Rheological Characterization of Paints and Coatings

Rheological Characterization of Paints

and Coatings
Sponsored by TA Instruments Sep 8 2015

Waterborne coatings do not have a priori, the same advantageous rheological

properties as solvent-based coatings. If not formulated correctly, they display
inferior characteristics with regard to flow properties, leveling, application
properties, film build, etc. The performance of waterborne paints can be improved
through the addition of thickeners and rheological modifiers. The addition of
traditional thickeners such as inorganic clays and high molecular weight polymers
improves the viscosity during application, but delivers inferior spatter resistance and
leveling to the paint.

Associative thickeners such as low molecular weight, water soluble polymers improve the
overall performance of waterborne coatings. Associative thickeners reduce viscosity at high
rates, thus providing low roller spatter and good film build. Furthermore, they maintain a low
viscosity at low rates, thereby improving flow, gloss and leveling. The disadvantage is the
instability of these systems (phase separation) and the strong pH dependence, which
influences the ionization of the carboxyl groups of the latex surfactants.

Rheological Characterization of Water-based Coatings

The rheological characterization of coatings is generally carried at low shear viscosity (LSV)
0.001 to 1s-1, medium shear viscosity (MSV) 1-1000s-1, and high shear viscosity (HSV) 103
to 106s-1 (Figure 1). The consistency of a coating (i.e., appearance, pouring and mixing
behavior) is defined by MSV. ASTM D562 (Stormer viscosity), ASTM D2196 (Brookfield
spindles), and DIN53019 are typical test standards.

Viscosity of structural coatings

Figure 1. Viscosity of structural coatings

The HSV correlates to coating application conditions like brushing, rolling, etc. The cone/
plate viscosity test at 104s-1 is the standard test method (ASTM D4287-88). Typical paints
are adjusted to 50–150 mPas for low drag during application. The LSV correlates to all low
rate processes like leveling, sagging, settling, etc. The LSV is usually determined at 0.3s-1.
Leveling will be improved if the viscosity range is 25-100Pas. Sagging will occur if the

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Rheological Characterization of Paints and Coatings

viscosity is below 10Pas.

Yield stress measurement is also performed for the characterization of the paint in the low
rate region. A profile for a good thin film water-based coating is given in Table 1:

Table 1. Profile of a thin film waterborne paint

Rate Viscosity Yield Stress

Coating Process
(1/s) (Pas) (Pa)
Storage 0,1 >50 >1
Transfer to brush w/o dripping 0 >2.5 >1
Transfer to substrate with good film build and w/o
104 0.1 to 0.3 >0.25
excessive brush drag
Drying with good levelling and minimum sag 1 5 to 10 >0.25
A yield stress τ y larger than 1 Pa and a LSV above 50 Pas (at rest, before mixing) are
typical values to prevent settling during storage. Good leveling and flow is obtained if τ y is
smaller than 0.25 Pa after high shear mixing. Table 1 shows a table with typical values for
the viscosity and yield stress at different rates, giving a profile for good thin film water-
based coating. It is necessary to maintain a low elongation viscosity and elasticity for a
paint to avoid spatter and stringing.

Application Examples
Storage Stability and Shelf Life
The LSV correlates to the storage stability of paint. However the LSV is a single point
measurement and does not provide adequate data to understand the complex settling
mechanisms under gravity and their effect on the long-term shelf life of a product.
Measuring the rheological behavior, yield stress, and yield point is crucial for formulation of
coatings with the desired long-term stability.

The long-term stability of coatings can be predicted using the knowledge about the network
structure and its ability to resist internal (Brownian motion) or external forces (gravity,
vibrations) less than the yield stress. Yield stress can be directly measured from the
viscosity maximum during a stress ramp (Figure 2). However, careful control of the test
parameters is essential due to their influence over the yield stress value.

Yield point from a stress ramp experiment for a latex paint

Figure 2. Yield point from a stress ramp experiment for a latex paint

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Rheological Characterization of Paints and Coatings

Yield stress and yield point from the on-set (critical strain) of nonlinear behavior can be
determined with the dynamic strain sweep (Figure 3). The material structure data can be
obtained from a frequency sweep at strain amplitude less than the critical strain (Figure 4).
A key parameter is the tan δ, the ratio of energy dissipation and storage mechanisms down
to low frequency. If tan δ is in the range of 1-1.5, the material exhibits optimum storage
stability.

Figure 3. Strain sweep to determine yield stress and yield point

Frequency sweep to characterize the material’s structure

Figure 4. Frequency sweep to characterize the material’s structure

High tan δ values mean that the flow is predominantly viscous and there is only weak
association between the particles. As a result, under gravity, sedimentation cannot be
prevented by the inter- particle forces. Low tan δ values will occur because of strong
interparticle interaction (higher elasticity). Low tan δ values result in coalescence and the
generation of large aggregates, which also settle with time.

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Rheological Characterization of Paints and Coatings

Leveling and Brush Marks

Brush mark leveling involves two opposing forces (surface tension and viscous force) for a
drive to equilibrium and smooth surface (Figure 5). As the surface tension σ, the film height
h, and the wavelength of the brush marks λ do not change much, the depth of the brush
marks relies predominantly on the leveling stress τ.

Figure 5. Leveling of brush marks

Leveling ends when τ becomes equal to the yield stress τy, it is then possible to calculate d
from the yield stress. The viscosity increase must be rapid to avoid sagging, but needs to
be slow enough at the same time to allow leveling to take place (Figure 6). Figure 7 shows
the determination of the thixotropic index from the thixotropic loop test. There is no good
correlation between the thixotropic index and the application behavior under all conditions.

Recovery of structure

Figure 6. Recovery of structure

Thixotropic loop test

Figure 7. Thixotropic loop test

Rheology During Roller Application

Slender strings or thin fibers are formed if coatings have high elongation viscosity. They
lengthen and eventually break during application, snapping back onto the roller and the
substrate and producing spatter by forming small air-borne paint droplets due to the release
of energy stored in the elongated fibers. Coating tracks or surface patterns are also created
on the substrate by the same mechanism.

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Rheological Characterization of Paints and Coatings

The elongation viscosity for some dispersion with various levels of spatter resistance is
shown in Figure 8. The elongation viscosity does not increase with the addition of
associative thickeners as they form a structure breaking at high rate and therefore no
energy can be stored during deformation to cause spatter.

Elongation viscosity of conventional thickeners with different molecular weight

Figure 8. Elongation viscosity of conventional thickeners with different molecular weight

Film Build During Drying

The Mooney equation can describe the viscosity during the film formation of a latex
dispersion (Figure 9). During solvent evaporation, the viscosity increases and so the
particle volume fraction increases. Capillary forces dominate the particle-particle repulsion
forces when the particles approach each other, causing coalescence into a solid film. The
polymer latex is plasticized by less volatile solvent during the final stage of evaporation to
aid film coalescence.

Viscosity increase during drying

Figure 9. Viscosity increase during drying

The solid content of the coating greatly affects the film building, providing poor sagging
behavior during application over vertical surfaces when the solid content is high. The
viscosity becomes a minimum for high solid content coatings during drying and curing at
high temperatures (Figure 10), influencing the film thickness and the sagging performance.

Viscosity during drying and curing of two coatings with different solid loading

Figure 10. Viscosity during drying and curing of two coatings with different solid loading

Heating rate also affects the viscosity during cure. Faster curing is achieved when the
temperature increase is rapid, but the viscosity minimum is lower (Figure 11). For low
heating rate, the viscosity minimum is higher, but the total cure time is longer.

Cure profile as a function of heating rate

Figure 11. Cure profile as a function of heating rate

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Rheological Characterization of Paints and Coatings

Performance of the Coating Film

The performance properties of the final coat are correlated with the glass transition of
coating film. The Tg (crosslinking density) is higher when the curing temperature is higher.
The glass transition is measured by observing the drop in modulus as a function of
temperature (Figure 12).

Tg as a function of the cure temperature

Figure 12. Tg as a function of the cure temperature

Impact resistance is a key parameter for automotive coatings. Impact times for gravel are
typically in the order of 10ms. The DMA traces, modulus and tan δ as a function of
temperature must be shifted to a reference time of 10ms or a reference frequency of 105s-1
for predicting impact performance (Figures 13 and 14).

DMA trace of an automotive clear coat

Figure 13. DMA trace of an automotive clear coat

Correlation of the impact resistance with the DMA trace referred to a frequency of 105s- 1

Figure 14. Correlation of the impact resistance with the DMA trace referred to a frequency
of 105s- 1

In Figure 15, no significant change in the Tg and the modulus is observed in the glassy
state and the rubbery state for a crosslinked polyacrylate film pigmented with TiO2 rutile for
concentrations up to 40% by volume. However, the temperature dependence of the
modulus varies significantly at a critical pigment concentration, above the glass transition in
particular. The rubber region disappears above the pigment concentration of 45% due to
the reduced segmental mobility of the binder and the contributions of the modulus of the
rigid particles.

Pigment (TiO2) concentration on Tg

Figure 15. Pigment (TiO2) concentration on Tg

Conclusions
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Rheological Characterization of Paints and Coatings

Characterization of paints and coatings using rheology provides information about material
flow during processing as well as the performance of the coating during application and of
the final coating. Rheology is an important tool for formulation engineers to create paints
and coatings with better application properties.

This information has been sourced, reviewed and adapted from materials provided by TA
Instruments.

For more information on this source, please visit TA Instruments.

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Rheological Characterization of Paints and Coatings

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