PREVENTION FROM INTER-GRANUAL CORROSION

Sometimes Intergranular corrosion is also called intercrystalline corrosion or interdendritic corrosion. In the presence of tensile stress, cracking may occur along grain boundaries. This type of corrosion is frequently called interranular stress corrosion cracking (IGSCC) or intergranular corrosion cracking. In most cases of corrosion, the grain boundaries behave in essentially the same way as the grains themselves. The grain boundaries can undergo marked localized attack while the rest of the material remains unaffected. The alloy disintegrates and loses its mechanical properties. This type of corrosion is due either to the presence of impurities in the boundaries, or to local enrichment or depletion of one or more alloying elements. For example, small quantities of iron in aluminum or titanium (iron has a low solubility), segregate to the grain boundaries where they can induce intergranular corrosion. Certain precipitate phases (Mg5Al8, Mg2Si, MgZn2, MnAl6, etc.) are also known to cause or enhance intergranular attack of high strength aluminum alloys, particularly in chloride-rich media. The exfoliation corrosion phenomenon observed in rolled aluminum alloys is usually, but not always, intergranular in nature. In this case, the corrosion products occupy a larger volume than the metal "consumed", generating a high pressure on the slivers of uncorroded metal, leading to the formation of blisters. Numerous alloy types can undergo intergranular attack, but the most important practical example is the intergranular corrosion of austenitic stainless steels, related to chromium depletion in the vicinity of the boundaries, due to the intergranular precipitation of chromium carbides (Cr23C6), during a "sensitizing" heat treatment or thermal cycle.

Exfoliation corrosion morphology inside a water pipeline Intergranular or intercrystalline means between grains or crystals. As the name suggests, this is a form of corrosive attack that progresses preferentially along interdendritic paths (the grain bourdaries). Positive identification of this type of corrosion usually requires microstructure examination under a microscopy although sometimes it is visually recognizable as in the case of weld decay.

The photos show the microstructure of a type 304 stainless steel. The figure on the left is the normalized microstructure and the one on the right is the "sensitized" structure and is susceptible to intergranular corrosion or intergranular stress corrosion cracking. This type of attack results from local differences in composition, such as coring commonly encountered in alloy castings. Grain boundary precipitation, notably chromium carbides in stainless steels, is a well recognized and accepted mechanism of intergranular corrosion. The precipitation of chromium carbides consumed the alloying element - chromium from a narrow band along the grain boundary and this makes the zone anodic to the unaffected grains. The chromium depleted zone becomes the preferential path for corrosion attack or crack propagation if under tensile stress. Intergranular Corrosion occurs when a grain boundary area is preferentially attacked because of the presence of precipitates in these regions.

Grain boundaries are preferred sites for Segregation Precipitation. Two types of segregates and precipitates Intermetallics (intermediate constitutes): Formed from metal atoms having identifiable chemical formulae. Can either be anodic or cathodic to the metal? Compounds: Formed between metals and the non-metallic elements, H, C, Si, N and O.Fe23C6 and MnS in steel are cathodic to ferrite. Any metal in which intermetallics or compounds are present at grain boundaries will be susceptible to intergranular stress corrosion cracking. Austenitic stainless steels are most susceptible to intergranular corrosion. 18-8 or type 304 stainless steel: Fe, 18%Cr, 8%Ni; When C% < 0.03%, only the austenite phase is stable. When C% > 0.03% austenite and ferrite mixed carbide (FeCr)23C6 are stable. The proportions of carbide obtained are dependent upon the rate of cooling Fast cooling by water/oil quenching from > 1000oC suppresses carbide formation. If the material is reheated within the range 600-850oC, carbide precipitation will occur at the grain boundaries. The material is thus said to be sensitized and is in a dangerous condition - susceptible to Intergranular corrosion cracking If the material is reheated below 600oC, the rate of diffusion of Cr is too slow for carbide precipitation to occur. 12%Cr + Fe === "stainless" steels precipitation of carbide (FeCr) 23C6 causes Cr depletion (Cr<12%) in the metal adjacent to the precipitates. The steel is no longer "stainless". Cr depleted zone is very anodic to the rest of the grains. Severe attack occurs adjacent to the grain boundary. Whole grains may become detached from the material Sensitization may occur during manufacturing welding operating If Cr carbide nuclei pre-exist in grain boundary regions, sensitization can occur at temperatures in the range 300320oC.Weld decay === Sensitization caused by welding.

Prevention
Use low carbon (e.g. 304L, 316L) grade of stainless steels. Lower the C content to below 0.03%, so that the carbides are not stable. Use stabilized grades alloyed with titanium (for example type 321) or niobium (for example type 347). Titanium and niobium are strong carbide- formers. They react with the carbon to form the corresponding carbides thereby preventing chromium depletion. Use high temperature solution heat treatment to dissolve the precipitates. (Post welds heat treatment of sensitized steel). Most likely cause of failure was intergranular cracking initiated by a network of grain boundary precipitates.

CONTROL FOR AUSTENITIC STAINLISS STEELS:

Three methods are used to control or minimize intergranualar corrosion of the austenitic stainless steels: Employing high temperature solution heat treatment, commonly termed quench-annealing or solution quenching. adding elements that are strong carbide formers( called stabilizers), and Lowering the carbon content to below 0.03%. Commercial solution-quenching treatments consist of heating to 1950 to 2050 F followed by water-quenching. Chromium carbide is dissolved at these temperatures, and a more homogeneous alloy is obtained. Most of the austenitic stainless steels are supplied in this condition. If welding is used during fabrication, the equipment must be quench-annealed to eliminate susceptibility to weld decay. This poses an expensive problem for large equipment and, in fact, furnaces are not available for heat-treating very large vessels. In addition, welding is sometimes necessary in the customers plant to make repairs or, for example, to attach a nozzle to a vessel.

Quenching or rapid cooling from the solution temperature is very important. If cooling is slow, the entire structure would be susceptible to intergranual corrosion. The strong carbide formers or stabilizing elements, columbium (or columbium plus tantalum) and titanium, are used to produce types 347 & 321 stainless steels, respectively. These elements have a much grater affinity for carbon than does chromium and are added in sufficient quantity to combine with all of the carbon in steel. The stabilized steels eliminate the economic and other objections of solution- quenching the unstabilized steels after fabrication or weld repair. Lowering the carbon to below 0.03% (type 304L) does not permit sufficient carbide to form to cause intrgranualar attack in most applications. One producer calls these the extra- lowcarbon (ELC) steels. The situation is same as above except that here weld decay is absent in the low carbon plate. The vertical trenches are due to a weld bead deposited on the back surface of the specimen. The original 18-8 steels contained around 0.20% carbon, but this was quickly reduced to 0.08% because of rapid and serious weld-decay failures. Lowering the carbon content much below 0.08% was not possible until it was discovered that it was possible to below oxygen through the melt to burn out carbon and until low-carbon ferrochrome was developed. These stainless steels have a high solubility for carbon when in the molten state and therefore have a tremendous propensity for picking up carbon. For example, the intent of the lowcarbon grades is obviated when the welder carefully cleans the beveled plate with an oily or greasy rag before welding! A few isolated carbides that may appear in type 304L are not destructive for many applications in which a continuous network of carbides would be catastrophic. In fact, the susceptibility to intergranualar corrosion of the austenitic stainless steels can be reduced by severely cold working the alloy. Cold-working produces smaller grains and many slip lines, which provide a much larger surface for carbide precipitation. This is not, however a recommended or practical procedure.

SENSITIZATION
Sensitization of metals involves the creation of galvanic corrosion cells within the microstructure of an alloy. Certain alloys when exposed to a temperature characterized as a sensitizing temperature become particularly susceptible to intergranular corrosion. In a corrosive atmosphere, the grain interfaces of these sensitized alloys become very reactive and intergranular corrosion results. This is characterized by a localized attack at an adjacent to grain boundaries with relatively little corrosion of the grains themselves. The alloy disintegrates (grains fall out) and/or loses its strength. Intergranular corrosion is generally considered to be caused by the segregation of impurities at the grain boundaries or by enrichment or depletion of one of the alloying elements in the grain boundary areas. Thus in certain aluminium alloys, small amounts of iron have been shown to segregate in the grain boundaries and cause intergranular corrosion. Also, it has been shown that the zinc content of a brass is higher at the grain boundaries and subject to such corrosion. High-strength aluminium alloys such as the Duralumin-type alloys (Al-Cu) which depend upon precipitated phases for strengthening are susceptible to intergranular corrosion following sensitization at temperatures of about 120C. Nickelrich alloys such as Inconel 600 and Incoloy 800 show similar susceptibility. Die-cast zinc alloys containing aluminum exhibit intergranular corrosion by steam in a marine atmosphere. CrMn and Cr-Mn-Ni steels are also susceptible to intergranular corrosion following sensitization in the temperature range of 400-850C. In the case of the austenitic stainless steels, when these steels are sensitized by being heated in the temperature range of about 500 to 800C, depletion of chromium in the grain boundary region occurs, resulting in susceptibility to intergranular corrosion. Such sensitization of austenitic stainless steels can readily occur because of temperature service requirements, as in steam generators, or as a result of subsequent welding of the formed structure. Several methods have been used to control or minimize the intergranular corrosion of susceptible alloys, particularly of the austenitic stainless steels. Thus a high-temperature

solution heat treatment, commonly termed solutionannealing, quench-annealing or solution-quenching, has been used. The alloy is heated to a temperature of about 1,060 to 1,120C and then water quenched. This method is generally unsuitable for treating large assemblies, and also ineffective where welding is subsequently used for making repairs or for attaching other structures. Another control technique for preventing intergranular corrosion involves incorporating strong carbide formers or stabilizing elements such asniobium or titanium in the stainless steels. Such elements have a much greater affinity for carbon than does chromium; carbide formation with these elements reduces the carbon available in the alloy for formation of chromium carbides. Such a stabilized titaniumbearing austenitic chromium-nickel-copper stainless steel is shown in U.S. Pat. No. 3,562,781. Or the stainless steel may initially be reduced in carbon content below 0.03 percent so that insufficient carbon is provided for carbide formation. These techniques are expensive and only partially effective since sensitization may occur with time. The low-carbon steels also frequently exhibit lower strengths at high temperatures.