Pinturas y Tinturas
Pinturas y Tinturas
Pinturas y Tinturas
P
Packaging see Crime-scene Investigation and Examination: Packaging.
Commercial, Domestic and basic elements: the vehicle, the pigments and exten-
ders, and the solvent. The following sections will
Automotive describe these elements of the paint.
L Brun-Conti, Michigan Department of State Police,
East Lansing, MI, USA
Vehicle or Polymeric Portion of Paint
Copyright # 2000 Academic Press
Table 1 Structure and properties of some common monomers used in acrylic resins
they impart to a film. Polymer chemists must formu- will have varying amounts of unsaturation. In es-
late the acrylic resin using just enough, but not too sence, the more unsaturation or double bonds, the
much of the monomers available to them, keeping in more readily the resin will dry. This becomes impor-
mind the properties which they desire and which tant when considering oxidation curing ability of a
monomers will impart those qualities to the film. film (see Film formation).
Alkyd and polyester resins Polyester resins have Epoxy resins Epoxy resins are made by polymeriz-
three basic components which polymerize to form ing an oxirane ring-containing compound, such as
the resin: fatty acids, polyols and dibasic acids (Fig. 1). epichlorohydrin, with bisphenol A (Fig. 2). The reac-
The fatty acid and the polyol form an ester linkage. tivity of the oxirane ring structure depends upon
The dibasic acid is then added to the mix. The whether the oxirane is internal or external. In most
molecular weight of the polyester resin will depend epoxy resins the oxirane ring is external.
upon the quantity of the dibasic acid and additional
polyol. The polyol used is generally glycerol, but Urethane resins Urethane resins are basically the re-
ethylene glycol (two ±OHs), pentaerythritol (four sult of a reaction between an isocyanate and an active
±OHs) or sorbitol (six ±OHs) may be used. The proton (Fig. 3). The reactive proton can be (in order of
dibasic acids used are usually phthalic anhydride, reactivity) alkyl-NH2, aromatic, R-NH2, primary
isophthalic acid and teraphthalic acid. The fatty ±OH, secondary ±OH, tertiary ±OH, aromatic ±OH,
acids and glycerol are occasionally replaced by oils carboxylic ±OH, primary amide. The isocyanate may
(three moles of a fatty acid plus one mole of glycerol come in an intermediate form as a diisocyanate. When
is a triglyceride or oil) and the resin is then known as the isocyanate is added to the active proton-contain-
an alkyd. When using oils in an alkyd, the alkyd is ing resin, the crosslinking begins immediately and
defined by amount of oil: a long oil alkyd contains therefore must be used within a limited period of
455% oil, a medium oil alkyd contains 31±55% oil, time. This `two-package' system may be cumbersome
and a short oil alkyd contains 530% oil. The oils are to use. To make urethanes more convenient to use a
made up of two or three different fatty acids which few different `one-package' urethane systems were
Figure 1
PAINTS AND COATINGS/Commercial, Domestic and Automotive 1143
Figure 2
Figure 3
Figure 4 Figure 6
1144 PAINTS AND COATINGS/Commercial, Domestic and Automotive
Figure 9
Figure 7
Oxidation Oxidation is the type of crosslinking that
occurs in resins containing oils or fatty acids: var-
nishes, polyesters and alkyds. As stated above, oil-
niques) but the final product desired is a solid. Film containing resins are classified as short, medium and
formation is achieved in four basic ways: evaporation long oil resins. The oils used are further classified as
of a solvent, polymerization, oxidation and coagula- drying, semidrying, and nondrying oils, depending on
tion. the degree of unsaturation of the fatty acid chain.
Drier additives may be added to aid the drying pro-
Evaporation of a solvent As the name implies, all cess. Dryers are heavy metal soaps of organic acids.
that is needed for this film former is time and circula- The exact mechanism of the oxidation process is not
tion of air. Common types of evaporation finishes are known. What is known is that hydroperoxides are
acrylic lacquers and nitrocellulose lacquers. The final formed on the double bonds and that the dryers
film of the solvent evaporation film formers are ther- catalyze the decomposition of the hydroperoxide to
moplastic and convertible. Organic solvents are used, the radical state. Some common oils used in oil-con-
such as methyl ethyl ketone, toluene or mineral spirits, taining resins are linseed oil, tung oil, soya oil and
depending on the solubility of the primer and the coconut oil.
intended application. Lacquer production is as simple
as dissolving an acrylic resin in solvent. Film modifiers Coagulation This type of film formation occurs in
such as nitrocellulose resin or vinyl resin may be added systems that involve emulsion technology: latex
to provide the final film with the desired qualities. (where water is the continuous or liquid phase) and
Pigments may be added as a solid or in a resin solution. nonaqueous dispersions (NAD) (where a solvent
other than water is the continuous phase). In an
Polymerization Polymerization is a polymer chain- emulsion, particles of the polymer are dispersed in a
forming reaction. It is used to form monomers into liquid in which they are not completely miscible. To
chains of polymers or in crosslinking two or more keep the two semimiscible phases from separating,
polymers together. This process is done by using heat emulsifiers must be added. When the solvent evapo-
or a catalyst. Two types of polymerization are addi- rates, the polymers coalesce on a macromolecule
tion and condensation (although oxidation, which scale. Common latex house paints are examples of
may also be included in this section, will be ad- this type of film formation.
dressed in the next section). Addition polymerization End uses
occurs when a free radical is formed and additional
compounds are added with no by-products (Fig. 8). Table 2, which is not exhaustive by any means, shows
Condensation polymerization occurs when two com- which resin systems may be found on different types
pounds combine and, during this process, by-pro- of products.
ducts such as water, hydrogen gas or carbon dioxide
are evolved (Fig. 9). Pigments, Fillers and Additives
Pigments, fillers and additives are in the liquid paint
as solids. That is where the similarity ends. Pigments
add color or metallic sheen, additives are used in
small amounts to impart certain qualities on the
paint or finished film, and fillers are generally used
to add body or bulk to the paint.
Pigments
Table 2 Some resin systems and their end uses strate shade differences using the lowest possible film
thickness. These types of pigment are also inexpen-
Resin system End use
sive but have low tinting strength, therefore more
Epoxy amine Marine pigment is required to obtain a change in color.
Industrial Table 3 lists some inorganic pigments.
Epoxy esters Automotive primers
Maintenance paints
Epoxy phenol Internal coatings for pipes White and black pigments The most widely used
Epoxy amine formaldehyde Brass white pigment is titanium dioxide (TiO2). TiO2
(clear) Aluminum refrigerator trays comes in two forms, rutile and anatase, which are
Epoxy acrylic enamel Appliance
crystal isomers. Rutile is the isomer of choice because
Outdoor furniture
Short oil alkyds Air dry primers and it has 25% more tinting strength (the ability to tint to
undercoats the desired color with the minimum amount of pig-
Primer on wood siding ment) than anatase. Anatase TiO2 is known to chalk
Long oil alkyds Exterior architectural paint or degrade when exposed to ultraviolet (UV) radia-
Metal maintenance paints
tion. Rutile TiO2 has a high refractive index (2.72)
Topside marine paints
Medium oil alkyds Automotive refinishing and that is what makes it such a good hiding pigment.
Traffic paints The lead whites (basic carbonate white lead, basic
Implement enamels sulfate white lead and basic silicate white lead) are
Acrylic emulsions Architectural paints (water- not used, owing to the lead content. Two other whites
soluble)
are the zinc whites, zinc oxide and zinc sulfide, but
Automotive paint (NAD)
Acrylic emulsions in water Dip coatings the hiding power of the zinc whites is not as good as
with amino crosslinking Industrial baked finishes that of TiO2.
polymers Waterborne basecoats There are four classes of black pigments: acetylene
(automotive) black, thermal black, furnace black and impingement
Acrylic lacquers Automotive refinishes
or lamp black. Due to their particle size, good exterior
Aluminum siding coating
Aircraft finishes durability and color, furnace and lamp blacks are used
Wood finishes
Acrylic melamine enamel Automotive
Phenolic varnishes Floors
Trim
Can coatings Table 3 Inorganic pigments
Printing inks
Pigment Color
are proprietary), although gold bronze and zinc are will also have an additional layer of colored or ab-
also available. Pearlescent pigments are generally sorptive pigment on the top and bottom of the TiO2-
Muscovite mica flakes coated with TiO2, iron oxide mica pigment (Fig. 12). For instance, if iron oxide is
or other colored pigments. Pearlescent pigments may the absorptive pigment and the interference color
also be flakes of bismuth oxychloride, basic lead (from the TiO2) is yellow, the color seen with reflec-
carbonate or natural pearl essence. tive light is gold.
Bismuth oxychloride is a crystal that may be used
Metallic pigments There are two types of aluminum alone to create pearlescent luster or can be deposited
pigment: leafing and nonleafing. Leafing pigments on mica flakes. Microscopically, basic lead carbonate
float to the surface of the coating while it is still appears as regular hexagonal crystals. These are
wet, producing a silvery metallic appearance. Non- being phased out owing to concern regarding lead.
leafing (the type used in automotive coatings) will Natural pearlescence comes from crystals consisting
disperse throughout the film, giving depth to the dry of the purines guanine and hypoanthine, crystallized
coating. from fish scales and skins. Natural pearlescence is
Gold bronze pigments are made by combining primarily used in cosmetics.
copper and zinc, atomizing them together and
making flakes of the atomized particles in a ball
mill. Zinc pigments are used in coatings at about Additives
90% zinc by weight with an organo silicate or an Additives are substances added to the paint to provide
epoxy ester. Extreme care must be taken to prevent various properties. They include UV absorbers, hin-
the introduction of moisture into a container of zinc- dered amine light stabilizers and antioxidants, which
containing paint because zinc plus water will produce help protect the finish from the effects of UV radia-
zinc dihydroxide and hydrogen gas, which can cause tion. Driers used in alkyd and other oil systems are
an explosion in a closed container. additives. Wetting agents, such as carboxcylic acids
and sulfuric esters used in the pigment-grinding pro-
Pearlescent pigments The platelet structure of all cess are also considered additives.
the nacreous or pearlescent pigments gives them their
rich appearance. Interference pigments is another
name for pearlescent pigments. In the case of the
TiO2-coated mica flakes, the TiO2 is deposited on Solvents
to both sides of the mica, sandwiching the mineral The primary function of solvents is to aid in the
between them (Fig. 11). The layers of TiO2 are called application of the coating and to regulate the rate of
`interference layers'. Reflected light will bounce off evaporation, flow properties and viscosity. Solvents
the top and bottom interference layers and will, de- include water, hydrocarbon solvents, terpene solvents
pending upon the thickness of the TiO2 layers, reflect and oxygenated solvents. The forensic value of sol-
a certain color. On the other hand, if light is trans- vents is limited, as most paint received as evidence is
mitted through the pigment, the color seen will be the in the form of a dry film. Properties that a paint
complementary color to the reflected color. For ex- chemist must consider when choosing a solvent are,
ample, if the reflected color is red, the transmitted among other things, solvency (the ability of a solvent
color will be green. Iron oxide may also be used to to dissolve or disperse a resin), volatility (the evapor-
coat the mica. These pigments will also act as inter- ation rate), odor and toxicity. Due to more stringent
ference pigments but will all have a red-yellow color, environmental regulations, the use of volatile organic
which is the absorptive color inherent to iron oxide. solvents is kept to a minimum. Reformulating the
The resulting colors of the iron oxide-coated mica solvent portion of the paint, along with more efficient
pigments are bronze to copper-red and will have a application techniques help paint manufacturers
metallic luster. Combination pigments are pearles- and production facilities comply with Environmental
cence pigments that will have the coating of TiO2 but Protection Agency regulations.