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Brno, 28-29th march 2012 – School of Rheology Part I: Rotational Rheometry How to measure
Brno, 28-29th march 2012 – School of Rheology
Part I: Rotational Rheometry
How to measure Shear Viscosity correctly?
ω
M
Rotation
Outline • Basic terms in shear rheometry • Principle of Operation: Rotational Rheometer • Applications:
Outline
• Basic terms in shear rheometry
• Principle of Operation: Rotational Rheometer
• Applications:
A) Steady State Flow Curves using a Rotational Rheometer:
Impact of particle size, volume fraction and polydispersity on dispersion flow
properties, Polymer Melt Rheology
B) Time-dependent Flow Behaviour
Yield Stress of Dispersions and it`s relation to Zeta Potential, Thixotropy,
Structure Recovery
- with Live Tests on Kinexus Rheometer
BasicBasic TermsTerms inin ShearShear RheometryRheometry displacementdisplacement uu TangentialTangential--forceforce FF
BasicBasic TermsTerms inin ShearShear RheometryRheometry
displacementdisplacement uu
TangentialTangential--forceforce FF
ss
areaarea == aa ·· bb
GapGap == ss
bb
aa
u
γ
=
strainstrain [][]
s
.
d
γ
γ
dt
=
ShearShear raterate [1/s][1/s]
F
τ tan
=
ShearShear stressstress [Pa=N/m[Pa=N/m 22 ]]
A
TypicalTypical ShearShear RateRate RangesRanges SaggingSagging,, LevellingLevelling Extrusion,Extrusion,
TypicalTypical ShearShear RateRate RangesRanges
SaggingSagging,,
LevellingLevelling
Extrusion,Extrusion, InjectionInjection MouldingMoulding
RollRoll CoatingCoating,, SprayingSpraying
MixingMixing
,, BladeBlade CoatingCoating,, BrushingBrushing
1010 --33
1010 --11
1010 00
1010 11
1010 22
1010 33
1010 44
1010 66
ss --11
RotationalRotational--RheometerRheometer
Sample:Sample: WaterWater upup toto solidssolids
Results:Results: ShearShear--Viscosity,Viscosity, YieldYield StessesStesses,, ViscoVisco--Elasticity,Elasticity, Relaxation Relaxation
HighHigh PressurePressure CapillaryCapillary--RheometerRheometer
Sample:Sample: WaterWater upup toto highhigh viscousviscous
Results:Results: ShearShear--Viscosity,Viscosity, ElongationalElongational--Viscosity,Viscosity, WallWall Slip Slip
ShearShear ViscosityViscosity ResistanceResistance ofof aa samplesample againstagainst thethe flowflow τ η = . γ
ShearShear ViscosityViscosity
ResistanceResistance ofof aa samplesample againstagainst thethe flowflow
τ
η =
.
γ
η
ShearShear ViscosityViscosity
τ
ShearShear StressStress
.
γ
ShearShear RateRate
TypicalTypical ShearShear ViscositiesViscosities MaterialMaterial ShearShear--ViscosityViscosity (Pas)(Pas) AirAir
TypicalTypical ShearShear ViscositiesViscosities
MaterialMaterial
ShearShear--ViscosityViscosity (Pas)(Pas)
AirAir
AcetonAceton
WaterWater
OliveOlive OilOil
GlycerolGlycerol
MoltenMolten PolymersPolymers
BitumenBitumen
GlassGlass atat 500500°°CC
GlassGlass atat ambientambient
1010
--66
1010
--44
1010
--33
1010
--11
1010
00
1010
33
1010
88
1010 1212
1010 4040
Units:
Remember
Pascal second
Poise
Pas (SI)
1 Pas
=
10 P
P
(CGS)
1 mPas
=
1 cP
ShearShear--Viscosity Viscosity depends depends on…… on τ . η (Τ, p, t, γ) = .
ShearShear--Viscosity
Viscosity
depends depends on…… on
τ
.
η (Τ, p, t, γ)
=
.
γ
•• PhysicalPhysical--chemicalchemical structurestructure ofof thethe samplesample
•• TemperatureTemperature (up(up toto 20%20% // K)K)
•• PressurePressure
•• TimeTime
•• ShearShear RateRate
SteadySteady--StateState FlowFlow BehaviourBehaviour Newtonian Shear Thinning Shear Thickening Shear Rate Shear Rate
SteadySteady--StateState FlowFlow BehaviourBehaviour
Newtonian
Shear Thinning
Shear Thickening
Shear Rate
Shear Rate
Silicon Oil, Suspension
Inks, Paints
Shear Rate
Cornflower
Shear Rate
Shear Rate
Shear Rate
Viscosity
Stress
Stress
Viscosity
Stress
Viscosity
Principle of Operation: Rotational Rheometer Stress- and Strain Control possible. Motor • The drive is
Principle of Operation: Rotational Rheometer
Stress- and
Strain Control
possible.
Motor
• The drive is situated above the sample,
not below.
Air bearing
• The driven spindle is air bearing
supported so torque can be measured.
Position
sensor
• The separate torque transducer is
eliminated!
Upper Measuring
Plate
Advantages:
Sample
• Wide Torque Range 10e-9 to 10e-1 Nm
• Short Response times
Temperature
• Small inertia design
Controller
• Direct Stress and Direct Strain
Choice of Geometry: From Fluids to Solids Apply Torque / Measure Torque M Measure Displ.
Choice of Geometry: From Fluids to Solids
Apply Torque /
Measure Torque
M
Measure Displ.
Apply Displacement
ω
δ
R
Rule of Thumb
for dispersions:
• the higher the viscosity,
the smaller the geometry
Gap Size > 10 * D90
• the higher the shear rate,
the smaller the gap.
Parallel Plates
Cup&Bob
Solids Fixture
Cone-Plate / Plate-Plate • Cone Adv: Const Shear Rate along the complete gap, easy cleaning,
Cone-Plate / Plate-Plate
• Cone Adv: Const Shear Rate along
the complete gap, easy cleaning,
low sample volume, wide viscosity
range
• Cone DisAdv: only for
homogeneous samples, for
disperse samples D90 < 10 x gap,
solvent evaporation
0s -1
10s -1
• Plate Adv: flexible gap, auto-tension
possible, low sample volume, often
used for temperature dependent
tests, good for disperse systems
10s -1
10s -1
10s -1
• Plate DisAdv: shear rate
dependency, solvent evaporation
Cup & Bob / Double Gap • Cup&Bob Adv: large gap, works well for disperse
Cup & Bob / Double Gap
• Cup&Bob Adv: large gap, works well
for disperse systems, also for samples
showing sedimentation, large surface
area, nearly no evaporation effects,
good for low viscous samples, less
impact of loading errors
Cup&BobCup&Bob accacc DIN53019DIN53019
• Cup&Bob DisAdv: high moment of
inertia limits oscillation and transient
steps, high cleaning effort, large
sample volumes (ca 2ml – 15ml)
• Double Gap Adv: highest sensitivity for
low viscous samples, lower inertia
compared to cup&bob, nearly no
impact on loading errors
DoubleDouble GapGap
• Double Gap DisAdv: large sample
volume (ca. 15ml – 30ml), difficult
cleaning
BasicBasic ViscometryViscometry:: HowHow toto runrun aa flowflow curvecurve CSCS--Mode:Mode: SteadySteady statestate
BasicBasic ViscometryViscometry:: HowHow toto runrun aa flowflow curvecurve
CSCS--Mode:Mode: SteadySteady statestate andand nonnon--steadysteady statestate measurementsmeasurements
.
SteadySteady state:state:
τ TableTable ofof stressesstresses
γγ
tt
tt
.
nonnon--steadysteady state:state:
τ LinearLinear rampramp
γγ
tt
tt
1. Steady State Flow Properties τ η = Newton: . γ . equivalent . .
1. Steady State Flow Properties
τ
η =
Newton:
.
γ
.
equivalent
.
.
Flow Curve:
τ = τ (γ)
γ = γ (τ)
CR-Mode
CS-Mode
Shear Viscosity
Curve:
.
equivalent
η = η (γ)
η = η (τ)
SteadySteady StateState ConditionCondition Kinexus Rheometer γ J = τ ⇒⇒ dLnJ/dLntdLnJ/dLnt == 11 forfor
SteadySteady StateState ConditionCondition
Kinexus Rheometer
γ
J =
τ
⇒⇒ dLnJ/dLntdLnJ/dLnt == 11 forfor purepure viscousviscous flowflow!!
⇒⇒ DeviationsDeviations showshow measurementmeasurement errorserrors!!
SteadySteady StateState CalculationCalculation ( ) ⎛ γ t ⎞ d ln ⎜ ⎟ d ln
SteadySteady StateState CalculationCalculation
( )
γ
t
d ln ⎜
d
ln
J
τ
d
(
ln
γ
( )
t
ln
τ
)
d
ln
γ
( )
t
d ln
τ
=
=
=
d
ln
t
d
ln
t
d
ln
t
d
ln
t
d
ln
t
t
τ
τ
Newtons Law
:
γ
=
dt
=
t
η
η
0
η
()
t
=
const
,
τ
()
t
=
const
τ
τ
d
ln ⎜
t
d ln ⎜
d
ln
γ
( )
t
d ln
τ
η
τ
η
d ln
d
ln
t
d ln
τ
=
=
=
+
=
d
ln
t
d
ln
t
d
ln
t
d
ln
t
d
ln
t
d
ln
t
d
ln
t
d ln
(
τ
ln
η
)
d
ln
t
d ln
τ
=
+
d
ln
t
d
ln
t
d
ln
t
d ln
τ
d ln
η
d
ln
t
d ln
τ
=
+
d
ln
t
d
ln
t
d
ln
t
d
ln
t
d
ln
J
= 1
for steady state
.
d
ln
t
ComparisonComparison StressStress-- andand RateRate ControlledControlled TestTest Shower Gel: Comparison CS □ und CR
ComparisonComparison StressStress-- andand RateRate ControlledControlled TestTest
Shower Gel:
Comparison CS □ und CR ∆ Shear Viscosity Curve
LiveLive MeasurementMeasurement onon KinexusKinexus::
ShowerShower GelGel FlowFlow CurveCurve
NormalNormal StressStress DifferenceDifference N1N1 Shower Gel F t F n Edge failure ⇒⇒ AlwaysAlways watchwatch
NormalNormal StressStress DifferenceDifference N1N1
Shower Gel
F t
F n
Edge failure
⇒⇒ AlwaysAlways watchwatch thethe NormalNormal StressStress duringduring aa ShearShear ViscosityViscosity MeasurementMeasurement!!
SteadySteady StateState FlowFlow CurvesCurves:: ImpactImpact ofof ParticleParticle SizeSize 10 2 Increase the size of
SteadySteady StateState FlowFlow CurvesCurves:: ImpactImpact ofof ParticleParticle SizeSize
10
2
Increase the size of latex
particles in a pressure sensitive
adhesive from D50=175µm to
10
1
175 µ m
D50=750mm
10
0
Polydispersity and Volume
Fraction similar
10
-1
750 µ m
10
-2
10 -1
10 0
10 1
10 2
10 3
10 4
10 5
10 6
.
γ (s -1 )
Smaller size means an increase in number of particles which causes an
increase in particle-particle interactions. Hence an increase in low shear
viscosity.
η (Pa.s)
Reason for Shear Rate Dependency Entanglement Network / Particle-Particle-Interaction Log γ Equilibrium Destruction
Reason for Shear Rate Dependency
Entanglement Network / Particle-Particle-Interaction
Log γ
Equilibrium
Destruction >
Recovery
No Entanglements
Molecules / Particles
Entanglements / Particle Interaction
Log η
SteadySteady StateState FlowFlow CurvesCurves:: ImpactImpact ofof ParticleParticle LoadingLoading Changing the Volume
SteadySteady StateState FlowFlow CurvesCurves:: ImpactImpact ofof ParticleParticle LoadingLoading
Changing the Volume Fraction of Particles…
Newtonian
Shear Thinning
Shear Thickening
φ
φ
φ
<0.1
0.1<
<0.5
>0.5
φ
φ
φ
m
m
m
Krieger-Dougherty:
[
η φ
]
m
η
⎜ ⎜ 1−
φ
=
η
φ
⎝ ⎠
medium
m
Volume Fraction
Log Zero Shear Viscosity
ShearShear ThickeningThickening ofof concentratedconcentrated dispersionsdispersions Kinexus Rheometer ⇒⇒ thosethose
ShearShear ThickeningThickening ofof concentratedconcentrated dispersionsdispersions
Kinexus Rheometer
⇒⇒ thosethose shearshear thickeningthickening effectseffects cancan havehave negativenegative impactimpact onon processabilityprocessability ––
seesee sectionsection capillarycapillary rheometryrheometry
SteadySteady StateState FlowFlow CurvesCurves:: ImpactImpact ofof PolydispersityPolydispersity We keep the volume
SteadySteady StateState FlowFlow CurvesCurves:: ImpactImpact ofof PolydispersityPolydispersity
We keep the volume fraction (φ) constant
But changing polydispersity…
Particle Size Distribution
20
15
10
5
0
0.1
1
10
100
1000
3000
Particle Size (µm)
What happens to the viscosity?
Volume (%)
ImpactImpact ofof PolydispersityPolydispersity onon FlowFlow BehaviourBehaviour Fine talc of different D50, mixed into an
ImpactImpact ofof PolydispersityPolydispersity onon FlowFlow BehaviourBehaviour
Fine talc of different D50, mixed into an epoxy resin
100%
175 µ m
100%
750 µ m
Krieger-Dougherty
0%0%
IncreasingIncreasing amountamount ofof 175175 µµmm particlesparticles
100%100%
[
η φ
]
m
η
φ
=
1−
η
φ
medium
m
100%100%
IncreasingIncreasing amountamount ofof 750750µµmm particlesparticles
0%0%
If you want to increase the solid content of the sample but keep the viscosity the same,
increase the particle size distribution (polydispersity) as well.
Conversely, narrow the particle size distribution to increase the viscosity.
Zero Shear Viscosity
SteadySteady StateState FlowFlow CurvesCurves:: ImpactImpact ofof MatrixMatrix AdditivesAdditives Xanthan Solution -
SteadySteady StateState FlowFlow CurvesCurves:: ImpactImpact ofof MatrixMatrix AdditivesAdditives
Xanthan Solution - measured with Cone Plate and Double Gap
1000
η
Mw= 2.400.000 g/mol
sp
2
=
[]
η
+
k
h [] c
1%
η
c
100
3
10
π
R
h
M
=
⋅ N
0.5%
3
A [η ]
10
1%
0.3%
0.5%
1
0.3%
0.1% CP
0.1%
0,1
0.1% DG
0,01
0,001
1,0E-04
1,0E-03
1,0E-02
1,0E-01
1,0E+00
1,0E+01
1,0E+02
1,0E+03
Shear Rate [1/s]
==>==> thethe higherhigher thethe concentrationconcentration ofof XanthanXanthan,, thethe higherhigher thethe zzeroero shearshear viscosity.viscosity.
Shear viscosity[Pas].
Further Factors Influencing Dispersion Rheology Laser Diffraction Spray Particle Analyzer volume fraction, φ
Further Factors Influencing Dispersion Rheology
Laser Diffraction
Spray Particle
Analyzer
volume fraction, φ
Particle size
Particle size distribution
Digital Microscopy
Light Scattering
Vs
Size and Zeta
Electrostatic interactions
Steric Hindrance
Particle shape
Dry
+ +
+
+
------
+ +
+
+
Wet
Polymer Melt Rheology: Determination of Mw from Flow Curves . γγ
Polymer Melt Rheology: Determination of Mw from Flow Curves
.
γγ
Polymer Melt Rheology: Effect of Molecular Weight Distribution A Polymer with a broad MWD exhibits
Polymer Melt Rheology: Effect of Molecular Weight Distribution
A Polymer with a broad MWD exhibits non-
Newtonian flow at a lower rate of shear than a
polymer with the same η 0 but has a narrow MWD
Narrow MWD
Broad MWD
Log Shear Rate (1/s)
)s.aP(ytisocsiVgoL
2. Time Dependent Flow Properties Viscosity is not only dependent on shear rate it is
2. Time Dependent Flow Properties
Viscosity is not only dependent on shear rate it is
also time dependent.
Think of paint. Thick in the can when left in the
shed for months, but thins when stirred.
However, it is thixotropic as it does not rebuild
straight away on stopping the stirring.
Thixotropic Example Two samples… one very thixotropic, one not so thixotropic. Bad paint – leaves
Thixotropic Example
Two samples… one very thixotropic, one not so
thixotropic.
Bad paint – leaves brush
marks.
Rebuilds too thick too quickly.
Time
Good paint – leaves smooth
finish.
Rebuilds quite slowly. Enough
time to allow ridges to smooth
out.
Time
Shear rateViscosity
Thixotropy 3- Step-Shear profile Thixotropy: Decrease of viscosity vs. time at constant shear + complete
Thixotropy 3- Step-Shear profile
Thixotropy: Decrease of viscosity vs. time at
constant shear + complete recovery under rest
11
22
33
1 = Initial Viscosity at low shear
2 = high shear phase (time-and rate dependent)
3 = Recovery
Another Time Dependent Property: Yield Stress Some samples require a certain stress until they flow
Another Time Dependent Property: Yield Stress
Some samples require a certain stress until they
flow – a yield stress.
A transition to go from solid to liquid.
Or…
Why toothpaste needs to be squeezed to get
out of the tube.
However, does not flow into bristles on tooth
brush.
Why Heinz tomato sauce needs a whack.
But still looks thick on the plate.
Or why pumps take time to get going.
RelationRelation toto FlowFlow CurvesCurves “YIELD STRESS” An ever increasing viscosity as the shear rate
RelationRelation toto FlowFlow CurvesCurves
“YIELD STRESS”
An ever increasing viscosity as the
shear rate approaches zero, i.e. a does
not flow / solid like when stationary.
ZERO SHEAR VISCOSITY
The viscosity plateau’s as the shear rate
approaches zero, i.e. flows / liquid like
when stationary.
THIXOTROPIC
Both materials can be, and tend to be
“thixotropic” – viscosity depends on time.
Rheometer measurement range
Viscometer
Measurement range
10
-6
10
6
Log Shear Rate
Studying weaker
interactions
Studying stronger
interactions
Log Viscosity
Yield Stress Determination by Stress Ramp and Creep Tests Viskoses Fleßen Schubspannung 3Pa Schubspannungen 1Pa,
Yield Stress Determination by Stress Ramp and
Creep Tests
Viskoses Fleßen
Schubspannung
3Pa
Schubspannungen
1Pa, 1.5Pa, 2Pa, 2.5Pa
Energy absorbed - strong association - no flow
Fließgrenze = 3Pa
LinearLinear oror logarithmiclogarithmic StressStress RampRamp
MutlipleMutliple CreepCreep TestsTests atat differentdifferent
StressesStresses
UsuallyUsually StressStress RampRamp isis usedused asas aa prepre--testtest,, whereaswhereas MultipleMultiple CreepCreep
givesgives preciseprecise YieldYield StressStress
Example: Stable Metal Oxide Dispersions In this case study we have a sample of silica
Example: Stable Metal Oxide Dispersions
In this case study we have a sample of silica
(silicon oxide) which has an average particle size
greater than 1 micrometer.
Conventional colloidal theory of
increasing the zeta potential
to ±30mV is insufficient to
counter the effect of gravity
on these large particles…
Particle Size Sample characterised on a Mastersizer 2000, showing a particle size greater the 1
Particle Size
Sample characterised on a Mastersizer 2000,
showing a particle size greater the 1 micrometer.
Laser Diffraction
Zeta Potential Titrating a silica sample with HCl on a Zetasizer Nano with MPT-2 autotitrator.
Zeta Potential
Titrating a silica sample with HCl on a
Zetasizer Nano with MPT-2 autotitrator.
The isoelectric point (where the zeta potential is
zero) is in the very acidic (pH 1) region.
Steady-Shear Viscosity vs Zeta-Potential Suspension with micron particles and zeta potential -> 0mV Associated
Steady-Shear Viscosity vs Zeta-Potential
Suspension with micron particles
and zeta potential -> 0mV
Associated structure
strong enough to induce
a yield stress.
Suspension with
sub-micron particles
and high zeta potential
Log Shear Stress
At isoelectric point the zero shear viscosity gets infinite
Stronger associated structures which resist even
high shear stresses.
Log Viscosity
Resultant Rheology for the Silica Supsension As the particles associate more, with pH’s closer to
Resultant Rheology for the Silica Supsension
As the particles associate more, with pH’s closer
to the iso-electric point, the viscosity increases.
pH2.42
pH3.52
pH3.97
Materials with higher low shear viscosities are
regards as more resistance to separation.
Resulting Yield Stress for the Silica Suspension Yields stress measurements (the stress at the peak
Resulting Yield Stress for the Silica Suspension
Yields stress measurements (the stress at the peak of
instantaneous viscosity) is a measurement of the internal
strength of material.
pH2.42 – yield stress = 15.8 Pa
pH3.52 – yield stress = 2.5 Pa
pH3.97 – no yield stress
Thank you for your attention! Please join our sessions on: Capillary Rheometry and Oscillatory Rheometry.
Thank you for your attention!
Please join our sessions on:
Capillary Rheometry and Oscillatory Rheometry.
AnyAny QuestionsQuestions?? torsten.remmler@malvern.detorsten.remmler@malvern.de