GalvInfoNote

6
Introduction

How Zinc Protects Steel

Rev 2.1 Aug-03

Steel sheet is a very versatile product. It comes in many sizes and types, and serves many purposes ranging from its use for steel buildings, automotive panels, signs, appliances, etc. The low cost, strength and formability of steel result in its widespread use in todays world. Unfortunately, steel sheet is prone to rusting, a phenomenon that causes the surface to become unsightly and, over time, may contribute to product failure. For this reason, steel has been protected by a variety of methods ranging from internal alloying (stainless steel, for example), to coating with paints or metallic coatings.

Fundamentally, corrosion is an electrochemical process that, in the case of steel sheet, oxidizes the iron in the steel and causes it to become thinner over time. Oxidation, or rusting, occurs by a chemical reaction between steel and oxygen. Oxygen is always present in the air or it can be dissolved into moisture on the surface of the steel sheet. During the rusting process, the steel actually dissolves during the corrosion reaction converting iron to corrosion products. In the case of most low-carbon steel sheet products, the iron oxide or rust that develops on the surface is not protective because it does not form as a continuous, adherent film. Instead, it spalls off the surface, exposing fresh iron to the atmosphere which, in turn, allows more corrosion to occur. This aspect of steel sheet behaviour is very undesirable, both aesthetically and from a performance basis. Eventually, often sooner than desired, the steel sheet is corroded sufficiently to cause degradation in the performance, i.e., loss of structural strength, perforation and intrusion of water, etc. Fortunately, today there are many coatings that can be applied to steel in a very cost-effective manner to confer sufficient corrosion protection to steel so that it can be used for a multitude of applications

Painted Steel
One well-developed coating for steel is paint. Numerous types of paint have been developed through the years that offer excellent performance on steel sheet. Paints are barrier coatings that, when applied and used properly, give sufficient corrosion protection to steel for many common applications. However, paints are not impervious to moisture, and over time, rust can occur underneath even a perfectly applied paint if the exposure to moisture is sufficiently long, or if the moisture contains corrosive chemicals. Also, exposed areas on the steel, such as sheared edges and scratches in the paint, are susceptible to the same rusting mechanisms as uncoated steel, and further rusting in these areas can cause degradation of the paint adhesion. For example, the iron oxide that forms at a scratch lifts the paint film immediately adjacent to the scratch. This allows further corrosion of the steel and eventual loss of paint adhesion. Some paints are better than others, but eventually, if there is sufficient moisture present, and especially if the moisture contains highly corrosive chemicals, unacceptable levels of rusting will occur. Even if the amount of rust does not adversely impact the strength of the steel, it does lead to an unsightly appearance.

Metallic Coatings
Metallic coatings can protect steel in two ways: 1. like paint, they provide barrier protection, and 2. in many instances, they provide galvanic protection.

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Each of these types of protection is described below. Barrier Protection The main mechanism by which galvanized coatings protect steel is by providing an impervious barrier that does not allow moisture to contact the steel - without moisture (the electrolyte) there is no corrosion. The nature of the galvanizing process ensures that the metallic zinc coating has excellent coating adhesion, abrasion, and corrosion resistance. Galvanized coatings will not degrade over time as with other barrier coatings such as paint. However, zinc is a reactive material and will corrode and erode slowly. For this reason, the protection offered by galvanized coatings is proportional to the coating thickness. The ability of a zinc coating to protect steel by acting as a barrier depends on zinc's corrosion rate. It is therefore important to understand zinc's corrosion mechanism and what factors affect its corrosion rate. Freshly exposed galvanized steel reacts with the surrounding atmosphere to form a series of zinc corrosion products. In air, newly exposed zinc reacts with oxygen to form a very thin zinc oxide layer. When moisture is present, zinc reacts with water, resulting in the formation of zinc hydroxide. The final corrosion product is zinc carbonate, which forms from zinc hydroxide reacting with carbon dioxide in the air. Zinc carbonate is a thin, tenacious, and stable (insoluble in water) layer that provides protection to the underlying zinc, and results in its low corrosion rate in most environments. Refer to GalvInfoNote #7 for more information on the films that form on zinc. Why does an aluminum coating on steel provide good barrier protection? Similar to steel and zinc, the thin aluminum coating reacts in the air to form an oxide film on the surface. However, contrary to the behaviour of oxides on steel, and similar to what happens with zinc, the aluminum oxide film that forms on the surface of aluminum does not spall off, but remains as an intact, very tightly adhering film on top of the aluminum coating. This intact film prevents exposure of fresh aluminum to the air and moisture; thus, continuing corrosion of the underlying aluminum is prevented. The coating remains as a stable non-corroding film. Galvanic Protection The second shielding mechanism is zinc's ability to galvanically protect steel. When base steel is exposed, such as at a cut edge or scratch, the steel is cathodically protected by the sacrificial corrosion of the zinc coating. This occurs because zinc is more electronegative (more reactive) than steel in the galvanic series, as shown below.

Galvanic Series of Metals and Alloys

Corroded End - Anodic (Electronegative) Magnesium Zinc Aluminum Cadmium Iron or Steel Stainless Steels (active) Lead Tin Copper Gold (Electropositive) Protected End - Cathodic or most noble Note: Any one of these metals and alloys will theoretically corrode while protecting any other that is lower in the series as long as both form part of an electrical circuit.
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In practice, this means that a zinc coating will not be undercut by rusting steel because the steel cannot corrode adjacent to the zinc coating. Any exposure of the underlying steel, because of severe coating damage or at a cut edge, will not result in corrosion of the steel and has minimal effect on the overall performance of the coating. The distance over which the galvanic protection of zinc is effective depends on the environment. When completely and continuously wetted, especially by a strong electrolyte, for example seawater, relatively large areas of exposed steel will be protected as long as any zinc remains. In air, where the electrolyte is only superficial or discontinuously present (such as from dew or rain), smaller areas of bare steel are protected. The throwing power is nominally about 0.125 in (3.2 mm), although this can vary significantly with the type of atmosphere. If the coating is consumed, why use it? In the case of a zinc coating, the rate of corrosion that it undergoes while protecting steel is considerably lower than that of the steel. In this way, a thin coating of zinc can be applied to steel to protect the steel for a long time. For example, in a rural atmosphere where the number and concentration of pollutants in the air is generally quite low, zinc might corrode at a rate of 1.0 m/year (0.04 mil/year) while low-carbon steel in this same environment might corrode at a rate 5 times as high (5 m/year or 0.2 mil/year) or even higher. A primary reason for the reduced rate of zinc corrosion versus the rate for steel is that, as it corrodes, it forms an adherent, protective oxide/carbonate film on its surface similar to the oxide film on the surface of aluminum. This film itself helps to prevent contact between the environment and fresh zinc. Thus, the rate of corrosion decreases. Recall that steel typically does not form a protective film in that the oxide layer spalls; thereby, constantly exposing fresh iron to the environment. The film that forms on the surface of zinc is not as protective as the aluminum oxide film on the surface of metallic aluminum. That is, the oxide is susceptible to dissolution if the moisture is sufficiently acidic, for example. This is good and bad. It is good in that, if the oxide film were totally protective, the zinc would no longer offer galvanic protection to the steel at exposed areas. Thus, rusting of steel would occur at scratches and other exposed areas. The downside of the somewhat incompleteness of protection of the oxide film on a galvanized sheet is that the coating, itself, corrodes and thus, has a defined life.

Other Galvanically Protective Coatings

Among the commercially available metallic-coated steel sheet products, zinc (galvanize) offers the most galvanic protection. Galfan behaves somewhat similarly with respect to the level of galvanic protection that it provides. Galvalume steel sheet offers somewhat reduced galvanic protection versus a galvanized or Galfan coating. What does this mean about the relative performance of these products? As with most things in life, everything comes with a price. Galvanically protective coatings are consumed by corrosion eventually. That is why a galvanized sheet has a definite life span; time before corrosion of the steel begins. Thus, the amount of zinc applied to the steel during manufacture, described as the coating weight (mass), is important to the life of the product. Coating weight (mass) is expressed as G60 (Z180), G90 (Z275), G200 (Z600) etc. per ASTM Specification A 653/A 653M. G60 (Z180) means that the coating weight (mass) is 0.60 oz/ft2 (180 g/m2), minimum (total coating on both sides of the sheet). This coating weight (mass) can be translated into thickness; a G60 (Z180) coating of zinc is about 0.00055 in. (0.014 mm) per side of the sheet. For a galvanized coating, the rate of corrosion of the coating is typically linear in most environments. That is, twice the coating thickness translates to twice the life. Of course, different environments are more or less corrosive than other sites, so that the life of the coating varies considerably for different environment types. This behaviour is shown in the following figure.

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Industrial atmosphere Marine atmosphere Thickness or mass loss Rural atmosphere

Increasing time of exposure

These three types of atmospheres all exhibit different rates of corrosion, but the behaviour is linear. For example, a G90 (Z275) coating will exhibit a longer life in a rural atmosphere than in a polluted industrial atmosphere, but still the rate is linear in both environments. Twice the coating thickness or coating mass will give twice the life of the coating. Now, consider the life of a Galvalume coating, a product that clearly exhibits less galvanic protection than a galvanized coating at least after some time of exposure. The Galvalume coating, being less galvanic in nature, is less reactive, and as a result, the life of a Galvalume coating is typically considerably longer than for a comparably thick galvanized coating. This behaviour of Galvalume is the reason why it is being used so successfully for bare roofing applications. Of course, there are applications where the highly galvanic nature of zinc is desired. Also, there are other considerations that need to be considered in selecting the product of choice for a specific application.

Life of a Galvanized Coating in Different Environments

We have established that a galvanized coating protects steel: 1. by two mechanisms barrier protection and galvanic protection, 2. by a linear rate of corrosion for any specific environment type, and 3. for a considerably different life-of-the-coating depending on the specific details of the environment What is the life of the product in specific applications? The answer to this question is very lengthy. There are textbooks written on this subject. Two excellent references are: Corrosion Resistance of Zinc and Zinc Alloys, by Frank C. Porter, published Marcel Decker, Inc., 1994 Corrosion and Electrochemistry of Zinc, by Xiaoge Gregory Zhang, published by Plenum Press, 1996

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The following table contains a small amount of the data in the book compiled by Frank Porter.

Location/Environment Type State College, PA/rural South Bend, In/semi-rural Middletown, OH/semi-industrial Kearny, NJ/Industrial-urban Kure Beach, NC/marine Daytona Beach, FL/marine Montreal, Quebec/industrial-marine Esquimalt, BC/rural-marine Sheffield, Great Britain/industrial

Corrosion Rate, m/year for 5 years 1.0 1.9 1.3 4.5 1.1 1.8 3.5 0.5 5.1

These data are for exposure in the atmosphere. There are many other applications for galvanized sheet in which the corrosion rate might be different. These might include: contact with water, buried in soil, contact with concrete, sheltered areas on buildings such as under eaves, ductwork inside buildings, etc. For each of these and other applications, the corrosion performance depends on many of the specific details about the application. For example, when exposed in contact with concrete, how often does the concrete/galvanized sheet interface get wet? When buried in soil, what is the pH of the soil and the soil permeability, the oxygen content, etc? When used for ductwork, does the product experience condensation periodically or on a regular basis? Are there pollutants in the condensate? Many of these types of questions are answered in the referenced textbooks. The graph on the next page further illustrates the effect of environment on the service life of galvanize. Marine climates, whether tropical or temperate, are very aggressive. Note that Halifax is more aggressive than close to the beach in both North Carolina and Florida. This is most likely due to the high times of wetness in Halifax, which results in the salt environment being even more corrosive. Locations inland can be seen to have three to five times the life of those close to the ocean. Note the very low corrosion rate in Arizona. This is a result of the arid climate. The lack of moisture does not allow corrosion cells to form.

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Atmospheric Corrosion Rates for Zinc

Source: ASM Metals Handbook 9th Ed - Vol 13
Phoenix AZ Ottawa ON Cape Kennedy-1 FL State College PA Detroit MI Point Reyes CA Kure Beach-1 NC Dungenes UK Newark NJ Cape Kennedy-2 FL Kure Beach-2 NC Halifax NS 0.000 0.050 0.100 0.150 Mils/Year 0.200 0.250 0.300 G90 = 0.8 mils each surface Kure Beach-2 = 30 yards from ocean Kure Beach-1 = 275 yards from ocean Cape Kennedy-2 = 60 yards from ocean Cape Kenndy-1 = 0.5 mile from ocean

Zinc Loss

Summary
Hopefully, this discussion helps to elucidate some of the issues associated with the effect of coatings on the corrosion behaviour of coated-steel sheet products. This field of technology has many aspects that cannot be explained in a brief article such as this. If you have additional questions on this very extensive subject, please contact the GalvInfo Center.

Copyright 2003 ILZRO

Disclaimer: Articles, research reports, and technical data are provided for information purposes only. Although the publishers endeavor to provide accurate, timely information, the International Lead Zinc Research Organization does not warrant the research results or information reported in this communication and disclaims all liability for damages arising from reliance on the research results or other information contained in this communication, including, but not limited to, incidental or consequential damages.

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