ASM Handbook, Volume 5B, Protective Organic Coatings Copyright # 2015 ASM InternationalW

K.B. Tator, editor All rights reserved

10.31399/asm.hb.v05b.a0006051 asminternational.org

Composition of a Paint Coating

Chrissy Stewart, KTA-Tator, Inc.

THIS ARTICLE PROVIDES a brief components remain in the coating and on the incorporated into the formulation. Volatile com-
introductory overview of paints/coatings and surface once applied. Volatile components evap- ponents include any solvents, or water in emul-
their composition. There is much more detail orate from the coating into the air after the coat- sions, added to the coating.
in other articles of this Volume regarding ing is applied to the surface. Therefore, volatile Figure 1 is not comprehensive, because there
coating resins, surface preparation, coating components are present in the wet film but not are many more elements available to a paint/
quality and measurement, and industry use in the dried film of the coating. Nonvolatile coating formulator in each column than are
of coating materials. In this Volume, the components typically include the resin or binder, listed. However, it provides a good overview
terms paints and coatings are often used the pigmentation, and any additives that may be of the composition of most paint/coatings.
interchangeably. However, for the most part,
paints are considered to be used primarily
for aesthetics, while coatings are used princi-
Industrial
pally to prevent substrate deterioration or for coatings
corrosion protection. Industrial coatings are
most commonly used for the protection of
Pigment
corrosion of a metal substrate in such struc- (NV) Vehicle
tures as bridges, pipelines, or exterior metal
tank surfaces, to name a few.
Inhibitors Colorants Extenders Resins Solvents Additives
Regardless of the use, a layer of paint or (NV) (NV) (NV) (NV) (V) (NV)
coating will protect the surface and will also
provide color, gloss, and other estate properties. Water
Accordingly, the old industry joke, “What is the Zinc Red Clay Acrylic Primary (solvent/ Thickeners
emulsifier)
difference between a paint and a coating?. . .
About $10 per gallon,” is still applicable, even
Secondary Ultraviolet
though the price is much higher for some coat- Chromate White Silica Alkyd
absorbers
ing materials. In this article, the word coatings
is used, although substituting the word paints
for coatings is not incorrect. Phosphate Blue Mica Oil Plasticizers
A coating can be defined as a substance
spread over a surface to provide protection or
to serve decorative purposes. This text focuses Borate Black Vinyl Catalysts
on paint coatings, particularly industrial coat-
ings. Industrial coatings are designed for pro-
tective properties rather than for aesthetic Yellow Epoxy Wetting
agents
qualities.
Figure 1 illustrates the basic ingredients of an
industrial protective coating. The chart divides Urethane
a coating into two major components: pigmen-
tation and vehicle. The pigmentation typically
consists of colorants, corrosion inhibitors, and Polyaspartic
extenders, although other insoluble raw materi-
als may also be included. The vehicle carries
the pigmentation to the surface and binds it into Siloxirane
the coating film. The vehicle typically consists
of the resin or binder, solvents, and any addi-
tives that may be included in the formulation. Polyureas
Thus, in this article and elsewhere in this Vol-
ume, the terms vehicle and binder are often
used synonymously. Silicates
The components can also be categorized as
nonvolatile or volatile. These are indicated
in the chart by (NV) and (V). Nonvolatile Fig. 1 Industrial coating elements. NV, nonvolatile; V, volatile

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 Composition of a Paint Coating / 11

Pigments and fill the interstices between them. In this case, electrical contact with iron/steel, it corrodes pref-
the film will be tight, having low permeability erentially in lieu of the steel, thus protecting it
In many industries, including the plastics indus- and high strength and gloss. If the PVC/CPVC from corrosion. Organic zinc primers can provide
try, the term pigment is used to identify a sub- ratio is above 1.0, the pigment particles will be better corrosion protection than galvanizing does
stance that is a colorant. In the coatings industry, coated with resin, but the interstitial spaces will at low and high pHs. The PVC/CPVC ratio is
the definition is much broader. While it is true that be at least partially filled with air. This results in of critical importance to the properties of organic
pigments often improve the appearance of coat- a porous coating of high permeability, low zinc primers. If too much resin is used relative to
ings, they also serve many other functions in coat- strength, and low gloss. The PVC can be adjusted the volume of pigment, the film will not be con-
ings. For example, some pigments improve the by changing the amount of pigment in a coating; ductive and thus will not provide cathodic protec-
physical properties of the film, such as its strength, the CPVC can be adjusted by changing the type tion. If not enough resin is used, the film will lack
permeability to moisture, and impact resistance, (s) of pigments in a coating. cohesive strength and will not adhere to the sub-
whereas other pigments protect the substrate from Corrosion inhibiting pigments play a large role strate. The ratio of zinc to resin in inorganic zinc
corrosion, fire, or mold. No matter what their in industrial coatings. Anticorrosive coatings primers is not as critical because in this type of
function is, most pigments used in the coatings used on steel include organic zinc primers, inor- primer, the resin does not encapsulate the zinc
industry are finely divided solids that are insoluble ganic zinc primers, inhibitive primers, and barrier particles but rather reacts with them. Before
in the other coating ingredients. Thus, most pig- coatings. Zinc provides cathodic protection to applying inorganic zinc primer, however, it is
ments do not dissolve in the resin or the solvent steel whether applied as a molten layer (galvaniz- critical that the surface of the substrate is clean
and instead are suspended in them. Coatings typi- ing) or added as a pigment to a coating. Zinc is a to ensure adhesion. Blast cleaning to at least a
cally do use not a single pigment but rather a blend more active metal than iron, and, when in near-white condition is often required.
of pigments to achieve the balance of aesthetic,
physical, and protective properties desired.
Pigments with refractive indices greater Table 1 Particle shape and coating film properties of pigments
than 2 are used to increase the opacity or hiding Particle
power of a coating. An unpigmented coating shape Benefit Usage Pigment type
will appear clear even if it contains a mixture Platey Barrier properties Barrier primers Aluminum
of resins, because the refractive indices of most Corrosion resistance Exterior house paints Mica
resins are very similar, ranging from 1.5 to 1.6. Bleed and stain killing Enamel holdout Interior high-PVC flats Glass flake
When a finely divided insoluble pigment with a TiO2 extension (spacers) in high-PVC Latex paints Stainless steel
flats (clays) Stain-killing paints Talc
refractive index of 2 or greater is added to the Stress relief via slippage of overlapping Zinc-rich primers Clays
continuous resin phase, the light is bent or plates Smooth finishes Sliver and nickel flake
refracted. As light passes from the resin to the Cracking and checking resistance Paper coatings Graphite
higher-density pigment, it is bent both as it Mudcracking resistance at high PVC/ Conductive coatings
CPVC Sealers and undercoaters
enters and as it leaves the pigment. If the differ- Soft in-can pigment sedimentation
ence between the refractive indices of the resin High vehicle demand
and pigment is large, the light will be bent by High viscosity
such a degree that it will exit the surface of Improved application properties
Good stain removal and scrub resistance
the coating before it reaches the substrate Acicular Film reinforcement Exterior coatings Wollastonite
underneath. If all of the light that enters a coat- Cracking and checking resistance Roof coatings Zinc oxide
ing returns to its surface, the substrate under- Improved durability Block fillers Chopped-fiber glass
neath is hidden and the coating appears Mudcracking resistance at high PVC/ Textured coatings Talc
CPVC Many of the organic pigments are slightly
opaque. The most widely used hiding pigment Texture acicular.
is the white pigment rutile titanium dioxide. It Fibrous Film reinforcement Roof coatings Asbestos
has a refractive index of 2.76. Cracking and checking resistance Block fillers Cut textile fibers
Along with the refractive index, the shape Mudcracking resistance at high PVC/ Textured coatings Celluosics
CPVC Zinc-rich primers Polyolefins
of the pigment contributes to various phy- Texture High-build mastics Acrylics
sical properties of the coating to which it is Thixotropy Asphaltic and coal tar Polyaramids
added. There are six defined shapes of pigment, High build capabilities coatings
which include platey, acicular, fibrous, nodular, Nonsagging Tennis court coatings
Nonsettling
spherical, and irregular. Examples of the film High viscosity
properties attributed to the pigment shapes Crack bridging
as well as several pigment types are listed in Nodular Excellent filling properties Gloss and semigloss Calcium carbonate silica
Table 1. Low vehicle demand coatings Titanium dioxide
Low viscosity Wood fillers Iron oxides
Extender pigments, such as barytes, calcium Water resistance (nodular silica) High-solids coatings Barytes
carbonate, silicates, and silica, have refractive Floor and deck coatings Nepheline syenite
indexes similar to resins and thus are relatively Mar and burning Chromium green oxide
weak opacifiers. Extender pigments are often resistance Most inhibitive pigments
Spherical Excellent filling properties Zinc-rich primers Zinc dust
used instead to adjust the pigment volume con- Low vehicle demand High solids Synthetic vesiculated spheres
centration (PVC), which is the ratio of the vol- Low viscosity Low-VOC systems
ume of pigment to the volume of the dried Opacity
coating. The critical pigment volume concen- Hardness (vesiculated spheres)
Irregular Excellent flatting properties Flat paints Diatomaceous silica
tration (CPVC) is the PVC at which there is just Moderate film reinforcement
enough resin to coat the pigment and fill the High vehicle demand
interstices between the pigment particles. The High viscosity
properties of the dried film are highly depen- Note: Properties conferred by any pigment on a coating will also depend on other pigment properties, such as particle size, particle size distribution,
dent on the ratio of PVC to CPVC. A PVC/ surface morphology and hardness, as well as chemical constitution. Thus, pyrogenic and other fine-particle silicas, while nodular in shape, have high
vehicle demand and are widely used for increasing viscosity, thixotropy, and for flatting. PVC, pigment volume concentration; CPVC, critical pig-
CPVC ratio below 1.0 indicates that there is ment volume concentration; VOC, volatile organic compound. Source: Ref 1
sufficient resin to coat the pigment particles

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 12 / Introduction

Previously in the coatings industry, chromate
salts and compounds containing lead were often
used to inhibit the corrosion of steel. These
compounds prevented rust by enabling the for-
mation of a thin, passive layer on the surface
of the steel. Lead compounds were more useful
than chromate salts because the presence of
chloride salts could counteract the protection
of chromium. Because of the toxicity of lead
and hexavalent chromium, their use has been
limited due to the increased costs associated
with worker protection and environmental com-
pliance when using coatings containing these
elements. In many countries, lead and hex-
avalent chromium (and other toxic pigments)
are outlawed. Other less effective inhibitors
are used today (2015), including phosphates,
molybdates, and borates. Molybdates and
borates are quite soluble in water and should
not be used in highly humid conditions.
Barrier coatings pigmented with micaceous
iron oxide and leafing aluminum pigments have
low moisture permeability. The lamellar structure
formed by these flat, platelike pigment particles
greatly increases the length of the pathway that
moisture must travel to reach the substrate.
Some coatings do not have a pigment compo-
nent; these are called clear coats. They are used
extensively in the automotive industry on vehi-
cles as topcoats over a color coat and also over
industrial coatings for additional gloss, graffiti
resistance, appearance, and corrosion protection.
Resin
The resin system cohesively binds the pig-
mentation and other components together and
adhesively binds the coating to the underly-
ing substrate or coating layer. This is what
allows the coating to form a solid/hard to
semihard (depending on the resin) plasticlike
film. The choice of resin system has a substan-
tial impact on the performance of a coating.
This is the reason a coating often is identified
generically by the type of resin it contains.
The advantages and limitations of principal
coating resins are listed in Table 2. Also,
many articles in this Volume, such as “Epoxy
Resins and Curatives” and “Alkyd Resins,”

Table 2 Advantages and limitations of principal coating resins

Resin type Advantages Limitations Comments

Auto-oxidative cross-linked resins

Alkyds Good resistance to atmospheric weathering and
moderate chemical fumes; not resistant to chemical
splash and spillage. Long-oil alkyds have good
penetration but are slow drying; short-oil alkyds are
fast drying. Temperature resistant to 105  C (225  F)
Epoxy esters Good weather resistance; chemical resistance better
than alkyds and usually sufficient to resist normal
atmospheric corrosive attack
Thermoplastic resins
Acrylics Excellent light and ultraviolet stability, gloss, and color Thermoplastic and water emulsion acrylics not suitable
retention. Good chemical resistance and excellent
atmospheric weathering resistance. Resistant to
chemical fumes and occasional mild chemical splash
and spillage. Minimal chalking; little if any darkening
on prolonged exposure to ultraviolet light
Water Resistant to water, mild chemical fumes, and weathering. Must be stored above freezing. Does not penetrate chalky
emulsion Good alkali resistance. Latexes are compatible with
latex most generic coating types, either as an undercoat or
topcoat.
Asphalt pitch Good water resistance and ultraviolent stability. Will not Black color only. Poor resistance to hydrocarbon
crack or degrade in sunlight. Nontoxic and suitable for
exposure to food products. Resistant to mineral salts
and alkalis to 30% concentration
Coal tar pitch Excellent water resistance (greater than all other types
of coatings); good resistance to acids, alkalis, and
mineral, animal, and vegetable oils
Cross-linked thermosetting resins
Bisphenol-A Excellent resistance to alkalis, most organic and
amine- inorganic acids, water, and aqueous salt solutions.
cured Solvent resistance and resistance to oxidizing agents
epoxies are good as long as not continually wetted. Amine
adducts have slightly less chemical and moisture
resistance.
Bisphenol-F Lower volatile organic compound (VOC) content than
epoxies bis-A epoxies. Better temperature and chemical
resistance than bis-A types. Intermediate temperature
and chemical resistance between bis-A and novolacs
Epoxy Greater chemical resistance and highest temperature
novolacs resistance of all epoxy resins used for most severe
immersion service
Polyamide- Superior to amine-cured epoxies for water resistance.
cured Excellent adhesion, gloss, hardness, impact, and
epoxies abrasion resistance. More flexible and tougher than
Source: Ref 2
Not chemically resistant; not suitable for application
over alkaline surfaces, such as fresh concrete, or for
water immersion
Generally the least resistant epoxy resin. Not resistant
to strong chemical fumes, splash, or spillage.
Temperature resistance: 105  C (225  F) in dry
atmospheres. Not suitable for immersion service
for any immersion service or any substantial acid or
alkaline chemical exposure. Most acrylic coatings are
used as topcoats in atmospheric service. Acrylic
emulsions have limitations described under the “Water
emulsion latex” entry.
surfaces. Exterior weather and chemical resistance not
as good as solvent- or oil-based coatings. Not suitable
for immersion service
solvents, oils, fats, and some organic solvents. Does
not have the moisture resistance of coal tars. Can
embrittle after prolonged exposure to dry
environments or temperatures above 150  C (300  F)
and can soften and flow at temperatures as low as
40  C (100  F)
Unless cross linked with another resin, is thermoplastic
and will flow at temperatures of 40  C (100  F) or less.
Hardens and embrittles in cold weather. Black color
only; will alligator and crack on prolonged sunlight
exposure, although still protective
Harder and less flexible than other epoxies; intolerant
of moisture during application. Coating chalks on
exposure to ultraviolet light. Strong solvents may lift
coatings. Temperature resistance: 105  C (225  F)
wet; 90  C (190  F) dry. Will not cure below 5  C
(40  F); should be topcoated within 72 h to avoid
intercoat delamination. Maximum properties require
curing time of approximately 7 days.
Less flexible; requires thorough blast-cleaning surface
preparation
Least flexible of epoxy resins; costly
Cross linking does not occur below 5  C (40  F).
Maximum resistances generally require 7 day cure
(continued)
Long-oil alkyds make excellent primers for rusted and
pitted steel and wooden surfaces. Corrosion resistance
is adequate for mild chemical fumes that predominate
in many industrial areas. Used as interior and exterior
industrial and marine finishes
A high-quality oil-based coating with good compatibility
with most other coating types. Used widely for
atmospheric resistance in chemical environments on
structural steel, tank exteriors, etc.
Used predominantly where light stability, gloss, and
color retention are of primary importance. With cross
linking, greater chemical resistance can be achieved.
Cross-linked acrylics are the most common
automotive finish. Emulsion acrylics are often used as
primers on concrete block and masonry surfaces.
Ease of application and cleanup. No toxic solvents. Good
concrete and masonry sealers because breathing film
allows passage of water vapor. Used as interior and
exterior coatings
Often used as relatively inexpensive coating in
atmospheric service, where coal tars cannot be used.
Relatively inexpensive. Most common use is as a
pavement sealer or roof coating
Used as moisture-resistant coatings in immersion and
underground service. Widely used as pipeline exterior
and interior coatings below grade. Pitch emulsions
used as pavement sealers. Relatively inexpensive
Good weather resistance. Excellent chemical resistance.
Excellent adhesion to steel and concrete. Widely used
in maintenance coatings and tank linings
Increasing use due to high reactivity and low VOC
content
Used for high-temperature chemical immersion service
Easier to apply, topcoat more flexible, and better
moisture resistance than amine-cured epoxies.
Excellent adhesion over steel and concrete. A widely

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 Composition of a Paint Coating / 13

Table 2 (Continued)
Resin type Advantages
amine-cured epoxies. Some formulations can cure on
wet surfaces and underwater. Temperature resistance:
105  C (225  F) dry; 65  C (150  F) wet
Epoxy powder Good adhesion and chemical and moisture resistance.
coatings Allows cathodic protection in shielded areas on
pipelines
Coal tar Excellent resistance to saltwater and freshwater
epoxies immersion. Very good acid and alkali resistance.
Solvent resistance is good, although immersion in
strong solvents may leach the coal tar.
Epoxy Excellent hot water and acid resistance. More flexible
phenolics than phenolic. Better alkali resistance than phenolic
Phenolics Greatest solvent resistance of all organic coatings
described. Excellent resistance to aliphatic and
aromatic hydrocarbons, alcohols, esters, ethers,
ketones, and chlorinated solvents. Wet temperature
resistance to 95  C (200  F). Odorless, tasteless, and
nontoxic; suitable for food use
Polyurethanes Aliphatic urethanes are noted for their chemically
(aromatic or excellent gloss, color, and ultraviolet light resistance.
aliphatic) Properties vary widely, depending on the polyol
coreactant. Generally, chemical and moisture
resistances are similar to those of polyamide-cured
epoxies, and abrasion resistance is usually excellent.
Polyureas Fast- to very-fast-curing, highly elastic thick-film
coatings with good strength, abrasion resistance,
and chemical resistance. Typically 100% solids
Polyaspartic Fast curing; tolerant of low temperatures; high film
esters build achievable. Provides excellent abrasion
resistance, corrosion resistance, and resistance
to ultraviolet exposure. Low VOC content
Zinc-rich coatings
Organic zinc- Galvanic protection afforded by the zinc content, with
rich chemical and moisture resistance similar to that of
coatings the organic binder. Should be topcoated in chemical
environments with a pH outside the range of 5 to 10.
More tolerant of surface preparation and topcoating
than inorganic zinc-rich coatings
Inorganic Provides excellent long-term protection against pitting
zinc-rich in neutral and near-neutral atmospheric and some
coatings immersion services. Abrasion resistance is excellent,
and dry heat resistance exceeds 370  C (700  F).
Water-based inorganic silicates are available for
confined spaces and compliance with regulations
regarding VOCs.
Source: Ref 2
Limitations
at 20  C (70  F). Slightly lower chemical resistance
than amine cured-epoxies
Color change is difficult due to extensive cleanup of
old powder. Like all epoxy resins, chalks on ultraviolet
exposure. Must be applied in shop. Hard to field repair
Embrittles on exposure to cold or ultraviolet light. Cold Good water resistance. Thickness of 0.25 mm (10 mils)
weather abrasion resistance is poor. Should be
topcoated within 48 h to avoid intercoat adhesion
 
problems. Will not cure below 10 C (50 F). Black or

dark colors only. Temperature resistance: 105 C
(225  F) dry; 65  C (150  F) wet
Not as alkali resistant as other epoxy resins. Applies in Linings for food and beverage processing storage tanks
thin films. Somewhat brittle
May be baked at a metal temperature ranging from
175 to 230  C (350 to 450  F). Coating must be
applied in a thin film (approximately 0.025 mm, or
1 mil) and partially baked between coats. Multiple thin
coats are necessary to allow water from the
condensation reaction to be removed. Cured coating is
difficult to patch due to extreme solvent resistance.
Poor resistance to alkalis and strong oxidants
Because of the versatility of the isocyanate reaction,
wide diversity exists in specific coating properties.
Carbon dioxide is released on exposure to humidity,
which may result in gassing or bubbling of the coating
in humid conditions. This is typically seen in the case
of aromatic polyurethanes. Aromatic urethanes may
also darken or yellow on exposure to ultraviolet
radiation.
Requires specialized spray equipment due to fast curing Concrete coatings for use in primary and secondary
Rate of curing has strong dependency on humidity.
Difficult to downgloss, especially clearcoats. Shorter
pot life may require smaller batch size. Potentially
shorter recoat windows due to fast cure time
Generally have lower service performance than inorganic Widely used in Europe and the Far East, while inorganic
zinc-rich coatings, but ease of application and surface-
preparation tolerance make them increasingly popular
Inorganic nature necessitates thorough blast-cleaning
surface preparation and results in difficulty when
topcoating with organic topcoats. Zinc dust is reactive
outside the pH range of 5 to 10, and topcoating is
necessary in chemical fume environments. Somewhat
difficult to apply; may mudcrack at thicknesses in
excess of 0.13 mm (5 mils)
Comments
used industrial and marine maintenance coating. Some
formulations can be applied to wet or underwater
surfaces.
Applied by electrostatic spray/fluidized bed. Increasing
use because of VOCs; used as pipeline and original
equipment manufacturer coatings
per coat. Can be applied to bare steel or concrete
without a primer. Low cost per unit coverage
A brown color results on baking, which can be used to
indicate the degree of cross linking. Widely used as
tank lining for alcohol storage and fermentation and
other food products. Used for hot water immersion
service. Can be modified with epoxies and other resins
to enhance water, chemical, and heat resistance
Aliphatic urethanes are widely used as glossy, light-fast
topcoats on many exterior structures in corrosive
environments. They are relatively expensive but
extremely durable. The isocyanate can be combined
with other generic materials to enhance chemical,
moisture, low-temperature, and abrasion resistance.
Aromatic urethanes are typically used as primers,
adhesion promoters, and intermediate coats.
containment of chemical tanks. Elastomeric roof
coatings
Application can occur through the use of plural-
component or conventional spray equipment as well as
brush or roller application.
zinc-rich coatings are most common in North
America. Organic binder can be closely tailored to
topcoats (e.g., epoxy topcoats over epoxy-zinc-rich
coatings) for a more compatible system. Organic zinc-
rich coatings are often used to repair galvanized or
inorganic zinc-rich coatings.
Ethyl silicate zinc-rich coatings require atmospheric
moisture to cure and are the most common type.
Widely used as a primer on bridges, offshore
structures, and steel in the building and chemical-
processing industries. Used as a weldable
preconstruction primer in the automotive and
shipbuilding industries. Eliminates pitting corrosion

describe the characteristics of coatings based on a
particular resin system.
The resin component of a coating is a poly-
mer. A polymer is formed by the covalent
bonding of many smaller molecules, linking
them together into a chain. The components of
the chain, which are called monomers, may be
all the same chemical or a mix of chemicals.
The composition of a polymer is chosen so that
the resin has the properties desired. The design-
ing of a polymer is sometimes referred to as
molecular engineering. The polymer chain
may be cross linked with other chains if its
individual components remain reactive after
the polymer is formed. A cross-linked polymer
is called a thermoset, whereas a polymer that
is not cross linked is called a thermoplastic.
A coating resin that is not dissolved in a solvent
is essentially a plastic. Thermosets do not melt
upon heating. Thermoplastics can be remelted
and resolidified indefinitely.
Additives
Various types of additives are used to
improve the consistency, flowout, surface wet-
ting, color, ultraviolet light (e.g., sunlight)
resistance, and flexibility and to prevent settling
in the can (suspending agents). For example, poly-
urethane coatings are formulated with hindered-
amine light stabilizers to help preserve gloss and
color on exposure to sunlight, and plasticizers
are formulated into hard or brittle coatings,
such as vinyls, to provide film flexibility.
Table 3 lists some common resin types and the
additives that are typically used with each resin
type.
Solvent
The solvent is the volatile component of
the vehicle and may include water or organic
liquids such as methyl ethyl ketone or min-
eral spirits. A list of solvent families and
the coatings resins in which the solvents are
typically used is provided in Table 4.
Although the solvent is part of the wet film
during application, it is not intended to be
part of the dry film once the coating dries

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 14 / Introduction

Table 3 Commonly used additives for common resin types

Resin type Additive Examples

Alkyd Driers Cobalt, calcium, manganese, lead, iron, zirconium

Acrylic Adhesion promoters Organosilane, titanate, zircoaluminates, zirconates, aryl/alkyl phosphate esters, chromium
Polyester Corrosion inhibitors Zinc, chromium, lead
Epoxy (thick, high solids) Reactive diluents Butyl glycidyl ether, C12-C14 aliphatic glycidyl ether, cresyl glycidyl ether, 2-ethylhexyl glycidyl ether
Polyurethane Ultraviolet absorbers Titanium dioxide, zinc oxide, cerium oxide, hindered-amine light stabilizers
Waterborne polymer Surfactants Polyethoxylated octyl phenol, sorbitan monoester, glycerol diester (diglyceride), abietic acid
Powder resin Flow agents Polyacrylates, polysiloxanes
Source: Ref 3

Table 4 Solvent families and typical coating resins Table 4 (Continued)

Solvent family Example solvents Typical coating resin Solvent family Example solvents Typical coating resin

Hydrocarbons Ethylene glycol monoethyl Acrylics

ether Cellulosics
Aliphatic hydrocarbonsHexane Oils
Ethylene glycol monobutyl
VM&P naphtha Long-oil alkyds
ether
Stoddard solvent
Propylene glycol monopropyl
Mineral spirits
ether
140 solvent
Diethylene glycol monomethyl
Aromatic hydrocarbons Toluene Long- and short-oil alkyds
ether
Xylene Chlorinated rubber
Diethylene glycol monobutyl
Medium-flash aromatic naphtha Acrylics
ether
High-flash aromatic naphtha Styrene and vinyl toluene
Dipropylene glycol
copolymer
monomethyl ether
Silicone resins
Esters Ethyl acetate Nitrocellulose
Some epoxies
Isopropyl acetate Urethanes
Chlorinated Methylene chloride Paint removers
n-propyl acetate Acrylics
hydrocarbons Methyl chloroform
Isobutyl acetate Vinyls
Terpenes Turpentine Oils
n-butyl acetate Epoxies
Dipentene Alkyds
sec-butyl acetate
Pine oil Epoxy esters
Amyl acetate
Use of terpenes has been
Isobutyl-isobutyrate
declining
2-ethylhexyl acetate
Oxygenated solvents Ethylene glycol monoethyl
ether acetate
Ketones Acetone Vinyls
Propylene glycol monomethyl
Methyl ethyl ketone Urethanes
ether acetate
Methyl isobutyl ketone Epoxies
Butyl lactate
Methyl isoamyl ketone Acrylics
Nitroparaffins and 2-nitropropane Epoxies
Methyl n-propyl ketone Nitrocellulose
miscellaneous Tetrahydrofuran Acrylics
Diacetone alcohol Cellulose acetate
Dimethyl formamide Vinyls
Cyclohexane
n-methyl-2-pyrrolidone Polyvinyl chloride
Isophorone
Polyvinylidine chloride
Alcohols Methanol Polyvinyl acetate
Alkyds
Ethanol, anhydrous Phenolics
Cellulosics
n-propanol Polyvinyl acetal resins
Urethanes
Isopropanol, anhydrous Inorganic zincs
Polyesters
Isobutanol Epoxies
Silicones
n-butanol Alkyds
Chlorinated rubbers
Secondary butanol
Tertiary butanol Water
Amyl alcohol (mixed isomers) ... ... Latex
Cyclohexanol
Highly hydroxylated acrylics
Glycol ethers Ethylene glycol monomethyl Epoxies
Highly hydroxylated polyesters
ether Polyesters
Elusions (epoxies, urethanes)
(continued)
Source: Ref 4
Source: Ref 4

or cures. It is uncommon for a coating to be
formulated with one type of solvent; typi-
cally, a blend of solvents is used, with each
type of solvent in the blend performing
a different function. Primary solvents are
the solvents that are formulated into the coat-
ing to reduce the viscosity of the resin, pig-
ment, and additives so that the coating can
be properly atomized through a spray gun
or applied with brush or roller. Secondary sol-
vents are slower-evaporating solvents, remain-
ing in the wet coating film a little longer than
the primary solvents. They help the coating to
flow out to form a uniform, continuous film.
Volatile Organic Compounds
A problem with many of the organic solvents
used in coating formulations or added as thin-
ners in the field is that, after evaporating from
the coating film into the air, they can react
with nitrogen oxides and carbon monoxide in
the presence of sunlight to produce ozone, a
component of smog. These organic solvents,
or volatile organic compounds (VOCs), are
regulated in the United States by the Environ-
mental Protection Agency (EPA) under the
Clean Air Act. In addition, some states and
regions restrict the level of VOCs even more
stringently than the federal regulations. The
amount of VOCs that can be legally emitted
into the atmosphere varies considerably from
location to location. For example, densely
populated areas such as southern California
and Houston, Texas, have very strict VOC

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regulations, while less populated areas typically
only need to comply with the federal limit. Cali-
fornia has led the nation in the recent march
toward coatings with ever-lower amounts of
VOCs.
The VOC content of a coating is typically
expressed in pounds per gallon or grams per
liter and is reported on the coating manufac-
turer’s product data sheet. Many manufacturers
also report the VOC content after addition of
thinner.
When a structure is being painted in the field,
the VOC limit is typically dictated by the proj-
ect specification or the local air pollution
agency. Fixed facilities such as painting shops
are sometimes required to log the number of
gallons of paint used over a specific period
(for example, 90 days) and the VOC content
of each type.
However, there are coatings formulated with
exempt solvents that do not count as VOCs.
Water is an exempt solvent whether used as
an emulsifier or a true solvent or diluent in a
coating formulation. Other exempt organic sol-
vents include acetone, p-chlorobenzotrifluoride,
methyl acetate and t-butyl acetate.
Thus, in summary, coatings are ideally for-
mulated with all the appropriate ingredients to
comply with environmental regulations and
worker health hazards, to enable ease of appli-
cation and formation of the finalized dry film,
and to provide a suitably long service life for
a given environment.
The formulation of coatings is not discussed
in this Volume, because that is an altogether
different science than the proper specification,
application, curing, and use of a formulated
coating. However, during the manufacture of a
batch of coating material, most ingredients of
the formulation are added on a weight basis.
A coatings container (for example, a 1 U.S.
gal, or 3.79 L, paint can) is illustrated in
Fig. 2 with its composition expressed as a per-
centage by weight and a percentage by volume.
Because pigments are usually inorganic metal-
lic particles, they are much heavier than an
equivalent volume of any other constituent.
Water/
solvent (volatile)
Additives
(nonvolatile)
Resin
(nonvolatile)
Pigment
(nonvolatile)
(a)
Fig. 2 Coating composition of a 1 U.S. gal (3.79 L) container. (a) Percent by weight. (b) Percent by volume
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Figure 2 pertains to a solvent- or waterborne
material; in the case of a 100%-solids material,
the entirety of the container would consist of
resin, pigments, and additives.
Thickness of a coating is a function of
volume rather than weight; for example, 1 U.S.
gal (3.79 L) of a 100% solids coating will theo-
retically cover 150 m2 (1600 ft2) of surface at a
thickness of 25 mm (1 mil). Thus, if a thickness
of 100 mm (4 mils) is desired, the coverage will
be 37 m2 (400 ft2). Similarly, if the coating
is 50% solids by volume, the coverage will be
75 m2 (800 ft2) at a thickness of 25 mm (1mil).
Accordingly, while the coating manufacturer
is usually more concerned with the weight of
the coatings constituents, coating applicators
are much more concerned with the volume
of the applied material because they must attain
the specified dry film thickness.
Film-Forming Mechanisms of
Various Coating Types
This section discusses lacquers, chemically
converting coatings, latex coatings, alkyds and
other resins that cure by oxidation, moisture-
curing polyurethanes and inorganic zinc pri-
mers, and powder coatings.
Lacquers. Thermoplastic resins used in coat-
ings include polyvinyl chloride, polystyrene,
poly(methyl methacrylate), and polystyrene-
butadiene copolymer. They are generally one-
pack systems (all components of the coating
are packaged in one container) that are fast dry-
ing and low solids. A coating containing a ther-
moplastic binder dissolved in organic solvent is
called a lacquer. Once a lacquer is applied, the
thermoplastic film hardens as the solvent eva-
porates. The polymer chains may entangle, but
no chemical reaction occurs as the film is
formed.
Because the resin is composed of large mole-
cules, the solids or nonvolatile content of lac-
quers must be kept low so that the viscosity of
the coating is not so high that application is
Dry film
composition
(b)
Composition of a Paint Coating / 15
difficult or impossible. The viscosity of a lac-
quer is also dependent on the molecular weight
of the resin. Unfortunately, the higher the
molecular weight of the binder, the better its
barrier properties but also the higher the viscos-
ity of the coating. For this reason, the molecular
weight of most binders used in lacquers is lim-
ited to 50,000.
When the solvent evaporates from the
applied film into the air, the resin, pigment,
and additives remain on the surface. Because
there is no subsequent curing reaction, the resin
can be redissolved by the solvent system that
evaporated from the coating film. A coating
that cures by solvent evaporation should not
be overcoated with a coating containing strong
solvents, because such solvents may redissolve
the underlying coating film.
Chemically Converting Coating. Lacquers
are not used as often today (2015) because of
regulations restricting the use of VOCs. The
binder of lacquers is dissolved in organic sol-
vents, and many of the solvents used are con-
sidered VOCs. Instead, two-pack systems
(in which coating components are packaged in
two containers to be mixed together at the time
of application) of chemically converting coat-
ings with high solids content are used. Each
pack contains a solution of small polymers.
When the packs are mixed together at ambient
temperatures, the small polymers begin to com-
bine to form polymers of high molecular
weight. When the mixed coating is applied,
the molecules still have not reacted to a point
that the viscosity is excessive, even though the
solids content of the mixture is high. Because
the components contain a high percentage of
solids, the percentage of solvent they contain
is low; thus, the VOC content is low.
The rate of chemical reaction, or curing,
increases markedly after the coating is applied.
As the solvent evaporates, the space between
the reacting molecules shrinks, and the proba-
bility that the molecules are close enough to
react greatly increases. If the cure involves the
cross linking of the polymer molecules, which
it typically does, the resulting film is a thermo-
set. Common two-pack systems used as indus-
trial coatings include epoxy amine coatings
and urethane coatings. Chemically converting
systems may be one-pack systems if the chemi-
cal reaction occurs at high temperatures and
does not occur under ambient conditions.
Multipack coatings must be mixed in the
correct proportion. To ensure a proper mix ratio,
usually only complete prepackaged kits are
blended. After blending, the freshly mixed coat-
ing may need to stand for a period of time,
called the induction or sweat-in time, if specified
on the product data sheet. Application of the
coating should be completed within the pot
life stated on the product data sheet. Coatings
become unusable after the pot life expires often
because their viscosity becomes excessively
high. The pot life may vary from a few minutes
to several hours, depending on the formulation
and application temperature of the coating.
 16 / Introduction
Latex Coatings. In latex coatings, polymers
of very high molecular weight exist in discrete
particles called micelles suspended in water.
To prepare a latex polymer, a small quantity
of anionic surfactant is added to a much larger
quantity of water. The anionic surfactant mole-
cules associate in roughly spherical particles,
with the negatively charged heads on the outside
and the nonpolar tails on the inside. When
monomer is added to the mixture, it diffuses
into the particle. The repulsive force provided
by the anionic surfactants on the surface of the
particles keeps the particles from coagulating.
Because the micelles are discrete particles, the
viscosity of the latex has little dependence on the
molecular weight of the polymer. The molecular
weight of the resin in latexes can be more than
10 times higher than the resin used in lacquers.
When a latex is applied, the water evaporates
from the film, and the particles of polymer
begin to coalesce. Coalescing solvents such as
propylene glycol are sometimes added when
the latex is prepared, to aid the fusing of the
particles. It is important that a latex not be
applied at a temperature below that specified
on the product data sheet, because the polymer
particles may be too hard to coalesce, resulting
in a poorly performing film coating. Should
the air temperature fall below the minimum
specified (typically above 2  C, or 35  F) before
the coalescing process is complete, curing may
stop and may not start again even when the
temperature recovers.
The resins used in latex coatings are typically
formed from the reaction of a mixture of mono-
mers. Examples include copolymers of styrene
and butadiene; terpolymers of vinyl chloride,
vinylidene chloride, and methyl and ethyl acry-
late; and commonly, acrylate copolymers.
In some of the more recent latexes, a chemical
cross-linking reaction occurs between copoly-
meric molecules formulated into the coating,
resulting in a cross-linked resin film. Water-
based epoxies, urethanes, and other resins
have been successfully formulated with dry
film properties approaching those of solvent-
based coatings.
Alkyds and Other Resins That Cure by
Oxidation. The film-formation mechanism of
alkyds and other coatings that contain drying
oils is initiated by oxygen in the air. After the
film is applied, the alkyd molecules in the resin
cross link through a chemical reaction involv-
ing the unsaturated (double) bonds of the oil
and oxygen. Drying oils, such as linseed oil
and fish oil, typically contain a fatty acid with
three or more sets of double bonds. Alkyds
are essentially polyesters reacted or modified
with drying oils. Other resins that are some-
times modified with drying oils include epoxy
esters, urethanes, and phenolic. The properties
of the coating are highly dependent on the type
and amount of the oil modification.
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The curing process never stops as long as the
coating is exposed to oxygen. As a result, many
alkyd systems become brittle over time.
Moisture-Curing Polyurethanes and Inor-
ganic Zinc Primers. Only a few industrial
coatings require moisture to cure. These include
moisture-curing polyurethanes and ethyl-silicate-
type inorganic zinc-rich primers. The curing
reaction in each of these systems involves hy-
drolysis, or the cleavage of chemical bonds
with water. As a result of the hydrolysis reaction,
moisture-curing urethanes release carbon diox-
ide (CO2), and inorganic zinc-rich primers
release ethyl alcohol.
Powder coatings can contain either thermo-
plastic or thermoset resins. The powder can be
applied by electrostatic spray or by passing
the preheated pieces through a fluidized bed of
the powder suspended in air. After the powder
is applied, the coated pieces are baked. If the
resin is a thermoplastic, the particles melt
together to form a film. If the resin is a ther-
moset, the particles chemically react to form
cross links. Resins commonly applied as
powder coatings include vinyls, epoxies, and
polyesters.
Although the list of curing mechanisms
included in this article is not inclusive of all
coating material curing mechanisms, these are
the ones most applicable to the industrial coat-
ings discussed in the text.
Coating Systems Defined
Coatings can, in many cases, be combined
to create a coating system. A coating system
includes both the surface preparation and the
application of one or more coating layers. If
multiple coats of the same product are specified,
contrasting colors are sometimes employed to
assist the applicator in assuring coverage.
Coating systems usually consist of a primer
and a topcoat. In many instances, an intermedi-
ate coat is also specified. When multiple coat-
ings are used to create a system, they must be
compatible with one another. Also, each coat-
ing layer has a function that is performed at a
given thickness. Accordingly, one cannot make
up for an inadequate zinc-rich primer thickness
by adding extra thickness to an epoxy interme-
diate coat. Each layer should be applied at the
optimum thickness (neither too thick nor too
thin) and verified for proper thickness prior to
the application of subsequent layers.
Function of the Primer. The function of the
primer is to bond the coating system to the sub-
strate. The primer often provides corrosion pro-
tection for a steel substrate by using one or
more methods of barrier, inhibitive, or galvanic
protection. The primer must also be tolerant of
the level of surface preparation performed and
must be compatible with the next layer applied.
If the primer is the sole layer present in the
coating system, as in a single-coat system, it
must also be resistant to the service environ-
ment. When additional coats are applied, the
primer typically has low gloss to promote the
adhesion of additional coats.
Function of the Intermediate Coat. An
intermediate coat is typically incorporated into
a coating system for the purpose of adding bar-
rier protection. The intermediate coat must be
compatible with both the primer and the top-
coat. Like the primer, the intermediate coat usu-
ally has lower gloss to promote the adhesion of
the topcoat.
Function of the Topcoat. The topcoat or
finish coat is the first line of defense in a
corrosion-protection system. It must also be
aesthetically compatible with the specifier’s
priorities and often will be required to main-
tain color and gloss levels for long periods of
time. Naturally, the topcoat must be resistant
to the service environment and must be com-
patible with the underlying layer (primer or
intermediate coat, as appropriate). In addition,
the topcoat must be able to accept a mainte-
nance overcoat.
As mentioned previously, each coating layer
has a function that is performed at a given thick-
ness. When applying coating materials, the vol-
ume solids, or nonvolatile matter expressed as
a percent of the liquid paint, is an important fac-
tor in determining the film thickness. Often,
coating manufacturers provide either a target
wet film thickness or target dry film thickness
in the literature associated with each coating
product. Many times, only one of the target film
thicknesses is provided. In these instances, cal-
culations employing the volume solids of the
coating and either the target dry film thickness,
or the target wet film thickness can be performed
to determine the wet or dry film thickness that
has not been specified.
REFERENCES
1. C.H. Hare, Pigments, Chap. 19, Protective
Coatings: Fundamentals of Chemistry and
Composition, Technology Publishing Co.,
Pittsburgh, PA, 1994, p 291
2. S.D. Cramer and B.S. Covino, Organic
Coatings and Linings, Corrosion: Funda-
mentals, Testing, and Protection, Vol 13A,
ASM Handbook, ASM International, 2003,
p 818
3. D. Brezinski, J.V. Koleske, and R. Springate,
2013 Additives Reference Guide, PCI Mag.,
June 2013, p 22–104, http://www.pcimag.
com
4. C.H. Hare, Solvent Families, Chap. 26,
Protective Coatings: Fundamentals of Chem-
istry and Composition, Technology Publish-
ing Co., Pittsburgh, PA, 1994, p 371–383