Outline of Lecture

Introduction to rheology terminology

Types of fluids
Instrumentation available
Testing methods
Controlling rheology

Definition of terms

Shear stress, shear rate, viscosity

Area (A)

Newtons Two-Plate Model

Force
Velocity

Distance (d)

(Pa) = shear stress

(force

/ area

= / D

(F) / Area

(A)

(v)

D(1/s)
= shear rate
(velocity
/ distance

(Pas) = viscosity
(resistance against flow
)

Simple Shear Flow

A = area

F = Force
V = speed

xo

Moving Plate

dy
yo

dvx

Fixed Plate

Shear Stress: = F/A

Strain:

= xo/yo

Shear Rate: = d/dt = V/y

Viscosity:

= /

Definition of terms - Newtonion flow behavior

-

Viscosity curve

Viscosity

viscosity curve
newtonian flow: = const.
=

shear rate

Definition of terms - Pseudoplastic flow behavior

-

Viscosity

Viscosity curve

pseudoplastic flow
: = f (D)
(shear thinning
)

viscosity curve

shear rate

Definition of terms - Thixotropic flow behavior

Viscosity curve and time dependency

= f `(time

t)

Viscosity

viscosity

Viscosity

sol curve

gel curve

D = const.

shear rate

D=0
Time

Influence of Shear Rate

dyn. viscosity [Pas]
[
storage
behavior after
application

Comments of litererature

1000

production

viscosity control
by rheological
additives

100
10

sagging
levelling

application
consistency
within container

pumping spraying
agitation

0.1sedimentation
0.01
0

,001

,01

Viscosity control by
binders, pigments
and solvents

,1

1 Shear rate
10

-1]
[s100

1000

10000

100000

PPG Industries Lacke GmbH, Ingersheim

Physical Analytical Support
Elke Fischle

Significance of Shear Rate in Coatings

Industry

Process
Spraying
Roll Coating
Brushing
Dip/Flow Coating
Dispersing
Mixing
Pumping
Leveling
Sagging
Pigment Settling

Shear Rate Range (1/s)

10,000-1,000,000
5,000-100,000
5,000-20,000
10-100
100-50,000
20-100
100-10,000
0.01-100
0.01-0.1
~0.001

Rheology Control in WBBCs

Via Binders
Acrylic Latices
Acrylic/PU Latices
Polyester-Melamines

- Core/Shell Resins
- Microgels

Via Additives
Organic Thickners - Watersoluble Acrylic Resins
- Watersoluble PU Resins
Inorganic Thickners- Silicates

Via Pigments

What is Viscosity?
Viscosity is:
lack of slipperiness
synonymous with internal friction
resistance to flow
The Units of Viscosity are:
SI unit is the Pascal second (Pa s)
cgs unit is the Poise
Poise is < Pa s by a factor of 10
10 Poise =1 Pa s
1 cP (centipoise) = 1 mPa s (milli-pascal second)

Viscosity Values
Examples of Viscosity Values:
Material
Air
Water
Olive Oil
Honey
Asphalt
Glass

Approximate Viscosity (cp)

10-2
1
10
104
1011
1015 (molten); >1040 (solid)

Common Coatings

1 - 108

Variables affecting Viscosity

Shear Rate
Time
Temperature
Pressure
History

Newtonian Flow
Strict definition of Newtonian behavior
Shear viscosity does not vary with shear rate.
is constant with time of shearing.
in fluid falls immediately to zero when shearing is
stopped. When sheared again, the returns to the
previously measured value (regardless of delay
between measurements).
measured in different types of deformation are in
proportion to one another.
measured in uniaxial extension is three times shear
(Troutons Ratio).

, Pa.s

, Pa

Newtonian Behavior

,1/s
,1/

,1/s
,1/

Examples: water, mineral oil, solvents, solvent-borne

automotive clearcoats, many resin solutions

Non Newtonian Behavior

Shear
Viscosity

Shear
Thinning

Thickening
Viscosity

Shear Rate

Shear Thinning Fluids

(Pseudoplastic):

- Viscosity decreases with increasing

load
- Examples: polymer solutions/melts,
shampoo, glue, blood, adhesives, basecoats,
primers, house paint

Shear Rate

Shear Thickening Fluids:

- Viscosity increases with increasing
load
- Examples: wet sand, high
concentration of starch

Shear Thinning
Shear thinning behavior is often a result of:
Orientation of non-spherical particles in the direction of flow.
An example of this phenomenon is the pumping of fiber
slurries.
Orientation of polymer chains in the direction of flow and
breaking of polymer chains during flow. An example is
polymer melt extrusion.
Deformation of spherical droplets to elliptical droplets in an
emulsion. An industrial application where this phenomenon
can occur is in the production of low-fat margarine.
Breaking of particle aggregates in suspensions. An example
would be stirring paint.

Shear Thinning of Automotive Waterborne

Basecoat
Diagram

10

cP
5

10

10

00-051-7E (hexanol)

10

10

10
-3
10

-2

10

-1

10

10

10
.

Shear Rate

10

10

1/s

10

Flow Behavior: Yield Point

Toothpaste: the daily overcoming of

yield stress

Stress

Yield Point
Shear Rate

Shear stress must surpass some critical value before flow occurs
Example: toothpaste, ketchups, lipstick, butter, dispersion paint, house
paint, inks
Advantages: better sag resistance, better Al flake orientation, less surface
defects
Disadvantages: plugging lines and pumps

Yield Stress in Automotive Basecoat

Diagram
10

Pa
10

10

Yield Stress

00-051-7E (Hexanol)

10

10

-1

-2

-3

10
0.0001 0.001

0.01

0.1

10

100

1/s

Shear Rate
Copyright (C) 1997 Physica Me

echnik GmbH

10,000

Shear Stress

Non-Newtonian, Time Dependent

Behavior
Thixotropy
A decrease in apparent viscosity with time under
constant shear rate or shear stress, followed by a
gradual recovery when the stress or shear rate is
removed.
Dilantancy ( Rheopexy)
An increase in apparent viscosity with time under
constant shear rate or shear stress, followed by a
gradual recovery when the stress or shear rate is
removed. Also called anti-thixotropy or negative
thixotropy.

Thixotropy
Many paints exhibit time-dependent behavior that is called
thixotropy (decrease in viscosity with time at a given shear stress
or shear rate).
Usually, paints that are thixotropic also are shear thinning
(example = architectural paints).
Once the stress is removed or reduced, the viscosity will increase
with time. This is called viscosity recovery.

Load

No
Load Load

No
Load Load

No
Load

Viscoelasticity
Viscoelasticity

+
Spring
(Elastic Component)

Dashpot
(Viscous Component)

Storage Modulus: the elastic

component of a liquid (similar to
Youngs modulus)
Loss Modulus: the viscous
component of a liquid (damping)

Caused by high MW material, structure in the paint or coating, resin-solvent

interactions, or contamination.
Hurts application. Can cause poor atomization, spits, strings, misting, even cobwebs,
roller spatter in roll coatings.
Interferes with flow and leveling after application.
However, it can help to achieve good flake orientation in automotive metallic
basecoats.

Spray Patterns: Latex Paint with High

MW Polyethylene Oxide

How do we Measure Viscosity?

Flow cups
Rotational viscometers
ICI cone/plate
Regular (spindle) Brookfield
Brookfield cone/plate
Research viscometers (including contolled
stress rheometers)

Flow Cups

45

0.30 in ID

1.68 in

2.0 in ID

Ford, Fisher, ISO, DIN,

Zahn, Shell, etc.
Stress: Gravity
Shear Rate: Rate of flow
Problems:

0.92 in

0.40 in

Poor temperature control

Poor precision
One point measurement
For Newtonian fluids
Variable shear rate

ICI Cone/Plate
Low angle cone rotates against flat
plate with specimen between them.
Gives viscosity at high shear rate
(~12,000 sec-1) of brushing,
spraying, reverse roll coating. Easy to
use, very easy to clean.
Single speed, limited viscosity range,
no paints with coarse pigments, cones
tend to wear.

The Problem with Single Point Measurements

Brookfield Spindle Viscometer

Rotational viscometer for

moderately low shear rates.
Widely used.
Multi-speed, rugged, easy to use,
inexpensive.
Non-standard geometry (disk or
cylinder in sea of fluid), gives
Brookfield viscosity not true
viscosity for shear thinning
fluids, no temperature control.

Cone/Plate Viscometers

Cone
Specimen

Plate

Small test specimen

Controlled testing
conditions
Accurate
Some instruments can do
oscillatory measurements,
follow cure of coatings,
measure viscoelasticity

Brookfield Cone/Plate

Improvement over standard Brookfield works well for paints.

Small test specimen. Well-defined geometry,
gives absolute viscosity at known shear
rates, allows good temperature control. Is
easy to use and clean.
Limited shear rate range (~0.6 to 750 sec-1).

Paar Physica Rheometer

Types of tests: shear rate, shear stress, creep and recovery, normal
force, stress relaxation, amplitude sweep, frequency sweep,
temperature sweep, multiwave, oscillation

Paar Physica Rheometer

Physica rheometers are used to investigate:
processability window
appearance: leveling and sagging (low shear viscosity behavior)
thermal stability, as well as stability under high shear/stress
time dependency and structural property (loss and elastic
moduli)
Thermal and UV cure kinetics
recovery after high shear
yield point

Flow Curves
1 ,0 0 0

Viscosity (cP)

With Clay

Control

100
0 .1

10

100

S h e a r R a te (1 /s )

1000

10000

Recovery after High Shear

Recovery Curve
10

New common white 20810 A 3

G'

Storage Modulus

New Bud blue 20657 N 1

G'

G'

Storage Modulus

New Bud red 20656 N 1

Pa

G'

Storage Modulus

New silver 20460 N 2

G'

10

100

150

200

250

300

Time t
Physica Messtechnik GmbH

350

400

Storage Modulus

Temperature Ramps
Flow Curve
4

10

cP

05-003-67A lower resin level 1

10

Viscosity

05-003-120 UV primer 1

Viscosity

05-003-120 A Ecova primer 1

10

10

70

80

90

10
Temperature T

110

120

Physica Messtechnik GmbH

130

140

Viscosity

Thermal Cure Kinetics

Cure Rheology
10

150

140

Pa
10

04-071-27A temp ramp 1

135
10

130

10

120

110

10

95
10

90
0

10
Time

15

20

25

min

Temperature

| *|

Complex Viscosity

Temperature

| *|

Complex Viscosity

Temperature

PCC 9721 temp ramp 1

105
10

04-071-27C temp ramp 1

115
10

Complex Viscosity

04-071-27B temp ramp 1

125
| *|

| *|

30

t
Physica Messtechnik GmbH

the slope gives insight into the cure kinetics

the temperature and viscosity values at the minimum give insight
into the final appearance of the coating

| *|

Complex Viscosity

Temperature

Thermal Cure: Gel Point

Cure Rheology
7

150

10
Pa
10
10

G'

10

140
135

130
4

120

G'' 10
10
10
10

PCC 9721 temp ramp 1

125

115

110

105
1

10

95
0

90
0

10
Time t

15

20

25

min

30

Physica Messtechnik GmbH

The crossover of the loss and storage moduli defines

the gel point.

G'

Storage Modulus

G''

Loss Modulus

Temperature

What Does Viscosity Tell Us?

In-the-can
- tendency to settle
-pumpability, ability to go through valves and orifices
- application properties, ability to be dispensed
In-the-air (catching paint from a gun)
- information on sag resistance, leveling
- possibly information on ability to keep flake oriented
On-the-part (or plate or spray and scrape)
- sag and crater resistance, leveling, ability to
keep flake oriented
Leveling and
Orange Peel

Crater

Sag

How do we Control Rheology?

Concentration (solids)
Molecular weight of resins
Resin flexibility (Tg)
Latex particle size
Quality of dispersion
Viscosity of solvent
Resin-solvent interactions
Additives

Rheology Modifiers

Thickeners (cellulosics, polysaccharides, water-soluble

polymers: PEO, PAA, clays)
Thixotropes (microgels, clays, silicas, Azko
Technology)

Pigments and extenders

Wetting agents, dispersants and other
surface-active materials

Effect of Rheology Modifiers on Paint

Performance
High viscosity at low shear: sag and surface defect
resistance, prevention of pigment settling and
control of aluminum flake orientation.
Fast recovery after high shear allows initial
flowout and leveling followed by the development
of sag resistance. May not be fast enough to
prevent formation of defects.
Flattening of the viscosity-temperature curve
improves sag and defect resistance during baking.

Summary

Rheology has a significant influence on

coatings process, application,
appearance/defect resistance etc.
It is important to understand the
fundamentals and apply them to the point
of interest.