GENERIC COATING TYPES

Lloyd M. Smith, General Editor, Corrosion Control Consultants and Labs

Inorganic Zinc-Rich
by Harlan H. Kline, Ameron International PCG

norganic zinc coatings contain metallic zinc dust in an inorganic binder. The binder in the cured film is a silicate. This class of coating is different because it protects the substrate by galvanic action. When 2 metals of different electrochemical potential are in contact, the more active (i.e., the more electronegative) metal corrodes preferentially to protect the more noble metal. Hence, the term sacrificial primer is used. Zinc is highly active and will protect less active metals, such as carbon steel, cast iron, copper, and many types of stainless steel. Electrical continuity is needed for the sacrificial action to occur. This continuity requires a high level of surface cleanliness so there is physical contact between the zinc and the metal of the substrate. It is also necessary to have electrical continuity within the coating. Therefore, inorganic zinc-rich coatings contain high levels of zinc dust in the formulation. They are used as primers and as single-coat systems.

Table 1

Requirements for Composition, ASTM D 520*

Type I Total zinc, minimum % Metallic zinc, minimum % Zinc oxide (ZnO), maximum % Calcium, calculated as CaO, maximum % Lead, maximum % Iron, maximum % Cadmium, maximum % Chloride, maximum % Sulfur, calculated as SO2, maximum % Moisture and other volatile matter, maximum % Coarse particles, maximum %: Total residue retained on a No. 100 (150-m) sieve Total residue retained on a No. 200 (75-m) sieve Total residue retained on a No. 325 (45-m) sieve *ASTM D 520, Specification for Zinc Dust Pigment4 97.5 94.0 6.0 0.7 0.1 none 4.0 Type II 98.0 94.0 remainder 0.7 0.01 0.02 0.01 0.01 0.01 0.1 0.1 0.8 3.0

History The development of inorganic zincrich coatings began in the 1930s when research was conducted at Cambridge University on the electrical conductivity and cathodic protection provided by coatings heavily loaded with metallic zinc dust.1 The first use of zinc-rich coatings occurred in 1941 when a water-borne, sodium silicate-zinc dust coating was applied on the now famous Morgan Wyalla above-ground pipeline in
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Australia.2 Applied and cured with heat, the coating was still reported to be in excellent condition after more than 50 years. Heat curing limited the practicality of the coating formulation. As a result, in 1950, a water-borne, postcured inorganic zinc dust coating was commercialized. It required application of the coating, application of a curing solution, and then washing the surface to remove residual salts and solution. While this was a vast improvement over heat curing, the process remained cumbersome because of its multiple steps. In the 1950s, a self-curing, water-borne,

zinc dust coating was introduced, followed in 1960 by a self-curing, solvent-borne, zinc-rich formulation. Formulation Binder SSPC-Paint 20, Zinc-Rich Primers (Type I, Inorganic, and Type II, Organic), is a specification of the Steel Structures Painting Council that classifies inorganic zinc-rich coatings into 3 categories3: Type I-Apost-curing, waterborne, Type I-Bself-curing, waterborne, and
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Table 2

Typical Zinc Dust Pigment Types, Particle Size Characteristics

Grade Property Weight median diameter (m) % < 10 m % < 44 m Surface area (m2/g) Coarse 8-10 55 98 0.11 Regular or Standard 6-8 65 98 0.14 Fine 4-6 95 99 0.17 Ultra Fine or Superfine 2-4 99 100 0.2

Type I-Cself-curing, solventborne. The binder in the water-borne formulations consists of alkali metal (sodium, potassium, or lithium) silicates, phosphates, quaternary ammonium silicates, and colloidal silica. The solvent-borne formulations contain binders of alkyl silicates, such as ethyl silicate, or titanates. Commercial products may contain small amounts of pigments for color, film reinforcement, or control of reaction rate. In addition, small amounts of an organic resin for initial hardness and stability, rheology modifiers for control of application, and anti-settling agents for package stability may be added. The water-borne inorganic zincrich coatings are two-component products with the zinc dust packaged separately from the liquid component. Solvent-borne formulations are packaged either in 2 components with the zinc dust packaged separately or in 1 component. Zinc The common component in all zincrich coatings is a high level of metallic zinc dust in the formulation. SSPC-Paint 20 defines an inorganic zinc-rich coating as having the following minimum characteristics. Total solids, percent by weight of
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paint78 percent Pigment, percent by weight of total solids85 percent Total zinc dust, percent by weight of pigment87 percent Total zinc dust, percent by weight of total solids74 percent ASTM D 520, Specification for Zinc Dust Pigment 4 , covers 2 types (grades) of zinc pigment, with the requirements presented in Table 1. The critical properties are chemical composition and particle size. The interest in chemical composition relates to heavy metal contaminants and not to performance. Heavy metals, particularly lead and chromium, are hazardous materials and, therefore, have detailed OSHA standards on worker exposure. While the probability of exposure above the limits in these standards is extremely low during application of zinc-rich primers, the probability increases when maintenance painting activities such as power tool cleaning or abrasive blasting are performed. Sources of zinc used in making zinc dust include low lead scrap, special high grade zinc, and prime western zinc. Zinc dust is available in different grades, according to particle size, as shown in Table 2. The regular or standard grade has normally been
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used in most inorganic zinc-rich coatings, both water-borne and solvent-borne. The fine grades are used in preconstruction primers, which allow the product to be applied at low film thicknesses (i.e., less than 1 mil [25 micrometers]). High solids, solvent-borne inorganic zinc-rich primers are formulated with the coarse grade. The selection of particle size by the manufacturer is critical to achieving optimum application properties in many products, especially waterborne products. For example, a critical characteristic of the zinc dust that influences the rheology of the product is surface area. Environmental Regulations Water-borne inorganic zincs (Types I-A and I-B) have very low volatile organic compound (VOC) content. Most contain no VOC at all. Solventborne inorganic zincs (Type I-C) historically exceeded VOC limits, but now a number of high-solids formulations have been developed to meet the regulatory limits. While there is no national hazardous waste regulation for zinc, regulations currently exist in California and Michigan. The California test method used to determine hazardous waste classification is different than the test method of the U.S. Environmental Protection Agency (EPA). Thus, the debris created from removing a zinc-rich coating in California has a high probability of being classified as a hazardous waste. However, in Michigan, which uses the EPA test method, tests performed on debris show the probability is extremely low for exceeding the 500 ppm (0.5 g/L) leachable zinc level set as hazardous. Cure of the Coating The inorganic zinc-rich coatings are classified in SSPC-Paint 20 by their curing mechanism (Fig. 1). Post-Curing, Water-Borne (Type I-A) When applied, the coating dries quickly to a hard state. However, it will remain water-soluble until cured, usually by application of a curing solution. The curing solution converts the alkali metal silicates into a water-insoluble binder. After the coating cures, the water-soluble residues must be removed by water washing before a topcoat is applied. Coating thickness measurements can be made after the coating is applied and dry. Adjustments to areas of low film thickness can be made at this time. High thickness areas can be noted so that the thickness can be corrected, or multiple applications of the curing solution can be made. Self-Curing, Water-Borne (Type I-B) The most commonly held theory is that Type I-B binders cure by reaction with carbon dioxide in the air in the presence of zinc. The coatings remain sensitive to water contact until the water solvent has evaporated and sufficient curing has occurred. The curing is a gradual process through which the coating develops an increasing resistance over time, the rate depending upon temperature and relative humidity. Early exposure of the coating to water can result in a range of conditions, including washing off of the coating during the early stages of cure, partial removal of the coating during intermediate stages of cure, and softening of the coating during the later stages of cure. Self-Curing, Solvent-Borne (Type I-C) Type I-C binders are usually organicmodified silicates. They cure by reaction with moisture in the air. The reaction liberates the organic group attached to the silicate, leaving an inorganic binder. The formulation dries quickly after it is applied, but requires
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Water-Borne Post-Cure

Na O OH + H3PO4
+

Zn O Zn
+

OH + Phosphates

Na O Si O Si O OH OH

Pb

Na O Si O Si O OH O Pb

Na Silicate

Water-Borne Self-Cure

M O OH + CO2
+

Zn O Zn OH + Carbonates

M O Si O Si O OH OH

Na O Si O Si O OH O Zn

M = K or Li Silicate

Solvent-Borne Self-Cure

R O

R O + H2O + Zn
Acid or Base

Zn O

Si O + R.OH

R O Si O Si O O R O R

Na O Si O Si O O Si O Zn

R = C2H5 (Ethyl or Higher) Silicate

Fig. 1 - Curing mechanisms of inorganic zinc-rich coatings

moisture to cure. The rate of cure depends on the vehicle formulation, catalyst, temperature, and relative humidity. The rate will be slow at low temperatures and low humidities. The rate of cure can be demonstrated by monitoring the changes in various properties such as hardness, abrasion resistance, or solvent resistance. Solvent-borne inorganic zinc-rich coatings become water-resistant more quickly than water-borne formulations. Also, solvent-borne inorganic zinc-rich coatings have better resistance to early water contact or water disturbing the coating. Factors Affecting Film Formation Drying The chemical reactions of the selfcuring inorganic zincs (Types I-B and I-C) are influenced by both temperature and humidity. After applicaCopyright 1996, Technology Publishing Company

tion, the first step in forming the coating is either evaporation of the water with precipitation of the alkali silicate (Type I-B), or evaporation of the organic solvent concentrating the alkyl silicate (Type I-C). High humidity and low temperature extend the time for water-borne inorganic zinc-rich coatings to dry, whereas solvent-borne inorganic zinc-rich coatings are less sensitive to high humidity but have extended drying times at low temperatures. Inorganic zinc-rich coatings dry quite fast in comparison to most other types of chemically curing coatings. They dry to touch in a matter of minutes, while typical chemically curing organic coatings take hours. Curing After the coating has dried, the cure process begins in different ways for

the 3 classifications of coatings: by heat or by treatment with a curing solution (Type I-A), by reaction with moisture and carbon dioxide (Type I-B), or by reaction with moisture (Type I-C). The speed of cure depends on the coating formulation and environmental conditions. Topcoating Water-borne and solvent-borne inorganic zinc coatings have a minimum cure time before topcoating, which can be as little as 2 hours for some Type I-B coatings, but is typically 16 to 24 hours at normal temperatures and relative humidities. The minimum time to topcoat does not mean that the coating has fully cured, but that a topcoat can be applied without any disturbance of the zinc-rich film and achieve satisfactory film
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formation. Since actual curing to ultimate film properties takes considerably longer than 24 hours at normal conditions, the coating system (inorganic zinc plus topcoat) initially will be more sensitive to mechanical stress. Recently, a solvent resistance test called the methyl ethyl ketone (MEK) rub test has been suggested as a criterion to establish when to topcoat a solvent-borne inorganic zinc.5 Resistance to MEK, however, can range from the normal 16 to 24 hours, to weeks and months. The time to MEK resistance depends on the formulation of the product as well as environmental conditions during cure. The manufacturer should be consulted about the validity of the test method and the acceptable level of MEK resistance before its use with a particular product. Completion of curing of a topcoated solvent-borne inorganic zinc depends on the water absorption, moisture vapor transmission rate, and solvent retention properties of the topcoat. Since water is required for the conversion of the ethyl silicate to a totally inorganic silicate, topcoats having fast solvent release with high water absorption and transmission, such as epoxies, will not materially impede the cure of the primer, which will occur in a period of weeks. No matter what topcoat is used, environmental conditions of temperature and relative humidity will determine the rate and amount of water that reaches the ethyl silicate through the topcoat to continue the hydrolysis reaction. After the typical 16- to 24-hour time to topcoat at normal temperatures and relative humidity above 40 percent for solvent-borne inorganic zincs, the sensitivities of the coating system will vary. Most coating systems will be moderately to highly sensitive at this time to mechanical damage. Some topcoats, such as vinyl, water-borne acrylic, and vinyl acrylic, can initially be sensitive to peeling. Adhesion will gradually increase as solvent or water evaporates and the topcoat film becomes harder, which can take weeks. Where the coating system (primer and topcoat) is fully applied in the shop, careful handling of the pieces is required after coating and during shipment. It usually is not practical to have the steel remain at the fabrication shop until the topcoat loses sensitivity to mechanical damage. Failures of topcoats over inorganic zinc primers by peeling or cracking may be caused by several factors. One is the sensitivity to mechanical damage from inadequate cure. Another factor is dry spray of the primer. Inorganic zincs that have been dry sprayed will remain powdery and will never harden. Powdery overspray not removed from the properly applied film will prevent proper adhesion of the topcoat. In addition, excessive thickness of the topcoat can result in shrinkage stress sufficient to cause the topcoat to crack and separate from the primer. Protection Mechanism of Untopcoated IOZ6,7,8,9 Inorganic zinc coatings protect steel differently from typical organic coatings such as epoxy, alkyd, or vinyl. Organic coatings depend on a continuous, unbroken barrier to oxygen and water to prevent corrosion on a steel surface. Inorganic zinc coatings, on the other hand, utilize 2 mechanisms: cathodic protection and barrier protection. Inorganic zinc coatings are porous when first applied, and they depend on the cathodic protection mechanism of the metallic zinc pigment to prevent corrosion. Inorganic zinc coatings have a finite protective life, since the zinc
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metal in the pigment gradually is depleted. The rate of depletion depends on the exposure conditions and amount of exposed steel, the same as with sacrificial anode cathodic protection systems, but with 1 major differencethe coating must also function in atmospheric service on the surface of the steel. The mechanism of protection for inorganic zinc coatings occurs in 2 basic steps. Initially, galvanic protection occurs when metallic zinc sacrifices itself to protect the steel. Second, the reaction products from the galvanic protection gradually react with atmospheric gases, primarily CO2 and O2, to form waterinsoluble zinc corrosion products such as zinc carbonates. These corrosion products fill the pores in the inorganic zinc coating, creating a barrier to water and oxygen that is typical of many organic coatings. Should the zinc-rich coating be damaged enough to expose the steel substrate, the remaining unreacted metallic zinc again becomes active and protects by galvanic action until the barrier is re-established. This mechanism is most effective for untopcoated inorganic zinc-rich primers. In continuous water immersion, the untopcoated inorganic zinc coating also protects by galvanic action. The reaction products are water-soluble, however, and are more readily removed from the coating. Thus, the barrier properties developed in atmospheric service are not as likely to form. Therefore, continuous water immersion, especially in flowing or agitated water, may lead to a more rapid depletion of the metallic zinc and a shorter service life than in atmospheric service. Where this service life is satisfactory and there are benefits from other performance properties, such as abrasion resistance, the use of inorganic zinc coatings in continuous water immersion can be beneficial.
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Performance Testing Inorganic zinc coatings have been put to the test continuously since their introduction. Various test programs by private companies and by the Steel Structures Painting Council (SSPC), National Aeronautics and Space Administration (NASA), and National Shipbuilding Research Program (NSRP) have investigated the

performance of inorganic zinc coatings with and without topcoats.10,11 Uses of Inorganic Zinc-Riches During the last 50 years, there have been significant advances in inorganic zinc coating technology. This technology and product development has aimed to improve applicacontinued

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tion properties and to maintain corrosion protection. Inorganic zinc primers are most often applied as a single coat; but in some instances, 2 coats are applied to achieve higher dry film thickness (more metallic zinc on the steel). Many coating systems have an inorganic zinc coating as the primer and 1 or more topcoats. The topcoats are used to extend the life of the inorganic zinc coating by reducing the rate of zinc depletion through galvanic protection, or to protect the metallic zinc from chemical attack in acidic or alkaline environments. It is recommended that a topcoat be used in environments where the pH is less than 5 or greater than 9, due to the reactivity of the zinc. Typical practice in the use of inorganic zinc coating systems varies with the exposure environment and type of structure. One coat of untopcoated inorganic zinc is often used for tank lining, structural steel in neutral environments, and refinery facilities in marine atmospheres.12 Two coats of untopcoated inorganic zinc are used to line suppression chambers in nuclear power plants and, in some instances, ships tanks. Inorganic zinc with a single topcoat is used on structural steel for industrial plants, power generation facilities, pulp and paper mills, bridges, tank exteriors, and stacks or hot equipment operating up to 750 F (399 C). Multiple topcoats over inorganic zinc coatings are standard coating systems for marine offshore structures, ship hulls, and marine pilings. Most offshore platforms, drill structures, and buoys have a first coat of inorganic zinc. Industrial plants, refineries, tanks, bridges, and launch structures in marine environments also use inorganic zinc either as a single coat or with a topcoat. Temperature Resistance Inorganic zinc coatings are used up to temperatures of 750 F (399 C), just below the melting point of metallic zinc, 787 F (419 C). Above these temperatures, the properties of the coating begin to change, which ultimately can result in decreased service life. The amount of change depends on the temperature above 750 F (399 C) and the length of exposure time. A few hours at 1,000 F (538 C) will change the coating significantly. Inorganic zinc coatings should be used in dry or only periodically wet conditions when they are subject to continuous elevated temperatures. When exposed to regular temperature cycling, water condensation can occur during the low-temperature cycle. If evaporation does not occur before heating begins, inorganic zinc may undergo rapid depletion of the
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GENERIC COATING TYPES

metal, and the substrate may undergo early rusting. An example is a kiln and duct work that operates 5 days a week and shuts down over the weekend in a locale with regular overnight condensation. The service life of the inorganic zinc coating can be extended significantly by topcoating with a temperature-resistant coating, such as silicone, silicone acrylic, or polysiloxane, which is formulated for elevated temperatures. A similar condition can occur under insulation at temperatures cycling from ambient to above 140 F (54 C). Any salts extracted from the wet insulation will accelerate the zinc reaction. Acid or alkaline environments under the insulation also will accelerate the zinc reaction at ambient temperatures, as reported by Delahunt.13 Tank Linings Inorganic zinc coatings resist many chemicals and provide single-coat protection, typically with 3 to 5 mils (75 to 125 micrometers) dry film thickness, in storage, rail car, and ship tanks. NACE 6A176, Inorganic Zinc Coatings for Immersion (Tank Lining) Service, provides a listing of chemical resistances.14 Users should refer to the inorganic zinc coating manufacturers chemical resistance charts for specific recommendations about chemical compatibility. Some inorganic zinc coatings (zinc-silicon dioxide matrix coatings) comply with 21 CFR 175.390 for use with food products. (Part 175 of Title 21 of the Code of Federal Regulations concerns Indirect Food Additives: Adhesives and Components of Coatings.) In addition, both water-borne and solvent-borne inorganic zinc coatings are used for tank linings. A number of precautions need to be observed when using inorganic zinc coatings with certain chemicals. When high purity needs to be maintained in the chemical being carried
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or stored, the inorganic zinc lining needs to be completely cured and thoroughly washed before loading the chemical. High purity chemicals for which there is no experience need to be tested for potential trace contaminations from the coating. Topcoating the inorganic zinc with a chemically resistant topcoat can reduce trace contamination.

Water Immersion Inorganic zinc coatings generally have not been used in continuous water immersion without topcoating. In those instances where inorganic zinc coatings have provided satisfactory service in water immersion, there are contributing factors, as described below.
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Cyclic service in sea water or fresh water can extend service life because this service allows water-soluble zinc reaction products to convert to water-insoluble compounds. Uses include ships ballast tanks and steel dam faces exposed to winter ice and cyclic water levels. Tanks lined with inorganic zinc in alternate sea water ballast and clean petroleum cargo with 150 F (66 C) waterjet cleaning have shown 15 or more years of service. Inorganic zinc coatings on dedicated sea water ballast tanks have shown more than 10 years of service. Service life can be influenced by ballast cargo cycling time (i.e., percent of time immersed in water). Still water with or without corrosion inhibitors or inert atmospheres, such as suppression chambers in nuclear power plants, can provide conditions for satisfactory service. Laboratory tests in continuous water immersion show that time to first rust depends on water temperature, turbulence, water type, coating thickness, and inorganic zinc coating type. The following generalizations apply. Increasing water temperature reduces protection time. Flowing water reduces protection time. Higher coating thickness extends protection time. Typical time to first rust ranges between 1 and 2 years to more than 3 years at higher coating thickness in 100 F (38 C) still distilled water and longer than 5 years in still tap water at 70 F (21 C). Flowing or agitated water reduces the protection time by about half. Slip Resistance Inorganic zinc coatings have the characteristics of slip resistance needed for corrosion protection of the faying surfaces in structural connections. Testing of inorganic zinc coatings for slip resistance started in 1961 in the United States. Since 1985, the American Institute of Steel Construction has endorsed a specification adopted by the Research Council on Structural Connections of the Engineering Foundation. It is titled Specification for Structural Joints Using ASTM A 325 or A 490 Bolts, and it includes an appendix: Testing Method to Determine the Slip Coefficient for Coatings Used in Bolted Joints. This test includes a slip coefficient determination and a creep test at appropriate loading, with 3 classifications based on test performance. The test method and classification system have been accepted by the American Association of State Highway and Transportation Officials (AASHTO) for bridge construction. A number of inorganic zinc coatings have been qualified to meet the requirements of the standard.
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