Alkyds

With their initial development in 1921, alkyd resins quickly became the polymer of choice for paint. Varnishes that were previously manufactured with a combination of hard resins and oils were changed to alkyd/oil polymers that improved durability and versatility. The alkyd varnishes were flexible and more consistent in their properties than the older resin varnishes. These versatile resins essentially replaced the natural resin component in a varnish with excellent toughness and clarity. The term enamel was first applied to alkyd based paints, due to their hard, vitreous-like finish, compared to the oil/rosin paints. Alkyds are defined as oil modified polyesters. Variations in the type of oils, acids or alcohols used in the manufacture of alkyds affect the performance and type of coating in which it will be used. The most commonly used types of oil modifiers for general purpose paints are soya and linseed. Alkyds containing these oils have all around good properties and are quite economical. Oils such as tung, safflower, fish, and castor produce more specialized products ranging from polyesters to marine varnishes. Alkyds also generally have a very high VOC, although recent developments in technology may enable higher solids, lower VOC alkyds as well as water-borne alkyd technology. Waterborne acrylics and acrylic blends, however, have advanced to take the place of many alkyd coatings. In air dry trade sales (aka architectural) and industrial alkyd coatings, curing or drying of the film is initiated through the use of metallic acid complexes that catalyze functional groups on the polymer and cross-link the molecules together. One form of sub-classification of alkyd resins is by the oil content or oil length. The long oil types are generally thinned with mineral spirits and as oil length is shortened the alkyd requires stronger solvents such as ketones, esters, aromatic hydrocarbons and acetates. The synthetic portion of the polymer is less soluble than the oil portion so the less oil, the stronger the solvent must be to dissolve or reduce it. The higher functionality of esters of pentarythyrol make resins with greater amounts of functional groups which in turn speeds up the curing. Generally, the longer the oil length, the longer the dry time of the alkyd. Oil length Very long oil Long oil Medium oil Short oil % Oil 65 - 80 % 40 - 65% 30 - 40% 15 - 30% Solvent Mineral spirits Mineral spirits Naphtha, toluene, xylene MEK, MIBK, Acetone Curing Air dry with metallic driers Air dry with metallic driers Air dry or heat cured Heat cure, baking

Alkyd resins are usually available in solution with a compatible solvent. The curing is generally at ambient temperatures and initiated with metallic driers, but with short oil alkyds, blended with compatible thermoset resins (urea and melamine formaldehyde resins), heat curing and baking is necessary. Thermoset alkyds are used on metal products such as furniture and license plates, and are solvent and chemical resistant.

Alkyd resins can be polymerized or modified with such materials as styrene, vinyl toluene, silicone polymers, epoxy, urethane, and others to improve various properties. The modification is most effective when done at the alkyd polymerization step during manufacture where the modifier becomes an integral part of the final resin. The alkyd/modifier co-polymers can show the strengths and weaknesses of both polymer types. For example, epoxy modified alkyds (epoxy esters) exhibit improved adhesion to metal (epoxy), ease of use, and lower cost (alkyd). The chemical resistance of the epoxy ester would not be as good as the epoxy system alone. Alkyd resins have been used for many years. They are economical and generally have good performance characteristics. They do, however, have a few disadvantages. Typical alkyds cure or dry by oxidation. The oxidation process will slow down once the coating is dry, but it never completely stops. So as the coating ages it will lose flexibility and become brittle. Used on exterior wood, alkyd topcoats eventually crack and lose film integrity. Alkyds (unless modified) will also chalk and lose gloss when exposed to ultra violet light. White alkyd paints will yellow badly with age especially on interior surfaces. Alkyds also have a very high VOC level. Waterborne acrylics and acrylic blends have taken the place of many alkyd coatings.

coatings technology: Pigments

Most pigments used in paints are inorganic in nature and many are derived from natural sources by mining and processing (grinding and classifying). Many synthetic pigments have been developed that are chemically similar to the natural material but the process allows for tight property and quality control. One example is iron oxide. This is available from naturally mined and processed material. The synthetic version can use scrap metals mixed with acids and heat to control color. Further processing yields a uniform colored and controlled particle size material. Pigments, which are dry particles, can vary in their particle shape. The most common inorganic pigments are generally:

Spherical: Round, relatively regular shape Lamellar: Platy: flat, with a length and width magnitudes greater than the depth. Nodular: Rounded, irregular or crystalline Acicular: Needle-like, length far greater with width and depth equal

Organic pigments can appear as very fine, intricately-shaped structures or in structures typical of inorganic pigments.

Pigment Classes:

Prime White Pigments: Highly refractive, white, opaque; used to opacify paint

Colored Pigments: Organic and inorganic pigments; used to create color. Metallic Pigments: Ground or flaked metal; used for color or to enhance appearance. Extender Pigments: Low refractive; used to control cost and modify physical properties. Functional Pigments: Used to add desirable characteristics; examples include anticorrosive, flame-retardant and stain-blocking types.

Refractive Index of Pigments The refractive index (RI) is a scale used to rate the ability of materials to refract or bend light. The refractive index of air is taken as 1.00 and all materials are rated relative to it. A mixture of two materials with differing refractive indexes will distort the light passing through it and create opaqueness. A good example of this is the appearance in air of an extender pigment like calcium carbonate. In this situation the pigment appears bright white due to the difference of the refractive index of air (1.00) and the calcium carbonate (1.59). If the pigment is then mixed in a latex emulsion at a volume lower than the volume of latex solids, there is little change to the appearance in the liquid mixture; when the mixture is dried on a glass panel, it will look relatively clear. This is due to the very little difference between the polymers refractive index (1.50 - 1.70) and the calcium carbonate (1.59). Add more pigment to the point that it exceeds the volume of latex solids, and the dried film appears opaque because now there is insufficient resin to completely encapsulate the pigment particles, and air voids will appear between them. The refractive index of air is very different from the RI of the pigment/resin blend, so light is bent. This effect is known as dry hiding and relates to the critical pigment volume concentration or CPVC. The particle size of the prime white or opaque pigments is critical to the efficiency in light scattering. A large particle of titanium dioxide (2 - 3 microns) has little opacity because titanium dioxide is a crystal and, as such, is clear. Reducing the particle size to between 0.2 and 0.4 microns maximizes the light scattering properties or reflection between particles relative to the wavelength of visible light. Further reduction in size would reduce the particle size to below the average wavelength of visible light into the ultra violet range and would appear transparent to the eye. Ultra fine titanium dioxide pigments are currently being evaluated as transparent UV inhibitors for coatings applications.

Binders
Depending on their molecular weight, binders can vary in their ability to wet or encapsulate pigments, and this can effect CPVC. In general, low molecular weight materials tend to wet pigments better. But the type of binder also has a significant effect on the pigment wetting properties. Dispersants and surfactants are used to improve the wetting and stabilizing of pigment dispersions. Paint type P.V.C. Gloss range (@ 60 degrees)

Flat Eggshell Semi gloss Gloss High gloss

50 - 80 35 - 55 20 - 40 10 - 20 7 - 15

0-5 10 - 25 35 - 70 70 - 85 85 +

One notable exception is the effect of flattening pigments such as the fumed and pyrogenic silicas; small additions of these pigments significantly reduce gloss. This is commonly seen in semi-gloss varnishes that can have a PVC as low as 5.

Pigment Volume Concentration (PVC)

Variations in the ratio of binder to pigment volume significantly affects the final product. Pigment volume concentration (PVC) is a number that represents the volume of pigment compared to the volume of all solids. PVC = Volume of Pigment/Volume of all Solids. This is expressed as a ratio of pigment to binder. For example, if a coating has a PVC of 30, then 30% of the total binder/pigment blend is pigment, and 70% is binder solids. (see fig. 2) A high PVC paint could be defined as one at 50 PVC or higher. A high PVC paint (more pigment, less binder) would be flat in finish, generally less adhesive, and likely more porous. A low PVC paint (less pigment, more binder) is expected to be glossier, more adhesive, and less porous. Technically, the PVC is called the Critical PVC or CPVC when the pigment and binder blend begin to create air interfaces or voids that increase porosity.

Levels of Pigmentation
As stated above, the point at which there is just enough binder to wet pigment particles is called the critical pigment volume concentration (CPVC). Pigment particles are entirely surrounded by binder below CPVC, and are not above CPVC. As pigment volume concentration increases above CPVC, void space and porosity increase while tensile properties decrease.

A film below the CPVC has excess resin and may exhibit a smooth surface that specularly reflects light (i.e. gloss paint); this light is perceived as gloss. Above the CPVC there is less vehicle present, and if the pigment particles protrude through the surface and the surface roughness increases, the light that is diffusely reflected will not be perceived as gloss and the paint will be a semi-gloss. When the volume of pigment is increased sufficiently, scattering also increases due to greater volume of air/pigment interfaces, and the paint appears flatter. From fig. (3), you can see that both blistering and gloss decrease as CPVC is reached. Permeability, however, increases as CPVC is reached. Above CPVC, voids in the paint are filled by air and the paint becomes discontinuous. Other properties that rise and fall above and below CPVC are tensile strength, scrub resistance, enamel holdout, rusting, and contrast ratio. CPVC can be calculated using the equation below: ________1_____ QA x p 1+ 93.5

CPVC=

where OA = oil absorption value: grams of oil to wet 100 grams of pigment. It can either be determined experimentally (ASTM D 281), or obtained from literature. p = Density (g/ml) CPVC (when several pigments are incorporated) = (V1 x CPVC1) + (V2 x CPVC2) + (V3 x CPVC3) + (V4 x CPVC4) + (Vn x CPVCn)