RHEOLOGY HANDBOOK
FOR WATERBASED FORMULATIONS
COATEX INSIDE
A FEW DROPS THAT MAKE
ALL THE DIFFERENCE SUMMARY
Even though they account for just 0.4% to 3% by weight of final FROM PAINT TO RHEOLOGY
formulations, rheology modifiers, thickeners and dispersants can
significantly improve their application properties. Their effectiveness Formulation properties
and the benefits they afford make them key components of your Homogeneous formulation = optimised dispersion .......................... 4
aqueous paint and coating formulations.
Paint stability = no sedimentation of particles .................................. 6
Many of your formulations properties are in fact directly correlated In-can appearance = consistency of the paint ................................. 6
with rheology and the characteristics of rheology modifiers. No liquid phase floating = control of syneresis
In-can appearance, sedimentation resistance, and optimum = associative acrylic thickeners ........................................................... 7
sag-leveling balance are related to the behavior of the paint subjected
to low stress and therefore low shear rate. As stress increases, Application properties
we encounter conditions corresponding to applying paints and coatings
by brush, roller or spray gun on their support. This stress increase can Good workability = low splatter
be measured by increasing the shear rate also known as increasing + accurate and efficient loading of the tool ..................................... 8
the velocity gradient. Covering power = film build and brushability . . ................................ 9
The purpose of this guide is to assist you in understanding the rheology Properties of the film
criteria that lead to the properties you are seeking for your paint, Even surface = no surface defects due to tools
and in choosing the right tools to help optimise your formulations. = control of flow and leveling .. .......................................................... 10
Our aim is to help you choose thickeners or dispersants, and ensure Water resistance = weathering resistance,
that your formulations fulfil your specification requirements as closely wet scrub resistance ............................................................................. 11
as possible.
Coatex offers a comprehensive range of additives that stand out FROM RHEOLOGY TO PAINT
by their excellent effectiveness, an extensive diversity in terms
of rheological behavior, as well as functionality that enhance the quality Rheology principles
of your formulations. Dispersion ............................................................................................... 13
Thickening mechanisms ....................................................................... 13
Viscosity .................................................................................................. 16
Measures equivalence............................................................... 22
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FROM PAINT TO RHEOLOGY
agent 3. Fillers
The presence of a large, possibly solid, can produce the lowest viscosities 200
deposit at the bottom of the can caused during deflocculation of the 100
by re-agglomeration of particles indeed pigment or the filler at their lowest 0,1 0,2 0,3 0,4 0,5 0,6 0,7
represents a negative criterion for the user. usage rate. % dispersing agent
Solids content of the slurry high loading in mineral and/or organic pigment Coadis 123 K
20 30 40 50 60 70 80 90
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FROM PAINT TO RHEOLOGY
Acrylic thickeners imparting a pseudoplastic type rheology are best improved appearence and creaminess, matt
or semi-matt paints
Rheotech 3800
suited to prevent sedimentation.
polyurethane thickener for outstanding color acceptance Coapur XS 71
ADVICE
TO OBTAIN YOU CAN USE smooth and rich appearance, semi-gloss and gloss
paints
Coapur 975 W
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FROM PAINT TO RHEOLOGY
APPLICATION
PROPERTIES
During the application of the paint, a large number of factors will prove Covering power = film build and brushability
decisive to evaluate its quality: its covering power, its body or film build,
Covering power results from the combination of the coatings inherent
its spatter resistance, its open time, and the ease with which it can be
opacity depending mostly on fillers, pigments and pigment volume
handled and applied.
concentration (PVC), and the thickness transferable onto the support.
Most of these properties are related to the rheological performance
of the formulation subject to high velocity gradients, from 1,000 to 10,000 s-1 Rheology should therefore help produce sufficient thickness deposited
for coatings of small to medium thickness (50 to 500 m wet) for brush or roller at every application (the film build), while maintaining ease of application
application, and 10,000 to 50,000 s-1 for spray (airmix or airless) application. (brushability). These properties can be quantified by measuring viscosity
at high velocity gradient.
Good workability = low spatter + accurate In this area, polyurethane type Newtonian thickeners (HEUR) prove idealy
and efficient loading of the tool suitable.
A paint is deemed to be user-friendly when it is easy to load on the brush The most newtonian acrylic thickeners (HASE) are also capable
or the roller, and then spread on the support, and its spatterability is low. of imparting excellent control of the film build effect, which helps mask
the supports blemishes more effectively whereas cellulose type thickeners
The quantity loaded on the tool depends on the viscosity of the product (HEC) often present major shortcomings.
at low and medium velocity gradient, and the spatterability of the viscosity
at medium and high gradient.
Optimising both these properties requires the use of thickeners With conventional With
with pseudoplastic to balanced profiles. cellulosic thickeners Coapur 3025
ADVICE ADVICE
TO OBTAIN YOU CAN USE TO OBTAIN YOU CAN USE
excellent tool load with semi-gloss excellent film build effect, no syneresis
or one coat matt paints
Rheotech 2800 & improved pigment compatibility
Rheotech 2000
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FROM PAINT TO RHEOLOGY
Although controlling paints rheology offers advantages Good water resistance means good resistance to water absorption
at the production and application stages, it also benefits the films for exterior coatings and good wet scrub resistance for interior coatings.
properties before and after drying. Coatings with a high binder content, hence a low pigment volume
concentration (PVC), naturally feature good water resistance.
By contrast, matt paints and coatings with a lower binder content offer
Even surface = no surface defects due to tools a lower water resistance potential.
= control of flow and leveling
Polyurethane type thickeners can improve the water resistance of coatings
Paint has good leveling when the support, once covered, features an with medium and low PVC thanks to their highly hydrophobic nature, which
even surface, with no application marks from the brush or the roller. notably marks them out from cellulose thickeners for example.
The qualities of the final films leveling are directly related to the paints Other solutions are available to improve water resistance:
flow properties under very low stress. It is particularly important
to obtain good leveling when applying low PVC paints (lacquer Combination of acrylic thickeners of an associative nature at low dose
and varnish, gloss to satin) as their surface must be perfectly even. with polyurethane thickeners, for lower thickening cost, and with constant
binder content.
The type of rheology profile needed to improve leveling is preferably
the Newtonian type. Increase in binder content and/or replacement of a traditional acrylic
thickener with an associative acrylic thickener.
The most suitable thickeners for precise adjustment of leveling without
affecting the film body are polyurethane thickeners. These solutions help keep down the additional cost incurred in improving
the quality of the formulation.
0,55% Medium
with conventional with accurate control MW HEC
cellulosic thickener of the application viscosity
0,55% balanced
PU (CoapurTM 830 W)
ADVICE 0 5 10 15 20 25 30 35 40 45
Average thickness (m)
TO OBTAIN YOU CAN USE
Wet Scrub resistance
excellent worse
balanced profile for satin & premium matt paints Coapur 830 W
Resistance to water absorption of the paint film is improved by using
newtonian profile for gloss paints Coapur 2025 polyurethane thickeners as shown in the diagram comparing a paint
including a cellulose thickener with one including Coapur 830 W.
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FROM PAINT TO RHEOLOGY FROM RHEOLOGY TO PAINT
RHEOLOGY
PRINCIPLES
ADVICE Dispersion
TO OBTAIN YOU CAN USE Particles generally have electron shortfalls at their surface that create
an overall positive charge and generate electrostatic repulsion
medium PVC, eggshell, satin paints Coapur 830 W forces between them. However, these are not sufficient: in fact, even
thoroughly dispersed, particles naturally tend to re-agglomerate in water
under the effect of Van der Waals attraction forces.
low PVC, semi gloss to gloss paints Coapur 3025
The dispersant can counteract this propensity by boosting the particles
repulsion potential (creation of double ionic layer and increase in zeta
= Dispersing agents of a hydrophobic nature potential). - - -
-
ELECTROSTATIC - +++
REPULSION - + --- +
In very high PVC systems, the quantity of available binder is not sufficient Stabilization - +-
-+ + +-
- - +
to ensure thorough coating of the mineral particles within the film. by adsorption - -- - +
A hydrophobic dispersant is therefore used to help partly offset this - + - + + + +
+ +
of a polyelectrolyte + + + - -
shortcoming. It delays the ingress of water and detergent during the wet dispersant + - -- -
+ - - +-
scrub test, and therefore increases the water resistance of such formulations. - -
-
+ --- - +
+ + + - -+
Wet scrub resistance of matt paint containing a hydrophobic dispersant - - -
+
-
The illustration below shows the performances of a hydrophobic dispersant + +
as opposed to a traditional acrylic dispersant in an early-rain-resistance
test. This formulation is used for waterproofing coatings (PVC = 40%). The chemical structure of acrylic dispersants comprises a large number
of carboxylic functions that are partly or fully neutralised by the addition
of a base. The resulting anionic functions then tend to attach themselves
2000 cycles 10000 cycles Polyacrylate Coadis 123K to the positively charged surface of the particles. This creates an
electron shortfall outside the particle + fixed polymer unit, and the
occurrence of an overall positive charge on the new ionic surface so
created, located further away from the centre of the particle.
The stability of the dispersion is then ensured both by the boosting of
the electrostatic repulsion potential resulting from a greater inter-particle
distance, and by a steric crowding effect.
Thickening mechanisms
Matt paint Early rain resistance test
PVC= 77% with Coadis 123K (deionised water sprayed on film
30 min after application)
ASE
ASE (Alkali Swellable Emulsion) acrylic thickeners are acrylic polymers
in a water emulsion. They feature acid groups that must be neutralised by
a base to be allowed to dissolve in water. The resulting anionic groups
immobilise the water molecules by hydrogen bond, generating a gel.
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FROM RHEOLOGY TO PAINT
They are effective Self-association mechanism They can thicken at high velocity gradient through the associative
at low velocity gradient. of thixotropic ASEs mechanism or at low velocity gradient through the association
COOH micelle made of mechanism.
COOH hydrophobic groups
polymeric backbone spacer
COOH Unlike acrylic thickeners, the thickening effect can be obtained
whatever the pH of the formulation, even if the pH is below 5.
+ H 2O
+ NaOH COOH COOH
COOH
It is nevertheless advisable to adjust the pH accurately in order
Na+
to obtain a reproducible thickening effect, and preferably in the alkaline
H COOH
+O COOH
COO COO H COO
realm for maximum effect.
urethane link hydrophilic backbone spacer linear hydrophobic
urethane link hydrophilic backbone
(PEG) spacer linear hydrophobic
end group
COO COO COO (PEG) end group(PEG)
long short short (PEG)
long
HASE long short short long
HASE (Hydrophobically modified Alkali Swellable Emulsion) type hydrophilic backbone branched hydrophobic
acrylic thickeners differ from ASEs by the modification of their chemical urethane linkhydrophilic backbone
(PEG) branched
spacer hydrophobic
end group
(PEG) end group
structure through the grafting of hydrophobic monomers. urethane link spacer
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FROM RHEOLOGY TO PAINT
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FROM RHEOLOGY TO PAINT
Thixotropic behavior: This additionally depends on shear duration, The dynamic properties of the paint during its application with a brush,
which induces a temporary decrease in viscosity. Viscosity reverts to its a roller or a spray gun -spreadability, film build, spatter resistance - can
initial value once shear has stopped after a period of time that depends be correlated with the viscosity measurements taken at high velocity
on the intensity and duration of shear. gradient.
100
The area between the two curves measures Measuring viscosity
90
the extent of the thixotropic character. The formulations viscosity is measured simply by means of a viscosimeter.
Viscosity (u.a.) = arbitrary unit
80
Measuring changes to the rheological properties of a material in relation
70
THIXOTROPIC to time, temperature or stress to which it is subjected requires a more
60
sophisticated apparatus, namely a rheometer.
50 she
are
40
Hy
ste
d Depending on the shear conditions, different types of viscosimeter and
ris
30
is a
rea
different methods will be chosen to measure and interpret the behavior
20
rec
ove of the system under consideration. The most widely used viscosimeters
ry
in the paint and coating industry are described below, as well as the
10
shear ranges to which they are best suited.
0
SHEAR
10 -2 10 -1 1 10 -1 10 -2 10 -3 10 -4 RATE (S -1)
10 -2 10 -1 1 10 -1 10 -2 10 -3 10 -4
Shear Rate (S ) -1
Low Medium High
Shear rates and paint properties
VISCOSIMETER ICI / CONE
Many properties can be correlated with viscosity measurements at TYPE
BROOKFIELD STORMER
& PLATE
the various velocity gradients applicable to paint.
Production
Brookfield viscosimeter
Storage Transportation Application
This viscosimeter typically used in Quality Control is the most common
SHEAR
RATE (S -1) of all. In the formulation industries, it is used to evaluate rheology
10 -2
10 -1
1 10 -1
10 -2
10 -3
10 -4
Good storage stability and good sagging resistance will be obtained immersed in a liquid at a given
in particular through sufficiently high viscosity at very low velocity and adjustable speed. The rod is
gradient. The degree of loading of the application tool being used - rotated by a motor on a shaft fitted
brush or spatula - can be controlled by considering the viscosity values with a calibrated spring. The shear
at low velocity gradient. strength will vary on the basis of
A measurement of viscosity at a medium shear rate will be representative the size of the mobile and/or the
of the perception of a user gently stirring the paint on opening the can. rotation speed.
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FROM RHEOLOGY TO PAINT
Stormer or Krebs viscosimeter Cone and plate or ICI type viscosimeters use a cone with a 0.5
The Stormer or Krebs viscosimeter is a rotation viscosimeter widely used angle in direct contact with the lower plate. Measurement consists
in the paint industry. in evaluating the pair (and therefore the stress) needed to obtain the
anticipated rotation speed generating a velocity gradient of 10000 s -1.
The viscosity of the fluid is
determined by measuring the pair 105
105
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MEASURES
EQUIVALENCE
Units
Viscosity Temperature
1 P = 1 gcm -1s -1 Conversion from Celsius to
1 Pas = 1 kgm-1s-1 = 10 P Fahrenheit: F = (9/5 x C) + 32
The relation to the SI unit is Conversion from Fahrenheit
to Celsius: C = 5/9 (F 32)
1 P = 0.1 Pas
1 cP = 1 mPas = 0.001 Pas F 95 86 77 68 59 50 41 32
Krebs Unit C 35 30 25 20 15 10 5 0
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