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oat ng
ngre ent
ects
oat ng
ngre ent
ects
RayFernando,Ph.D.
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KeyIngredientsKeyIngredients LatexPolymerLatexPolymer
PSD,Shape,Surface,LoadingPSD,Shape,Surface,Loading
gmentsan ersgmentsan ers
PSD,Shape,Surface,LoadingPSD,Shape,Surface,Loading
eo ogyeo ogy o ero er os mpor anos mpor an
Water
QualityWater
Quality p , ec ro y esp , ec ro y es
OtherAdditivesOtherAdditives
DispersantsDispersants
2
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Formulations
norgan cs
Cellulosics
SyntheticPolymers
3
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Inor anic
Inor anic
RheoloRheolo ModifiersModifiersUltra-Fine Clays(e.g. Laponites)
Inorganic Other Inorganics(Smectite Cla s, Atta ul ite)
+
+
_ __ _
Positive Edges & NegativePositive Edges & NegativeFacesFaces
Weak Structure, HighlyWeak Structure, HighlyShear ThinningShear Thinning
4
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OCH2
H
H
HO
H
OR
H
n
R= CH2CH2OH=Hydroxyethyl
+
2
R= C2H5, CH2CH2OH,=Ethyl,Hydroxyethyl
R= CH3, CH2CH2OH,=Methyl,Hydroxyethyl
5
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EffectofMolecularWeightonEffectofMolecularWeighton
ThickeningThickening
10.00
1.3M1.0M
0.1000
.
ity
(Pa.s
)
Natrosol 250
720K
0.01000
visco
HHRHRMR
1 inwater
300K
0.01000 0.1000 1.000 10.00 100.0 1000
1.000E-3
LR 90K
s ear ra e s
6
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CellulosicThickenersCellulosicThickeners
HMW HEC
MMW HEC
Viscosit LMW HEC
LSV
LowShearViscosity
Thickener Wt.%
HMW HEC
MMW HEC
LMW HEC HSV Highsity
ShearViscosityVi
sc
Thickener Wt.
7
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EffectofHEConCoatingViscosityEffectofHEConCoatingViscosity
Semi-gloss Formulation
10
3
10
.
HEC 0.66Wt.%10
2
)
q. . .
0
101
E
ta(
A
[P]
10
-1
No Thickener
10-2 10
-110
010
110
2
103
10-2
-1a e s
8
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CellulosicsCellulosics ThickeningMechanismsThickeningMechanisms
.. onr u on o y ro ynamcVolume
B.B. Chain Entanglements
cosity
Vi
9
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CellulosicsCellulosics ThickeningMechanismsThickeningMechanisms.. Depletion Flocculation
NonNon--Adsorbing Polymer Causes Depletion Flocculation &Adsorbing Polymer Causes Depletion Flocculation &Aggregation Leading toAggregation Leading to
1 Viscosit Chan es1 Viscosit Chan es
G = H - T S
2) Phase Separation (2) Phase Separation (SyneresisSyneresis))
Saucy,D.Paint&CoatingsIndustry, August2008
10
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EffectofParticleFlocculation/AggregationEffectofParticleFlocculation/Aggregation
onViscosityonViscosity
Welldispersed
y
Viscosi
% Volume Solids 64
11
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CellulosicsCellulosics Advantages&Advantages&
Advantages - Cellulosicsare Low Cost Universal Thickeners
Based on Natural Resources
Disadvantages:
Poor Leveling (High LSV; Yield Stress)
Reduction of Gloss (Depletion Flocculation; Poor Leveling) Roller Spatter(Extensional Viscosity)
Water Sensitivity (WSP Hydrophilicity)
Bio-degradation (Enzyme Attack on beta 1-4 Linkage)
Syneresis (Depletion Flocculation)
12
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CellulosicsCellulosics versusAssociativeThickenersversusAssociativeThickeners
OCH2
OR
OH
H
)
RO
H
OR
H
is
cosit
Associativethickeners e.g.HEUR
log(
10-2 10-1 100 10+1 10+2 10+3 10+4 10+5 10+6
-1
13
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HECVersusAssociativeThickenersHECVersusAssociativeThickeners
HEC
Glass,Fernando,Jongewaard,andBrown,J.OilColourChem.Assoc.,67,256(1984)
14
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Associative
ThickenersAssociative
ThickenersFirst Introduced to Coating Industry in Late 1970s
Several Different Types Currently in the Market
HEUR(HydrophobicallyModifiedEthoxylated
Urethanes) HA E Hy rop o ca yMo e A a we a e
Emulsions)
HMHEC H dro hobicall Modified HEC
HMPE(HydrophobicallyModifiedPolyether)
HEAT(HydrophobicallyModifiedAminoplast Ether)
15
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Associative
thickeners
Associative
thickeners
HEURHEUROO OOOO OO
RR--NN--CC--(O(O--CHCH22--CHCH22))xx--[[OO--CC--NN--RR --NN--CC--(O(O--CHCH22--CHCH22))xx]]nn--OO--CC--NN--RR--HH
--HH
--HH
--HH
R, R = CR, R = C1212
--CC1818
; R = C; R = C77
--CC3636
; x = 90; x = 90 -- 455; n = 1455; n = 1--44
12 25 , . . .
Amphiphilic polymers
16
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CH
(-CH2-C-) (-CH2-CH-) (-CH2-C-)C=O = C=O
AlkaliSwellable,Associative
ThickenerDispersionat
HighConcentration
(30%)
OH OC2H5 O
CH2
(
CH2O(
AspHincreases
C18H37
17
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Associative
Thickeners
HASE
TypeCH3
CH3
- H2
- - - H2
- H- - H2
- -
C=O C=O C=O
OH 2 5CH
2
(
Hulden, Colloids and Surfaces A 1994
2
O(20
Jenkins et al., Polymeric Dispersions: Principles andApplications (1997)
Oleson et al., Progress in Organic Coatings (1998) En hlish et al., J. Rheolo 1997 ; Ind. En . Chem Res.
18 37(2002) Kulicke et al., Colloid Polymer Sci. (1998) Tam et al., J. Polym. Sci.: Part B (2000) Talwar et al., J. Rheolo 2006
18
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AssociativeThickenersAssociativeThickeners HEATTypeHEATType
Steinmetz,A.L.,FSCTSymposium (2004)US5,627,232 Glancy &Steinmetz
US5 629 373 Glanc &Steinmetz
HEATsareGlycolurilbased;
M.W.30 000 80 000
19
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AssociativeThickenersAssociativeThickeners HEURAssociationModesHEURAssociationModes
Many Association Modes Possible
epen ng on oecuar rc ecure
Adsorption Hydrophobic
IonDi ole
SelfAssociation IntraMolecular
n er
o ecu ar MixMicelleFormation
20
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AssociativeThickeningMechanismsAssociativeThickeningMechanisms EffectofEffectof
AdsorptionAdsorption
NoAdsorption
05nm
50nm
sity
5nm
Layer
Visc
%Volume
Solids 64 50nm
Layer
Adsorption
21
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2
A queo us T h ickene r S o lu tion s
Natrosol 250HR 1.0%
101
) HASE T -935 1.0
0Eta
(A
[P]
HEUR SCT-275 1.0%
1 0-2 10
-110
010
110
2
1 03
1 0-1
.
R ate [s-
]
22
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S C T -275 S olution / 0.5% S C T -275 in 809 S emi-G loss P aint
EffectofHEUR275onCoating ViscosityEffectofHEUR275onCoating Viscosity
103
10
2
em-goss ormua on
44 Wt.%; 25 PVC withAcrysol SCT275 0.5Wt.%
101
Eta
(A
)
[P]
100
Acrysol SCT275 1.0Wt.%
-2 10-1
100
101
102 3
10-1
R ate [s-1
]
23
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Sensitivit
of
Associative
ThickenersSensitivit
of
Associative
Thickeners
--
Major Drawback of Associative ThickenersMajor Drawback of Associative Thickeners
LatexParticleCharacteristics
Dispersants
Cosolvents
24
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HEURHEUR2020(1.0wt.%)/Latex(30wt.%)AqueousBlends2020(1.0wt.%)/Latex(30wt.%)AqueousBlends
1.E+04
)
- ; - ; - ; - EVCl; - UrAcr; -Acr; - VAcr
1.E+03
(m
P
a
s
1.E+01
.
iscosit
1.E+00
1.E- 02 1.E- 01 1.E+00 1.E+01 1.E+02 1.E+03 1.E+04
Shear Rate (s-1)
Fernando,Wickmann,Louie,andChelius,ICE Proceedings,2000
26
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HECHECLR(1.0wt.%)/Latex(30wt.%)AqueousBlendsLR(1.0wt.%)/Latex(30wt.%)AqueousBlends
1.E+05- VAE155; - VAEVCl; - VAE145;
- EVCl; - UrAcr; -Acr; - VAcr
1.E+04
(m
Pa
s)
1.E+03
isc
osity
1.E+01
.V
1.E- 02 1.E- 01 1.E+00 1.E+01 1.E+02 1.E+03 1.E+04
Rate (s-1)
27
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SyneresisSyneresis ExperimentsExperiments
10May
12
28
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SyneresisSyneresis Heights(mm)ofHECHeights(mm)ofHECLR(1.0wt.%)/Latex(30wt.%)BlendsLR(1.0wt.%)/Latex(30wt.%)Blends
45
)
- VAE155; - VAEVCl - VAE145; - EVCl
- UrAcr; - Acr; - VAcr
30
35
40
ht(m
m
15
20
25
s
isHei
5
10
Syner
0 5 10 15 20 25 30 35 40
Sample Age (days)
29
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AssociativeThickenerSensitivitytoSurfactantAssociativeThickenerSensitivitytoSurfactant
Flat(57PVC)formulationswithsmallparticle(100nm),allacryliclatex
Surfactanttype
varied;
amount
constant
(4.28x10
4
moles/100g)
Tergitol NP40
Tergitol NP
4 ThickenersaddedtoadjustStormer Viscosityat
TargetKUs
105
30
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Assoc.ThickenerSensitivitytoSurfactantin90KUAssoc.ThickenerSensitivitytoSurfactantin90KU
Surfactant Wt.% KU Wt.% KU Wt.% KU
NP-40 1.16 86 0.61 90 0.38 86
NP-4 0.56 89 0.40 86 0.32 80
NP-40 1.50 102 0.77 102 0.47 105
- . . .
31
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HECThickenerInsensitivityHECThickenerInsensitivitytoSurfactanttoSurfactant
Tergitol 15S7Additionto0.75%Natrosol Solution
100000
1000000
1000
10000
centipoise
0.00%
0.10%
2.00%
1
10
100
Viscosity,
1.0E2 1.0E
1 1.0E+0 1.0E+1 1.0E+2 1.0E+3
ShearRate,s1
32
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AssociativeThickenerAssociativeThickenerSensitivitytoSurfactantSensitivitytoSurfactant
Tergitol 15S7AdditiontoHASE9350.5%Solution
100000
1000000
1000
10000
ce
ntipoise
0.00%
0.10%
2.00%
1
10
100
Viscosity,
1.0E2 1.0E
1 1.0E+0 1.0E+1 1.0E+2 1.0E+3
ShearRate,s1
33
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AssociativeThickenerAssociativeThickenerSensitivitytoSurfactantSensitivitytoSurfactant
Tergitol15S7Additionto0.5%HASE935Solution
200000
6000
7000
ShearRate,s1
100000
ce
ntipois
3000
4000
50000.08
8.00
0
50000
Viscosity,
0
1000
. . . . . .
TergitolConcentration
34
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AssociativeThickenerAssociativeThickenerSensitivitytoSurfactantSensitivitytoSurfactant
Polymer / surfactantcomplex formation
35
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ARealWorldProblemARealWorldProblem Rheology ofmoderntintbaseformulationsarehighly
sensitivetocolorconcentrates
Sauc ,D.Paint&Coatin sIndustr , Au ust2008
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37
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AssociativeThickenersAssociativeThickeners HEATTypeHEATType
Steinmetz,A.L.,
FSCT
Symposium (2004)
US5,627,232 Glancy &Steinmetz
US5 629 373 Glanc &Steinmetz
HEATsareGlycolurilbased;
M.W.30 000 80 000
38
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EthoxylatedEthoxylated,,OctylphenolOctylphenol SurfactantsUsedintheStudySurfactantsUsedintheStudy
TritonX45(n=4.5)
Tr tonX100 n=9.5
TritonX102
(n=
13)
TritonX405(n=40)
OCCH
CH3
C
CH3
CH CH CH O H
CH3
CH3
nProceedingsofICE2007
39
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CMCandHLBValuesofSurfactantsCMCandHLBValuesofSurfactants
CMCCMCur ac anur ac an mm
(wt.%)(wt.%)
Triton XTriton X--4545 0.110.11 0.00450.0045 9.89.8
Triton XTriton X--100100 0.240.24 0.01500.0150 13.413.4
Triton XTriton X--102102 0.280.28 0.0220.022 14.414.4
Triton XTriton X--405405 0.810.81 0.160.16 17.617.6
40
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ShearthickeningofHEATL100solutions
Viscosity dependence on shear rate of Triton X-45 surfactant (varyingconcentrations) and Optiflo L-100 (1.0 Wt.%) aqueous blends. Data point
41
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ShearthickeningofHEATL100solutions
Viscosity dependence on shear rate of Triton X-45 surfactant (1.5 Wt.%) and Optiflo L-100 (1.0Wt.%) aqueous blend. Data point equilibration time 30 & 90 seconds represented by circleand square symbols, respectively.
Manion,Johnson,andFernando,JCTRes2011
42
Shear thickening of L100 solutions
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ShearthickeningofL100solutions
Viscosity dependence on shear rate of Triton X-45 surfactant (1.0 Wt.% - closed circles &2.5 Wt.% - open circles) and Optiflo L-100 (1.0 Wt.%) aqueous blends.1 Shear rate ramp-up; 2 Shear rate ramp-down.
43
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ComplexViscosityofHEATL100Solutions
complex viscosity (h*) dependence on frequency of Triton X-45 surfactant(varying concentrations) and Optiflo L-100 (1.0 Wt.%) aqueous blends.
44
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C clodextrinC clodextrin StructureStructure
Capable
of
removing
hydrophobic
interactions
by
forminginclusioncomplexes
45
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EffectofEffectofmmCDCD onviscosityofHEURonviscosityofHEURC16C1651K
(2%
in
water)51K
(2%
in
water)
46
Proposed viscosity reduction
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Proposedviscosityreduction
mec an sm
47
l d t i ff t L 100
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cyclodextrin effectonL1001% L-100
0.1
1% L-100
2% L-100
0.1
)
2% L-100
with 1% BCD
0.01
Viscos
ity
(Pa*s)
0.01
Viscosity(Pa*s
0.001
1 10 100 1000
Shear Rate (1/s)
0.001
1 10 100 1000
Shear Rate (1/s )
3% L-100 4% L-100
0.1
(Pa*s)
3% L-100
with 1% BCD
0.1
sity
0.001
0.01
Visc
osity
0.001
.
V
isco
4% L-100
with 1% BCD
Shear Rate (1/s ) Shear rate (1/s )
48
l d t il d t i ff tff t
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cyclodextrincyclodextrin effectoneffecton
enen1% L-100
1% L-100
0.1
with 1% BCD and
1% X-45with 1% X-45
0.01si
ty(Pa*s)
Visco
0.0011 10 100 1000
Shear Rate (1/s)
49
Effect of order of order of additionEffect of order of order of addition
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EffectoforderoforderofadditionEffectoforderoforderofaddition1% L-100
0.1
*s)
1.5% L-100
0.1
s)
0.01
Vis
cosity
(Pa
X-45 equilibratedfirst
BCD equilibrated
0.01
Visc
osity
(Pa*
X-45 EquilibratedFirst
BCD Equilibrated
0.001
1 10 100 1000
Shear Rate (1/s )
0.001
1 10 100 1000
Shear Rate (1/s )
2% L-100 3% L-100
0.01
0.1
y
(Pa*s)
0.01
.
ty(Pa*s)
0.001
Viscosi
X-45 Equilibrated
First
BCD Equilibrated
First
0.001
Vi
scosi
X-45 Equilibrated
First
BCD Equilibrated
First
1 10 100 1000Shear Rate (1/s )
1 10 100 1000Shear Rate (1/s )
50