Chem550 Spring 04 4

CHEM 550 Formulation of Modern Coatings
Spring 2006
Coating Rheology - Outline

Rheological Properties of Coatings
Viscosity, ShearShear-thinning, Thixotropy,
Thixotropy, Viscoelasticity,
Viscoelasticity,
Surface & Interfacial Tension, etc.
Impact of Rheology on Coating Process

Paint Mixing, Application, Sag & Leveling, etc.
Effect of Coating Formulation Aspects on

Rheology
Solids Level, Binders, Pigments, Additives,
Interactions
ppt00 1
Rheological Properties of Coatings

Rheology & Viscosity Definitions
Effect of Shear Rate on Viscosity
Newtonian Vs Non-Newtonian Behavior
Shear-Thinning, Pseudoplasticity, Thixotropy,
etc.
Shear Vs Extensional Viscosity
Viscoelasticity
Measurement of Rheological Properties
ppt00 2
Polymers and Coatings Program

California Polytechnic State University
Spring 2006
Coating Process Overview

Raw Materials
Mixing / Blending
Storage (Shelf / Pot)
Delivery to Applicator
What are the Requirements

in Each Step?
Application
Flow & Leveling
Drying / Curing
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Rheology
Science concerned with the

flow and deformation of
materials
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Spring 2006
Which is more viscous?

Water or cooking oil?
Cooking oil or honey?
Honey or mayonnaise?
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Viscosities of Common Materials

Viscosity (cps)
Water
Olive Oil
100
Glycerine
1000
Honey
5000
100 centipoise (cps) = 1 poise

10 poise = 1 Pa s
1 cps = 1 mPa s
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Spring 2006
Viscosity
Viscosity is resistance of a material to flow
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Viscosity
Velocity = V
Velocity = 0
Viscosity
Measure of the resistance of a fluid to an
imposed flow
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Spring 2006
Viscosity Quantitative Definition

A - Area
F - Force
Velocity = V1
Velocity = V2
Shear Rate = (V1-V2)/d [ s-1]

Shear Stress = F/A [N cm-2]
Viscosity = Shear Stress / Shear Rate [Pa s]

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Viscosity, Pa s
Shear Stress, Pa
If Viscosity is Independent of Shear

Rate Coating is Newtonian
Shear Rate, s-1

Stress
ppt00 10

Shear Rate, s-1
=&
Rate
Viscosity
10
Spring 2006
Bubble Viscometers
Similar in Concept to Falling Ball.
However, Bubble is Deformable Theoretical Analysis is Difficult.
e.g. Gardner Bubble Viscometer
(ASTM D1545)
Falling Body Type has Very Limited
Control Over Measurement
Parameters (Shear Rates, Shear
Stress)
Not Recommended for nonNewtonian Fluids
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11
Orifice Viscometers (Viscosity Cups)

(stoke) = (poise)3
(g/cm )
For low viscosity (<10cps)
Kinetic Energy Correction
can be as high as 90%
Not Suitable for nonNewtonian Fluids

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12
Spring 2006
Rotational Viscometers
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13
Non-Newtonian Viscosity Behavior

Brookfield Viscosities @ Different RPMs
Waterborne Coating
RPM
0.5
1
2.5
5
10
20
50
100
ppt00 14

Viscosity (cps) Spindle #

8000
4
5000
"
2560
"
1520
"
1000
"
550
2
316
"
227
"
14
Spring 2006
Shear-Thinning Behavior
Viscosity Measured with
Brookfield
Viscosity (cps)
4
"
10000
"
"
"
2
"
"
1000
100
0.1
10
100
RPM
ppt00 15
As viscometer RPM increases Shear Rate increases

Coating is Shear-Thinning
15
Shear Thinning Behavior

Viscosity Measured with ARES
Viscosity (cps)
100000
10000
1000
100
10
0.01
0.10
1.00
10.00
100.00
1000.00
Shear Rate (s-1)
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16
Spring 2006
Shear Thinning & Thickening Behavior
= K& n (n > 1)
Shear Stress, Pa
=&
= K& n (n < 1)
Shear Rate, s-1
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17
What makes a coating nonNewtonian?

Continuous Phase
Composition
Thickener, Other
Hydrodynamic Volume
Chain Entanglements
Volume Fraction and

Nature of Dispersed
Components
Binder, Pigment, Filler
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18
Spring 2006
Polymer Conformation
Volume
Rheology
Intrinsic Viscosity, []
Hydrodynamic
= K Mva
Mv - Viscosity average molecular weight

K - Huggins Constant
a - Mark-Houwink Constant
a = 0.5 at theta() conditions

(e.g., polyisobutylene in benzene
at 24oC)
a > 0.5 in a good solvent
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19
Polymer Concentration
Dilute
Critical
(Overlapping)
Rheology
Concentrated
(Entanglements)
Viscosity dependence on shear-rate increases

Viscosity dependence on time increases
ppt00 20

20
10
Spring 2006
Polymer Molecular Weight Effect on

Viscosity
Log Viscosity
Polymer
3.4
Log Mc
1.0
Critical MW
Polyethylene
4,000
Polystyrene
30,000
Polymethyl methacrylate
28,000
Polycarbonate
13,000
Cis-polyisoprene
10,000
Polyisobutylene
15,000
1,4 polybutadiene
5,000
Polyvinyl acetate
23,000
Polydimethyl siloxane
24,000
Chain entanglements above a critical polymer chain length

Ferry,
Viscoelastic Properties of Polymers, 3rd ed, Wiley, New York, 1980
ppt00 21
Viscosity
Viscosity
High shear can break up

entanglements
21
LSV
HSV
Molecular Weight
Shear Rate
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22
11
Spring 2006
Polymer MWD impacts shear thinning
Viscosity
Narrow
Broad
Shear Rate
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23
Effect of Molecular Weight on

Thickening
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HMW
Shear-thinning
LMW
Newtonian
24
12
Spring 2006
Effect of HEC Concentration on Viscosity
Glass, J. Oil Colour Chem. Assoc., 58, 169 (1975)
ppt00 25
Thixotropy
Viscosity
25
Viscosity
Shear Stress
Time
Shear Rate
ppt00 26

Shear Rate
26
13
Spring 2006
Ultra-Fine Clay Thickeners

Highly Shear thinning
High Yield Stress
Low Thixotropy
_
_ __
+
+
Positive Edges & Negative
Faces Weak Structure
e.g., Laponite
ppt00 27
27
Effect of Dispersed Phase on

Viscosity
Viscosity
Cubic Packing
Critical Volume
Fraction - 0.5236
% Volume Solids
64
Hexagonal Packing
Critical Volume
Fraction - 0.7405
For Random Packing, Critical

Volume Fraction - 0.64
ppt00 28

28
14
Spring 2006
Krieger, Trans. Soc. Rheol., 7, 101 (1963)
ppt00 29
29
Monodispersed
Viscosity
Effect of Particle Size Distribution

on Viscosity
Monodispersed
Polydispersed
% Volume Solids 64
Polydispersed
ppt00 30

30
15
Spring 2006
Effect of Particle Shape on

Viscosity
Platelets
Needles
Viscosity
Spheres
% Volume Solids
64
ppt00 31
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Flocculation & Aggregation of

Particles in Coatings
DLVO Theory
(Two Particles)
S
ppt00 32

Inter-Particle Forces
a - Van der Waals, Long-range (Attractive)
b - Electrostatic, Long-range (Attractive or
Repulsive)
c - Steric, Short-range (Repulsive)
d - Solvation, Short-range (Attractive or
Repulsive)
e - Born, Atomic-range (Repulsive)
32
16
Spring 2006
Flocculation & Aggregation of

Particles in Coatings
Potential Energy
Repulsive
c
e
Attractive
Potential Energy
Repulsive
S
Flocculation/
Agglomeration
Aggregation
ppt00 33
Attractive
33
Effect of Particle Flocculation /

Aggregation on Viscosity
Viscosity
Non-aggregated
Aggregated
% Volume Solids
ppt00 34

64
34
17
Spring 2006
Effect of Solids Level on Viscosities

at Various Shear Rates
MediumMedium-Shear
log (Viscosity)
LowLow-Shear
HighHigh-Shear
Solids
Increases
log (Shear Rate)
ppt00 35
35
Effect of Solids Level on Viscosities

at Various Shear Rates
High-Shear
MediumMedium-Shear High-
Viscosity
LowLow-Shear
ppt00 36

%Volume Solids
36
18
Spring 2006
Types of Viscosity Behavior

Stress
1 / 2 = 01 / 2 + 1 / 2&1 / 2
Casson
Approx.
Plastic
Shear-thinning (Pseudo-plastic)
Newtonian
Yield
Stress
Dilatant (Shear-thickening)
Rate
ppt00 37
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Summary
Viscosity
Hydrodynamic Volume
Shear Thinning
Chain Entanglements
Flocculation / Aggregation
Thixotropy
Chain Entanglements
Flocculation / Aggregation
Yield Stress
Weak Structure (gel)
ppt00 38

38
19
Spring 2006
What is the Ideal Viscosity Profile?
log (Viscosity)
Shear-Thinning
Newtonian
10-2 10-1 100 10+1 10+2 10+3 10+4 10+5 10+6

log (Shear Rate (s-1))
ppt00 39
39
Shear Rates for Coating Sag

Shear Rate
gt
2
t - film thickness
- density
- viscosity
For a 1.1g cm-3 density, 3 mil
(0.0076cm) thick, 1Pa s (10 poise)
coating,
sag shear rate is 0.4 s-1
ppt00 40

40
20
Spring 2006
Shear Rates for Reverse-Roll Application

Reverse Roll Coater Nip Region
V = 100 F/min
d = 2 mil
Shear Rate =
d/2
3
200x12x10
___________
60x2
Shear Rate = 2.0x104 s-1
ppt00 41
41
Shear Rates for Various Sub-Processes

log (Viscosity)
Sag & Leveling

Settling
Wicking
Brush/Roll
Pick Up
Mixing
(Slurries)
Roll
Coating
Spray
Coating
10-2 10-1 100 10+1 10+2 10+3 10+4 10+5 10+6

log (Shear Rate (s-1))
ppt00 42

42
21
Spring 2006

V is c o s ity M e a s u re d w ith A R E S
Viscosity (cps)
10 0 0 0 0
10 0 0 0
10 0 0
10 0
10
0 .0 1
0 .10
1.0 0
10 .0 0
10 0 .0 0
10 0 0 .0 0
S h e a r R a te (s -1 )
ppt00 43
43

V is c o s ity M e a s u re d w ith A R E S
18 0 0 0
Viscosity (cps)
16 0 0 0
14 0 0 0
12 0 0 0
10 0 0 0
8000
6000
4000
2000
0
0 .0 0
50 .0 0
10 0 .0 0
150 .0 0
2 0 0 .0 0
2 50 .0 0
S h e a r R a te (s -1 )
ppt00 44

44
22
Spring 2006
Other Non-Newtonian Phenomena

(Viscoelasticity)
ppt00 45
45
Surface Tension? Other Forces?

What are all the forces impacting flow?
Externally applied force
Gravitational force
Inertial force
Surface (interfacial) tension force

Other forces
Viscous resistance force
ppt00 46

46
23
Spring 2006
Surface Tension
l
Surface tension =
Energy required to
expand soap bubble
(creating surface)
w
Soap Film
dl
Force = w x 2
Energy = w dl x 2
w
Soap Film
is surface tension (dynes/cm) or free

surface energy (ergs/cm2)
ppt00 47
47
Surface Tension
Molecules at the surface are
subject to a net attractive force
towards bulk liquid.
Liquid
Water
Ethyl Alcohol
ppt00 48

Surface Tension
(dyne/cm)
72
22.8
This is the origin of

Surface Tension
48
24
Spring 2006
Why does water have

such a high surface tension ?
H
H
O
O
H C H
H C H
H
H
Small positive charge
on H atom
H
O
Small negative charge

on O atom
Hydrogen bonding attractions

ppt00 49
49
Surface (Interfacial) Tension

Causes Flow
Water - 72 dynes/cm
Waxed Surface 32 dynes/cm
ppt00 50

50
25
Spring 2006
Surfactants are used to lower

surface tension of water
lipophilic
hydrophilic
C2H5OH
Surface Tension
C12H25SO4-Na+
CMC
Surfactant concentration
ppt00 51
51
Solvent Surface Tension Values

Solvent
Surface Tension
(dynes/cm)
ppt00 52

Water
72.3
Ethylene glycol
48.4
Propylene Glycol
36.0
O-Xylene
30.0
Toluene
28.4
Dowanol PM
27.7
N-Butanol
24.6
MEK
24.0
Hexane
18.0
52
26
Spring 2006
Surface Tension of Common

Substrates
Substrate
Steel
Surface Tension
(dynes/cm)
>55
Most Organic
Coatings
PMMA
35-50
PP, PE
29-31
PTFE
16
41
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53
Contact Angle Wetting

Zero Contact Angle
Spontaneous Wetting
& Spreading
- Contact Angle
Interfacial tension between

Liquid / Air
Solid / Air
Solid / Liquid
Must be considered
ppt00 54

54
27
Spring 2006
ppt00 55
55
Equilibrium vs Dynamic
Surface Tension
What is the surface tension of just mixed
surfactantl/water ?
What is it sometime later ?
What is it in between ?
Surface
Tension
This is important when creating new

surfaces/interfaces
e.g., creation of spray droplets
creation of coating films
ppt00 56

Time
56
28
Spring 2006
Marangoni Effect Flow Driven by

Surface Tension Force
Evaporation of alcohol
raises surface tension
near the rim of glass
Alcohol-rich wine flows
upwards due to surface
tension force
Drops cascade down as
gravity takes over
ppt00 57
57
Surface Tension flows

Crawling: When
impurities
<
film,
the coating naturally begins to
minimize free surface energy by flowing from low

leaving a crater with the impurity in the center
to high ,
Low Surface Tension
Fluid Flow
Fluid Flow
Low Surface Tension
Contaminant
Substrate
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58
29
Spring 2006
CRATERS
Courtesy of Werner Blank, King Ind.
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59
DEWETTING
ppt00 60
Courtesy
of Werner Blank, King Ind.

60
30

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CHEM 550 Formulation of Modern Coatings

Coating Rheology - Outline

Impact of Rheology on Coating Process

Effect of Coating Formulation Aspects on

Rheological Properties of Coatings

Polymers and Coatings Program

CHEM 550 Formulation of Modern Coatings

Coating Process Overview

What are the Requirements

Science concerned with the

Polymers and Coatings Program

CHEM 550 Formulation of Modern Coatings

Which is more viscous?

Cooking oil or honey?

Viscosities of Common Materials

100 centipoise (cps) = 1 poise

Polymers and Coatings Program

CHEM 550 Formulation of Modern Coatings

Polymers and Coatings Program

CHEM 550 Formulation of Modern Coatings

Viscosity Quantitative Definition

Shear Rate = (V1-V2)/d [ s-1]

Viscosity = Shear Stress / Shear Rate [Pa s]

If Viscosity is Independent of Shear

Shear Rate, s-1

Polymers and Coatings Program

Shear Rate, s-1

CHEM 550 Formulation of Modern Coatings

Orifice Viscometers (Viscosity Cups)

Not Suitable for nonNewtonian Fluids

Polymers and Coatings Program

CHEM 550 Formulation of Modern Coatings

Non-Newtonian Viscosity Behavior

Polymers and Coatings Program

Viscosity (cps) Spindle #

CHEM 550 Formulation of Modern Coatings

As viscometer RPM increases Shear Rate increases

Shear Thinning Behavior

Shear Rate (s-1)

Polymers and Coatings Program

CHEM 550 Formulation of Modern Coatings

Shear Thinning & Thickening Behavior

What makes a coating nonNewtonian?

Volume Fraction and

Polymers and Coatings Program

CHEM 550 Formulation of Modern Coatings

Mv - Viscosity average molecular weight

a = 0.5 at theta() conditions

a > 0.5 in a good solvent

Viscosity dependence on shear-rate increases

Polymers and Coatings Program

CHEM 550 Formulation of Modern Coatings

Polymer Molecular Weight Effect on

Chain entanglements above a critical polymer chain length

High shear can break up

Polymers and Coatings Program

CHEM 550 Formulation of Modern Coatings

Polymer MWD impacts shear thinning

Effect of Molecular Weight on

Polymers and Coatings Program

CHEM 550 Formulation of Modern Coatings

Effect of HEC Concentration on Viscosity

Glass, J. Oil Colour Chem. Assoc., 58, 169 (1975)