CORROSION AND DEGRADATION

Chapter 17- 1

THE COST OF CORROSION

Corrosion:
--the destructive electrochemical attack of a material. --Al Capone's
ship, Sapona, off the coast of Bimini.
Photos courtesy L.M. Maestas, Sandia National Labs. Used with permission.

Cost:
--4 to 5% of the Gross National Product (GNP)* --this amounts to just over $400 billion/yr**

Chapter 17- 2

The Rusting Mechanism

4Fe + 6H2O + 3O2 4Fe(OH)3 gives ferric hydroxide 2Fe(OH)3 Fe2O3 3H2O gives iron oxide (rust) and water

(Peel)

Basic rusting or corrosion requirements 1. The metal is oxidized at the anode of an electrolytic cell 2. Some ions are reduced at the cathode 3. There is a potential or voltage difference between the anode and cathode 4. An electrolyte (fluid) must be present 5. The electrical path must be completed

Chapter 17- 2

Factors affecting Corrosion

Material properties Metallurgical factors Passivity Environment

(Peel)

Metallurgical factors Chemical segregation Presence of multiple phases Inclusions Cold Work Non-uniform stresses

Passivity Example with steel in nitric aciddilute solutions will cause rapid attack, strong solutions have little visible effect. Surface film can be formed Some types of steel may do this with rust Aluminum does this Need to watch passive film, but can be used for simple protection
Chapter 17- 2

GALVANIC SERIES
Ranks the reactivity of metals/alloys in seawater
Platinum Gold Graphite Titanium Silver 316 Stainless Steel Nickel (passive) Copper Nickel (active) Tin Lead 316 Stainless Steel Iron/Steel Aluminum Alloys Cadmium Zinc Magnesium

Based on Table 17.2, Callister 6e. (Source of Table 17.2 is M.G. Fontana, Corrosion Engineering, 3rd ed., McGrawHill Book Company, 1986.)

Chapter 17- 8

TYPES OF CORROSION
Stress corrosion
Stress & corrosion work together at crack tips.

Uniform Attack
Oxidation & reduction occur uniformly over surface.

Erosion-corrosion
Break down of passivating layer by erosion (pipe elbows).

Selective Leaching
Preferred corrosion of one element/constituent (e.g., Zn from brass (Cu-Zn)).

Pitting
Downward propagation of small pits & holes.
Fig. 17.8, Callister 6e. (Fig. 17.8 from M.G. Fontana, Corrosion Engineering, 3rd ed., McGraw-Hill Book Company, 1986.)

Intergranular
Corrosion along grain boundaries, often where special phases exist.

Galvanic
Dissimilar metals are physically joined. The more anodic one corrodes.(see Table 17.2) Zn & Mg very anodic.

Crevice Between two

pieces of the same metal.
Rivet holes

Fig. 17.9, Callister 6e.

Fig. 17.6, Callister 6e. (Fig. 17.6 is courtesy LaQue Center for Corrosion Technology, Inc.) Chapter 17- 9

Uniform attack
Uniform Attack Uniform attack is the most common form of corrosion. It is normally characterized by a chemical or electrochemical reaction which proceeds uniformly over the entire exposed surface or over a large area. The metal becomes thinner and eventually fails. For example, a piece of steel or zinc immersed in dilute sulfuric acid will normally dissolve at a uniform rate over its entire surface. A sheet iron roof will show essentially the same degree of rusting over its entire outside surface. Uniform attack, or general overall corrosion, represents the greatest destruction of metal on a tonnage basis. This form of corrosion, however, is not of too great concern from the technical standpoint, because the life of equipment can be accurately estimated on the basis of comparatively simple tests. Merely immersing specimens in the fluid involved is often sufficient. Uniform attack can be prevented or reduced by (1) proper materials, including coatings, (2) inhibitors, or (3) cathodic protection.

Chapter 17-

Uniform Attack

Chapter 17-

Stress Corrosion
Stress-corrosion cracking refers to cracking caused by the simultaneous presence of tensile stress and a specific corrosive medium. Many investigators have classified all cracking failures occurring in corrosive mediums as stress-corrosion cracking, including failures due to hydrogen embrittlement. However, these two types of cracking failures respond differently to environmental variables. To illustrate, cathodic protection is an effective method for preventing stress-corrosion cracking whereas it rapidly accelerates hydrogenembrittlement effects. Hence, the importance of considering stresscorrosion cracking and hydrogen embrittlement as separate phenomena is obvious. During stress-corrosion cracking, the metal or alloy is virtually unattacked over most of its surface, while fine cracks progress through it. This cracking phenomenon has serious consequences since it can occur at stresses within the range of typical design stress. Exposure to boiling MgCl2 at 310F (154C) is shown to reduce the strength capability to approximately that available at 1200F.

Chapter 17-

Stress Corrosion
The two classic cases of stress-corrosion cracking are "season cracking" of brass, and the "caustic embrittlement" of steel. Both of these obsolete terms describe the environmental conditions present which led to stress-corrosion cracking. Season cracking refers to the stress-corrosion cracking failure of brass cartridge cases. During periods of heavy rainfall, especially in the tropics, cracks were observed in the brass cartridge cases at the point where the case was crimped to the bullet. It was later found that the important environmental component in season cracking was ammonia resulting from the decomposition of organic matter. Many explosions of riveted boilers occurred in early steam-driven locomotives. Examination of these failures showed cracks or brittle failures at the rivet holes. These areas were cold-worked during riveting operations, and analysis of the whitish deposits found in these areas showed caustic, or sodium hydroxide, to be the major component. Hence, brittle fracture in the presence of caustic resulted in the term caustic embrittlement. While stress alone will react in ways well known in mechanical metallurgy (i.e., creep, fatigue, tensile failure) and corrosion alone will react to produce characteristic dissolution reactions; the simultaneous action of both sometimes produces the disastrous results.
Chapter 17-

Stress Corrosion

Chapter 17-

Erosion Corrosion
Erosion corrosion is the acceleration or increase in rate of deterioration or attack on a metal because of relative movement between a corrosive fluid and the metal surface. Generally, this movement is quite rapid, and mechanical wear effects or abrasion are involved. Metal is removed from the surface as dissolved ions, or it forms solid corrosion products which are mechanically swept from the metal surface. Sometimes, movement of the environment decreases corrosion, particularly when localized attack occurs under stagnant conditions, but this is not erosion corrosion because deterioration is not increased. Erosion corrosion is characterized in appearance by grooves, gullies, waves, rounded holes, and valleys and usually exhibits a directional pattern. In many cases, failures because of erosion corrosion occur in a relatively short time, and they are unexpected largely because evaluation corrosion tests were run under static conditions or because the erosion effects were not considered

Chapter 17-

Erosion Corrosion

Chapter 17-

Selective Leaching
Selective leaching is the removal of one element from a solid alloy by corrosion processes. The most common example is the selective removal of zinc in brass alloys (dezincification). Similar processes occur in other alloy systems in which aluminum; iron, cobalt, chromium, and other elements are removed. Selective leaching is the general term to describe these processes, and its use precludes the creation of terms such as dealuminumification, decobaltification, etc. Parting is a metallurgical term that is sometimes applied, but selective leaching is preferred.

Chapter 17-

Corrosion Fatigue
It may be described as the reduction of fatigue strength by the corrosive environment. This type of corrosion occurs by the simultaneous effect of environment and cyclic fluctuations of stress, leading to early failure of the component. The effect of corrosion on S-N Curve
Chapter 17-

The effect of corrosion on S-N Curve

Chapter 17-

Intergranular Corrosion
Grain boundary effects are of little or no consequence in most applications or uses of metals. If a metal corrodes, uniform attack results since grain boundaries are usually only slightly more reactive than the matrix. However, under certain conditions, grain interfaces are very reactive and intergranular corrosion results. Localized attack at and adjacent to grain boundaries, with relatively little corrosion of the grains, is intergranular corrosion. The alloy disintegrates (grains fall out) and/or loses its strength. Intergranular corrosion can be caused by impurities at the grain boundaries, enrichment of one of the alloying elements, or depletion of one of these elements in the grain-boundary areas. Small amounts of iron in aluminum, wherein the solubility of iron is low, have been shown to segregate in the grain boundaries and cause intergranular corrosion. It has been shown that based on surface tension considerations the zinc content of a brass is higher at the grain boundaries. Depletion of chromium in the grain-boundary regions results in intergranular corrosion of stainless steels.

Chapter 17-

Pitting
Pitting is a form of extremely localized attack that results in holes in the metal. These holes may be small or large in diameter, but in most cases they are relatively small. Pits are sometimes isolated or so close together that they look like a rough surface. Generally a pit may be described as a cavity or hole with the surface diameter about the same as or less than the depth. Pitting is one of the most destructive and insidious forms of corrosion. It causes equipment to fail because of perforation with only a small percent weight loss of the entire structure. It is often difficult to detect pits because of their small size and because the pits are often covered with corrosion products. In addition, it is difficult to measure quantitatively and compare the extent of pitting because of the varying depths and numbers of pits that may occur under identical conditions. Pitting is also difficult to predict by laboratory tests. Sometimes the pits require a long time-several months or a year-to show up in actual service. Pitting is particularly vicious because it is a localized and intense form of corrosion, and failures often occur with extreme suddenness
Chapter 17-

CONTROLLING CORROSION
Self-protecting metals!
--Metal ions combine with O2 to form a thin, adhering oxide layer that slows corrosion.
Reduce T (slows kinetics of oxidation and reduction) Add inhibitors --Slow oxidation/reduction reactions by removing reactants (e.g., remove O2 gas by reacting it w/an inhibitor). --Slow oxidation reaction by attaching species to the surface (e.g., paint it!). Cathodic (or sacrificial) protection --Attach a more anodic material to the one to be protected.

Adapted from Figs. 17.13(a), 17.14 Callister 6e. (Fig. 17.13(a) is from M.G. Fontana, Corrosion Engineering, 3rd ed., McGraw-Hill Book Co., 1986.)

Chapter 17- 10

SUMMARY
Corrosion occurs due to:
--the natural tendency of metals to give up electrons. --electrons are given up by an oxidation reaction. --these electrons then are part of a reduction reaction.

Metals with a more negative Standard Electrode Potential are more likely to corrode relative to other metals. The Galvanic Series ranks the reactivity of metals in seawater. Increasing T speeds up oxidation/reduction reactions. Corrosion may be controlled by:
-- using metals which form a protective oxide layer -- reducing T -- adding inhibitors -- painting --using cathodic protection.
Chapter 17- 11