Auto oxidative Cross-Linked Resins

Dry coatings
Ultimately cross link by reaction with oxygen from the
atmosphere
Contains drying oils, which consist mainly of polyunsaturated
fatty acids, and undergo film -formation by oxidative drying.
The drying reaction is accelerated by the presence of
metallic -salts such as Co, Mg, and Pb napthenates or
octoates.
The autooxidation reaction occurs at a relatively fast rate
shortly after application of the wet paint, and it continues
throughout the life of the coating at a slower rate with time.
The autooxidative reaction is a decomposition reaction that
results in the formation of hydroperoxides. Although
autooxidative cross linking is necessary to attain the
ultimate resistant properties of the film, with time, the
hydroperoxides formed as a result of the autooxidative cross
linking decompose into organic acid constituents, leading to
chemical deterioration of the film. Similarly, the
autooxidative reaction results in the hardening and ultimate
embrittlement of the film, causing reduced distensibility and
flexibility with the passage of time. This brittleness and
accompanying hydroperoxide decomposition result in an
aging deterioration of the film and loss of protective
capability.zinc oxide and lead containing pigments are
particularly useful in absorbing hydroperoxides and slowing
the rate of film deterioration.
Short oil coatings have good moisture and chemical
resistance but are relatively hard and brittle. The medium oil
modifications are a compromise between the long and short
oil modifications.
Thermoplastic Resins
Softening at elevated temperatures.
The molecular structure is not cross linked into a rigid
molecule, as are the chemically cross-linked or the
autooxidized coating systems.Rather, the resinous binder is

dissolved in a suitable solvent, mixed with the pigment and

other constituents comprising the formulated paint.
On application, the solvent volatilizes, and the resinous
binder, along with the pigment, is deposited onto the surface
being coated as a solid film.
two types of coatings based on thermoplastic resins:
1- lacquers those deposited by evaporation of a solvent.
In all cases, because no chemical change takes place to the
resin on drying, it stands to reason that the applied coating
redissolves if it is exposed to the same solvents that it was
originally dissolved in on formulation. such coatings have no
resistance to the solvents in which they were originally
dissolved or in solvents of equal or greater solvency for that
particular resin(if they are exposed to).
They are resistant to weathering, acid or alkali exposures,
and moisture.
solvent susceptibility of these thermoplastic coatings is often
an advantage. When maintenance repainting is necessary,
the same system can be reapplied, and the solvents in the
new topcoat partially redissolve the existing old coat,
resulting in intermolecular entanglement of the new coating
with the old and giving excellent adhesion. Thus, solvent
solutions of these thermoplastic resins have excellent
recoatability with the same system, even after extended
periods of time. This cannot be said for either the
autooxidative cross-linking coatings or the chemically cured
coatings.
The principal disadvantage of a solvent-deposited lacquer
system is that large amounts of solvent must be used to
dissolve the relatively high-molecular-weight resins used in
the coating. Accordingly, most lacquer coatings cannot
comply with the lower volatile organic compound (VOC)
legislation in effect today. Thus, nowadays are rarely used.
2- waterborne those deposited by evaporation of water.
Water-borne coatings are defined as coatings where water has been purposely introduced
into the coating.
Four classes of water-borne coatings:
Water-reducible coatings

Resins are not soluble in water and are high- solid solutions in water-miscible solvents
with either carboxylic acid groups of the resin neutralized with low-molecular-weight
amines or with amine groups of resins that are partially neutralized with low-molecularweight acids. The water-reducible binders commonly used are alkyds, polyesters,
epoxies, and polyurethanes. Electro-deposition coatings, including automotive coatings,
are based on water-reducible resin technologies. Additionally, interior linings for
beverage cans and dip coating applications commonly use water-reducible technology.
After heating in a baking oven, the water evaporates, and the reactive moieties come
together and react at the elevated baking temperature.
Water

emulsion coatings
These materials consist of a liquid epoxy resin solution in one package and a second
package containing an amine-terminated cross-linking agent with a nonionic surfactant or
with nitroethane. The amine cross-linker package is diluted with water, and on
application, the epoxy resin solution is added with vigorous stirring. As the water
evaporates, the epoxy resin reacts with the amine groups to cross link in conventional
fashion.
Epoxy emulsion paints are used in hospitals and food-processing plants, where a solvent
odor is not acceptable and hard, easily cleaned wall and/ or floor coatings are needed.
Nitrocellulose lacquers emulsified into water are used as topcoats for wood furniture.
These emulsions have significantly lower VOC than solvent-borne lacquers but require a
longer dry time.
Bituminous emulsions are used as pavement and parking lot surfaces.
Latex coatings
Dispersions of solid polymer particles in water. The solid polymer particles are most
commonly based on polyacrylate resins (usually the acrylates and methacrylates) but can
include vinyl chloride-vinyl acetate copolymers, styrene-butadiene, and others. Usually, a
high-molecular weight resin is suspended in a water medium.
After application, water evaporates, and the polymer particles coalesce (come together).
The latex forms a film by coalescence of the polymer particles. Coalescence can occur
only if the film-formation temperature is higher than the glass transition temperature (Tg)
of the polymer particles. The Tg is the temperature at which the polymer softens. In the
case of most air-dry coatings, slow final coalescence is not a real problem, so the filmformation temperature needs to be only a little above the Tg.
In the case of baked coatings, film formation must be complete by the end of the baking
time; therefore, baking temperatures should be significantly above the Tg.

Alkali silicate coatings

The most commonly used coatings for air-dry maintenance and marine protection are
latex-based coatings based on acrylic polymers, and inorganic zinc-rich coatings based on
alkali silicate resins. However, two-package epoxy and polyurethane water emulsion
coatings are being used.

The binders are water-soluble silicates of alkali metals (sodium, potassium lithium) and
related quaternary ammonium silicates. The zinc-rich coatings are pigmented with zincdust particles, and other
coatings may be pigmented using titanium dioxide (titanates).
After application, water evaporates, and the alkali silicates concentrate as a silica gel. The silica
gel is still
water soluble, but gradually it hydrolyzes to form silicic acid, which in turn reacts with the
pigment, the
substrate, or both. This makes the gel increasingly insoluble. Further hydrolysis and alkali
neutralization occur
by reaction with an acid curing solution or carbonic acid formed from the atmospheric reaction
of carbon
dioxide and water. This neutralization reaction forms a silicate matrix holding the pigment
particles together
and to the substrate. However, a by-product of the neutralization reaction is the formation of
water-soluble
reaction salts that may lead to blistering of topcoated silicates in water immersion. Inorganic
alkali-silica-based
zinc-rich paints, concrete surface hardeners, and other silicate-based masonry water-repellent
coatings are all
based on this technology.
Characteristics of Water in a Water-Borne Coating. Water, as a constituent of the environment, is
environmentally friendly. Accordingly, water-borne coatings are generally environmentally
acceptable,
although most of them use a cosolvent as a coalescing aid, freeze-thaw stabilizers, and/or wetedge aids to
adjust the drying rate and improve flow and leveling. These cosolvents are generally added in
volumes of 20%
or less of the water constituent.
Water-borne coatings are not flammable and do not support combustion during application and
while liquid.
Moreover, there is no objectionable solvent odor (although, depending on the formulation and
the use of
cosolvents, they do have a mild, nonlingering odor).
As is evident with all four classes of water- borne coatings, water is a major constituent.
Furthermore, in each
case, the water must evaporate in order for a subsequent film-forming mechanism to occur and
for the coating
to attain its final moisture and chemical resistance.
Water-borne coatings are significantly different than solvent-borne coatings, due entirely to the
character of
water. In solvent-borne coatings, blends of solvents with different solvency can be used to
dissolve a resin.
Those solvents then volatilize with different evaporation rates from the applied coating. There
are no such

things as blends of water, and the freezing temperature and boiling point of water are constant.
The evaporation
rate of water is highly dependent on temperature and humidity. As water evaporates from a
coating, the
humidity above the coating surface increases such that water evaporation is low. If there is no air
movement or
circulation above the coating surface, humidity may reach 100%, at which time no further water
evaporates
from the coating. Moreover, if temperatures are low, the ability of the air to contain moisture is
substantially
diminished. At low temperatures (much below 10 C, or 50 F), water evaporation is slowed
sufficiently that
many water-borne coatings may not form a suitable film. This is not the case with organic
solvents, which can
volatilize independent of humidity (however, the organic solvent vapor pressure is a function of
the solvent
concentration at the coating-air interface). The film formation of water-borne coatings may be
further disrupted
when the temperature falls below the Tg of the resin, preventing the resin particles from properly
flowing or
coalescing.