ChE EL 22: PAINTS AND COATINGS

RHEOLOGICAL PROPERTIES OF PAINTS AND COATINGS

INTRODUCTION TO RHEOLOGY

– The science of rheology is concerned with the deformation of flow of matter and with the
response of the materials to the application of mechanical force (stress) or to deformation
– Such responses include irreversible (viscous) flow and reversible (elastic) deformation or a
combination of both
– Examples include response of glass when hit with hammer, rubber band and when hung
with load
– A knowledge of colloid science is important in understanding rheology of emulsions,
suspensions and dispersions as polymer science is to rheology of polymer melts

REVIEW OF COLLOID SCIENCE

– Small particles with a dimension from several nanometers to several micrometers are
defined as colloidal particles
– Colloid is a mixture in which one substance is divided into minute particles (called colloidal
particles) and dispersed throughout a second substance. The substances are present as
larger particles than those found in solution, but are too small to be seen with a microscope.
There are no strict boundaries on the size of colloidal particles, but they tend to vary
-9 -6
between 10 m to 10 m in size
– Every colloid consists of two parts: colloidal particles and the dispersing medium. The
dispersing medium is the substance in which the colloidal particles are distributed

TYPES OF COLLOIDS
Dispersed Dispersed in Gas Dispersed in Liquid Dispersed in Solid
Material

Gas (bubbles) Not possible Foams: soda pop; whipped Solid foams: plaster,
cream; beaten egg whites pumice

Liquid (droplets) Fogs: mist; clouds; Emulsions: milk; blood; Butter;cheese

hair sprays mayonnaise

Solid ( grains) Smokes: dust; Sols and gels: gelatin; Solid sol: pearl;
industrial smoke muddy water; starch colored glass;
solution porcelain; paper

– The control of rheology is essential to the manufacture and usage of large numbers of
products in a modern industrial society

For example
– The smoothening of cosmetic cream on the face
– The taste and texture of foodstuffs such as sauces and mayonnaise

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– The application of paints to a surface by spraying, brushing etc

Why do we need to Study Rheological Properties of Paints?

– Rheological measurements of paints and coatings build the basis for the evaluation of their
quality.
– The structural regeneration, surface leveling, and sagging behavior are referred to as the
thixotropic behavior. These properties are essential indicators whether a product can be
perfectly processed or not

Rheological Properties of Paints and Coatings

– Viscosity – Viscoelasticity
– Shear- thinning – Surface and Interfacial Tension
– Thixotropy
Viscosity
– Viscosity is a resistance of a material to flow

Viscosity- Quantitative Definition

Viscosity = Shear Stress/ Shear Rate
Shear Stress = F/A
Shear Rate = ΔV/ Δy

History of Viscosity Measurements

– EC Bingham defined rheology as the science of deformation and flow of matter
– Heraclitus of Samos stated that everything flows
– Designers of water-clock in ancient Egypt showed the flow of simple liquid through
capillaries
– Newton in his Principia gave modern definition of viscosity
– Hooke in 1678 discovered experimentally the proportionality in between stress and strain
for elastic material
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– During the 18 century came the development of hydrodynamics
– Bernoulli
– Coulomb discovered the measurement of gas liquid viscosity using the decay of oscillation
of a disk suspended in the test sample
– Brookfield viscometer
– Hagen and Poiseuille developed the reference method for measuring the viscosity of
Newtonian liquids namely capillary viscometry
– Couette established the use of concentric cylinders as an experimental method of
measuring viscosity

Types of Rheological Behaviour

– The relationship between the shear stress and shear rate in a real fluid are part of the
science of rheology
– Shear stress is a stress state where the stress is parallel to the surface of the material

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– Shear rate is the rate of change of velocity at which one layer of fluid passes over an
adjacent layer

Newtonian and Non- Newtonian Fluids

– For some liquids, viscosity is the material constant that only relies on temperature and
pressure. These liquids are called Newtonian liquids. Non- Newtonian liquids do not follow
this proportional ratio
– Time- dependent viscosity is known as thixotropy. Shearing at a constant velocity gradient
causes a slow drop in the viscosity of a liquid. Viscosity will recover and reach the original
value as soon as the removal of the shear forces
– Increasing shear rate causes the viscosity of pseudoplastic materials to drop (shear
thinning)
– Conversely, the viscosity of dilatant products increases with the application of shear forces
(shear thickening). The liquid becomes more viscous during the application of shear forces.

Viscosity Measurement
– In the paint industry, viscosity is determined by a variety of measurement techniques,
from simple flow cup to compute controlled rotation viscometers

1. DIP CUPS
– Dip cups are engineered for determining efflux times for paints and similar fluids rapidly
and approximately at paint manufacturers and paint user sites
2. Flow Cups
- Knowledge about the absolute viscosity of a paint system is crucial for many applications
and parameters allowing for a relative classification and calculation is often needed. The
measurement of the efflux time in seconds has been established as a practical solution
- The efflux time is measured by flow cups of different designs, which are outlined in the
appropriate international/ national standards. These cups hold a defined volume of liquid
that flows through an orifice. The reproducibility of such measurements relies on the
following factors
a. The Newtonian flow behavior of the liquid
b. A constant temperature during measurement
c. The accuracy of the size of the cup
3. Bubble Viscometer
- The Direct Time Method employs a single 3 line timer tube to determine the ‘ bubble
seconds” needed for an air bubble to travel a known vertical distance through a bore of
known diameter. These “bubble seconds” may then be converted to stokes. Both
techniques are subject to changes according to the following variables:
a. Temperature: ±1°C = 10% error
b. Vertical Control ±5°C slant = 10% error
c. Tube I.D. Control ±0.1 mm = 2% error
4. Rotational Viscometers
- Many different rotational viscometers are used to determine the viscosity of non-
Newtonian liquids, which show different viscosities based on the applied shear rate

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Paint Density: Measuring film thickness

– A number of factors affect coating thickness, including improper thinning, environmental
conditions or mixing ratios when using two or multiple- component coatings. These are all minor
things that can add up to a major problem
– Coatings manufacturers put a lot of work into formulating their products, with each product
designed to work in specific environments and provide specific protective qualities
– Often, the thickness of the coating is critical in ensuring there is not a premature failure.

What affects coating thickness?

– Improper thinning (wrong mixing ratios)
– Applying the coating in the wrong environmental conditions
– Application technique
– Porosity and the surface profile of the substrate
– Generally speaking, higher quality paints have higher volume solids
than do economy paints

How do you calculate film thickness?

– The rule of thumb, in ideal circumstances, is that the vehicle to solids
ratio will tell you how much dry thickness you’ll have
– Say you have a coating that contains 50 percent solids. You apply it
on a perfectly smooth substrate at a thickness of 10 mils when wet. When it is dry, 50 percent
will be gone, and you’ll be left with a 5 mil cured coating. If you apply a 10-mil coating that has
75 percent solids, you’ll have a 7-5 mil cured thickness

So, how much of a coating product do you need for a particular object?
– Say you are using a product that has 100 percent solids and will cover 1,604 square feet at 1-mil
thickness. If you need a dry coating of 4 mils, you need to divide 1,604 by 4 to learn the product
will cover only 401 square feet at that thickness

How do you measure film thickness?

Wet- film thickness can be measured by a variety of gauges, but notch ( also known as step or comb
gauges) are inexpensive and the most commonly used field gauges
– A notch gauge has calibrated notches on its edges. You place the gauge squarely into the film
and on the substrate when the coating is wet. When you remove the gauge, look at the notches.
The film’s thickness lies halfway between the last coated notch and the adjacent uncoated
notch. While not precise, notch gauges are good for approximating film thickness and they come
in aluminum, steel or plastic.
– If the measurement of the wet coating is more critical, other devices, such as an eccentric roller
gauge, lens gauge or needle micrometer can be used.

Dry-film thickness can be measured either in a destructive or non- destructive manner

– Non- destructive paint thickness gauges generally fall into one of the three categories
a. Magnetic gauges – for measuring over steel

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- Magnetic Gauges measure the attractive force between the magnet in the gauge and the steel
substrate. As the coating thickness increases, the magnet becomes easier to pull away
- By measuring the pull- off force, you can determine the film thickness. “ The weaker the force,
the thicker the coating.”

b. Eddy current gauges – for measuring over most other metals

- Electronic and eddy current gauges are more expensive, but also more accurate, with a typical
tolerance of plus - or- minus one percent. Plus, “ they are faster and provide a variety of options
such as the ability to download stored measurement results to a printer or computer.”

c. Ultrasonic gauges – for measuring over non- metal substrates

– Ultrasonic gauges are ideal for measuring coating over non-metal substrates, such as
wood, concrete and plastic. These instruments send a pulse through the coating. The pulse
is reflected back from the substrate and converted into an electrical signal that is used to
determine the film thickness

Destructive Tests
– To measure film thickness generally require cutting through the coating to the substrate.
The coating is then measured with a micrometer or by viewing it microscopically. Another
method is to weigh a section of the substrate before and after coating. Laboratories are
best suited to handle these tests.

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