FUNDAMENTALS of RHEOLOGY

- From Deformation to Flow of Materials

Abel Gaspar-Rosas
TA Instruments, Inc. USA
2003 Sales Meeting
Marbella, Spain

Objective
Objectives

Review of fundamental concepts of rheology

Practical issues
Advances in rheometry
Advanced evaluation methods

Keypoints
Deformation
Flow
Practical view
Rheology equipment
Evaluation methods

DefinitionofRheology

Rheologyisthescienceofflow
anddeformationofmatter.

(everything flows)

Heraclitus de Samos (500

B.C.)

Time scale in rheology

Deborah Number

De = / texp

material

texp us (you and me)

Flow and Deformation

???

Interest:RheologicalProperties
ClassicalExtremes
IdealSolid--[External Force]-Ideal Fluid
STEEL

WATER
Strong structure
Weak structure
Rigidity
Deform
Retain/recover shape
Store Energy

(purely Elastic R. Hooke, 1678)

[Energy]

Fluidity
Flow
Lose shape
Dissipate Energy
(purely Viscous I. Newton, 1687)

ELASTICITY
Storage Modulus

VISCOSITY
Loss Modulus

REALBehavior
Apparent Solid[Energy + time]Apparente Fluid

- viscoelastic materials -

FlowandDeformationParameters:
[Shear Stress, Shear Strain, Shear Rate]

Stress:Forceperunitarea.
Symbol:
Units:Pa(SI)ordynes/cm(cgs)

ShearStrain:Relativedeformationinshear.
Symbol: Units:None

ShearRate:Changeofshearstrainperunittime.
Symbol: Units:[1/s]=s-1

SimpleShearDeformationandFlow
Shear Deformation

x(t)

F
=
A
h

A
z

Strain

V =

x(t)
h

Shear Flow
StrainRate

. = V = 1 x(t)
h
h t

RigidityG =

Viscosity = .

SummaryofTypesofFlow

Shear Stress,

flow

Bingham (Newtonian with yield stress)

Bingham Plastic
(shear-thinning with yield stress)
Shear Thinning (Pseudoplastic)

Newtonian
Shear Thickening (Dilatant)

deformation

Shear Rate,

ModelFitting-ShearStressvs.Shear
Rate
Summary of Viscosity Models

Newtonian

Pseudoplastic

( n 1)

Dilatant

( n 1)

Bingham

Casson
Herschel-Bulkley

1
2

1
2

1
2

y K

log

TheIdealizedFlowCurve
1)Sedimentation
2)Leveling,Sagging
3)Drainingundergravity
4)Chewingandswallowing
5)Dipcoating
6)Mixingandstirring
7)Pipeflow
8)Sprayingandbrushing
9)Rubbing
10)Millingpigmentsinfluid
base
11)HighSpeedcoating

4
5
6
1
1.00E-5

1.00E-4

2
1.00E-3

0.0100

0.100

7
1.00

10.00

shearrate(1/s)

9
11

10
100.00

1000.00

1.00E4

1.00E5

1.00E6

ModelsFittolog-logPlots
PredictstheshapeofthecompleteFlowCurve
Cross

0 -
-

=(K ) m

Sub-setsoftheCrossEquationwhichpredictportionsofthe
completeFlowCurve
PowerLaw
Sisko

= K1

1
n

= + K1 n-1

Williamson

= o - K1 n 1

RotationalTesting
DeformationandFlow

upperplate
moving
sample
lowerplate
fixed

NewtonianandNon-Newtonian
BehaviorofFluids
1.000E5

Non-Newtonian
Region

NewtonianRegion
Independentof

1.000E5

= f()

10000

(Pa)

(Pa.s)

1000

100.0

10.00

Flowdependence
10000
1.000E-5

1.000E-4

1.000E-3

0.01000

shearrate(1/s)

0.1000

1.000
1.000

CMT-StressRampTest-ContinuousRamp
Stress is applied to material at a constant rate.

Stress (Pa)

Stress (Pa)

Resultant strain is monitored with time.

m = Stress
rate
(Pa/min)

flow

y
deformation

time(min.)
USES
Yieldstress
ScoutingViscosityRun

Shear Rate,

AutomotivePaintSamples:
DatafittoHerschel-BulkleyModel
10000

SMT Sample

Viscosity (Pa.s)

1000

LMT Sample

a: yield stress: 6.582 Pa

b: viscosity: 0.3777 Pa.s
c: rate index: 0.8319

a: yield stress: 5.207 Pa

b: viscosity: 0.2909 Pa.s
c: rate index: 0.8426

100.0

10.00
Shortmillingtime
Longmillingtime

1.000

0.1000

0.01000

50.00

100.0

150.0

200.0

Shear Stress (Pa)

250.0

300.0

AutomotivePaintSamples:
Viscosityvs.ShearStress
10000

Viscosity (Pa.s)

1000

Shortmillingtime
Longmillingtime

100.0

10.00

1.000

0.1000

0.01000
1.000

10.00

100.0

Shear Stress (Pa)

1000

SMTTechnology-StepRate

In a step rate test (stress growth), a step strain rate is applied to the
material and the stress and normal force is recorded over time.

Select the step rate test to measure the transient

viscosity or normal stress difference

SMTTechnology-Thixotropy

In a thixotropy experiment, the strain rate is varied linear with time

up and down and the stress is recorded over time.

The strain rate ramp is ideal for a fast viscosity scan as a

function of shear rate for lower to medium viscosity fluids

SMTTechnology-SteadyRateSweepTest

In a steady rate experiment the equilibrium stress upon application of

a step strain rate is measured. The equilibrium stress or viscosity is
recorded as a function of the strain rate.

In a steady experiment, only the equilibrium value is

measured over a manual selected time period

Stress

CreepRecoveryExperiment

t1 tim
t2
e
ResponseofClassicalExtremes

Strain

Strain

t1

tim

t2

Stain rate for t>t1 is

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

Strain for t>t1 is

constant
Strain for t >t2 is 0

t1

tim t2

AutomotivePaintSamples:
Creep/RecoveryTest
80.0

70.0

Recovery

%strain

60.0
50.0

Creep

Long milling time

Short milling time

40.0

30.0

Recovery

20.0
10.0
0

0.0

globaltime(s)

600

Automotive Paint Samples:

Creep Recovery Test

30.0

25.0

%strain

20.0

Long milling time

Short milling time

inside
the ?
1

Elastic Ringing

15.0

10.0

5.00

0
1.000E-3

0.01000

0.1000
time(s)

1.000

10.00

SMTTechnology-CreepTest

In a creep test, a step stress is applied to the material and the

deformation is recorded over time. If the stress is removed after a time
t1 the recoverable deformation (recoil) is obtained.

The recoil test is the most sensitive test to determine aq

materials elasticity

OscillatoryTesting
DeformationandFlow

upperplate
moving
sample

lowerplate
fixed

DynamicFlowTesting

Anoscillatory(sinusoidal)
deformation(stressorstrain)
isappliedtoasample.
Thematerialresponse

Deformatio
n
Response

(strainorstress)ismeasured.
Thephaseangle , orphase

shift,betweenthecontroland
theresponseismeasured.

Phase angle

Fundamentals of Rheology
The fundamental definition of rheology indicates that for a material to flow
its original structural composition must first exceed a critical limited
deformation.
Rheology, the science of deformation and flow of materials characterizes
materials through parameters such as;

storage modulus (G)

loss factor (Tan )
viscosity ( )
characteristic times ( )
...

loss modulus (G)

critical deformation c
yield point ( y)
flow index (n)

With exquisite presicion, rheology describes the behavior of materials as

viscoelastic fluids (G>G and -> 90)
to
viscoelastic solids (G>G and -> 0)
Information commonly used to improve formulations optimize processes,
select aplication conditiosn, evaluate product performance, determine
shelf life, evaluate product economy, and more.

LinearandNon-LinearStress-Strain
BehaviorofSolids
1000

LinearRegion
Gisconstant

Non-LinearRegion

G=f()
osc. stress (Pa)

G' (Pa)

100.0

10.00

Deformation

1.000
0.010000

0.10000

100.0

Flow

1.0000
10.000
% strain

100.00

0.01000
1000.0

AutomotivePaintSamples:
StressSweepafterTimeSweep
100.0

10.00

G'(Pa)

Elastic Component
1.000

0.1000

Short milling time

Long milling time
0.01000

Yield Stress y

Frequency=6.28rad/s
1.000E-3
1.000E-3

0.01000

0.1000

1.000

10.00

osc. stress (Pa)

100.0

1000

SMTTechnology-StrainSweepTest

In a strain sweep, the strain is varied linear or logarithmic over the

selected range. Strain, stress amplitude and phase shift are recorded.

The non-linear monitor (NLM) senses the end of the linear

viscoelastic range

FrequencySweep:MaterialResponse

logG'andG"

Terminal
Region

Rubbery
Plateau
Region

Transition
Region

GlassyRegion

StorageModulus(E'orG')
LossModulus(E"orG")

logFrequency(rad/sorHz)

DynamicModuliofaPolymerMeltvs.Frequency
1000000

1000000

1.00E7

PDMSat20C
100000

100000
1000000
10000

1000

1000

100.0

100.0

10.00

10.00

1.000

1.000

100000

10000

G
"

1000

G'

0.1000 0.1000
1.000E-3
1.000E-4

0.01000

0.1000

1.000

10.00

ang. frequency (rad/sec)

100.0

100.0
1000

* (Pa.s)

G'' (Pa)

G' (Pa)

10000

SMTTechnology-TemperatureSweepTest

In a temperature sweep, the temperature is varied continuously or

discrete over the selected range. Strain, stress amplitude and phase
shift are recorded.

In all temperature dependent test, the AutoTension function is

available

Practical Issues
Samplehandling
Samplehandling
Samplehandling

Non-Newtonian,TimeDependentFluids
Thixotropy
Adecreaseinapparentviscositywithtimeunder
constantshearrateorshearstress,followedbya
gradualrecovery,whenthestressorshearrateis
removed.
Rheopexy
Anincreaseinapparentviscositywithtimeunder
constantshearrateorshearstress,followedbya
gradualrecoverywhenthestressorshearrateis
removed.AlsocalledAnti-thixotropyornegative
thixotropy.
Reference:Barnes, H.A., Hutton, J.F., and Walters, K., An Introduction to Rheology,
Elsevier Science B.V., 1989. ISBN 0-444-87469-0

Non-Newtonian,TimeDependent
Fluids

Viscosity

Rheopectic
ShearRate=Constant
Thixotropic

time

AutomotivePaintSamples:
StructuralChangeStructureRebuild(Thixotropy)
100.0

Osc. > Rotat. -> osc

Elasticidad
G' (Pa)

10.00

Shortmillingtime
Longmillingtime

1.000

Pre_shear: 1000 1/s for 60 sec

Stress = 0.1 Pa
Frequency = 6.28 rad/s
0.1000
0

100.0

200.0

300.0

400.0

500.0

600.0

time (s)

700.0

800.0

900.0

1000

No-Newtonianrheologicalbehavior(shear-thinning)must
produceabalanceofpropertiesduringtheformationofthe
coatingfilm.
formulation,estability,aplication
satisfactoryleveling
uniformthickness
resistancetosag/drainage

ADDITIVES-cancausenondesiredeffects.
toomuchelasticity(rapidcontractionofstructure)
extremeshear-thinning
flocculationofpigment

ResponseforaViscoelasticMaterial
Atshorttimes(highfrequencies)the

responseissolid-like
Atlongtimes(lowfrequencies)theresponse

isliquid-like
THEHISTORYOFLOADINGISCRUCIAL

ExponentialClose

Gap
RapidClose

~1000-2000microns
fromfinalgap

Controlled
Close

Time

SqueezeFloweffect
islesspronounced

ComparisonofStandardandExponential
SampleGapCloseonPaint
250

Exponential
Close

G'(Pa)

200
150

FastLinear
Close

100
50
0

200

400

600

Time(s)

800

1000

SolventTrapSystem
Reduces errors due to solvent evaporation
Available for cones, plates, and concentric

cylinders [cover only]

Visual confirmation of Materials Response

SteadyStateRotationalFlow

Shear
Rate

Tim
e

(ddt)

SteadyStateOscillatoryFlow

Advances
inRheologyEquipment

Interest:RheologicalProperties
ClassicalExtremes
IdealSolid--[External Force]-Ideal Fluid
STEEL

WATER
Strong structure
Weak structure
Rigidity
Deform
Retain/recover shape
Store Energy

(purely Elastic R. Hooke, 1678)

[Energy]

Fluidity
Flow
Lose shape
Dissipate Energy
(purely Viscous I. Newton, 1687)

ELASTICITY
Storage Modulus

VISCOSITY
Loss Modulus

REALBehavior
Apparent Solid[Energy + time]Apparente Fluid

- viscoelastic materials -

TAs New Concept-SMT

CMT Technology
The Rheometric Series

and

Historically - ControlledStressorControlledStrainrheometers
Today
- Instrumentscandoboth- to a greater or lesser degree
TAs Rheometry Technology Concept

SMT CMT -

Separate Motor & Transducer

- Controlled Strain

Combined Motor & Transducer - Controlled Stress

SMT

CMT

ARES

AR

5models

5models

SMT RHEOMETRY - The ARES

from water to steel and everything in between!

Independent measure of Torque & Strain

System inertia has no effect on Measurement
Force Rebalance transducer (spring for RDA)
Controlled Strain
Oscillatory testing on low viscosity fluids
Simultaneous measurements
Rheo-Optical
System Optimized for Application
Best Normal Force
LCD display for status information
ARES a highly recognized name
Powerful Software and Analysis
Powerful, $$$

CMT RHEOMETRY - The AR2000

from water to steel and everything in between!

Controlled Stress
Creep / Recovery test
High Angular Resolution
Advanced Electronics
Mobius Drive Strain
Smart Swap technology
Very low Shear Rate FC
Signals for each point
Status window
Powerful Software & Analysis
Easy Manual measurements
Versatile, Powerful, great $$$

RheometricsSeries-Labels

TAistheONLYcompanythatoffersSMT&CTMtechnology
withthebesttechnicalsupport

The AR2000
Advanceddesign!!!
MobiusDrive
SmartSwap-
InterchangeablePeltier
Plate,PeltierConcentric
Cylinder,andETC
Airbearingdrive
Normalforcesensor
Opticalencoderresolution
Casting
FastElectronics

AR2000SmartSwap
Pushbuttontoreleaseandattachtemperature

systems
Firmwareautomaticallysensestypeofsystemand
configuressoftwareaccordingly
Allconnectorsareonfrontofunit
Takeslessthan30stoexchangetemperature
systems
Allsystemsarepoweredandcontrolledfromthe
mainelectronics

SmartSwap-Removal
PressReleasebutton
Flashinggreenstatus
lightindicatesitissafe
tounplug
Press
Release
buttonagain

Continuousgreenstatuslight
indicatesattachmentcanbe
removed

: Specifications
Torque range CS:

0.1N.m to 200mN.m

Torque range CR:

0.03N.m to 200mN.m

Speed range CS:

1E-8 to 300rad/s

Speed range CR:

1E-4 to 300rad/s

Inertia:

~15N.m2

Frequency range:

1.2 E-7 to 100Hz

Step change in speed:

< 30ms

Step change in strain: < 60ms

Step change in stress:

<1ms

and much more

AR2000: Angular Resolution - 40nRad

0.1000

0.0100

resolutioncheck-0002o
resolutionlimit

d
i
s
p
l
a
c
e
m
e
n
t

(
r
a
d
)

1.00E-3

1.00E-4

1.00E-5

1.00E-6

1.00E-7

1.00E-8

1.00E-9
0.10

1.00

10.00

100.00
1000.00
osc.torque(microN.m)

10000.00

1.00E5

1.00E6

Oscillation Amp. Sweep

20.00

10000.00

17.50
1000.00

15.00

100.00

|n*|(Pa.s)

10.00

10.00

7.500
1.00

5.000

0.10
2.500

0
1.00E-7

0.03Nm

1.00E-6

1.00E-5
1.00E-4
displacement(rad)

1.00E-3

0.01
0.0100

osc.torque(microN.m)

12.50

Performance on ~1Pa.s Oil

1000

100.0

velocity(rad/s)

10.00

1.000

0.1000

0.01000

1.000E-3

1.000E-4
1.000E-3

0.01000

[rad/s]

Time to
10% [s]

Time to
1% [s]

0.1

0.015

0.018

1.0

0.014

0.022

10

0.017

0.025

100

NA

NA

0.1000

1Pa.soil[0.1radpersec
1Pa.soil[1.0radpersec
1Pa.soil[10radpersec
1.000

time (s)

10.00

100.0

Real Rheological Data

1000

1.000E5

Certifiedvalue1.43Pa.s
100.0
10000

1000
1.000

0.1000
100.0

0.01000
1Pa.soil0.1radpersec
1Pa.soil1.0radpersec
1Pa.soil10radpersec

1.000E-3

1.000E-4
1.000E-3

0.01000

0.1000

1.000

time (s)

10.00

10.00

1.000
100.0

viscosity (Pa.s)

velocity (rad/s)

10.00

Stress Relaxation on PDMS

1.2
1

% strain

0.8
0.6
0.4
0.2
0
0.001

0.01

0.1

10

100

Within 1% of set value in

30ms

time [s]

6
5

% strain

Within 1% of set value in

30ms

3
2
1
0
0.001

0.01

0.1

10

100

time [s]

Within 1% of set value in

30ms

12
10
% strain

8
6
4
2
0
0.001

0.01

0.1

1
time [s]

10

100

Visual confirmation of Materials Response

SteadyStateRotationalFlow

Shear
Rate

Tim
e

(ddt)

SteadyStateOscillatoryFlow

Visual confirmation of Steady State Flow

time

strain

1.000E7
strain

viscosity(Pa.s)

strain

1.000E8

1.000E6

time

time

Carreau
a:zero-rateviscosity:4.982E7Pa.s
b:infinite-rateviscosity:0.4928Pa.s
c:consistency:2.007E5s
d:rateindex:0.5756
standarderror:7.506

1.000E5

10000
1.000E-7

1.000E-6

1.000E-5

1.000E-4
1.000E-3
shearrate(1/s)

0.01000

0.1000

1.000

VisualConfirmation-OscillationFrequencySweep
PDMS

1.000E6
1.000E5

1.000E6

1.000E5

1.000E5
10000
1000

100.0

100.0

|
n
*
|

(
P
a
.
s
)

10000
1000

10.00
1000

10.00

1.000

1.000

0.1000

G
''
(
P
a
)

G
'
(
P
a
)

10000

0.1000
PDMSExtendedfrequencysweep-0001o,Frequencysweepstep

0.01000
100.0
1.000E-5
1.000E-4
1.000E-3
0.010000.1000 1.000
frequency(Hz)

10.00

0.01000
100.0

Evaluation Methods
ViscoelasticTransformations

Background

Each materialhasauniquesetofviscoelasticproperties

investigatedbyoscillatoryflow,creep/recoverytest,or
stressrelaxationtest.
Ifeachtestisperformedwithinthelinearviscoelastic
regionofthematerial,theinformationshouldbethesame
eventhougheachtestprovidesdifferentsectionsofthe
totalrheologicalcharacterizationprofile.
Polymertransformationsoftwareasatoolmayinterconvertlinearviscoelasticfunctions.
Itisnowpossibletoeasilytransformdataobtainedfrom
onetechniqueintoanother.

Interconversion routes
oscillation
GG

relaxation
spectrum
H()
stress
relaxation
G(t)

creep
compliance
J(t)

StressRelaxationvs.FrequencySweep
TransformedData

Theblacklineontheplotwascalculatedbytransformingafrequency
sweepfilethroughthediscreterelaxationspectrumandthenontoastress
relaxationfile
1.00E5

G t(P a )

10000.000
1000.000
100.000
10.000
1.000
0.01000

0.1000

1.000
time(s)

10.00

100.0

Creep Test Data vs. Frequency Sweep

Transformed Data
c
o
m
p
lia
n
c
e

(
m
^
2
/
N
)

2.5000E-3
2.2500E-3
2.0000E-3
1.7500E-3
1.5000E-3
1.2500E-3
1.0000E-3
7.5000E-4
5.0000E-4

Real data - shows creep ringing

Transformed data no ringing

2.5000E-4
0
0

0.10000.20000.30000.40000.50000.60000.70000.80000.90001.000
time(s)

EvaluationMethods
FromH()MWD
oscillation
GG

relaxation
spectrum
H()
stress
relaxation
G(t)

creep
compliance
J(t)

MWD

Blend of Low and High Mw

1.000E6

1.000E6

1.000E5

1.000E5

115k1150kBlend
10000
G
''(P
a
)

G
'(P
a
)

10000

1000

1000

100.0

100.0

10.00
1.000E-5 1.000E-4 1.000E-3

0.01000
0.1000
1.000
ang.frequency(rad/sec)

10.00

100.0

10.00
1000

Resultant Continuous Spectrum

1.000E7

Recipricolpluse^(PI/2)
1.000E6

1.000E5

H (P a )

10000

1000

100.0

10.00

1.000
1.000E-41.000E-3 0.01000 0.1000

1.000

10.00
Tau(s)

100.0

1000

10000

1.000E5 1.000E6

Resultant MWD
0.3000
CalculatedRousesubtraction

0.2500

w (M )

0.2000

0.1500

0.1000

0.05000

6
Log[Molarmass(g/Mol)]

* Comparison
1.000E9
Molecularweight(WLF)
n0:1.365E8Pa.s
Mw:1.164E6g/mol
1.000E8

115k
1150k
115k1150kBlend

1.000E7

|n * | ( P a . s )

Molecularweight(WLF)
n0:2.020E7Pa.s
Mw:6.613E5g/mol

1.000E6

1.000E5

Molecularweight(WLF)
n0:1.691E5Pa.s
Mw:1.606E5g/mol

10000

1000
1.000E-5

1.000E-4

1.000E-3

0.01000
0.1000
1.000
ang.frequency(rad/sec)

10.00

100.0

1000

KeyPoints-(review)
Deformation
Flow
Practical view
Advances in rheology equipment
Advances in evaluation methods

CONCLUSIONS..
- Rheology describes the structural behavior and
physicalpropertiesofmaterials
-SMTandCMTtechnologyprovidethemostcomplete
rheologicalcharacterizationofmaterials
-Rheologicaltestingisaverypracticalandversatiletool
-Viscoelastictransformationaddmorepowerto
rheologyinstrumentation
-TAIistheONLYcompanythatoffersSMT&CMT
technologywithbesttechnicalsupportandservice
next

(Know)

Interest:RheologicalProperties
ClassicalExtremes
IdealSolid--[External Force]-Ideal Fluid
STEEL

WATER
Strong structure
Weak structure
Rigidity
Deform
Retain/recover shape
Store Energy

(purely Elastic R. Hooke, 1678)

[Energy]

Fluidity
Flow
Lose shape
Dissipate Energy
(purely Viscous I. Newton, 1687)

ELASTICITY
Storage Modulus

VISCOSITY
Loss Modulus

REALBehavior
Apparent Solid[Energy + time]Apparente Fluid

- viscoelastic materials -

WE ARE a company operating at