MNL17-EB/Jun.

1995

Inorganic Anti-Corrosive Pigments

by M. Jay Austin 1
W H A T IS C O R R O S I O N ?
CORROSION IS AN ELECTROCHEMICAL PROCESS t h a t t a k e s p l a c e

on the surface of metals, deteriorating them a n d - - i f not halted--destroying them. The process usually occurs in a liquid or gaseous environment and may take the form of a direct chemical attack, electrochemical reaction, electrolysis, or oxidation. During deterioration, the metal may form compounds or be taken into solution. The following factors must be present for corrosion to take place: 9 A thermodynamically unstable metal. 9 An electrolytic conductor of ions. 9 An electrolyte (an electrical conductor such as a moist path). 9 An electron acceptor. If corrosion is extreme, the metal will, in essence, return to the more stable composition of its original ore, disintegrating into oxides, carbonates, and sulfates. For instance, the rusting of iron metal occurs naturally under atmospheric conditions, since rust, a hydrated form of the common iron ore, ferric oxide, is more stable than iron metal [1]. In this example, the unstable iron metal is also an electrical conductor. Salt water is usually the electrolytic conductor of ions, and dissolved oxygen is the electron acceptor [2]. Rates of corrosion vary, often depending on the electrolyte. Normally, metallic surfaces in contact with acidic solutions (such as salt water [3]) will exhibit the most rapid rate of corrosion; neutral solutions will be somewhat less corrosive and alkaline solutions the least corrosive. Metal may also corrode in the presence of soil or a dissimilar metal [4]. While many types of corrosion exist, this discussion is limited to the degradation which occurs when a metal's natural protective oxidative film is attacked and worn away. Common examples of this sort of corrosion include the progressive red rusting of iron, the white rusting of zinc, and the tarnishing of copper.

and mechanisms. For our purposes, we will limit our discussion to examination of the following five mechanisms of protecting metals by using coatings: 9 Barrier effect of film or vehicle. 9 Barrier pigment effect. 9 Sacrificial pigments. 9 Vehicle enhancement (film formulation and development). 9 Active inorganic inhibitive pigmentation.

Barrier Effect
Among the oldest inhibitive methods known, barrier coatings provide a protective, physical shield between a metal and air, moisture, or chemicals. While the composition and thickness of barrier coatings vary widely, they generally have a low permeability or moisture vapor transmission rate. As a rule, the lower the transmission rate, the less likelihood that oxygen and moisture will reach the substrate. Some common barrier coatings include organic paints and lacquers, metallic coatings (hot dip), and heavy mastics.

Barrier Pigment Effect

Pigments not only add color to coatings but can also protect metal from corrosion by reinforcing the film and limiting permeability. "Lamellar" pigments, for example, such as mica and micaceous iron oxide, form a wall of flat, thin particles within a paint film. These resist penetration, forcing water to wend a long, tortuous path toward the substrate (Fig. 1). Metallic flakes of aluminum, bronze, or steel produce similar effects. Since not all pigments are compatible with all resin systems, care must be taken when adding pigments to a coating. In highly acid or alkaline environments, inert or chemically resistant pigments should be used.

Sacrificial Pigments
Zinc is a "natural" for use in protective coatings since zincrich coatings offer cathodic protection when applied to ferrous substrates, that is, the zinc acts as a cathode during the corrosion process, receiving the attack normally suffered by the ferrous metal [5]. To some degree, the duration of the pigment's efficacy is dependent on the thickness of the sacrificial coating.

T H E U S E OF COATINGS TO P R O T E C T METALS AGAINST C O R R O S I O N

Before the beginning of recorded time and ever afterward, mankind has battled corrosion with a multitude of methods
1Vice President and technical director, HALOX Pigments, a division of H a m m o n d Lead Products, 1326 S u m m e r Street, H a m m o n d , IN 46320-2240.

Vehicle Enhancement
The formulation of a coating itself can add greatly to corrosion protection. The addition of pigments, for example, can 238

Copyright9 1995 by ASTM International

www.astm.org

CHAPTER 27--1NORGANIC ANTI-CORROSIVE PIGMENTS

Coating with Metallic Pigment or Mica Water
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enhancing polarization by raising the concentration of positively charged hydrogen ions at the cathode. Inhibitive pigments such as zinc chromate, phosphate, silicate, and borate suppress corrosion by enhancing anodic passivation in acid solutions. In neutral solution, the pigments are adsorbed onto the metal surface, reducing anodic activity. Oxidativepassivation--Though oxidation is usually thought to contribute to the deterioration of a metal, oxidation sometimes creates a protective layer on a metallic surface. Passivation can occur if a metal is oxidized to a stable compound that is part of the electrolyte [9]. Consider, for example, the protective layer of aluminum oxide on aluminum metal. The oxide minimizes atmospheric corrosion despite the reactive nature of the metal. Strong oxidizing conditions are normally required for passivation to occur. Take the case of iron and nitric acid. Exposed to concentrated nitric acid, iron will develop a very thin inhibitive passive film; dilute nitric acid, however, will attack the metal [10]. Neutralization--Another mechanism of inhibitive pigments is neutralization of corrosive substances as sulfates, acids, and chlorides. This can often be achieved through the use inhibitors in a basic environment, which decrease the corrosive effect of acids and enhance the precipitation of corrosive elements.

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Substrate Substrate FIG. 1 -Barrier pigment effect. Water takes a straight path through an unreinforced film, but is forced to take an extended path through lamellar particles of a metallic flake or mica-reinforced film (after Alan Smith, Inorganic Primer Pigments [2]).
help reinforce film structure and reduce permeability (as mentioned earlier). Some pigments, such as red lead, react with components in linseed oil/alkyd primers to produce lead soaps which increase the corrosion resistance of the paint film [6]. Other additives are used to enhance other coating or film characteristics, such as drying time, flow, adhesion, and mildew resistance. Binder selection and manufacturing methods may also be adjusted to offer maximum corrosion prevention.

Inorganic Inhibitive Pigments

The majority of this chapter will focus on the following active inorganic inhibitors: borates, chromates, leads, molybdates, phosphates, phosphites, and silicates. These pigments help prevent corrosion by increasing the likelihood of a chemical reaction which can produce a protective coating on the surface of a metal or otherwise foiling the chemical reaction between metal and corrosive solution. The ability to render a metal surface passive is called passivation and is covered here in two forms: (1) cathodic/anodic and (2) oxidative. Cathodic and Anodic Passivation--Inhibitive inorganic pigments minimize corrosion in neutral solutions by acting as polarizing agents to retard the three elements of the corrosion process: cathodic reactions, anodic reactions, and ionic currents in the solution and the metal itself [7]. Since the cathodic and anodic processes are the basis for the corrosion process, control of these processes can play an important role in corrosion inhibition. The cathodic process consists of electrons passing from the metal to an electron acceptor, such as oxygen or hydrogen ions at the negative terminal, or cathode. In the anodic process, metal ions pass into the solution at the positive terminal, or anode (Fig. 2). As polarizing agents, inhibitive pigments work in a variety of ways. Some slow the electrolytic process by retarding the reactions through resistance polarization, that is, by increasing a film's electrical resistance on the surface of the anode or cathode [8]. Some inhibitors, such as zinc, magnesium, and manganese, form insoluble deposits with hydroxyl ions in neutral solutions at the cathode. These deposits create a visible film on metal surfaces and help increase cathodic resistance polarization. Some inhibitors work in acid solutions,

S O M E W E L L - K N O W N I N O R G A N I C ANTICORROSIVE PIGMENTS
Coatings industry suppliers are developing high-performance inorganic pigments to meet the growing demand for nontoxic inhibitive coatings that are both economical and highly effective. The section that follows discusses the chemistries, physical properties, functions, advantages, and disadvantages of some of the most common inorganic inhibitive pigments. Wherever available, the specific gravity, color, pH, oil absorption, and water solubility of each pigment is recorded, supplied in most cases from pigment manufacturers' published data. Large discrepancies can exist between such data

240

PAINT AND COATING TESTING MANUAL

Current flow
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Metallic conductor

Anode (Metal 1)

Cathode (Metal 2)

Oxidation reaction occurring . . . . at anode

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Oxygeninelectrolyte
Electrolyte

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occurring at cathode

Reduction reaction

Current flow through electrolyte FIG. 2-Electrochemical corrosion. A simple cell showing the components required for cathodic and anodic corrosion processes (after Dean Burger, "Fundamentals and Prevention of Metallic Corrosion," Corrosion and Corrosion Protection Handbook, Philip A. Schweitzer, Ed., Marcel Dekker, Inc., New York and Basel, 1983).
and actual measurements, and verification of the published data is therefore recommended before any formulation project is initiated since significant differences in data can dramatically affect formulation performance. This author, for example, measured oil absorptions as high as 85 for some zinc chromate samples, although the published data report an oil absorption of approximately 25. For the following pigments, specific gravity is expressed as g/cm3; color indicates general appearance; pH is measured on a 10% slurry; oil absorption is expressed as g/100 g and normally determined by the spatula rubout method, ASTM D 281-84; and water solubility is expressed as percent soluble. Recommended loading levels for many of the pigments are also included for general formulation assistance, and these are expressed as a percentage of total weight based on typical paint density of 1200 g/L or 10 lb/U.S, gallon. If paint densities vary widely from these figures, simple extrapolations may be made. TABLE 1--Typical properties of modified barium metaborates.
Grade I G r a d e II G r a d e III

Specific gravity Color pH Oil absorption Water solubility Typical loading levels:

3.30 3.70 3.30 White White White 10.0 9.1 10.0 30 20 23 0.3% 0.2% 0.4% 3 to 15%, based on total weight. Some heavy duty maintenance coatings may require up to 40%

Borates
A. Barium Metaborate (BaO-B203.H20) [11-14]
The grades shown in Table 1 indicate three grades of commercially available modified barium metaborate, the most commonly used borate inhibitor. Grade I is the primarily barium metaborate, and Grades II and III are modifications of Grade I which are said to decrease the reactivity of the pigment, thus increasing its formulation versatility. Grade II includes approximately 27% zinc oxide, and Grade III includes approximately 18% zinc oxide and 29% calcium sulfate. Modified barium metaborates may be used in many kinds of applications in a broad range of solvent and water-based resin systems. The pigment's alkalinity contributes to inhibi-

tion, and the anodic passivation from the metaborate ion adds to the pigment's anti-corrosion performance. Barium metaborates are often considered environmentally acceptable alternatives to more traditional, toxic pigments; however, it must be remembered that soluble barium is an acute toxicant, and its presence in high levels may cause pigments to be classified as hazardous wastes. The pigment has other disadvantages. As a soluble compound, it may be quite reactive with many systems. To control its solubility, it is often coated with a silica modification. When barium metaborate is formulated with certain acidic resins or acid-catalyzed baking systems, the resultant coating may exhibit stability problems. Therefore, care must be taken when formulating water-reducible and latex resin systems using this pigment to minimize its solubility and reactivity.

B. Zinc Borate
Zinc borate, usually used to provide flame retardancy in plastics and cellulosic fibers, is not normally thought of as an inhibitive pigment. However, recent research indicates that zinc borate, used in combination with modified barium metaborate or zinc phosphate, exhibits synergistic performance properties resulting in enhanced corrosion prevention. This

CHAPTER 27--INORGANIC ANTI-CORROSIVE PIGMENTS

effect is most likely the result of the blended product's decreased solubility.

241

are applied at fairly low film thicknesses, these wash primers have very poor hiding ability.

C. Strontium Chromate (SrCrO4)

Chromates
Chromates have long been used as inhibitors since the soluble chromate ion is itself inhibitive and the chromate passivating ion is among the most efficient passivators known. Unfortunately, chromates are less widely used than in the past since hexavalent chromium pigments are either confirmed or suspected human carcinogens [15]. Evidence indicates that strontium, calcium, and zinc chromates are among the most carcinogenic forms of hexavalent chromium. Also, lead chromate is considered a suspected carcinogen by the American Conference of Governmental Industrial Hygienists (ACGIH), while zinc chromate is considered a confirmed carcinogen [16].

Specific gravity Color pH Oil absorption Water solubility

3.70 Yellow 8.5 ~35 0.05%

A. Zinc Potassium Chromate (4ZnO.6K20.4CrOr3H20)

Specific gravity Color pH Oil absorption Water solubility 3.45 Yellow 7.5 25 0.1% [17]

Strontium chromate is mainly used to prevent corrosion on aluminum, and primers containing this pigment are standard for the aviation industry. Strontium chromate is so effective at low loadings that it is often used to provide inhibition for coil coatings despite the fact that it is the most expensive chromate inhibitor. The pigment is sometimes combined with zinc chromate in water-based formulations. In these cases, to avoid stability problems, loadings are kept at low levels, about 2% total chromate.

D. Other Chromate Inhibitors

Barium chromate, calcium chromate, and ammonium dichromate are also used to control corrosion and flash rust, but their use is very limited and merits no further discussion here.

This inhibitive pigment, also known as zinc chromate or zinc yellow, is the product of reactions among potassium dichromate, zinc oxide, and sulfuric acid. Versatile and highly efficient, zinc chromates are effective inhibitors even at relatively low loading levels. Because of their yellow color, they are generally limited to use as primers. Although zinc chromates have a threshold limit value of 0.001 mg/m 3 and are therefore fairly toxic, these pigments are among the most widely used anti-corrosive products. In the United States, they still make up more than 30% of the entire inhibitive pigment market. How do zinc chromates prevent corrosion? While the specific mechanism is not wholly understood, there are several theories on the subject, i.e.: 9 Zinc chromates are anodic inhibitors. 9 Zinc chromates improve the corrosion protection of the existing oxide film [18]. 9 The ferrous salts precipitated by zinc chromates contain a protective mixture of ferric and chromic oxides.

Leads
Lead, though not a direct inhibitor, reacts with certain resin systems to form lead soaps which are active inhibitors. Lead pigments have proven themselves over the years to be outstanding anti-corrosives which perform particularly well over insufficiently prepared surfaces. However, since it accumulates in body tissue, lead is generally considered an acute and chronic toxicant and has become the subject of strict environmental regulations, especially regarding waste disposal and worker protection. Although they are still used to produce heavy duty maintenance coatings and lead chromate colors, regulations have caused the use of lead pigments to decline.

A. Red Lead (Pb304)

Specific gravity Color pH Oil absorption Water solubility 8.85 Orange 6.5 6 <0.001%

B. Zinc Tetraoxychromate (ZnCrO4-4Zn[OH]z)

Specific gravity Color pH Oil absorption Water solubility 3.65 Yellow 7.5 53 <0.01%

Often referred to as basic zinc chromate, zinc tetraoxychromate is commonly used in the manufacture of twopackage poly(vinyl butyryl) (PVB) wash primers, which consist of phosphoric acid and zinc tetraoxychromate dispersed in an alcoholic poly(vinyl butyryl) solution. These primers, also called etch primers or tie coats, are used to passivate steel, galvanized, and aluminum surfaces, improving the adhesion of topcoats. Because they are usually low in solids and

One of the first recorded inhibitors and still one of the most effective, red lead has been widely used in primers for structural steel. The pigment is available in four grades containing from 85 to 98% Pb304. While red lead is an oxidizing agent, its inhibitive mechanism is much more complicated than mere oxidation. When formulated with linseed oil, red lead forms soaps which, in the presence of water, release soluble lead compounds and organic acids. These soaps also improve the mechanical properties of the paint film and promote passivation through three mechanisms: 9 Anodic adsorption of soluble lead compounds. 9 Anodic adsorption of acid molecules. 9 Anodic precipitation by oxidation [19].

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PAINT AND COATING TESTING MANUAL A. Basic Zinc Molybdate [20]

Specific gravity Color pH Oil absorption Water solubility Typical loading levels 5.06 White 6.5 14 <0.01% 5 to 15%

Although soap formation is red lead's chief protective mechanism, use of the pigment is not restricted to oil-based paints. Epoxides, chlorinated rubbers, and vinyls are just some of the "oil-less" systems which are often formulated using red lead. There are questions regarding whether red lead functions as an inhibitor in these systems. It is more likely that the pigment exhibits the low oil absorption, pigment packing characteristics, and fine particle size of an ideal extender.

Recommended for use in alkyds, epoxides, epoxy esters, polyesters, and other solvent-based resin systems.

B. Basic Lead Silicochromate (BLSC)

Specific gravity Color pH Oil absorption Water solubility 4.1 Orange 14 <0.01%

B. Basic calcium zinc molybdate [21]

Specific gravity Color pH Oil absorption Typical loading levels 3.0 White 8.5 18 2.5 to 10%

Developed as a substitute for red lead, BLSC was once widely used in heavy duty maintenance coatings. It contains two active ingredients: monobasic lead chromate and gamma tribasic lead silicate. The former enhances the stability of the coating package and contributes a chromate ion, thus improving inhibition; the latter provides exceptional inhibitive characteristics. BLSC offers several advantages over red lead: 9 Reduced density minimizes problems with pigment suspension and settling and lowers the density of finished paint. 9 Improved resistance to chalk and carbonation for better weather resistance and application in topcoats. 9 Lower tint strength for a broader range of color formulation. Because it contains both lead and hexavalent chromium, BLSC is no longer as widely used as it once was.

Recommended for use in water-reducible and latex-based resin systems as well as two-component polyurethane and epoxy systems.

C. Basic Zinc Molybdate/Phosphate [22]

Specific gravity Color pH Oil absorption Water solubility 4.0 White 5.5 14 <0.01%

Recommendations are the same as for basic zinc molybdate. This product, however, is reported to provide enhanced performance over rusted steel substrates.

D. Basic Calcium Zinc Molybdate/Zinc Phosphate [23]

Specific gravity Color pH Oil absorption Typical loading levels 3.0 White 7.5 l8 5 to 15%

C. Other Lead Pigments

The following lead-based products have been used to inhibit corrosion in very specific or very limited applications: lead suboxide; basic carbonate white lead and lead cyanamide (mirror back coatings); basic lead silicate (electrodeposition primers); tribasic lead phosphosilicate; basic lead silicosulfate; dibasic lead phosphite; lead chromosilicate; lead sulfate; and calcium plumbate.

This inhibitor, a mixture of basic calcium zinc molybdate and zinc phosphate, is reported to offer improved adhesion over ferrous metals. Recommended for use in both solventand water-based systems.

Molybdates
Molybdate-based pigments are anodic passivators, preventing corrosion by forming a protective layer of ferric molybdate on the surface. This layer is insoluble in neutral and basic solutions. However, since most commercial molybdate pigments contain zinc, the formation of inhibitive zinc soaps in oleoresinous systems may add to the anti-corrosive properties of molybdate products. Although molybdate inhibitors are free of lead and chromate, they are limited in market value due to their expense. To make these more accessible, molybdate/phosphate compositions have been introduced, though these are difficult to disperse. Micronized versions of molybdate/phosphate are available to counteract the dispersion problem. Following are the four most popular molybdate inhibitors available on the market today.

Phosphates
A. Zinc Phosphate [Zn3(PO4)2-2HzO]
Specific gravity Color pH Oil absorption Water solubility Typical loading levels 3.2 White 7.5 25 <0.01% 5 to 10% in waterbased systems; 5 to 15% in solventbased industrial systems; 10 to 30% in maintenance coatings

Zinc phosphate's formulation versatility has probably led to its status as one of the most widely used "nontoxic" inorganic inhibitors. Zinc phosphate can be readily used in a wide

CHAPTER 2 7 - - I N O R G A N I C ANTI-CORROSIVE PIGMENTS

variety of resin systems, including high acid number alkyds, water-reducible coatings, high-performance resins and acidcatalyzed baking systems. The pigment's low reactivity and low solubility give it a distinct formulating advantage over more basic, less stable nontoxic pigments. Zinc phosphate is thought to inhibit corrosion in three ways: 9 Through phosphate ion donation. 9 By forming a protective anodic film. 9 By forming anti-corrosive extracts in the presence of certain oleoresinous vehicles. Zinc phosphate has a creditable track record of effective performance in real-world testing, but rates much lower in salt spray testing and other accelerated tests. This poor performance may be explained by the fact that salt water and high humidity often impair the performance of the pigment.

243

TABLE 2--Typical properties of aluminum triphosphate.

Grade I Specific gravity Color pH Oil absorption Water solubility (max) 3.0 White 6.5 37 1% Grade II 3.1 White 6.5 32 1% Grade III 3.0 White 6.5 30 1%

suitable for water-based coatings. Grade II is modified with zinc and silicate. Grade III--For solvent and water-based systems. Easier dispersion makes the pigment more effective in low build coatings. Grade III is modified with zinc.

Phosphites
A. Zinc Hydroxy Phosphite [[2ZnO(OH)z.
ZnHPaOa].X2H2-O, w h e r e X = 1 to 17] [27] Specific gravity Color pH Oil absorption Water solubility (Max.) Typical loading levels 3.9 White 7.0 18 0.04% 10-25% in maintenance applications; 5-15% in general industrial and waterbased applications

B. Modified Zinc Phosphates [24,25]

The coating industry has produced several variations of zinc phosphate that make use of other inorganic inhibitors and organic surface treatments to improve the pigment's performance in salt spray testing. The formulation versatility and recommended loading levels of these modified versions of zinc phosphate are about the same as those of standard unmodified zinc phosphate. Although the modified zinc phosphates appear to offer improved performance in accelerated testing, there is little evidence to uphold these claims in actual commercial applications. Modified versions of zinc phosphate include: Aluminum zinc phosphate--The higher phosphate content and solubility of this aluminum/zinc coprecipitated phosphate contribute to its enhanced corrosion inhibition. Basic zinc phosphate hydrate--An organic surface treatment (claimed to be an electrochemically effective inhibitor) enhances the performance of this pigment. Basic zinc molybdenum phosphate--This pigment makes use of a low level of molybdate (1.5%) to enhance inhibition. Zinc silicophosphate hydrate--This pigment appears to be a complex composite of barium sulfate, silica, magnesium oxide, and sodium dichromate. Trace amounts of hexavalent chromium may account for the pigment's improved performance, but even these very low chromate levels could possibly present waste disposal problems.

Zinc hydroxy phosphite (also called zinc phospho-oxide) results from the reaction between zinc oxide and phosphorous acid. Anodic passivation of the phosphite ion is the primary mechanism of inhibition, although the pigment's ability to form inhibitive zinc soaps in oleoresinous systems also contributes to corrosion prevention. While not recommended for use in high-acid-number or water-soluble resins, the pigment is compatible with a variety of resin systems.

Silicates
Silicate pigments contribute to corrosion inhibition in several ways, chiefly through anodic and cathodic passivation. In addition, in oleoresinous systems, these pigments form inhibitive soaps of barium, calcium, strontium, and zinc. The inhibitive value of silicate pigments is further enhanced by their alkalinity and solubility.

C. A l u m i n u m Triphosphate [26]
Available commercially in three grades (Table 2), aluminum triphosphate is a relatively recent chromate-free inhibitor. A condensation product, it is often modified with zinc ion or silicate to minimize its solubility and reactivity. Inhibition is thought to result from the tripolyphosphate ion's ability to chelate iron ions, as well as higher phosphate levels resulting from the depolymerization of the tripolyphosphate ion into orthophosphate ions. These pigments exhibit typical phosphate performance relative to loading levels. Each grade is recommended for specific applications: Grade / - - F o r use in solvent-based primers (alkyds and epoxides). Grade I is modified with zinc and silicate. Grade H - - F o r use in solvent and water-based systems. The pigment's lower water solubility apparently makes it more

A. Calcium Borosilicate [28-30]

Available in three commercial grades (Table 3), calcium borosilicate is effective in a range of applications: a. Grades I and III--Recommended for use in protective coating systems-based on traditional alkyd technology, these pigments differ primarily in their B203 content: 10.6% for Grade I and 15.6% for Grade III. They are generally used for such applications as trade sales, industrial maintenance, railroad and tank coatings, and shop primers. While they can be used in a variety of resin systems, including medium and long oil alkyds, epoxy-esters, and modified alkyds, they are not suited for use in highacid-number resins, acid-catalyzed systems, water-based

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PAINT AND COATING TESTING MANUAL

TABLE 3--Typical properties of calcium borosilicates.
Grade I Grade II 2.71 White 10.1 27 0.34% 10-20% in primers, 2.5-10% in topcoats and DTM finishes Grade III 2.65 White 10.1 41 0.37% 10-20% tive in thin film applications and in systems requiring a high gloss.

Specific gravity 2.65 Color White pH 10.1 Oil absorption 36 Water solubility 0.35% (max) Typical loading levels 10-20%

M i s c e l l a n e o u s Inhibitive Pigments

A. Ion Exchange Pigment

Specific gravity Color pH Oil absorption 1.8 White 9.2 50 [35]

resins, epoxides, and other high-performance resins, or for immersion or semi-immersion service. b. Grade H--This pigment, a low-oil-absorption version of the other two grades, is used primarily in high solids, medium gloss topcoats, direct-to-metal (DTM) coatings, and self-priming alkyd systems. PVC levels range from 40 to 45% in primers and 15 to 25% in topcoats and DTM coatings.

Claimed to be effective in all paint systems, this pigment uses the mechanism of ion exchange with corrosive species to prevent corrosion. Loading levels should be half the levels of typical corrosion-inhibiting pigments.

B. Zinc Oxide
Research has suggested that zinc oxide possesses both passivating and cathodic inhibitive capabilities [36,37]. Also, when used in latex metal primers and certain oleoresinous systems (such as SSPC Paint No. 25) [38], zinc oxide exhibits obvious anti-corrosive action. ~ Often used with more conventional active inhibitors such as zinc chromate and calcium borosilicates, zinc oxide appears to raise the cross-link density of many paint films, making them harder. Zinc oxide may also absorb ultraviolet light, thus protecting the resin. Since the pigment tends to have seeding problems and can cause film brittleness, care must be taken when using zinc oxide in inhibitive coating applications.

B. Phosphosilicates [31-34]
Four modifications (see Table 4), each representing a different commercial grade, are available for a variety of uses. Calcium Barium Phosphosilicate (Grade/)--This pigment is for use in conventional and high solids solvent-based epoxy systems. The pigment is also used in organic zincrich primers as an anti-settling agent. Calcium Barium Phosphosilicate (Grade II)--A low-oil-absorption version of this pigment, Grade II is for use in most water-borne systems, including latexes and water-reducible systems. When formulated in alkyds, this product, like many other phosphate pigments, will demonstrate excellent real-world performance, but poor performance in accelerated testing. Calcium Strontium Phosphosilicate (Grade III)--This pigment is for use in most water-based acrylic lacquers, as well as water-reducible caulks and sealants. When the product used with zinc phosphate in water-based lacquer systems in a 1:1 ratio, a synergistic effect is produced which improves performance.

Zinc Metal in Primers

The prime focus of this discussion is inorganic inhibitive pigments which function through the mechanism of soluble inhibitive species; however, zinc metal--which functions through the mechanism of cathodic protection--deserves a brief mention. In many applications, including the protection of steel structures, zinc-rich coatings offer the best corrosion inhibition available, especially when topcoated with either epoxy or urethane. Actual particles or flakes of zinc in the paint film protect the ferrous substrate by acting as the anode and corroding sacrificially. While the correct loading level of zinc metal in zinc-rich primers is still a matter of debate, these coatings usually contain 80 to 85% zinc metal. Zinc-rich primers can be formulated as inorganic coating systems (ethyl silicate binders) or organic systems (such as epoxides). Zinc-rich primers require near-white blast surface preparation and must be fully cured before topcoating. Two major problems associated with zinc-rich formulation are pigment settling and hydrogen gassing.

Calcium Strontium Zinc Phosphosilicate (Grade IV)--This

grade is for use in a broad range of resin systems, including traditional and high-solid alkyds, latexes, epoxides, waterreducible alkyds, high-acid-number resins, vinylidene chloride latexes, and catalyzed baking systems. A recent development, Grade IV is the most versatile and effective of the phosphosilicate inhibitive pigments. Because of its fine particle size and low oil absorption, this pigment is effec-

TABLE 4--Typical properties of phosphosilicate inhibitors.

Grade I Specific gravity 2.97 Color White pH 7.9 Oil absorption 44.5 Water solubility 0.02% Typical loading levels 5-10% GradeII GradeIII GradeIV

Barrier Pigments

2.97 2.90 3.01 White W h i t e White 8.3 7.8 7.0 31.5 53.5 26.0 0 . 0 2 % 0 . 0 3 % 0.02% 5-10% 5-10% 2.5-15%

A. A l u m i n u m Flake
Aluminum flake, typically supplied as a slurry, is produced by atomizing molten aluminum and ball-milling the powder into a solvent. The resultant flake is frequently used to improve the appearance and anti-corrosion performance of

CHAPTER 27--INORGANIC ANTI-CORROSIVE PIGMENTS

coatings for tanks, bridges, roofs, railroad cars, automobiles, and office equipment. Coatings containing aluminum flake stand up well to heat and moisture. They also resist the damaging effects of ultraviolet light, cooling the substrate and preventing deterioration of the binder. Aluminum flake is available in two grades, leafing and nonleafing. A stearate coating on the leafing grade allows the pigment to float on the surface of a paint film. Because this coating is also associated with intercoat adhesion failure in primer coats, leafing grade aluminum flake is normally used in topcoat formulations. Typical loadings range from 20 to 25%. A disadvantage of using aluminum flake is that the pigment is very reactive with water, and hydrogen gassing may occur if moisture levels are not maintained below 0.15%.

245

B. Steel Flake
Stainless steel and a number of steel alloys are sometimes used to make steel flake, which is used in coatings for applications requiring m a x i m u m resistance to abrasion.

nated with lead and chromate-based pigments. Under these regulations, containment and disposal of these materials could well increase the cost of a typical maintenance repainting project by tenfold. Regulations concerning the disposal of industrial wastes in the United States are strict, due in part to revisions of the Drinking Water Regulations of the Safe Drinking Water Act, which is an effort to prevent contamination of the water supply. The coatings industry is under legislative pressure to develop environmentally acceptable, high-performance, longlasting replacements for lead and chromate-based pigments and reduce levels of VOC. These are not easy tasks. Some of the formulation and application factors which affect the industry's efforts at compliance have already been discussed; the following is a look at some of the stringent techniques in use to evaluate the performance of new, less toxic inhibitors and protective coatings.

C. Micaceous Iron Oxide (MIO)

Specific gravity Color Oil absorption Typical loadings 4.9 Dark Gray 11 30-50%

HOW FORMULATION AFFECTS THE P E R F O R M A N C E OF I N H I B I T I V E PIGMENTS

When formulating with inhibitors, a host of formulation factors must be taken account since these factors often determine the selection of inhibitive pigments and greatly affect the development of inhibitive coatings. The most critical formulation factors include PVC (pigment volume concentration), selecting an extender pigment, solubility and reactivity (that is, selecting a vehicle and understanding how its components interact), and the complex interrelationships between all these factors.

A naturally occurring form of hematite with an Fe2Oa content of about 92 to 95%, MIO has been used in protective coating formulations for over 100 years. Because of its lamellar structure, it is typically used in primers to improve their barrier resistance. Used in topcoats, MIO enhances resistance to ultraviolet light.

Pigment Volume Concentration

ENVIRONMENTAL CONSIDERATIONS
Health and safety factors have always been seriously considered during the development and evaluation of new protective coatings. Use of lead, hexavalent chromium compounds, and other toxic pigments is constantly monitored to ensure that current, acceptable limits are met. Environmental regulations have driven the inhibitive coatings industry to increase efforts to develop and evaluate new, nontoxic products to replace lead, chromates, and traditional inhibitors with long-standing performance records. Two primary environmental concerns within the industry are worker protection and waste disposal. Several steps have been taken to ensure worker safety. For example, all workers have the right to know the dangers involved with handling the materials they are exposed to every day and the right to be offered the capability to handle these materials safely. Because absorption of toxic pigments through inhalation is a major concern, workers are protected by engineering controls (ventilation), respiratory controls (masks, filters, and other equipment), and extensive safety training. The preferred option is to completely eliminate the hazardous material and substitute a less toxic pigment, if possible. Waste disposal pertains to plant waste produced by paint manufacturing and waste from painting operations. The latter includes overspray and spent blast abrasives contami-

Pigment volume concentration (PVC) is the ratio of pigment volume to the total nonvolatile volume in a coating. Probably the most important formulation factor to consider when evaluating anti-corrosive pigments, PVC is especially crucial when two or more inhibitors are being considered for a given application. Essential to the understanding of the importance of PVC is the concept of a "formulation window." This term represents the PVC range at which an inhibitive pigment will give its best performance and is clearly depicted in Fig. 3. Here, the performance in a salt fog cabinet of three popular chromate-free inhibitors is compared to that of zinc chromate in a medium oil alkyd primer. Loadings are equal--about 10% of total formula weight--across a PVC ladder at constant volume solids. In the figure, the three nontoxic inhibitors each yielded performance equivalent to zinc chromate, but only within a specific PVC range, a rather narrow formulation window. Conversely, zinc chromate offered far greater formulation versatility, performing over a much broader PVC range. The figure illustrates both the importance of addressing the variable of PVC and poses a problem facing the formulator: None of the environmentally acceptable inhibitors--including the three in the figure--come close to matching the traditional lead and chromate-based pigments for overall efficiency and formulation flexibility. While each of the three chromate-free inhibitors was formulated to equal the per-

246

PAINT AND COATING TESTING MANUAL

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PVC Loading Levels (Formulation Windows) of Chromate-free Inhibitors and Zinc Chromate
FIG. 3 - M e d i u m oil alkyd PVC ladder: salt spray performance. Formulation windows of four inhibitive pigments,

formance of zinc chromate, each performed at a much narrower formulation window, thereby severely restricting its
use.

Many factors influence the formulation window of an inhibitive pigment in a given formulation. All these factors must be satisfied to maximize the performance of an inhibitor. Crucial factors to consider in association with PVC are: (1) specific gravity, oil absorption, and other physical properties of an inhibitor; and (2) the effect of these properties on CPVC (critical pigment volume concentration). The concept of CPVC, introduced in the late forties, postulates the existence of a level of pigmentation in a dry paint film at which there is just enough binder to coat the pigment particles and fill the spaces between them [39,40]. Since many nontoxic inhibitors are lower in specific gravity and higher in oil absorption than more traditional inhibitors, it is easy to formulate anti-corrosive coatings which exceed CPVC and therefore deliver unacceptable levels of inhibition. To avoid this situation, it is necessary to evaluate inhibitive pigments across a PVC range to achieve optimum performance. To do this, coatings should be made at each extreme of the PVC range; then weight blends of these paints may be used to generate the intermediate levels.

"rule" worked as long as formulators used red lead and other lead-based pigments whose very high specific gravities and low oil absorptions permitted relatively high loadings. When large amounts of nonlead inhibitors are used in formulations, the resulting coatings often perform well in accelerated corrosion tests. However, most nonlead inhibitors are much more reactive in vehicle systems than lead-based inhibitive products, and this reactivity can lower the actual performance of coatings formulated with high inhibitor loadings. In general, inhibitor loading should be carefully balanced, keeping in mind that more is not necessarily better, at least as far as less-toxic, more-reactive inhibitors are concerned. Comparing inhibitive pigments--Certainly not as straightforward a matter as comparing apples to oranges, comparing pigments may be accomplished in several different ways: on the basis of equal volume, equal weight, equal cost, or equal performance. The choice of method can drastically affect the results of a formulator's evaluations. Equal Volume--This is the easiest evaluation method and
by far the least desirable. Replacing a given volume of one inhibitor with the same volume of another is simple and requires the least number of formulation changes. However, the wide variations in specific gravities of inhibitors (from a low of 2.5 to a high of 9.1) and oil absorptions, which vary from 10 to 70, make the results of these evaluations highly questionable. Equal Weight--This is a valid method of evaluating inhibitors with loading levels equal to or exceeding 120 g per liter

Inhibitor Loading Levels

In the "old days" of inhibitive coatings formulations, before the advent of environmental regulations, the rule of thumb was to add as much inhibitive pigment as possible. The assumption: if a little was good, then a lot must be better. This

CHAPTER 27--INORGANIC ANTI-CORROSIVE PIGMENTS

(1 lb/gal). Care must be taken to adjust the levels of extender pigment and vehicle solids when replacing one inhibitor with another. This is to ensure that the inhibitors can be compared at a constant loading level over a given PVC range at constant volume solids. Equal Cost--This method is valid if the inhibitor levels are less than 120 g per liter (1 lb/gal), as long as comparisons are conducted at a constant loading level over a PVC range at constant volume solids. Equal Performance--The most tedious approach, this method ensures the most cost-effective formulation possible. Basically a combination of simultaneous evaluations of a PVC ladder and an inhibitor loading ladder, this approach permits the formulator to evaluate each inhibitor for its optimum formulation window.

247

Extender Pigments
Although a wide choice of extenders is available for inhibitive coatings formulation, extender selection traditionally has not received much attention. This may be the result of the former widespread use of lead and chromate-based inhibitors, whose excellent performance masked any flaw contributed by an extender. With emphasis on environmentally acceptable (and less effective) inhibitors, however, selection of suitable extenders is an important factor in the formulation of inhibitive coatings. Figure 4 contains the results of work in latex maintenance coatings. The data here clearly show that the performance of extender pigments depends to a great extent on the type of vehicle and inhibitor used in the formulation, that is, the performance of extenders will vary from system to system. Selecting the appropriate extender, therefore, may be as crucial to coating performance as selecting the vehicle system or inhibitive pigment [41].

problems arising from reactivity and solubility. For example, a pigment must have some solubility within a given system in order to participate actively in passivation. Also, a highly reactive pigment can react with binders and other ingredients in a coating system, causing instability. Adverse chemical reactions between the inhibitor and the vehicle in the can or the cured paint film can effect coating properties such as viscosity, drying time, cure, adhesion, and weatherability. Therefore, inhibitive pigments must be chosen carefully to prevent these formulation problems [42]. Some chemical reactions, such as the reactions between basic pigments and acid catalysts, neutralize inhibitive action by preventing film cure. Some reactions may even accelerate corrosion. Others may do good or harm, depending on where they occur. For example, the formation of metallic soaps on a paint film caused by a reaction between red lead and linseed oil acids promotes corrosion inhibition; however, if this same reaction occurs in the paint can, viscosity may increase to the point that the liquid paint becomes unusable. Generally, inhibitive pigments retard or prevent blistering caused by corrosion in pinholes or scribes or by moisture drawn into the paint film by electrical activity of the corrosion cells. But use of inhibitors may lead to osmotic blistering, especially during humidity and condensation testing. Osmotic blistering is caused by the presence of water and soluble pigment at the juncture of the substrate and the coating film [43]. To prevent this condition, low-solubility pigments should be used.

A P P L I C A T I O N A N D P R O T E C T I V E COATING PERFORMANCE
Coating application (how, where, why, and for how long a coating will be used) must be carefully considered when formulating environmentally acceptable alternatives to traditional toxic inhibitors. The length of time a protective coating can effectively protect a ferrous surface has been said to

Reactivity and Solubility

Inhibitors should be carefully selected for compatibility with given coating systems to prevent common formulation
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248

PAINT AND COATING TESTING MANUAL EVALUATING INHIBITIVE PIGMENT AND COATING P E R F O R M A N C E
Pigment and coating evaluation techniques--especially accelerated laboratory tests--are more important now than ever before. The reason: Users and manufacturers alike demand that new inhibitive products not only meet environmental regulations, but also meet or exceed the performance standards set by established, environmentally unacceptable pigments. This discussion will deal with the two principle methods of evaluation used by the coatings industry: accelerated testing and "real-world" (natural atmospheric) testing.

depend on the following application factors: the environment, how the coating is applied, the substrate, and the surface preparation of the substrate [44]. Consider the environment where the inhibitive coating will be used: Will the coating be exposed to harsh chemicals, abrasion, industrial atmospheres, heavy traffic, high heat, or other extreme conditions? Or will it be used in a rural setting, exposed to the elements? Answering these questions will help determine the proper vehicle system and application techniques to be used with the coating. Other factors to consider when deciding how to apply a protecting coating include the type of applicator (brush, roller, spray, or dip), adequate and uniform film thickness [45], drying time, and temperature. Though application techniques are often given little attention, they can profoundly affect the performance of a protective coating. Substrates are also important factors in testing protective coatings and inhibitive pigments. For example, untreated cold rolled steel generally shows more undercutting at scribes than sandblasted hot-rolled steel or treated steel. Because it is easier to differentiate between pigments on untreated steel, that substrate is frequently used to compare the performance of different inhibitive pigments. On the other hand, use of a phosphatized substrate seems to improve the performance of protective coatings, apparently enhancing adhesion, passivating the surface, and improving the coating's inhibitive properties. A word of caution: When selecting substrates for testing inhibitive coatings systems, care must be taken to conduct final evaluations of a system on the substrate that the coating will be applied to in actual use. For screening purposes, however, evaluations m a y be conducted on any appropriate substrate. Protective coatings are frequently applied to the following ferrous substrates [46]: cold-rolled steel; polished cold-rolled steel; zinc phosphate-treated cold-rolled steel; iron phosphate-treated cold-rolled steel; hot-rolled steel; abrasive blasted hot-rolled steel; pre-rusted hot rolled steel, and galvanized steel. No matter what the substrate, the surface preparation of the substrate, or its condition, is vital to the evaluation of protective coatings and an important factor in determining the life expectancy of a coating system. In addition to cleaning a surface, improving adhesion, and maximizing the performance of the inhibitive pigment, surface preparation helps remove contaminants--such as chlorides and sulf a t e s - f r o m the substrate's surface [47]. Though many methods of surface preparation exist, their effectiveness varies widely. For example, studies suggest that a protective coating will last four times longer on a blasted surface than on a hand-cleaned or weathered substrate [48]. This improved longevity is attributed to better adhesion and a more intimate contact between substrate and coating, which allows the inhibitor to maximize its performance. Some of the commonly used surface cleaning techniques are [49]: centrifugal blasting; metallic and nonmetallic abrasives; abrasive air blasting and water blasting; by hand and power tools; chemicals; pickling. Less common methods include hot gas, flame, bacterial, zinc shot, ice particles, and ultrasonic.

Accelerated Corrosion Testing

In real-world applications, protective coatings are often expected to provide up to 20 years of service. Accelerated testing attempts to predict the life expectancy of a protective coating in a short span of time, from half a year to a year. This evaluative "fast forwarding" meets the needs of manufacturers and users alike, who demand prompt development and commercialization of new products. Though several kinds of accelerated testing procedures are in use, all have essentially the same purposes: to significantly shorten the time needed for a coating to fail and to evaluate the causes of its failure. Although accelerated corrosion testing is the most commonly used evaluation method for inhibitive pigments and protective coatings, the results of accelerated tests correlate poorly with the results of real-world testing. Because of this, the validity of accelerated testing, particularly the salt spray test, has been the target of serious doubts and questions. Is accelerated testing relevant to real-world conditions? Do the tests accurately predict product performance? Evidence is growing to support the theory that many formulation variations used to enhance a coating's salt spray performance may actually detract from the coating's real-world performance. It has already been demonstrated that, in many cases, accelerated testing is an unreliable predictor of a coating's longterm protective performance. Figure 5 clearly illustrates this deficiency, depicting salt spray results which totally contradict the results of natural exposure testing for two protective coatings. Despite such strong evidence against the reliability of the salt spray test, its popularity continues. For good or bad reasons, it is the driving force behind the establishment of performance evaluation criteria for many protective coating systems and is often the only criterion used to evaluate an inhibitive coating. In some cases, raw material suppliers are forced to offer products based solely on their salt spray performance, often without regard to the coatings' performance in the real world. Another section of this book discusses this situation further and details the research the industry is doing to address the problem.

Real-World Corrosion Testing (Natural Atmospheric Exposure Testing

Considered by many researchers to be the most dependable method of predicting the performance of a protective coating, real-world testing exposes products to real-time, actual atmospheric conditions. In essence, the tests approximate the types of environments for which the coatings were designed.

CHAPTER 2 7 - - I N O R G A N I C ANTI-CORROSIVE PIGMENTS

249

thicknesses. Neither of these procedures are effective, however, since neither represents the application for which the coating was designed. 2. Lack of Controls--Establishing controls and measuring a coating's consistency of performance is a real challenge in real-world testing. In outdoor exposures, environmental factors such as temperature and humidity change from year to year at the same site, making reproducible results next to impossible. 3. Multiple Stresses--Because a coating exposed to an outdoor environment encounters many stresses, it is not easy to determine the effects of each individual stress. 4. Varying Environments--In outdoor testing, establishing a standard test environment is virtually impossible. Environments vary dramatically from one part of the country to the other, from desert to seashore, from mountains to alluvial plains. Local industries and fluctuations in weather patterns also contribute to the problem. In spite of these drawbacks, real-world testing is emerging as a viable alternative to traditional accelerated testing. Even comparatively brief exposures of six to eight months can yield important data. However, the value of these data depends on sound experiments and proper evaluation techniques. Formulators can no longer depend on "one paint/one panel" test designs.

Statistical Analysis
Another method of correlating performance data and predicting coating performance is the use of statistical analysis, which is growing in popularity. Various techniques used to design more meaningful, accurate evaluations include correlation methods, survival analysis, curve fitting, time series analysis, and reliability and life analysis. Several techniques have been developed for assessing macroscopic damage to protective coatings. Though coatings have traditionally been assessed by visual inspection, these procedures can apparently detect early stages of corrosion, giving more relevant, accurate information in a shorter exposure period.

RECENT TRENDS AND DEVELOPMENTS

New Product Development
The Federation of Societies for Coatings Technology (FSCT) monitors the development and performance evaluations of many new products, many of which reflect the trend toward less toxic inhibitors [51]. Another growing trend is the development of products with lower oil absorption, necessary for the formulation of high solids vehicles. Because proper use of auxiliary extenders can enhance inhibitive properties of protective coatings (especially those incorporating nontoxic inhibitors), the trend toward developing auxiliary extender pigments is likely to continue. Auxiliary pigments are standard extenders modified by surface treatments of silanes, titanates, ziconates, and other compounds. Some commonly used auxiliary pigments include calcium carbonates, clays, talcs, silicas, and wollastonite.

FIG. 5-Protective coating performance data. Despite their excellent ability to measure and predict anticorrosive coating performance, outdoor exposure tests have four obvious disadvantages compared to accelerated tests [50]:

1. Long Duration--Monitoring the degradation of protective

coatings is a marathon task lasting from 5 to 20 years. To accelerate the rate of failure in outdoor exposures, testing labs have exposed the paints to very harsh environments or applied the coatings at lower-than-recommended film

250

PAINT AND COATING TESTING MANUAL ing Practice, 2nd ed., J. D. Kean, Ed., Steel Structures Painting
Council, Pittsburgh, PA, 1982. [7] Shreir, L. L., Corrosion, Vol. 2--Corrosion Control, John Wiley and Sons, Inc., New York, 1963. [8] Shreir, L. L., Corrosion, VoL 2--Corrosion Control, John Wiley and Sons, Inc., New York, 1963. [9] Scully, J. C., The Fundamentals of Corrosion, 2nd ed., Pergamon Press, Oxford and New York, 1975. [10] Scully, J. C., The Fundamentals of Corrosion, 2nd ed., Pergamon Press, Oxford and New York, 1975. [11 ] Technical Bulletin RTP-771010, Buckman Laboratories, Memphis, TN. Technical Bulletin B1, Buckman Laboratories, Memphis, TN. [12] Technical Bulletin B23W, Buckman Laboratories, Memphis, [13] TN. [14] Technical Bulletin PC-23W, Buckman Laboratories, Memphis, TN. [15] Levy, L. S. and Martin, P. A., "Effect of a Range of Chromium Containing Materials on Rat Lung," unpublished multi-sponsor study, University of Aston, Birmingham, England, July 1983. [16] American Conference of Governmental Industrial Hygienists, "Threshold Limit Values for Chemical Substances and Physical Agents and Biological Exposure Indices (pamphlet)," 19901991. [17] Raw Materials Index, National Paint & Coatings Association, Washington, DC. [18] Jordan and Whitby, 16th Bulletin Research Association of British Paint, Colour and Varnish Manufacturers, Teddington, England, 1936. [19] Appleby, A. J. and Mayne, J. E. O. in Journal of Oil Colour Chemists' Association, Vol. 50, 1967. [20] Technical Bulletin X65 ZM 0101, Sherwin-Williams Chemicals, Coffeyville, KS. [21] Technical Bulletin X65 ZM 0212, Sherwin-Williams Chemicals, Coffeyville, KS. [22] Technical Bulletin X65 ZM 0332, Sherwin-Williams Chemicals, Coffeyville, KS. [23] Technical Bulletin X65 ZM 0425, Sherwin-Williams Chemicals, Coifeyville, KS. [24] Heubach Technical Bulletin 10/84, Hans Heubach GmbH and Co., Longelsheim, Federal Republic of Germany. [25] Heubach Technical Bulletin h 86-7, Hans Heubach GmbH and Co., Longelsheim, Federal Republic of Germany. [26] Technical Bulletin "K-White Aluminum Triphosphate," Tayca Corp., Osaka, Japan. [27] Technical Bulletin PB 173 MGW, NL Chemicals, Hightstown, NJ. [28] Technical Bulletin "HALOX CW-22/221," HALOX Pigments, Hammond, IN. [29] Technical Bulletin "HALOX CW-291," HALOX Pigments, Hammond, IN. [30] Technical Bulletin "HALOX CW-2230," HALOX Pigments, Hammond IN. [31] Technical Bulletin "HALOX BW-111," HALOX Pigments, Hammond, IN. [32] Technical Bulletin "HALOX BW-191," HALOX Pigments, Hammond IN. [33] Technical Bulletin "HALOX SW-111," HALOX Pigments, Hammond, IN. [34] Technical Bulletin "HALOX SZP-391," HALOX Pigments, Hammond, IN. [35] Technical Bulletin "Shieldex News," W. R. Grace & Co., Baltimore, MD. [36] Mayne and Van Rooyen, in Journal of Applied Chemistry (London), Vol. 4, July 1954, p. 384. [37] Evans, U. R., Metallic Corrosion, Passivity and Protection, Longmans Green and Co., New York, 1945.

O t h e r Testing Procedures
Driven by changing r e g u l a t o r y s t a n d a r d s a n d the industry's need for p r o m p t p r o d u c t development, a variety of alternative accelerated testing p r o c e d u r e s are being r e s e a r c h e d a n d developed. The challenge is to m a k e accelerated testing accurately reflect real-world conditions a n d yield meaningful, realistic results. The Corrosion C o m m i t t e e of the F e d e r a t i o n of Societies for Coating Technology (FSCT) c o m m i s s i o n e d a survey [52] on this subject directed to m a n u f a c t u r e r s a n d users of protective coatings. The results of the survey s h o w e d that the p a r t i c i p a n t s were exploring the use of the following kinds of modified accelerated testing techniques: (1) cyclic tests; (2) cyclic n a t u r a l exposures; (3) electrochemical testing; a n d (4) physico-chemical, physical, a n d m e c h a n i c a l testing procedures. The Steel Structures Painting Council (SSPC) is evaluating the m o s t p r o m i s i n g of these accelerated cyclic c o r r o s i o n tests. The survey itself is too extensive to be included here b u t is readily available from the FSCT.

CONCLUSION
Before the b e g i n n i n g of r e c o r d e d history a n d ever since, p r o t e c t i n g ferrous surfaces from the disintegrating effects of c o r r o s i o n has been one of m a n k i n d ' s m o s t c o m m o n a n d perplexing battles. F r o m the lead c o m p o u n d H o m e r ' s blacksmiths s m e a r e d on their w a g o n wheels to the sophisticated protective coatings used today, the science of preventing corr o s i o n is as complex as the corrosion process itself. Over the years, m a n y factors have arisen w h i c h d e m a n d consideration: s u b s t r a t e selection, surface p r e p a r a t i o n , vehicle a n d p i g m e n t selection, a n d PVC, to n a m e just a few. N o w the coatings i n d u s t r y is engaged in a new a p p r o a c h to the age-old c o r r o s i o n - p r o t e c t i o n problem: developing effective n e w nontoxic inhibitors to take the place of t r a d i t i o n a l lead a n d c h r o m a t e - b a s e d pigments. The r e s e a r c h is well underway, a n d the next ten years m a y well see the w i d e s p r e a d a c c e p t a n c e of these safe, h i g h - p e r f o r m a n c e alternatives. This progress will b e a c c o m p l i s h e d not by scientific curiosity o r c o m m e r c i a l d e m a n d alone, b u t also b y c o n c e r n for the protection of o u r fragile h u m a n habitat.

REFERENCES
[1] Chilton, J. P., Principles of Metallic Corrosion, The Royal Institute of Chemistry, W. Heifer and Son LTD, Cambridge, England, 1964. [2] Smith, A., Inorganic Primer Pigments, Federation Series on Coatings Technology, Federation of Societies for Coatings Technology, Philadelphia, PA, 1988. [3] Chilton, J. P., Principles of Metallic Corrosion, The Royal Institute of Chemistry, W. Heifer and Son LTD, Cambridge, England, 1964. [4] Schweitzer, P. A., What Every Engineer Should Know About Corrosion, Marcel Dekker, Inc., New York and Basel, 1987. [5] Gleekman, L. W., "Selecting Materials of Construction," Corrosion and Corrosion Protection Handbook, P. A. Schweitzer, Ed., Marcel Dekker, Inc., New York and Basel, 1983. [6] Eickhoff, A. J,, "Corrosion Inhibitive Pigments and How They Function," Steel Structures Painting Manual, Vol. 1, Good Paint-

CHAPTER 27--INORGANIC ANTI-CORROSIVE PIGMENTS

[38] Steel Structures Painting Manual, Vol. II, Systems and Specifications, Steel Structures Painting Council, Pittsburgh, PA. [39] Asbeck and Van Loo, "Critical Pigment Volume Relationships," Industrial and Engineering Chemistry, Vol. 41, 1949, p. 1470. [40] Wicks, Z. W. Jr., Corrosion Protection by Coatings, Federation Series on Coatings Technology, Federation of Societies for Coatings Technology, Philadelphia, PA, 1987. [41] Austin, M. J. and Devaney, J. G., "Inhibitive Pigments for Latex Coatings: Do They Make a Difference?," Journal of Protective Coatings & Linings, Vol. 7, No. 6, June 1990. [42] Smith, A. Inorganic Primer Pigments, Federation Series on Coatings Technology, Federation of Societies for Coatings Technology, Philadelphia, PA, 1988. [43] Smith, A., Inorganic Primer Pigments, Federation Series on Coatings Technology, Federation of Societies for Coatings Technology, Philadelphia, PA, 1988. [44] Eickhoff, Arnold J., "Corrosion Inhibitive Pigments and How They Function," Steel Structures Painting Manual, Vol. 1, Good Painting Practice, 2nd ed., J. D. Kean, Ed., Steel Structures Painting Council, Pittsburgh, PA, 1982. [45] Steel Structures Painting Council, "Minimum Paint Film Thickness for Economical Protection of Hot Rolled Steel Against Corrosion," Pittsburgh, PA. [46] Smith, Alan, Inorganic Primer Pigments, Federation Series on Coatings Technology, Federation of Societies for Coatings Technology, Philadelphia, PA, 1988. [47] Steel Structures Painting Council, Guide 5, Guide to Maintenance Painting Programs, Pittsburgh, PA. [48] Burns, R. M. and Bradley, W. W., Protective Coatings for Metals, Reinhold Publishing Corporation, New York, 1955. [49] Hitzrot, H. W., "Surface Preparation," Steel Structures Painting Manual, Vol. 1, Good Painting Practice, 2nd ed., J. D. Deane, Ed., Steel Structures Painting Council, Pittsburgh, PA, 1982. [50] Appleman, B. R., "Survey of Accelerated Test Methods for AntiCorrosive Coating Performance," Journal of Coatings Technology, Vol. 62, No. 787, August 1990. [51] Hare, C. H., Anti-Corrosive Barriers and Inhibitive Primers, Federation Series on Coatings Technology, Unit 27, Federation of Societies for Coating Technology, Philadelphia, PA, 1979. [52] Appleman, B. R., "Survey of Accelerated Test Methods for AntiCorrosive Coating Performance," Monograph prepared for the Corrosion Committee of the Federation of Societies for Coatings Technology, Philadelphia, PA, June 1990.

251

BIBLIOGRAPHY
American Conference of Governmental Industrial Hygienists, "Threshold Limit Values for Chemical Substances and Physical Agents and Biological Exposure Indices," pamphlet, 1990- 1991.

Austin, M. J. and DeVaney, J. G., "Extender Pigments for Latex Coatings: Do They Make a Difference?" Journal of Protective Coatings & Linings, Vol. 7, No. 6, June 1990. Appleiaaan, B, R., "Survey of Accelerated Test Methods for AntiCorrosive Coating Performance," Journal of Coatings Technology, Vol. 62, No. 787, August 1990. Burns, R. M. and Bradley, W. W., Protective Coatings for Metals, Reinhold Publishing Corporation, New York, 1955. Chilton, J. P., Principles of Metallic Corrosion, The Royal Institute of Chemistry, W. Heifer and Son LTD, Cambridge, England, 1964. Collie, M. J., Ed., Corrosion Inhibitors, Noyes Data Corp., Parkridge, NJ, 1983. Eickhoff, A. J., "Corrosion Inhibitive Pigments and How They Function," Steel Structures Painting Manual, Vol. 1, Good Painting Practice, 2nd ed., J. D. Kean, Ed., Steel Structures Painting Council, Pittsburgh, PA, 1982. Fontana, M. G., Corrosion: A Compilation, The Press of Hellenbeck, Columbus, OH, 1957. Hare, C. H., Anti-Corrosive Barriers and Inhibitive Primers, Federation Series on Coatings Technology, Unit 27, Federation of Societies for Coating Technology, Philadelphia, PA, 1979. Hitzrot, H. W., "Surface Preparation," Steel Structures Painting Manual, Vol. 1, Good Painting Practice, 2nd ed., J. D. Deane, Ed., Steel Structures Painting Council, Pittsburgh, PA, 1982. Jackson, M. A., "Guidelines to Formulation of Water-Borne Epoxy Primers: An Evaluation of Anti-Corrosive Pigments," Journal of Protective Coatings and Linings, April 1990. Mansfield, F., Corrosion Mechanisms, Marcel Dekker, Inc., New York and Basel, 1987, Munger, C. G., Corrosion Protection by Protective Coatings, National Association of Corrosion Engineers, Houston, TX, 1984. Schweitzer, P. A., Ed., Corrosion and Corrosion Protection Handbook, Marcel Dekker, Inc., New York and Basel, 1983. Schweitzer, P. A., What Every Engineer Should Know About Corrosion, Marcel Dekker, Inc., New York and Basel, 1987. Scully, J, C., The Fundamentals of Corrosion, 2nd ed., Pergamon Press, Oxford and New York, 1975. Shreir, L. L., Corrosion, Vol. 2: Corrosion Control, John Wiley and Sons, Inc., New York, 1963. Smith, A., Inorganic Primer Pigments, Federation Series on Coatings Technology, Federation of Societies for Coatings Technology, Philadelphia, PA, 1988. Speller, F. N., Corrosion--Causes and Prevention, McGraw-Hill Book Co. Inc., New York and London, 1951. Suzuki, I., Corrosion-Resistant Coatings Technology, Marcel Dekker, New York, 1989. Uhlig, H. H., Ed., The Corrosion Handbook, John Wiley and Sons, Inc., New York. Wicks, Z. W., Jr., Corrosion Protection by Coatings, Federation Series on Coatings Technology, Federation of Societies for Coatings Technology, Philadelphia, PA, 1987.