Fundamentals of Corrosion and Corrosion Control

Corrosion can be defined as the degradation of a material due to a reaction with its environment. Degradation implies deterioration of physical properties of the material. This can be a weakening of the material due to a loss of crosssectional area, it can be the shattering of a metal due to hydrogen embrittlement, or it can be the cracking of a polymer due to sunlight exposure. Materials can be metals, polymers (plastics, rubbers, etc.), ceramics (concrete, brick, etc.) or composites-mechanical mixtures of two or more materials with different properties. Because metals are the most used type of structural materials most of this web site will be devoted to the corrosion of metals. Most corrosion of metals is electrochemical in nature. Click here for a brief introduction to electrochemistry.

Forms of Corrosion
The forms of corrosion described here use the terminology in use at NASA-KSC. There are other equally valid methods of classifying corrosion, and no universally-accepted terminology is in use. Keep in mind that a given situation may lead to several forms of corrosion on the same piece of material.

Uniform Corrosion
This is also called general corrosion. The surface effect produced by most direct chemical attacks (e.g., as by an acid) is a uniform etching of the metal. On a polished surface, this type of corrosion is first seen as a general dulling of the surface and, if allowed to continue, the surface becomes rough and possibly frosted in appearance. The discoloration or general dulling of metal created by its exposure to elevated temperatures is not to be considered as uniform etch corrosion. The use of chemical-resistant protective coatings or more resistant materials will control these problems.

While this is the most common form of corrosion, it is generally of little engineering significance, because structures will normally become unsightly and attract maintenance long before they become structurally affected. The facilities shown in the picuture below show how this corrosion can progress if control measures are not taken.

Galvanic Corrosion
Galvanic corrosion is an electrochemical action of two dissimilar metals in the presence of an electrolyte and an electron conductive path. It occurs when dissimilar metals are in contact. It is recognizable by the presence of a buildup of corrosion at the joint between the dissimilar metals. For example, when aluminum alloys or magnesium alloys are in contact with steel (carbon steel or stainless steel), galvanic corrosion can occur and accelerate the corrosion of the aluminum or magnesium. This can be seen on the photo above where the aluminum helicopter blade has corroded near where it was in contact with a steel counterbalance.

Anodic (most active) The natural differences in metal potentials produce galvanic differences, such as the galvanic series in sea water. If electrical contact is made between any two of these materials in the presence of an electrolyte, current must flow between them. The farther apart the metals are in the galvanic series, the greater the galvanic corrosion effect or rate will be. Metals or alloys at the upper end are noble while those at the lower end are active. The more active metal is the anode or the one that will corrode. Control of galvanic corrosion is achieved by using metals closer to each other in the galvanic series or by electrically isolating metals from each other. Cathodic protection can also be used to control galvanic corrosion effects.

Concentration Cell Corrosion

Concentration cell corrosion occurs when two or more areas of a metal surface are in contact with different concentrations of the same solution. There are three general types of concentration cell corrosion: 1.metal ion concentration cells 2.oxygen concentration cells, and 3.active-passive cells. Metal Ion Concentration Cells In the presence of water, a high concentration of metal ions will exist under faying surfaces and a low concentration of metal ions will exist adjacent to the crevice created by the faying surfaces. An electrical potential will exist between the two points. The area of the metal in contact with the low concentration of metal ions will be cathodic and will be protected, and the area of metal in contact with the high metal ion concentration will be anodic and corroded. This condition can be eliminated by sealing the faying surfaces in a manner to exclude moisture. Proper protective coating application with inorganic zinc primers is also effective in reducing faying surface corrosion.

Pitting Corrosion
Passive metals, such as stainless steel, resist corrosive media and can perform well over long periods of time. However, if corrosion does occur, it forms at random in pits. Pitting is most likely to occur in the presence of chloride ions, combined with such depolarizers as oxygen or oxidizing salts. Methods that can be used to control pitting include maintaining clean surfaces, application of a protective coating, and use of inhibitors or cathodic protection for immersion service. Molybdenum additions to stainless steel (e.g. in 316 stainless) are intended to reduce pitting corrosion.

The rust bubbles or tubercules on the cast iron above indicate that pitting is occurring. Researchers have found that the environment inside the rust bubbles is almost always higher in chlorides and lower in pH (more acidic) than the overall external environment. This leads to concentrated attack inside the pits. Similar changes in environment occur inside crevices, stress corrosion cracks, and corrosion fatigue cracks. All of these forms of corrosion are sometimes included in the term "occluded cell corrosion." Pitting corrosion can lead to unexpected catastrophic system failure. The split tubing above left was caused by pitting corrosion of stainless steel. A typical pit on this tubing is shown above right. Sometimes pitting corrosion can be quite small on the surface and very large below the surface. The figure below left shows this effect, which is common on stainless steels and other film-protected metals. The pitting shown below right (white arrow) led to the stress corrosion fracture shown by the black arrows.

Crevice Corrosion
Crevice or contact corrosion is the corrosion produced at the region of contact of metals with metals or metals with nonmetals. It may occur at washers, under barnacles, at sand grains, under applied protective films, and at pockets formed by threaded joints. Whether or not stainless steels are free of pit nuclei, they are always susceptible to this kind of corrosion because a nucleus is not necessary. Cleanliness, the proper use of sealants, and protective coatings are effective means of controlling this problem. Molybdenum-containing

grades of stainless steel (e.g. 316 and 316L) have increased crevice corrosion resistance.

Filiform Corrosion
This type of corrosion occurs under painted or plated surfaces when moisture permeates the coating. Lacquers and "quick-dry" paints are most susceptible to the problem. Their use should be avoided unless absence of an adverse effect has been proven by field experience. Where a coating is required, it should exhibit low water vapor transmission characteristics and excellent adhesion. Zinc-rich coatings should also be considered for coating carbon steel because of their cathodic protection quality.

Exfoliation Corrosion

Exfoliation is a form of intergranular corrosion. It manifests itself by lifting up the surface grains of a metal by the force of expanding corrosion products occurring at the grain boundaries just below the surface. It is visible evidence of intergranular corrosion and most often seen on extruded sections where grain thickness is less than in rolled forms. This form of corrosion is common on aluminum, and it may occur on carbon steel.

Stress Corrosion Cracking

Stress corrosion cracking (SCC) is caused by the simultaneous effects of tensile stress and a specific corrosive environment. Stresses may be due to applied loads, residual stresses from the manufacturing process, or a combination of both.

Fretting Corrosion
The rapid corrosion that occurs at the interface between contacting, highly loaded metal surfaces when subjected to slight vibratory motions is known as fretting corrosion.

This type of corrosion is most common in bearing surfaces in machinery, such as connecting rods, splined shafts, and bearing supports, and often causes a fatigue failure. It can occur in structural members such as trusses where highly loaded bolts are used and some relative motion occurs between the bolted members.

Microbial Corrosion
Microbial corrosion (also called microbiologically-influenced corrosion or MIC) is corrosion that is caused by the presence and activities of microbes. This corrosion can take many forms and can be controlled by biocides or by conventional corrosion control methods. There are a number of mechanisms associated with this form of corrosion, and detailed explanations are available at the web sites listed at the bottom of this section. Most MIC takes the form of pits that form underneath colonies of living organic matter and mineral and biodeposits. This biofilm creates a protective environment where conditions can become quite corrosive and corrosion is accelerated.

Design

Engineering design is a complicated process that includes design for purpose, manufacturability, inspection, and maintenance. One of the considerations often overlooked in designing manufactured products is drainage. The corrosion of the automobile side panel above could have been minimized by providing drainage to allow any water and debris to fall off of the car instead of collecting and causing corrosion from the far side of the panel.

Protective Coatings
Protective coatings are the most commonly used method of corrosion control. They are the subject of several sections of this web site. Protective coatings can be metallic, such as the galvanized steel shown below, or they can be applied as a liquid "paint." Most of the research and testing of protective coatings at the Kennedy Space Center is related to paint-like protective coatings.

Inhibitors and Other Means of Environmental Alteration

Corrosion inhibitors are chemicals that are added to controlled environments to reduce the corrosivity of these environments. Examples of corrosion inhibitors include the chemicals added to automobile antifreezes to make them less corrosive. Most of the Kennedy Space Center's corrosion inhibitor research involves the effectiveness of inhibitors added to protective coatings.

Cathodic Protection
Cathodic protection is an electrical means of corrosion control. Cathodic protection can be applied using sacrificial (galvanic) anodes or by means of more complicated impressed current systems.