Documente Academic
Documente Profesional
Documente Cultură
Abel Gaspar-Rosas
TA Instruments, Inc. USA
2003 Sales Meeting
Marbella, Spain
Objective
Objectives
Keypoints
Deformation
Flow
Practical view
Rheology equipment
Evaluation methods
DefinitionofRheology
Rheologyisthescienceofflow
anddeformationofmatter.
(everything flows)
B.C.)
De = / texp
material
???
Interest:RheologicalProperties
ClassicalExtremes
IdealSolid--[External Force]-Ideal Fluid
STEEL
WATER
Strong structure
Weak structure
Rigidity
Deform
Retain/recover shape
Store Energy
[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
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)
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
100.0
10.00
Shortmillingtime
Longmillingtime
1.000
0.1000
0.01000
50.00
100.0
150.0
200.0
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
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.
SMTTechnology-Thixotropy
SMTTechnology-SteadyRateSweepTest
Stress
CreepRecoveryExperiment
t1 tim
t2
e
ResponseofClassicalExtremes
Strain
Strain
t1
tim
t2
t1
tim t2
AutomotivePaintSamples:
Creep/RecoveryTest
80.0
70.0
Recovery
%strain
60.0
50.0
Creep
40.0
30.0
Recovery
20.0
10.0
0
0.0
globaltime(s)
600
25.0
%strain
20.0
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
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;
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
Yield Stress y
Frequency=6.28rad/s
1.000E-3
1.000E-3
0.01000
0.1000
1.000
10.00
100.0
1000
SMTTechnology-StrainSweepTest
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
100.0
100.0
1000
* (Pa.s)
G'' (Pa)
G' (Pa)
10000
SMTTechnology-TemperatureSweepTest
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
Elasticidad
G' (Pa)
10.00
Shortmillingtime
Longmillingtime
1.000
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
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
[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 -
CMT Technology
The Rheometric Series
and
Historically - ControlledStressorControlledStrainrheometers
Today
- Instrumentscandoboth- to a greater or lesser degree
TAs Rheometry Technology Concept
SMT CMT -
- Controlled Strain
SMT
CMT
ARES
AR
5models
5models
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
0.03N.m to 200mN.m
1E-8 to 300rad/s
1E-4 to 300rad/s
Inertia:
~15N.m2
Frequency range:
< 30ms
<1ms
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
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
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
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
% strain
0.8
0.6
0.4
0.2
0
0.001
0.01
0.1
10
100
time [s]
6
5
% strain
3
2
1
0
0.001
0.01
0.1
10
100
time [s]
12
10
% strain
8
6
4
2
0
0.001
0.01
0.1
1
time [s]
10
100
Shear
Rate
Tim
e
(ddt)
SteadyStateOscillatoryFlow
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
(
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
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
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
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
[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 -