coating ingredient effects on rheology

7/28/2019 Coating Ingredient Effects on Rheology

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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.

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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

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EffectofParticleFlocculation/AggregationEffectofParticleFlocculation/Aggregation

onViscosityonViscosity

Welldispersed

y

Viscosi

% Volume Solids 64

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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)

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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

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HECVersusAssociativeThickenersHECVersusAssociativeThickeners

HEC

Glass,Fernando,Jongewaard,andBrown,J.OilColourChem.Assoc.,67,256(1984)

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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)

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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

Saucy,D.Paint&CoatingsIndustry, August2008


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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

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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

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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

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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

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AssociativeThickeningMechanismsAssociativeThickeningMechanisms EffectofEffectof

AdsorptionAdsorption

NoAdsorption

05nm

50nm

sity

5nm

Layer

Visc

%Volume

Solids 64 50nm

Layer

Adsorption

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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-

]

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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

]

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Sensitivit

of

Associative

ThickenersSensitivit

of

Associative

Thickeners

--

Major Drawback of Associative ThickenersMajor Drawback of Associative Thickeners

LatexParticleCharacteristics

Dispersants

Cosolvents

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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

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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)

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SyneresisSyneresis ExperimentsExperiments

10May

12

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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)

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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

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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

- . . .

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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

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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

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Tergitol15S7Additionto0.5%HASE935Solution

200000

6000

7000

ShearRate,s1

100000

ce

ntipois

3000

4000

50000.08

8.00

0

50000

Viscosity,

0

1000

. . . . . .

TergitolConcentration

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Polymer / surfactantcomplex formation

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ARealWorldProblemARealWorldProblem Rheology ofmoderntintbaseformulationsarehighly

sensitivetocolorconcentrates

Sauc ,D.Paint&Coatin sIndustr , Au ust2008

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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

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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

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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

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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

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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.

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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.

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C clodextrinC clodextrin StructureStructure

Capable

of

removing

hydrophobic

interactions

by

forminginclusioncomplexes

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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 )

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coating ingredient effects on rheology

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