Basic Rheological Principles

&
Applications from the Nano Torque Level
to Advanced Testing Accessories

Abel Gaspar-Rosas
TA Instruments - Waters Inc.
Email: agr@tainstruments.com
Phone: +1 302 363 0524

Ing. Mara del Pilar Pearanda C.

LANZETTA RENGIFO Y CA. LTDA.
ppenaranda@lanzettarengifo.com.co
Cel: 320-4227868
Objective
The workshop sections will reveal how to:
identify the testing capabilities of rheometers with Nano
Torque control
design of testing procedures
verification of rheological properties
adjustments to testing procedures
sequence of testing procedures
oscillatory
transient
rotational shear
interpretation of results
making sense of all generated results.
A Rheological Paradox
Fundamentals:

Why Rheology ?
Fundamental Rheology Concepts and Parameters
Fundamental Rheometry Concepts
Viscosity, Viscoelasticiy and the Storage Modulus
The Linear Viscoelastic Region (LVR)

Steps for a reliable Rheological Characterization of

Materials (polymers, foods, cosmetics, paints, etc.)
BECAUSE

If a material is pumped, sprayed, extended,

extruded, molded, coated, mixed, chewed,
swallowed, rubbed, transported, stored,
heated, cooled, aged

RHEOLOGY is important .!!

 BECAUSE Typical DSC Transitions

Oxidation
or
Decomposition

Melting
Heat Flow

Glass
Transition Cross-Linking
Crystallization (Cure)

Describe Thermal Transitions of the Materials Structure

Temperature
 (everything flows )
- Heraclito de Samos (500 A.C.)

Time Scale in Rheology

Deborah Number De = / texp

Judges 5:5

Our rheological vision should include the fundamental concept of time:

material characteristic response time and texp us

material characteristic recovery time and texp us
 FUNDAMENTAL CONCEPTS and PARAMETERS

CONCEPTS
Time
Distance
Mass
Force
Temperature

PARAMETERS Compliance
Shear Stress Storage Modulus
Torque
Shear Strain Loss Modulus
Angular Velocity
Shear Rate Loss Factor
Angular Frequency
Viscosity Phase Angle
Angular Displacement
Shear Modulus Characteristic Times
Inertia
Complex Viscosity Normal Force

Definition of Rheology

Rheology is the science of deformation

and flow of matter under controlled
testing conditions .

Flow is a special case of deformation

Deformation is a special case of flow
Simple Shear Deformation and Shear Flow

Shear Deformation
x(t)
Strain, y0
F x(t) =
= V
A
. V 1 d x(t
Strain Rate, y= y d t
0 0
y
y
0
A
Viscosity, .=
z x

. = Shear Modulus, G =
t
Range of Rheological Material Behavior

Rheology: The study of deformation and

flow of matter at specified conditions.

Range of material behavior

Solid Like --------- Liquid Like
(Ideal Solid ------------- Ideal Fluid)

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

100.0

osc. stress (Pa)

G
G' (Pa)

10.00

1.000 0.01000
0.010000 0.10000 1.0000 10.000 100.00 1000.0
% strain
 Newtonian and Non-Newtonian
Behavior of Fluids
1.000E5 Non-Newtonian 1.000E5
Newtonian Region Region
Independent of = f()
10000

1000

(Pa)
(Pa.s)

100.0

10.00

10000 1.000
1.000E-5 1.000E-4 1.000E-3 0.01000 0.1000 1.000

shear rate (1/s)

PARAMETERS for Rheological Properties
Classical Extremes
Ideal Solid -- [External Force] -- Ideal Fluid
STEEL WATER
Strong Structure Weak Structure
Rigidity Fluidity
Deformation Flow
Retains/recovers form Losses form
Stores Energy Dissipates Energy
(Purely Elastic R. Hooke, 1678) [Energy] (Purely Viscous I. Newton, 1687)
ELASTICITY VISCOSITY
Storage Modulus Loss Modulus
REAL Behavior
Apparent Solid [Energy + time] Apparente Fluid

- viscoelastic materials -
Viscometer vs. Rheometer
Viscometer: instrument that measures the viscosity of a
fluid over a limited shear rate range

Rheometer: instrument that measures:

Viscosity over a wide range of shear rates, and
Viscoelasticity of fluids, semi-solids and solids

TWO fundamental technologies SMT and CMT

SMT Separated Motor & Transducer
CMT Combined Motor & Transducer

TA Instruments ONLY company that offers both Technologies

TWO RHEOMETER technologies - SMT and CMT

Combined Motor and Transducer

Separated Motor and Transducer
 Design of Rotational Rheometers

Strain Controlled Stress Controlled

SMT Separated motor & Xducer CMT Combined motor & Xducer

Displacement
Torque Transducer Sensor
(Stress) Strain or Rotation
Measured Measured

Non-Contact
Drag Cup
Motor

Torque
(Stress)
Applied

Strain Direct
(Displacement Drive FIXED Plate
applied)
Motor
Constitutive Relations

Stress
Modulus
Strain

Stress
Vis cos ity
Shear rate
Measuring Systems - Geometries
Rectangular
Concentric Cone and Torsion
Parallel
Cylinders Plate Plates

Very Low to Very Low to Low Viscosity

Medium High to soft
Viscosity Viscosity Solids
Soft to Rigid
Solids

Decane Water Steel

Controlled Strain SMT Specifications
Controlled Stress CMT Specifications
INERTIA
SMT & CMT Rheometers
 Inertial Effects

Definition: That property of matter

which manifests itself as a resistance
to any change in momentum of a
body
CMT: Inertia Ratio (Torque - System/Sample)

Inertia Torque
TI Ik g
< 10
Sample Torque TS * As * decreases, Torque
ratio increases

A torque ratio of 10 means the torque consumption due to

Inertia is tenfold the energy consumption of the sample.
For 100 cP fluid a ratio of 10 is reached at a frequency of 20 rad/s
For a 10 cP fluid a ratio of 10 is reached at a frequency of 2 rad/s
 Torque ratio: CMT Rheometer
Inertia/Sample torque ratio

TI Ik g 1000

Ratio10cP

TS * 100
Ratio100cP

Frequency
10
limit for
Torque ratio

arbitrary
1
ratio TI/TS
= 10
0.1

0.01
0.01 0.1 1 10 100 1000
Frequency [rad/s]
SMT: Inertia Torque Sample Torque ratio

TI CTR I 2

TS (1 CTR I )
2

Note that the torque ratio for an SMT rheometer is

independent of the materials viscosity.
The torque ratio depends on the transducers inertia and
compliance.
Torque ratio: SMT Rheometer
Inertia/Sample torque ratio
10

TI CTR I 2
1 Ratio 2KFRTN1
Ratio 1KFRTN1
TS (1 CTR I 2 ) 0.1

0.01

Torque ratio
1E-3

Error at 100 rad/s: 1E-4

1E-5
- 2KFRTN1: 1.83%
- 1KFRTN1: 3.4% 1E-6

1E-7
628 rad/s
1E-8
0.01 0.1 1 10 100 1000
Frequency [rad/s]
Frequency Range

ARES (SMT)
Frequency range is independent on the sample being
tested
Depends only on the Transducer

AR (CMT)
Frequency range is dependent on samples viscosity
This is inherent in all CMT designs
Must account for system inertia for all tests
Can be determined directly when plotting frequency versus
a variable called RAW PHASE for Oscillatory Tests
Other instruments
Do not allow/offer all information/access needed
Inertial Effects in Oscillation for AR

Concern in oscillation experiments particularly

at high frequency with low viscosity fluids

Minimize correction by using low mass geometries

Plot raw phase and delta.
If raw phase is close to 150 then inertia is dominating results

raw phase Inertia Correction = delta =

AR Correction for Inertia
1.000E6 1.000E6 70.00 70.00
Negligible correction at low frequencies
Pdms-ar-04o
60.00 60.00

50.00 50.00

1.000E5 1.000E5

rawph
40.00 40.00
'' (Pa)

delta (degrees)
' (Pa)

ase (degrees)
G

30.00 30.00

10000 10000

20.00 20.00

10.00 10.00
Increasing correction at higher frequencies

1000 1000 0 0
0.01000 0.1000 1.000 10.00 100.0
frequency (Hz)
AGENDA

Why Rheology ?
Fundamental Rheology Concepts and Parameters
Fundamental Rheometry Concepts
Viscosity, Viscoelasticiy and the Storage Modulus
The Linear Viscoelastic Region (LVR)

Ten Steps for a reliable Rheological Characterization of

Polymers
Dynamic Testing

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

The phase angle , or phase

shift, between the deformation Phase angle
and response is measured.
Dynamic Viscoelastic Material Response

Phase angle 0 < < 90

Stress

Strain
Viscoelastic Parameters

The Complex Modulus: Measure of

materials overall resistance to G* = Stress*/Strain
deformation. G* = G + iG
The Elastic (Storage) Modulus:
Measure of elasticity of material. The
ability of the material to store energy.
G' =
(stress*/strain)cos
The Viscous (loss) Modulus:
The ability of the material to dissipate G" =
energy. Energy lost as heat.
(stress*/strain)sin
Tan Delta:
Measure of material damping - such
as vibration or sound damping. Tan = G"/G'
Dynamic Time Sweep (Time Ramp)

Deformation
Stress or Strain

The material response

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

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

Why Rheology ?
Fundamental Rheology Concepts and Parameters
Fundamental Rheometry Concepts
Viscosity, Viscoelasticiy and the Storage Modulus
The Linear Viscoelastic Region (LVR)

Ten Steps for a reliable Rheological Characterization of

Polymers
Dynamic Stress or Strain Sweep
(Torque Ramp)

Deformation
Stress or Strain

The material response

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

USES
IdentifyLinear Viscoelastic Region
Strength of dispersion structure - settling stability
Resilience
 Dynamic Strain Sweep: Material Response

1000 Non-Linear Region 100.0

Linear Region
G is constant G = f()

100.0

osc. stress (Pa)

G' (Pa)

10.00

Critical Strain c

1.000 0.01000
0.010000 0.10000 1.0000 10.000 100.00 1000.0
% strain
Frequency Sweep
Stress or Strain

Deformation The material response to

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

USES
Viscosity Information - Zero Shear , shear thinning
Elasticity (reversible deformation) in materials
MW & MWD differences Polymer Melts and Polymer solutions.
Finding Yield in gelled dispersions
High and Low Rate (short and long time) modulus properties.
Extend time or frequency range with TTS
Oscillation Model Fitting for Classic Polymer
Data [Polyacrylamide Soln.]
The Sequence of a Rheological Experiment

Identify the purpose of the experiment

Design, program and run the test

Evaluate and optimize test and data

(if necessary)

Present Results
Sequence of a Rheological Experiment
Identify the purpose of the experiment
1. Understand why doing the measurement

Design, program and run the test

2. Understand your instrument
3. Know your sample
4. Selecting correct test fixtures Points 3 through 8 are
5. Oscillation testing guidelines sample specific
6. Transient testing guidelines Polymers
7. Steady shear testing guidelines Structured Fluids
8. Loading the sample Foods

Evaluate data and optimize if necessary

9. Instrument limitations

Results
10. Presenting the data
Ten Steps to Rheologically Characterize Polymers

1. Understand why you are doing the measurement

2. Understand your instrument
3. Know your sample
4. Selecting the correct test fixture
5. Loading the sample
6. Oscillation testing guidelines
7. Transient testing guidelines
8. Steady shear testing guidelines
9. Some instrument limitations
10. Presenting the data
1. Understand Why you are Doing the
Measurement
The first step in any rheological experiment is to
identify the purpose of your experiment.

The 3 principal reasons for Rheological Testing are:

Characterization of structure in terms of:

- MW, MWD, formulation, state of flocculation, etc.
Predicting process performance, such as:
- Extrusion, blow molding, pumping, leveling, etc.
Understand end-use performance
- Strength, use temperature, dimensional stability,
settling stability, etc.
Rheological Testing Approach
Use rheometer to characterize flow and
viscoelastic properties to:

1. Understand structure
Requires understanding of how structure affects rheological
properties

2. Predict processing performance

Requires understanding of what rheological properties are desired
for processing

3. Predict product performance

Requires understanding of desired performance characteristics
and how they relate to rheological properties
Influence of MW and MWD on Viscosity

The zero shear viscosity increases with increasing molecular weight.

[TTS was applied to obtain the extended frequency range]
7
10
SBR Mw [g/mol]
130 000
10
6
230 000 The high
320 000 frequency
Viscosity * [Pa s]

430 000
10
5
behavior
(slope -1) is
Z
eirsoS
shite
yar independent of
ZeroShearViscosityo[Pas]

4
10 V co
106 the molecular
10
3
Slope3.08+/-0.39 weight
105
100000
10
2
M
olecilarweightM
w[D
altons]

-4 -3 -2 -1 0 1 2 3 4 5
10 10 10 10 10 10 10 10 10 10
Frequency aT [rad/s]
Influence of MW on G and G

The G and G curves are shifted at lower frequency

with increasing molecular weight.

Freq [rad/s]
Influence of MWD on G and G
6
10

The maximum in G is a
5
good indicator of the
Modulus G', G'' [Pa]

10

broadness of the
distribution
4
10
SBR polymer melt
G' 310 000 broad
3 G" 310 000 broad
10 G' 320 000 narrow
G" 320 000 narrow 2.0x10
5
narrow
-3 -2 -1 0 1 2 3 4
10 10 10 10 10 10 10 10 5
1.5x10

Modulus G'' [Pa]

Frequency aT [rad/s]

1.0x10
5
broad
The G, G cross-over
point is another
4
5.0x10

measure of the 0.0 SBR G'' 320 000

SBR G'' 310 000 (broad)
broadness of the 10
-3 -2
10
-1
10 10
0
10
1
10
2 3
10
4
10
distribution Frequency aT [rad/s]
Why do we do the measurement?
Predict Processability
Predict End-Use Performance
Glass Transition and secondary transitions
Damping behavior
Determine working temperature range, impact behavior,
residual strain trapped in moldings, etc..
Degree of curing, post curing
Aging
Compatibility, Dispersion,
Morphology characterization, Crystallinity,
Fingerprint of materials
Defining Shear Rate Ranges
Situation Shear Rate Examples
Range
Sedimentation of fine powders in liquids 10-6 to 10-3 Medicines, Paints, Salad Dressing

Leveling due to surface tension 10-2 to 10-1 Paints, Printing inks

Draining off surfaces under gravity 10-1 to 101 Toilet bleaches, paints, coatings
Extruders 100 to 102 Polymers, foods
Chewing and Swallowing 101 to 102 Foods
Dip coating 101 to 102 Confectionery, paints
Mixing and stirring 101 to 103 Liquids manufacturing
Pipe Flow 100 to 103 Pumping liquids, blood flow
Brushing 103 to 104 Painting
Rubbing 104 to 105 Skin creams, lotions
High-speed coating 104 to 106 Paper manufacture
Spraying 105 to 106 Atomization, spray drying
Lubrication 103 to 107 Bearings, engines
Ten Steps to Rheologically Characterize Polymers

1. Understand why you are doing the measurement

2. Understand your instrument
3. Know your sample
4. Selecting the correct test fixture
5. Loading the sample
6. Oscillation testing guidelines
7. Transient testing guidelines
8. Steady shear testing guidelines
9. Some instrument limitations
10. Presenting the data
Ranges of Rheometers and DMAs

Some Viscoelastic
log E' (G') and E" (G")

Liquid
Characterization
Possible with
Shear Sandwich

Range of DMA/RSA

Range of AR/ARES Rheometer

Storage Modulus (E' or G')

Loss Modulus (E" or G")

Temperature
Rotational Rheometer Designs

ARES Separated AR Series Combined

motor & transducer motor & transducer
Transducer Displacement
Measured Sensor
Torque Measures Strain
(Stress)
or Rotation
Non-Contact
Drag Cup
Motor

Applied
sample Torque
(Stress)

Applied Direct
Static Plate
Strain or Drive
Rotation Motor
Foods or Polymers or Paints or
Identify the purpose of the experiment
1. Understand why your doing the measurement
Design, program & run test
2. Understand your instrument
3. Know yoursample
4. Selecting correct test fixtures
5. Oscillation testing guidelines
6. Transient testing guidelines
7. Steady shear testing guidelines
8. Loading the sample
Evaluate data and optimize if necessary
9. Instrument limitations
Results
10. Presenting the data
Important Rheometer Specifications
Rheology is the science of flow and deformation of matter
or
Rheology is the science of deformation and flow of matter
or
the study of stress strain (deformation) relationships

Fundamentally a Rotational Rheometer or DMA will control or

measure:
1. Force or Torque
2. Displacement or Angular Displacement
3. Linear or Angular Velocity
4. Normal Force
5. Temperature
3. Know your sample

Polymers samples come in different forms (powder,

granule, gels,suspensions, emulsions, pellets) and are
sensitive to environmental conditions.
Careful sample preparation techniques are required to
prepare good test specimens for reproducible testing.

Molding a sample...
Handling powders, granul, gels...
Controling the environment...
4. How to select the correct test fixture
(Geometries)
Concentric Cone and Rectangular Torsion
Parallel
Cylinders Plate Plates

Very Low to Very Low to Low Viscosity

Medium High to soft
Viscosity Viscosity Solids
Soft to Rigid
Solids

Decane Water Steel

Parallel Plate

For filled and unfilled polymer systems. This

geometry is predominately used for oscillation
measurements in the linear-viscoelastic range.

R
Strain Constant: K = 20
H 40
2M 60
Stress Constant: K = (R)3 mm Shear
Stress

Caution: the shear rate varies with the radius!

Cone and Plate
For unfilled polymer melt systems. Primarily to be
used in transient and steady test modes, outside of
the linear viscoelastic range.

1 20
Strain Constant: K =
40
3 *M 60
Stress Constant: K = mm Shear
(R) 3
Stress

Note: the shear rate is constant over the radius.

Limitations of the Cone & Plate

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]!!

5. Loading the Sample

LoadingaMoldedDisk

Environmental system
to set test temperature.
Load disk onto plate
Close oven.
Bring upper plate to
gap position.
Watch Normal force set to final gap
To 1000 to 2000m
Open oven
Trim sample.
Close oven. sample trimming
Adjust gap
Normal Force Gap Closing

Most sensitive as the sample itself determines how

fast the gap is closed
Gap Closure is halted when a normal force > the
registered maximum value, and the sample is
allowed to relax before closure continues. This
avoids overload of the transducer when loading
high viscosity melts
The greater the maximum registered value the
faster the close
Closure may take some time for highly viscous
polymers. Loading at higher temperature will
speed the process up
Normal Force During Loading PDMS
30 7000

100microns/sec
25 50microns/sec 6000

Sample is still

gap (micro m)
20 5000
relaxing even
normal force (N)

after the
15
measurement gap 4000

is reached
10 3000

5 2000

0 1000
0 10.00 20.00 30.00 40.00 50.00 60.00 70.00 80.00 90.00

time (s)
6. Oscillation Testing Guidelines

Review Stimulus (stress )

1.5
Response (strain )
Amplitude
strain or 0
stress 0 6.3

phase angle,
-1.5
Time t (Period T = 1/frequency)

Applied: Frequency, strain or stress amplitude

Measured: Phase angle and ratio of strain and stress amplitude
Calculated:
G = Elastic Modulus: stored energy or elasticity
G = Viscous Modulus: dissipated energy
Tan G/G : damping factor
= Complex Viscosity: resistance to flow
 Testing in the Linear VE Region

100

10
In the LVR,
Linear Region
1
the dynamic
G is constant
parameters
Modulus G', G" [Pa]

Torque M [mN m]
100

Torque [mNm]
0.1
are indepen-
G' [Pa]
0.01 dent of strain.
Non-Linear
1E-3 Test results
Region G= f()
10 Critical strain c 1E-4 must be
1E-5 compared in
1E-7 1E-6 1E-5 1E-4 1E-3 0.01 0.1
the LVR.
Strain Amplitude [rad ]

Outside of the LVR the material response is no longer sinusoidal!

Testing the Frequency Dependence

C G
Represents the
A G viscoelastic nature
10
4 * [Pas]
of a material in time
G' [Pa], G'' [Pa]; * [Pas]

Provides information
10
3
about the material at
different processing
or application rates
()
.
2
10

0 1 2
10 10 10

Frequency [rad/s]

The upper frequency is limited by the instrument (but),

the lower frequency is typically 10-5 rad/s, a practical
limit is 0.1 or 0.01 rad/s
Importance of Frequency Sweeps

Tells about the materials reaction to short or long

excitation (elastic or viscous or both) times
Provides a quantitative measurement of the
elasticity (reversible deformation) in a material
Measurement of Viscosity:
Zero Shear viscosity at low frequency,
Steady viscosity at larger frequencies (Cox-Merz)
Power law index,

The frequency dependence of viscosity and

modulus correlates with MW & MWD.
3.4
G' Mw
0 M w3.4 and J e 2

( G" ) M z
 Stress Sweep on Polymer Melt in Parallel Plates
LLDPE at 150C and 1 Hz (6.28 rad/s)
1.000E5 100000.0

10000.0

osc. torque (micro N.m)

1000.0
G' (Pa)

100.0

Critical Strain 10.0

torque End of linear Region

10000 1.0
1.0000E-3 0.010000 0.10000 1.0000 10.000 100.00
% strain
Frequency Sweep: Material Response

Transition
Rubbery Region
Terminal Plateau
Region Region
log G'and G"

Glassy Region

1
2 Storage Modulus (E' or G')
Loss Modulus (E" or G")
 Dynamic Moduli of a Polymer Melt vs. Frequency

1000000 1000000 1.00E7

PDMS at 20C
100000 100000
1000000
10000 10000
G'' (Pa)

*
100000
1000 1000

100.0 100.0 10000

10.00 10.00
G
" 1000
1.000 1.000

G'
100.0
0.1000 0.1000
1.000E-4 1.000E-3 0.01000 0.1000 1.000 10.00 100.0 1000
ang. frequency (rad/sec)
Ten Steps to Better Rheological Measurements
1. Understand why you are doing the measurement.
2. Understand the instrument first.
3. Know your sample.
4. How to select the correct test fixture
5. Loading the sample
6. Oscillation testing guidelines
7. Transient testing guidelines
8. Steady shear testing guidelines
9. Some instrument limitations
10. Presenting the data
Stress Relaxation Experiment

Strain 0
time

Response of Classical Extremes

Hookean Solid Newtonian Fluid

Stress

Stress
stress for t>0 is 0
stress for
t>0
is constant
0 0
time time
Stress Relaxation Experiment (contd)

Response of Material

Stress decreases with time

Stress
starting at some high value
and decreasing to zero.
0
time
For small deformations (strains within the linear region)
the ratio of stress to strain is a function of time only.

This function is a material property known as the

STRESS RELAXATION MODULUS, G(t)
G(t) = (t)/t
Creep Recovery Experiment

Stress
t1 time t2
Response of Classical Extremes

Stain for t>t1 is

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

t1 time t2 t1 time t2
Creep Recovery Experiment:
Response of Viscoelastic Material
Creep t1> 0 Recovery t 2= 0 (after steady state)

/
Recoverable
Strain

Strain

t 1
t2
time

Strain rate decreases In the recovery zone, the viscoelastic

with time in the creep fluid recoils, eventually reaching a
zone, until finally equilibrium at some small total strain
reaching a steady state. relative to the strain at unloading.

Reference: Mark, J., et.al., Physical Properties of Polymers ,American Chemical Society, 1984, p. 102.
 Creep Recovery Curve on Polymer Melt in
Parallel Plates LLDPE at 150C
2.5000E-3 Data Fit to Straight Line Model to get slope of
Creep Compliance at equilibrium: Slope = 1/
2.2500E-3 Slope from fit = 2.451E-5 so = 1/2.415E-5 = 40,799.6 Pa.s
a: y-intercept: 4.691E-5
b: slope: 2.4511E-5
2.0000E-3 [4sf cgssi=1]: -1.817
regression: 0.99998
standard error: 0.3606
1.7500E-3
c o m p l i a n c e (m ^ 2 / N )

1.5000E-3
Creep Compliance = Jc
Equilibrium Recoverable
1.2500E-3
Compliance = Jeo
1.0000E-3

7.5000E-4

5.0000E-4 Recoverable Compliance = Jr

2.5000E-4

0
0 50.00 100.0 150.0 200.0 250.0 300.0 350.0 400.0 450.0 500.0
global time (s)
Ten Steps to Better Rheological Measurements
1. Understand why you are doing the measurement.
2. Understand the instrument first.
3. Know your sample.
4. How to select the correct test fixture
5. Loading the sample
6. Oscillation testing guidelines
7. Transient testing guidelines
8. Steady shear testing guidelines
9. Some instrument limitations
10. Presenting the data
Controlling vs. Measuring Shear Rate
1000 10.00

Minimum
Minimum
Velocity 1.000
Velocity
Measured
Controlled
100.0 0.1000
viscosity (Pa.s)

Controlled Shear Rate 0.01000

Controlled Shear Stress

velocity (rad/s)
10.00 1.000E-3

1.000E-4

1.000 1.000E-5

1.000E-6

0.1000 1.000E-7
1.000E-51.000E-41.000E-3 0.01000 0.1000 1.000 10.00 100.0 1000
shear rate (1/s)
 Flow Curve on Polymer Melt in Parallel Plates
LLDPE at 150C
1.000E5 1.000E5

Data Fit to Williamson Model

Zero Shear Viscosity = 41,350 Pa.s
10000

v is c o s ity ( P a .s )

1000

s h e a r s tr e s s ( P a )
a: zero-rate viscosity: 41350 Pa.s
b: consistency: 0.8478 s
c: rate index: 0.5729
standard error: 32.84

100.0

10.00

Stress

10000 1.000
1.000E-5 1.000E-4 1.000E-3 0.01000 0.1000 1.000
shear rate (1/s)
Ten Steps to Better Rheological Measurements
1. Understand why you are doing the measurement.
2. Understand the instrument first.
3. Know your sample.
4. How to select the correct test fixture
5. Loading the sample
6. Oscillation testing guidelines
7. Transient testing guidelines
8. Steady shear testing guidelines
9. Some instrument limitations
10. Presenting the data
Instrument Compliance

How do you see and compensate for

compliance in dual head instrument
Look at actual and commanded strain in the
spreadsheet.
If actual strain is < 5-10% of the commanded
strain, then sample geometry should be changed
to reduce stiffness of sample
Inertial Effects

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

Angular motion: M = I d /dt

M is the torque (Nm)
is the angular velocity (rad / s)
I is the moment of inertia (Nm s kg m)
I = mr
m is the mass at distance r from the axis of rotation
 Inertial Effects in Oscillation for the AR Series

During one oscillation cycle, the material is accelerated to

maximum speed and then decelerated to zero speed =>
inertia effects are always present
Concern in oscillation experiments is particularly at high
frequency with low viscosity fluids or very low stiffness
samples

In AR rheometers corrections can be minimized by

lowering the inertia of the test geometries. Use
aluminum instead of steel, or use acrylic instead of
aluminum.
Inertia affects the measured phase.
In AR rheometer, plot raw phase. If raw phase is above
150 then inertia is dominating your test results.
Correction for Inertia in Oscillation for AR
Negligible correction at low frequencies
1.000E6 1.000E6 70.00 70.00

Pdms-ar-04o

raw phase (degrees)

60.00 60.00

50.00 50.00

delta (degrees)
1.000E5 1.000E5
G'' (Pa)
G' (Pa)

40.00 40.00

30.00 30.00

10000 10000
20.00 20.00

Increasing correction at higher frequencies

10.00 10.00

1000 1000 0
0
0.01000 0.1000 1.000 10.00 100.0
Frequency (Hz)
Effect of Inertia on Gand G

10000 10000

1000 1000
G' (Pa)

G'' (Pa)
100.0 100.0

7cm plate
10.00 10.00
0.1000 1.000 10.00 100.0 1000 4cm plate
ang. frequency (rad/sec) 2cm plate
Ten Steps to Better Rheological Measurements
1. Understand why you are doing the measurement.
2. Understand the instrument first.
3. Know your sample.
4. How to select the correct test fixture
5. Loading the sample
6. Oscillation testing guidelines
7. Transient testing guidelines
8. Steady shear testing guidelines
9. Some instrument limitations
10. Presenting the data
Presenting the Data

Accurate data interpretation, model fitting, and

comparisons of rheological data require selection of
appropriate parameters and plot scaling.
Meaningful information can be masked if the data are not
presented the right way.
After running experiment, always check and make sure the
data you are presenting are within instrument
specifications, and unaffected by artifacts.
It is a good practice to include notes on plots that display
information pertinent to how the data was run and
important to the interpretation, such as pre-shear rate and
time, temperature in a frequency sweep, frequency in a
temperature sweep, clamp type or geometry, etc.
Presenting the Data

Dont overload plots with unnecessary parameters. Better

to make two plots rather then confuse the interpretation.

Legends

Colors/symbols/lines

Stamp critical points and fits such as end of linear region,

cross-over frequency, transition peaks, onsets, etc.
Oscillation Tests

Time Sweeps
X-axis: Plot time on linear scale
Y-axis: Plot G or * on log scale
Strain Sweeps
X-axis: Plot same as sweep mode log or lin
Y-axis: Plot G& G on log scale
Stress Sweeps
X-axis: Plot or same as sweep mode log or lin
Y-axis: Plot G & G on log scale
Oscillation Tests

Frequency Sweeps
X-axis: Plot angular frequency on log scale
Y-axis: Plot G, G, tan & * on log scale
Temperature Sweeps and Ramps
X-axis: Plot temperature on linear scale
Y-axis: Plot G& G on log scale
Y-axis: tan can be plotted on log or linear scale
A single transition over a temperature range is often best
observed on a linear scale.
When multiple transitions are present, weaker secondary
transition peaks may not be obvious when tan is plotted on
linear scale.
Examination of Oscillation Point Graph

900.0

800.0

700.0

600.0

500.0

400.0

300.0

200.0

100.0

0
0.010000 0.10000 1.0000 10.000 100.00 1000.0
% strain
 Typical Oscillatory Data
PDMS

1.000E6
1.000E5 1.000E6

1.000E5 1.000E5

10000 10000

10000
s)

1000 1000
)

a.
a

P
P

G
|(
'(

100.0 100.0
G

'' (
n *

P
|

a
10.00 10.00

)
1000

1.000 1.000

0.1000 0.1000

PDMS Extended frequency sweep-0001o, Frequency sweep step

0.01000
100.0 0.01000
1.000E-5
1.000E-4
1.000E-3
0.010000.1000 1.000 10.00 100.0
frequency (Hz)
Polydimethylsiloxane - Cox-Merz Data
Dynamic data gives high
shear rates unattainable in flow Dynamic
Frequency
Sweep

Creep or Equilibrium
Flow
 PET Bottle Resin Cold Crystallization
1.000E10
0.4000 Temperature Ramp at 3C/min. 1.000E10
Frequency = 1 Hz
Strain = 0.025% - transition
0.3500
Tg = 88.0C
G
1.000E9
0.3000 1.000E9

0.2500
Cold
tan(delta)
G' (Pa)

Crystallization

G'' (Pa)
1.000E8
0.2000 1.000E8
G
0.1500

1.000E7
0.1000 - transition 1.000E7

-56.62C
0.05000 tan

1.000E60 1.000E6
-200.0 -150.0 -100.0 -50.0 0 50.0 100.0 150.0 200.0 250.0
temperature (Deg C)
PET Bottle Resin Before and After DMA
Scan

Pressed PET
Bottle Resin

PET After Temperature

Ramp Scan
(Cold Crystallization)
 PET Bottle Resin - Repeat Run After Cold
Crystallization
Temperature Ramp at 3C/min.
1.000E10
2.250 1.000E10
Frequency = 1 Hz
G Strain = 0.025%
2.000 Melt
1.000E9
Tm = 240C 1.000E9

1.750

G
1.000E8
1.500 1.000E8
tan(delta)
G' (Pa)

1.250

G'' (Pa)
1.000E7 1.000E7

1.000

1.000E6
0.7500 1.000E6

- transition
0.5000 Tg = 103C
1.000E5 tan 1.000E5

0.2500

100000 10000
-200.0 -150.0 -100.0 -50.0 0 50.0 100.0 150.0 200.0 250.0
temperature (Deg C)
 PET Bottle Resin - Comparison of G
1.000E10

Repeat Run After Cold

Crystallization

1.000E9

Initial Scan on Pressed

Resin
P
'(
G a
)

1.000E8

1.000E7 Cold
Crystallization
Temperature Ramp at 3C/min.
Frequency = 1 Hz
Strain = 0.025%

1.000E6
-150.0 -100.0 -50.0 0 50.0 100.0 150.0 200.0 250.0
temperature (Deg C)
Nano_Torque Controlled Rheology
 Rheology of Gelation of a Hydrocolloid

AR G2 rheometer with Peltier temperature control system and 60mm

parallel plate was used for the rheological analysis.

Figure 1 shows the temperature ramp test results at heating and

cooling rates of 1 and 2C/min. Upon cooling, gelatin solution forms a
hydrogel at temperatures lower than 22-24C. The viscosity of the
solution increased up to 5 decades during gelation. The mechanical
strength of the sample (elastic modulus G) also increased over 105.
Since gelation (or formation of the triple-helix) is more of a kinetically
controlled process, the sol-gel transition (G crossover) appears at
lower temperatures with higher cooling rates. Upon heating, the
hydrogel begins to melt at 31C. The helical structure totally
dissociates and the protein chains revert to random coils. This
gelation process is thermally reversible.
 Figure 1: Rheology of Gelation

1C/min.

2C/min.

Blue curves: cooling; Red curves: heating

Figure 2 shows the results of gel strength at different
concentrations at 10C. When the concentration was
lower than 2%, G was higher than G in the frequency
sweep test, which indicates no gel formation. At higher
concentrations, the gelatin solutions form gels and the gel
strength increases with increasing concentration.
 Figure 2: Analysis of Gel Strength

1.000E5 1.000E5
Frequency Sweep at 10C
10000 10000

1000 1000

100.0 100.0

10.00 10.00

1.000 1.000

0.1000 0.1000

Gelatin 1%
0.01000 0.01000
Gelatin 2%
Gelatin 3%
1.000E-3 Gelatin 5% 1.000E-3
Gelatin 10%
1.000E-4 1.000E-4
0.1000 1.000 10.00 100.0
ang. frequency (rad/s)
Interfacial Rheology of hydrocolloid with air

Du Noy ring positioned at the

interface.
 Interfacial Rheology

Instrument
AR G2 rheometer with Du Noy Ring
Sample
0.5% and 1% gelatin solution
Experimental
Temperature 25C
Dynamic time sweep
Ang. Displacement: 5 mrad
Frequency: 0.1 Hz
 Interfacial Rheology

0.1000 0.1000
Gelatin 0.5%

0.01000 0.01000

1.000E-3 1.000E-3

1.000E-4 1.000E-4
0 20.0 40.0 60.0 80.0 100.0 120.0
time (min)
 Interfacial Rheology

0.1000 0.1000
Gelatin 1%

0.01000 0.01000

1.000E-3 1.000E-3

1.000E-4 1.000E-4
0 20.0 40.0 60.0 80.0 100.0 120.0
time (min)
 Thermal Activity Monitoring.
What does it measure and what is it used for?

A series of complementary techniques that measure various

properties of materials as a function of temperature and/or time
Differential Scanning Calorimetry (DSC)
Measures Heat Flow into or out of a sample
Modulated DSC Seperates Heat Flow into Heat Capacity ,
Reversing and Non Reversing Heat Flow
Thermo Gravimetric Analysis (TGA)
Weight loss, weight gain , compositional and thermal
stability of sample.
Provides information to aid in the interpretation of DSC
data. Very complementary to DSC.
Thermo Mechanical Analysis (TMA)
Measures the dimensional changes of a sample, coefficient
of thermal expansion, glass transition
MicroCalorimetry Nano-DSC, Nano-ITC, TAM III
Measures Heat Flow of very weak events under highly precise
temperature control and typically isothermally
 WHAT IS DSC?

Differential Scanning Calorimetry(DSC) most

popular thermal analysis technique
DSC measures endothermic and exothermic
transitions as a function of temperature
Used to characterize polymers,
pharmaceuticals, foods/biologicals, organic
chemicals and inorganics
Transitions measured include Tg, melting,
crystallization, curing and cure kinetics, onset
of oxidation and heat capacity
Thermal Monitoring: DSC Q2000
 DSC Transitions

Endothermic Heat Flow Exothermic Heat Flow

Evaporation Crystallization
Melting Decomposition/ Oxidation
Enthalpic Recovery Thermoset Curing and
Protein Denaturation Crosslinking
Starch Gelatinization

Heat flows due to Heat Capacity

Heat Capacity
Glass Transition
 Typical DSC Transitions

Oxidation
or
Decomposition
Heat Flow

Melting
Glass
Transition Cross-Linking
Crystallization (Cure)

Describe Thermal Transitions of the Materials Structure

Temperature
 Thermal Technique: DSC Q2000

Figures 3 and 4 show the DSC cooling and heating

curves for various concentrations 1-10% of gelatin
solutions, respectively. Solutions weighing between 5-
20mg were loaded into Tzero hermetic pans and
ramped at 5C/min between the temperatures of -10 and
80C. As shown, the DSC could detect the
gelation/melt processes for sample concentrations down
to 3%. As compared with rheological data in Figure 1,
the sol-gel transition was shifted to even colder
temperatures (~10C) due to increased cooling rate.
Whereas the temperature observed for the melt
transition was similar (~28-30C).
 Figure 3: DSC Q2000 - Cooling

0.34 1%
Heat Flow (W/g)

0.32

0.30


GELATIN 1%
GELATIN 2% 10%
GELATIN 3%
GELATIN 5%
GELATIN 10%

0.28
-10 0 10 20 30 40 50 60 70 80
Exo Up Temperature (C) Universal V4.5A TA Instruments
 Figure 4: DSC Q2000 - Heating

-0.30

GELATIN 1%
GELATIN 2%
GELATIN 3%
GELATIN 5%
GELATIN 10%
Heat Flow (W/g)

-0.35

-0.40
-10 0 10 20 30 40 50 60 70 80
Exo Up Temperature (C) Universal V4.5A TA Instruments
 Thermal Monitoring: Nano_DSC

The Nano DSC uses an innovative dual-capillary design,

operating in power compensation mode. The capillary
design often delays the onset of protein aggregation until
after the unfolding is complete. The result is a DSC
measurement of unparalleled sensitivity, accuracy and
precision.
 Thermal Technique: Nano_DSC

Figures 5 and 6 show the Nano DSC cooling and heating curves for
various concentrations 1-10% of gelatin solutions, respectively.
The heat flow signals shown have no baseline correction applied.
Gelatin solutions were loaded into the 0.3 mL capillary cell and
ramped at 1C/min between the temperatures of 1 and 60C. As
shown, the Nano DSC had better sensitivity detecting the sol-gel
transitions at low concentrations. There was a large shift in the
maximum temperature observed with concentration for the sol-gel
transition upon cooling (10-19C) compared to the melt transition
upon heating (25-27C). This is also evidence for the kinetic effect
on the gelation mechanism.
 Figure 5: Nano_DSC - Cooling

0
10.42C

12.68C

14.12C
Heat Flow (W)

-200

1% Gelatin
15.95C 2% Gelatin
3% Gelatin
5% Gelatin
-400 10% Gelatin

-600
18.60C

0 10 20 30 40 50 60

Temperature (C) Universal V4.5A TA Instruments

 Figure 6: Nano_DSC - Heating

26.52C
800

1% Gelatin
2% Gelatin
3% Gelatin
600 5% Gelatin
10% Gelatin
Heat Flow (W)

25.66C

400

25.77C

200
25.33C

25.53C

0 10 20 30 40 50 60

Temperature (C) Universal V4.5A TA Instruments

 Conclusions

Gelatin is a partially hydrolyzed protein, widely used in food, cosmetic

and pharmaceutical industries. Therefore it is important to better
understand the physical and thermal properties of gelatin.
Rheological analysis can measure the mechanical properties of
hydrogels and their sol-gel transitions and kinetics.
DSC can measure the energy required for gelation and melting of
gelatin. Increased sensitivity of the Nano DSC provides the ability to
detect transitions at lower concentrations and heating rates.
Results show that both rheological and thermal techniques can
complement each other.
It has been shown that gelation of this hydrocolloid material is kinetic
in nature. By varying the heating rate, additional kinetic information
would be possible to attain.
The End

..any Questions