reaching the user
defined ‘Closure Distance’

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ϮϱϬ
Exponential Close
ϮϬϬ
G' (Pa)

ϭϱϬ
Fast Linear Close
ϭϬϬ

ϱϬ

Ϭ
Ϭ ϮϬϬ ϰϬϬ ϲϬϬ ϴϬϬ ϭϬϬϬ
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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ƒ Monitor the viscosity signal during the pre-shear to

determine if the rate and duration are appropriate
ƒ 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
ƒ The viscosity should decrease and then level off
ƒ Typical Pre-Shear: 1- 100 sec-1, 30-60 seconds
ƒ Use an amplitude sweep to determine what strain to use
for time sweep
ƒ A high strain will break down the sample, and not allow rebuilding
ƒ A low strain will give a weak signal
ƒ Based on the Time Sweep, determine an appropriate
equilibration time for that sample

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ƒ The goal for pre-shear is to remove the sample history at loading

ƒ For high viscosity sample, use low rate (10 1/s) and long time (2 min.)
ƒ For low viscosity sample, use high rate (100 1/s) and short time (1 min.)

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1. 2. 3.

Three consecutive time sweeps:

ƒ Time sweep within LVR (check if loading destroyed structure)
ƒ Time sweep at large strain
ƒ Time sweep back to LVR (check structure rebuild)

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ƒStructured 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.

ƒThere 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?

ƒ to avoid sedimentation and increase the shelf live
ƒ to reduce flow under gravity
ƒ to stabilize a fluid against vibration

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ƒ Stress is ramped linearly from 0 to a value above Yield Stress and the stress at
viscosity maximum can be recorded as Yield Stress
ƒ 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

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When the Yield Stress is small, a flow rate sweep from high
to low shear rate is preferred
ƒ Eliminates start-up effects for
more accurate measurements
slope: -0.995
ƒ Initial high shear rate acts as a
pre-shear, erasing loading effects

ƒ Steady State sensing allows the

sample time to rebuild

ƒ The plateau in shear stress is a

measure of the yield stress.

ƒ At the plateau, Viscosity vs.

Shear Rate will have a slope of -1

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1000 ƒ Perform strain or stress

Sun Block Lotion
sweep in oscillation

ƒ 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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ƒ Low shear viscosity 10-3 to 1 s-1

ƒ leveling, sagging, sedimentation

ƒ Medium shear viscosity10-103 s-1

ƒ mixing, pumping and pouring

ƒ High shear viscosity 103 - 106 s-1

ƒ brushing, rolling spraying

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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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The thixotropy characterizes the time dependence of

reversible structure changes in complex fluids. The
control of thixotropy is important to control:
ƒ process conditions for example to avoid structure build up in pipes
at low pumping rates i.e. rest periods, etc....

ƒ sagging and leveling and the related gloss of paints and coatings,
etc..

Sag Leveling

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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
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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]

‫ ܩ‬ᇱ ‫ ݐ‬ൌ ‫ܩ‬Ԣ௢ ൅ ሺ‫ܩ‬Ԣஶ െ ‫ܩ‬Ԣ௢ ሻሺͳ െ ݁ ௧Ȁఛ ) τ = characteristic recovery time

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ĐсĐŚĂƌĂĐƚĞƌŝƐƚŝĐƌĞĐŽǀĞƌLJƚŝŵĞ;τͿ

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ƒThe 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.

ƒThe 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
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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)

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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)

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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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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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Sticks: Rheology and process performance

ƒ use small particles to reduce sedimentation speed

ƒ add rheological modifier like clay to stabilize the suspension

and keep the particles in suspension

ϭнϬϴ
x x x x x x
x
ϭнϬϳ x The temperature
x
DŽĚƵůƵƐ'Ζ΀WĂ΁

ϭнϬϲ x dependence of the

modulus governs the
ϭнϬϱ
x behavior during the
ϭнϬϰ x application to the skin
ϭнϬϯ
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dĞŵƉĞƌĂƚƵƌĞ΀΁

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Cosmetic lotion
ƒ Many dispersion exhibit
2.0
solid like behavior at rest
Modulus G', G'' [Pa]; Viscosity η* [Pa s]

3
10
1.5

ƒ 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]

ƒ Note: strain amplitude has to be in the linear region

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DIN Vane

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ƒ Browse the contents list or

search using the search tab.

ƒ Access to Getting Started

Guides also found through
the help menu.

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ƒFrom www.tainstruments.com click on Videos, Support or Training

ƒSelect Videos for TA Tech Tips, Webinars and Quick Start Courses

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Quickstart e-Training Courses Strategies for Better Data - Rheology

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ƒ Check the online manuals and error help.

ƒ Contact the TA Instruments Hotline
ƒ Phone: 302-427-4070 M-F 8-4:30 EST
ƒ Select Thermal , Rheology or Microcalorimetry Support
ƒ Email: [email protected] or
[email protected] or
[email protected]
ƒ Call your local Technical or Service Representative
ƒ Call TA Instruments
ƒ Phone: 302-427-4000 M-F 8-4:30 EST
ƒ Check out our Website: www.tainstruments.com
ƒ For instructional videos go to: www.youtube.com/user/TATechTips

TAINSTRUMENTS.COM
 Thank You

The World Leader in Thermal Analysis,

Rheology, and Microcalorimetry

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(E' or G') (E' or G')

(E" or G") (E" or G")

log Frequency Temperature

ƒ Linear viscoelastic properties are both time-dependent and
temperature-dependent
ƒ Some materials show a time dependence that is proportional to the
temperature dependence
ƒ Decreasing temperature has the same effect on viscoelastic
properties as increasing the frequency
ƒ 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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ƒ TTS can be used to extend the frequency beyond the

instrument’s range
ƒ Creep TTS or Stress Relaxation TTS can predict
behavior over longer times than can be practically
measured
ƒ Can be applied to amorphous, non modified polymers
ƒ Material must be thermo-rheological simple
ƒ One in which all relaxations times shift with the same shift factor aT

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ƒ If crystallinity is present, especially if any melting

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

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ƒ Decide first on the Reference Temperature: T0. What is the

use temperature?

ƒ 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.

ƒ If you want to obtain information at lower frequencies or

longer times, you will need to test at temperatures higher
than T0.

ƒ 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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aT=140
aT=150
aT=160

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ƒ Master Curves can be generated using shift factors

derived from the Williams, Landel, Ferry (WLF)
equation
log aT= -c1(T-T0)/c2+(T-T0)
ƒ aT = temperature shift factor
ƒ T0 = reference temperature
ƒ c1 and c2 = constants from curve fitting
ƒ Generally, c1=17.44 & c2=51.6 when T0 = Tg

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ƒ Sometimes you shouldn’t use the WLF equation (even if it

appears to work)
ƒ If T > Tg+100°C
ƒ If T < Tg and polymer is not elastomeric
ƒ If temperature range is small, then c1 & c2 cannot be calculated
precisely

ƒ In these cases, the Arrhenius form is usually better

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

ƒ aT = temperature shift factor

ƒ Ea = Apparent activation energy
ƒ T0 = reference temperature
ƒ T = absolute temperature
ƒ R = gas constant
ƒ Ea = activation energy

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Polystryene

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Polystryene

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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.

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Control variables:
ƒ Shear rate
ƒ Velocity
ƒ Torque
ƒ Shear stress

ƒ Thixotropic loop be done by adding another ramp step

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Control variables:
ƒ Shear rate
ƒ Velocity
ƒ Torque
ƒ Shear stress

Steady state algorithm

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To minimize thermal
lag, the ramp rate
should be slow.
1-5°C/min.

Control variables:
ƒ Shear rate
ƒ Velocity
ƒ Torque
ƒ Shear stress

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Control variables:
ƒ Osc torque
ƒ Osc stress
ƒ Displacement
ƒ % strain
ƒ Strain

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Pre-shear can be setup

by adding a
“conditioning” step before
the time sweep.

ƒ The strain needs to be in the LVR

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Pre-shear step

Structure Recovery

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ƒ Strain control mode ƒ Stress control mode

ƒ Fast data acquisition is used for monitoring fast changing

reactions such as UV initiated curing
ƒ The sampling rate for this mode is twice the functional oscillation
frequency up to 25Hz.
ƒ The fastest sampling rate is 50 points /sec.

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Control variables:
ƒ Osc torque
ƒ Osc stress
ƒ Displacement
ƒ % strain
ƒ Strain

ƒ Common frequency range: 0.1 – 100 rad/s.

ƒ Low frequency takes long time
ƒ As long as in the LVR, the test frequency can be set either from
high to low, or low to high
ƒ The benefit doing the test from high to low
ƒ Being able to see the initial data points earlier
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Control variables:
ƒ Osc torque
ƒ Osc stress
ƒ Displacement
ƒ % strain
ƒ Strain

ƒ The strain needs to be in the LVR

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To minimize thermal
lag, recommend
using slow ramp rate
e.g. 1-5°C/min.

ƒ The strain needs Control variables:

to be in the LVR ƒ Osc torque
ƒ Osc stress
ƒ Displacement
ƒ % strain
ƒ Strain

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ƒ It is important to setup normal force control during any temperature

change testing or curing testing
ƒ Some general suggestions for normal force control
ƒ For torsion testing, set normal force in tension: 1-2N ± 0.5-1.0N
ƒ For curing or any parallel plate testing, set normal force in
compression: 0 ± 0.5N

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Creep Recovery

ƒ Rule of thumb: recovery time is 2-3 times longer than creep time

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Requires measured
modulus to start feed
back loop

ƒ Motor and transducer work in a feedback loop

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ƒ Set up a pre-test and get the sample information into the loop
ƒ Stress Control Pre-test: frequency sweep within LVR

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Control variables:
ƒ Shear rate
ƒ Velocity
ƒ Torque
ƒ Shear stress

ƒ Multiple rate can be done by adding more peak hold steps

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Control variables:
ƒ Shear rate
ƒ Velocity
ƒ Torque
ƒ Shear stress

ƒ Thixotropic loop be done by adding another ramp step

ƒ Or go through the template

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Control variables:
ƒ Shear rate
ƒ Velocity
ƒ Torque
ƒ Shear stress

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Control variables:
ƒ Shear rate
ƒ Velocity
ƒ Torque
ƒ Shear stress

Steady state algorithm

ƒ 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.
ƒ An average value for the dependent variable is recorded over the Sample period.
ƒ When consecutive average values (Consecutive within tolerance) are within the
Percentage tolerance specified here, the data is accepted.
ƒ 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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To minimize thermal
lag, the ramp rate
should be slow.
1-5°C/min.

Control variables:
ƒ Shear rate
ƒ Velocity
ƒ Torque
ƒ Shear stress

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Variables:
Stress
Torque

ƒ For running an unknown sample, it is recommended to sweep torque instead of

stress. Because stress is geometry dependent
ƒ The starting torque can be from the lowest of the instrument specification
ƒ 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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Control variables:
ƒ Osc torque
ƒ Osc stress
ƒ Displacement
ƒ % strain
ƒ Strain

ƒ The strain needs to be in the LVR

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ƒ The goal for pre-shear is to remove the sample history at loading

ƒ For high viscosity sample, use low rate (10 1/s) and long time (2 min.)
ƒ For low viscosity sample, use high rate (100 1/s) and short time (1 min.)

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Control variables:
ƒ Osc torque
ƒ Osc stress
ƒ Displacement
ƒ % strain
ƒ Strain

ƒ Common frequency range: 0.1 – 100 rad/s.

ƒ Low frequency takes long time
ƒ As long as in the LVR, the test frequency can be set either from
high to low, or low to high
ƒ The benefit doing the test from high to low
ƒ Being able to see the initial data points earlier

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Control variables:
ƒ Osc torque
ƒ Osc stress
ƒ Displacement
ƒ % strain
ƒ Strain

ƒ The strain needs to be in the LVR

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To minimize thermal
lag, recommend
using slow ramp rate
e.g. 1-5°C/min.

Control variables:
ƒ Osc torque
ƒ Osc stress
ƒ Displacement
ƒ % strain
ƒ The strain needs to be in the LVR
ƒ Strain

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During a test

Before starting a test

ƒ It is important to setup normal force control during any temperature

change testing or curing testing
ƒ Some general suggestions for normal force control
ƒ For torsion testing, set normal force in tension: 1-2N ± 0.5-1.0N
ƒ For curing or any parallel plate testing, set normal force in
compression: 0 ± 0.5N

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ƒ Motor and transducer work in a feedback loop

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ƒ Rule of thumb: recovery time is 2-3 times longer than creep time
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Default
values
shown

ƒ During the test, the angular velocity is monitored with time to

determine when stability has been reached.
ƒ An average value for the angular velocity is recorded over the
Sample period.
ƒ When consecutive average values (Consecutive within
tolerance) are within the tolerance specified here, the data is
accepted.

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ƒ Instrument Calibrations
ƒ Inertia (Service)
ƒ Rotational Mapping
ƒ Oscillation Mapping (recommended for interfacial measurements)

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ƒ Go to the Calibration tab and select Instrument

ƒ Make sure there is no geometry installed and then click calibrate

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ƒ Geometry Calibrations:
ƒ Inertia
ƒ Friction
ƒ Gap Temperature
Compensation
ƒ Rotational Mapping

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ƒ 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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ƒ Instrument Calibrations
ƒ Temperature Offsets
ƒ Phase Angle (Service)
ƒ Measure Gap Temperature
Compensation
ƒ Transducer

ƒ Geometry Calibrations:
ƒ Compliance and Inertia (from table)
ƒ Gap Temperature Compensation

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ƒ Gap Temperature Compensation

ƒ Enter manually or run calibration

ƒ Compliance and Inertia

ƒ (from table in Help menu)

ƒ Geometry Constants
ƒ Calculated based on dimensions

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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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ƒ Air Supply
ƒ Dry particulate-free air (dew point -40 °C)
ƒ Check filters/regulators on a periodic basis to ensure proper
pressure, free of moisture/oil/dirt buildup.
ƒ If air must be turned off, then make sure that the bearing lock is
fastened
ƒ NOTE: Do not rotate drive-shaft if air supply is OFF!

ƒ Location
ƒ Isolate the instrument from vibrations with a marble table or
Sorbathane pads.
ƒ 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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ƒ Circulator Maintenance
ƒ Proper operation of a fluid circulator is vital for correct
and efficient operation of Peltier-based temperature
control devices.

ƒ Check fluid levels and add anti-fungal additive regularly.

ƒ 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.
ƒ Example: add ~20% v/v ethanol to water

ƒ Keep it clean!
ƒ Flush and clean circulator, Peltier system, and tubing at
first sight of contamination.

ƒ When not in use, it is strongly recommended to

deactivate the Peltier device and turn off the circulator.

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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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ƒ Polymer samples come in different forms (e.g. powder, flakes,

pellets) and can be sensitive to environmental conditions
ƒ Careful sample preparation techniques are required to prepare
good test specimens for reproducible testing
ƒ Molding a sample

ƒ Handling powders, flakes

ƒ Controling the environment

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ƒ The best approach is to mold a sample plate (50x50 mm2 or 100x100 mm2)
ƒ Molding temperature: 10 - 20°C > than test temperature
ƒ Apply pressure: 8 – 12,000 lbs
ƒ Keep at elevated temperature long enough to let the sample relax
ƒ Cool down slowly under pressure to avoid orientations
ƒ Punch out a sample disk (8 or 25 mm)

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ƒ Before molding at high temperature, the sample has to be compacted

cold to reduce the volume
ƒ The compacted samples are transferred to the mold
ƒ Follow steps from the molding pellets procedure
ƒ Note: Sample may need to be stabilized or dried to avoid degradation

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ƒ Cut rectangular sheets of prepreg or adhesive (30x30mm)

ƒ Alternate direction of layer approx. 5 layer on top of each other
(remove release paper from PSA)
ƒ Compress the stack of sample layers in a press (4 – 5000 lbs)
ƒ Punch out 25 mm disks

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ƒ Polypropylene and Polyolefines in general tend

to degrade fast – need to be stabilized by
adding antioxidents
ƒ Moisture sensitive materials such as
polyamides and polyester require drying in
vacuum or at temperatures around 80°C.
ƒ Materials such as Polystyrene or Polymethyl-
methacrylate (PMMA) also absorb moisture. In
the melt phase, the gas separates into bubbles
and the sample foams
ƒ Pre-drying in vacuum is essential prior to
Vacuum oven
testing

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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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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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ƒ Structured fluids can range in consistency from low viscosity (e.g. milk)
to high viscosity, pasty materials (e.g. tooth paste)
ƒ Structured materials are very sensitive to mechnical and
environmental conditions
ƒ Be aware of largest particle size in sample and choose the geometry
appropriately (cone vs parallel plate vs vane geometry)
ƒ Samples can also be time dependent – how you treat the sample
(handling, loading, pre-conditioning) may affect test results!
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ƒ Fluid samples which pour freely are relatively easy to handle prior to loading
ƒ Keep the container closed to avoid evaporation of solvent or continuous phase
ƒ Shake or stir sample to remove concentration gradients in suspensions
ƒ Adequate shelf temperature may be necessary to avoid phase separation in
emulsions
ƒ Never return used sample into original flask to avoid contamination

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ƒ Deposit fluid in the middle of the plate

ƒ Set a motor velocity of ~ 1 rad/s and move to geometry gap
ƒ Add additional material along the sides of the geometry – capillary forces will
draw the sample between the gap
ƒ When finished, click on the “Stop Motor” button
ƒ 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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ƒ The structure of high viscosity pastes and slurries may change with time
ƒ Food samples, like dough, can change continuously
ƒ The test samples need to be prepared carefully and consistently for
each experiment to obtain reproducibility
ƒ Slurries that may settle can gradually build a cake – these samples
have to be tested before sedimentation

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ƒ Scoop up the paste with a spatula and deposit it at the center of the lower plate
ƒ For less viscous materials, a syringe with a cut-off tip can be used
ƒ Load ~ 10-20 excess material to ensure complete sample filling
ƒ Set the gap to the trim gap and use exponential gap closure profile to minimize
shear in the sample
ƒ Lock the bearing, trim excess material and set final gap

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ƒ Gels, especially chemical gels, may change irreversibly when large deformations
are applied (for example, while loading)
ƒ Prepare (formulate) the sample in the final shape required for the measurement
so it can be loaded without deforming (cut, punch, …)
ƒ Alternatively, prepare the sample in situ – on the rheometer Æ systemic rheology
ƒ Take care to avoid introducing air bubbles!

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