Basics of Fluid Basics of Fluid Rheology Rheology BasicsofFluid BasicsofFluidRheology Rheology

RayFernando,Ph.D.
Rheology Rheology
Science concerned with the Science concerned with the Scienceconcernedwiththe Scienceconcernedwiththe
flowanddeformationof flowanddeformationof
materials materials
2
Overview Overview
Rheology Rheology
Science concerned with the flow and deformation of Science concerned with the flow and deformation of Scienceconcernedwiththeflowanddeformationof Scienceconcernedwiththeflowanddeformationof
materials materials
Rheology Rheology includes includes gy gy
Viscosity,Shear Viscosity,Shearthinning& thinning&thickening, thickening,Thixotropy Thixotropy, ,
Viscoelasticity Viscoelasticity
EffectofFormulationAspectsonRheology EffectofFormulationAspectsonRheology
Latex,Pigments,Additives,etc.,andtheirInteractions Latex,Pigments,Additives,etc.,andtheirInteractions
Impactof ImpactofRheology Rheology onProcesses onProcesses
3
Process Overview Process Overview ProcessOverview ProcessOverview
RawMaterials
Mixing/Blending
Storage(Shelf/Pot)
DeliverytoApplicator
Application
Flow&Leveling
Drying/Curing
4
Vi it Vi it R i t t fl R i t t fl Viscosity Viscosity Resistancetoflow Resistancetoflow
5
Viscosity Quantitative Definition Viscosity QuantitativeDefinition
Velocity=V
Velocity=0
Shear Stress = F/A [N cm
2
]
ShearRate=(V 0)/d[s

1
]
ShearStress=F/A[Ncm ]
6
Vi it Vi it Q tit ti D fi iti Q tit ti D fi iti Viscosity Viscosity QuantitativeDefinition QuantitativeDefinition
A Area
d
V l it V
A Area
F Force
2
Velocity=V
2
Velocity=V
1
ShearRate=(V
1
V
2
)/d[s

1
]
ShearStress=F/A[Ncm
2
]
Viscosity=ShearStress/ShearRate[Pas]
7
Whichismoreviscous? Whichismoreviscous?
Wateroroliveoil?
Olive oil or honey? Oliveoilorhoney?
Honey or mayonnaise? Honeyormayonnaise?
8
Typical Viscosity Values Typical Viscosity Values TypicalViscosityValues TypicalViscosityValues
Viscosity
cps mPa.s Pa.s
Water 1 1 0.001
Olive Oil 100 100 0.01
Glycerol 1000 1000 1
Honey 5000 5000 5 Honey 5000 5000 5
Polymer Melt 1,000,000 1,000,000 1000
9
CommonViscosity y
MeasuringDevices
CupMethods
[e.g.Zahn]
PaddleMethods
[e g Stormer]
SpindleMethods
[e.g.,Brookfield]
[e.g.,Stormer]
10
Stormer Viscosities(KU)ofCommercialLatex
P i t Paints
Paint Sample
Unstirred
(KU)
Stirred
(KU)
PaintSample
(KU) (KU)
Commercial
SatinBase
119 117
Commercial
SatinWhite
109 108
BYKInstrumentsProductCatalog
11
Sag CommercialLatexPaints g
119/117KU
CommercialSatinBase
/
CommercialSatinWhite
109/108KU
BYKInstrumentsProductCatalog
12
Leveling Commercial Latex Paints Leveling CommercialLatexPaints
119/117 KU
Commercial Satin Base
119/117KU
Commercial Satin White
CommercialSatinBase
109/108KU
CommercialSatinWhite
BYKInstrumentsProductCatalog
13
IfViscosityisIndependentofShear IfViscosityisIndependentofShearRate, Rate,
Fl id Fl id i N t i i N t i Fluid FluidisNewtonian isNewtonian
e
s
s
,

P
a
P
a

s
S
h
e
a
r

S
t
r
e
V
i
s
c
o
s
i
t
y
,

P
Shear Rate, s
-1
Shear Rate, s
-1

Stress Rate
Viscosity
q t

=
y
14
Non NonNewtonianViscosityBehavior NewtonianViscosityBehavior
BrookfieldViscosities@DifferentRPMs
WaterborneCoating
RPM Viscosity (cps) Spindle #
0.5 8000 4
1 5000 "
2.5 2560 "
5 1520 " 5 1520
10 1000 "
20 550 2
50 316 "
100 227 "
15
Shear ShearThinningBehavior ThinningBehavior
4
"
"
"
ViscosityMeasuredwith
Brookfield
10000
"
"
2
"
"
1000
i
t
y

(
c
p
s
)
1000
V
i
s
c
o
s
i
100
0.1 1 10 100
RPM
As RPM(Shear Rate)
Coating is Shear Thinning
Viscosity
Coating is Shear-Thinning
16
ShearThinningBehavior ShearThinningBehavior
Viscosity Measured with ARES
10000
100000
p
s
)
1000
c
o
s
i
t
y

(
c
p
10
100
0.01 0.10 1.00 10.00 100.00 1000.00
V
i
s
Shear Rate (s-1)
Cone and
Plate Plate
17
Shear Thinning & Thickening Behavior Shear Thinning & Thickening Behavior ShearThinning&ThickeningBehavior ShearThinning&ThickeningBehavior
) ( 1 >
n

q t

) ( 1 > = n
n
K t
r
e
s
s
,

P
a
q t =
) ( 1 <
n
K

S
h
e
a
r

S
t
r
) ( 1 < = n
n
K t
Shear Rate, s
-1
18
What makes a Latex Formulation What makes a Latex Formulation WhatmakesaLatexFormulation WhatmakesaLatexFormulation
Non NonNewtonian? Newtonian?
ContinuousPhaseComposition ContinuousPhaseComposition
Thickener Other Thickener Other Thickener,Other Thickener,Other
HydrodynamicVolume HydrodynamicVolume
ChainEntanglements ChainEntanglements
VolumeFractionandNatureof VolumeFractionandNatureof
DispersedComponents DispersedComponents
Binder,Pigment,Filler Binder,Pigment,Filler
19
PolymerConformationHydrodynamic PolymerConformationHydrodynamic
V l Rh l V l Rh l VolumeRheology VolumeRheology
IntrinsicViscosity, |q| = KM
v
a
M
v
- Viscosity average molecular weight
K - Huggins Constant
a - Mark-HouwinkConstant
a = 0.5 at theta(u) conditions
(e.g., polyisobutylene in benzene
at 24
o
C)
a > 05 in a good solvent a > 0.5 in a good solvent
20
Polymer Concentration Polymer Concentration Rheology Rheology PolymerConcentration PolymerConcentrationRheology Rheology
C t t d
Dilute Critical
(Overlapping)
Concentrated
(Entanglements)
Viscosity dependence on shear-rate increases
Viscosity dependence on time increases
21
PolymerMolecularWeightEffecton PolymerMolecularWeightEffecton
Viscosity Viscosity Viscosity Viscosity
Polymer Critical MW
Polyethylene 4,000
Polystyrene 30,000
3.4
Polystyrene 30,000
Polymethyl methacrylate 28,000
Polycarbonate 13,000
s
c
o
s
i
t
y
Cis-polyisoprene 10,000
Polyisobutylene 15,000
1 0
LogM
c
L
o
g

V
i
s
1,4 polybutadiene 5,000
Polyvinyl acetate 23,000
P l di th l il 24 000
1.0
LogM.W.
Polydimethyl siloxane 24,000
Chain entanglements above a critical polymer chain length
Ferry,Viscoelastic PropertiesofPolymers,3
rd
ed,Wiley,NewYork,1980
22
Hi h h b k Hi h h b k Highshearcanbreakup Highshearcanbreakup
entanglements entanglements
LSV
V
i
s
c
o
s
i
t
y
HSV
o
s
i
t
y
Molecular Weight
V
i
s
c
Shear Rate
23
P l MWD i h P l MWD i h hi i hi i PolymerMWDimpactsshear PolymerMWDimpactsshear thinning thinning
Narrow
c
o
s
i
t
y
Broad
V
i
s
c
Broad
Shear Rate
24
EffectofMolecularWeightonThickening
10.00
1.000
a
.
s
)
1.3M
1.0M
0.1000
v
i
s
c
o
s
i
t
y

(
P
a
HHR
Natrosol 250
1%inwater
720K
0.01000
v
HR
MR
GR
LR
300K
90K
0.01000 0.1000 1.000 10.00 100.0 1000
shear rate (1/s)
1.000E-3
25
EffectofSolidsLevelonViscositiesat EffectofSolidsLevelonViscositiesat
VariousShearRates VariousShearRates
Low Low--Shear Shear Medium Medium- -Shear Shear
High High--Shear Shear
s
i
t
y
)
gg
l
o
g

(
V
i
s
c
o
Solids Solids
Increases Increases
Low Low--Shear Shear
Medium Medium- -Shear Shear High High- -Shear Shear
l
log (Shear Rate)
o
s
i
t
y
V
i
s
c
o
%Volume Solids
26
TypesofViscosityBehavior TypesofViscosityBehavior
s
s
Plastic
S
t
r
e
Plastic
Shearthinning(Pseudoplastic)
Newtonian
Dilatant(Shearthickening)
Yield
Stress Stress
Rate
2 / 1 2 / 1 2 / 1
0
2 / 1
q t t

+ =
Casson
Approximation
27
Viscosity Viscosity vs vs Shear Rate Curves Shear Rate Curves Viscosity Viscosityvs vs ShearRateCurves ShearRateCurves
Shearthinning
Shearthinning(YieldStress)
t
y
t
y
V
i
s
c
o
s
i
V
i
s
c
o
s
i
t
ShearRate ShearRate
28
Thixotropy Thixotropy Thixotropy Thixotropy
y
V
i
s
c
o
s
i
t
Time
c
o
s
i
t
y
a
r

S
t
r
e
s
s
V
i
s
c
S
h
e
ShearRate
ShearRate
29
ViscosityBehaviorofHEAT/SurfactantMixtures
Shearthickening
ViscositydependenceonshearrateofTritonX45surfactant(1.5Wt.%)andOptifloL100
(1.0Wt.%)aqueousblend.Datapointequilibrationtime 30&90secondsrepresented
bycircleandsquaresymbols,respectively.
Manion,Johnson,andFernando,JCTRes2011
30
ShearRateDependenceof ShearRateDependenceof Viscosifying Viscosifying Mechanisms Mechanisms
Brownian Motion Brownian Motion
Flocculation
Aggregation
Chain Entanglements
Intermolecular Associations Intermolecular Associations
Hydrodynamic Volume
Adsorption
V
i
s
c
o
s
i
t
y
) Aggregation
Intermolecular Associations
Hydrodynamic Volume
Adsorption
l
o
g

(
V
10
-2
10
-1
10
0
10
+1
10
+2
10
+3
10
+4
10
+5
10
+6
log (Shear Rate (s
1
)) log (Shear Rate (s
-1
))
31
What is the Ideal Viscosity Profile? What is the Ideal Viscosity Profile? What is the Ideal Viscosity Profile? What is the Ideal Viscosity Profile?
y
)
Shear-Thinning
s
c
o
s
i
t
y
Newtonian
l
o
g

(
V
i
10
-2
10
-1
10
0
10
+1
10
+2
10
+3
10
+4
10
+5
10
+6
log (Shear Rate (s
-1
))
32
ShearRatesforVariousSub ShearRatesforVariousSubProcesses Processes
Settling
Sag & Leveling
o
s
i
t
y
)
Settling
Wicking
Mixing
R ll S
Brush/Roll
PickUp
(
V
i
s
c
o
(Slurries)
Roll
Coating
Spray
Coating
Pick Up
10
-2
10
-1
10
0
10
+1
10
+2
10
+3
10
+4
10
+5
10
+6
l
o
g

10
2
10
1
10
0
10
+1
10
+2
10
+3
10
+4
10
+5
10
+6
log (Shear Rate (s
-1
))
33
ShearRatesforCoatingSag ShearRatesforCoatingSag
gt
=
Shear Rate
t - film thickness
density
2
- density
- viscosity
Fora1.1gcm
3
density,
3mil(0.0076cm)thick ( )
1Pas(10poise)coating,
sagshearrateis0.4s
1
34
Shear Rates for Reverse Shear Rates for ReverseRoll Application Roll Application ShearRatesforReverse ShearRatesforReverse RollApplication RollApplication
ReverseRoll Coater NipRegion Reverse Roll Coater Nip Region
V =100 F/min
d =2 mil
v
d/2
Shear Rate =
___________
200x12x10
3
60x2
v
60x2
Shear Rate = 2.0x10
4
s
-1
35
AreCommonViscosityMeasurement AreCommonViscosityMeasurement
MethodsAdequate? MethodsAdequate?
CupMethods[Zahn]
SpindleMethods
[Brookfield]
P ddl M h d PaddleMethods
[Stormer]
36
LimitationinSingle LimitationinSinglePointViscosity PointViscosity
MMMeasurements Measurements
o
s
i
t
y
)
BrookfieldSingleRPMViscosity
g

(
V
i
s
c
o
l
o
g
log (Shear Rate) log(ShearRate)
InFormulaDevelopmentthisbehaviormustbeknown InFormulaDevelopmentthisbehaviormustbeknown
beforedefiningproductionviscosityspecs beforedefiningproductionviscosityspecs
37
Stormer Viscosity(KU)ofCommercial
LatexPaints
PaintSample
Unstirred
(KU)
Stirred
(KU)
p
(KU) (KU)
Commercial
SatinBase
119 117
Commercial
SatinWhite
109 108
BYKInstrumentsProduct
Catalog
38
ViscosityDependenceonShear
RateCommercial Latex Paints Rate CommercialLatexPaints
100.0
1000
s
)
CommercialSatinWhite
109/108KU
10.00
o
s
i
t
y

(
P
a
.
s
Commercial Satin Base
1.000
v
i
s
c
o CommercialSatinBase
119/117KU
0.01000 0.1000 1.000 10.00 100.0 1000
shearrate(1/s)
0.1000
shear rate (1/s)
39
StressDependenceonRate
CommercialLatexPaints
6000 600.0
a
)
CommercialSatinBase
119/117KU
r

s
t
r
e
s
s

(
P
a
s
h
e
a
r
CommercialSatinWhite
109/108KU
0 1000 shear rate (1/s)
0
40
StressDependenceonRate
l CommercialLatexPaints
10.00
CommercialSatinWhite
P
a
)
109/108KU
e
a
r

s
t
r
e
s
s

(
P
s
h
e
CommercialSatinBase
119/117KU
0 2.000 shear rate (1/s)
0
YieldStress
41
Honey&Mayonnaise? Honey&Mayonnaise?
10000
1000
P
a
.
s
)
Honey
Mayonnaise
100.0
v
i
s
c
o
s
i
t
y

(
P
10.00
0.01000 0.1000 1.000 10.00 100.0 1000
shear rate (1/s)
1.000
42
Honey&Mayonnaise? Honey&Mayonnaise?
90.00
100.0
70.00
80.00
P
a
)
40.00
50.00
60.00
e
a
r

s
t
r
e
s
s

(
P
Honey
M i
20.00
30.00
s
h Mayonnaise
0 1.000 shear rate (1/s)
0
10.00
43
OptimumFlow
Behavior Behavior
Performance
Rheology
FormulationFeatures
Structure
Property
44
SecondGroupExercise SecondGroupExercise
ArchitecturalCoating
20PVC
28%NVV
62nmAcrylicLatex
SprayConditions
25 psi Fluid Pressure 25psiFluidPressure
55psiAirPressure
Flow Rate 22 ml/s FlowRate 22ml/s
ShearRate(s
1
) Viscosity
(mPa.s)
Fluid Tube (Diameter 2 cm) FluidTube(Diameter 2cm)
Nozzle(Diameter 0.20mm)
45
Shear Rate (s-1) Viscosity (cps)
SecondGroupExercise SecondGroupExercise
0.02 16802.4
0.03 15280.8
0.05 11713.5
0.08 8323.11
Viscosity Measured with ARES
0.13 5649.32
0.20 3938.28
0.32 2833.88
0.50 2026.3
10000
100000
p
s
)
0.80 1463.92
1.26 1064.13
2.00 780.768
3.17 577.941
100
1000
V
i
s
c
o
s
i
t
y

(
c
5.02 430.816
7.96 324.244
12.62 246.411
20.00 189.604
10
0.01 0.10 1.00 10.00 100.00 1000.00
V
Shear Rate (s-1)
31.70 148.027
50.24 117.209
79.62 94.5705
126.19 77.4144
200.00 64.328
46
SecondGroupExercise SecondGroupExercise Solution Solution
Noslip
Linear velocity profile Linearvelocityprofile
2Q
-
3
2
r
Q
H
=
-

FlowRate 22ml/s
ShearRate(s
1
) Viscosity(mPa s)
FluidTube(Diameter 2cm) 14 ~300
Nozzle(Diameter 0.20
mm)
14x10
6
???
)
47