BRC-CORP 37.74.F = Section 29. INTERGRANULAR CORROSION % inition of thy Jom Intergranular corrosion is localized attack at and adjacent to grain boundaries of metals and alloys with relatively little corrosion of the bulk grains. The attacked areas of an alloy virtually disintegrate. It is also called intercrystalline corrosion, intergranular attack (IGA), weld decay, “sugaring", knife-line attack and sensitization. Intergranular corrosion can be caused by impurities at the grain boundaries of the alloy, enrichment of one of the alloying elements, or depletion of one of these elements in the grain boundary areas. Most corrosion resistant alloys are subject to intergranular sorrocion in come corrosive, expecially if che alloy has received adverse thermal treatment (as in welding). Discussion of the Praklem When austenitic stainless steels are heated in the temperature range of approximately 510-788°C (950-1450°F), they become sensitized, or in other words, susceptible to intergranular corrosion in some environments. In this temperature range, chromium carbide (and carbon) is virtually insoluble and precipitates out of solid solution (preferentially at the grain boundaries) Af ule carbon content of the alloy 18 about 0.02% or higher. The chromium is thereby removed from solid solution, and the result is metal with lowered chromium content in the area adjacent to the grain boundaries. This chromium depleted sone (conoiticed region) doce uot wuutain sufficient corrosion resistance to resist attack in many corrosive environments, particularly acids, ‘The severity of sensitization depends upon several factors, including the amount of carbon in the alloy, the temperature to which the alloy is exposed during fabrication and the length of time the alloy is held at the sensitizing temperature (Figure 29-1). For example, a thick (about 0.250 inch) austenitic stainless steel with 0.08% carbon content may sensitize severely during welding whereas a thin tube of exactly the same alloy may not cenodeize ofguificautly during welding. rnis 1s due to the fact that the thick section holds more heat than the thin section, so the length of time in the sensitizing temperature range is longer. The degree of sensitization does reach a maximum, under severe conditions, when all the available carbon near the alloy grain boundaries is precipitated as chromium carbides. Thereafter, if the temperature Temains high (in the sensitizing temperature region or above), it 1s possible to homogenize the alloy structure, thereby reducing the effects of sensitization. In practice, this state is seldom acheived and not very Practical to obtain, but chis procedure could represent one method of controlling intergranular corrosion, if other methods were not applicable. Tn practice, the conoitdeation of alloys iv intergranular attack results from one or more of these situations: e e e e e e e e e e e e e e e of e e e e e e e e e e e e e e e (2) Welding, which causes local merat temperatures to ge through the sensitizing range.182 BRC-CORP 37-74. (2) Stress relieving an assenbly in the sensitization temperature range. (2) Glow cooling fivu au aumealing, casting, oF rorging temperature through the sensitization temperature range. Welding is probably the most common cause of intergranular corrosion. Base metal on both sides of the weld is heated into the sensitizing range for a time, causing the precipitation of chromium carbides. "Weld decay” is sometimes used to describe intergranular corrosion of a band of metal adjacent to the weld. Examples of this type of intergranular corrosion are shown in Figures 29-2 and 29-3. Nnife-line actack (KLA) 1s also intergranular corrosion similar to weld decay in that they both are associated with welding, but the major differences are: (1) KLA occurs in a narrow band in the parent metal immediately Jdjacent to the weld, whercao weld decay develope over a wide: baud aud ut a appreciable distance from the weld, (2) KLA only occurs in stabilized stain- less steels, and (3) the thermal history of the metal is different. An example of this corrosion is shown in Figure 29-4..The caure of KLA is due to very localized and somewhat complex interaction of high temperatures and microstructural changes, In general, KLA may occur in mlti-pass welded structures or structures that have been welded and then stress-relieved. A list of corrosives that have induced intergranular attack of sensitized stainless steels is presented in Table 29-1. Concentration and feuperature have a wacked effect upon initiation and severity of attack. Thus, the presence of these corrosives under certain conditions, such as low concentrations and temperatures, does not necessarily mean that intergranular corrosion will occur. Further, the omfesion of other corrosives does not preclude the possibility that they would lead to intergranular corrosion of sensitized stainless steels. There is some evidence to indicate that resistance to other forms of corrosion besides intergranular attack also deteriorates when the alloy is sensitized. Pitting, crevice corrosion, and stress corrosion cracking have #12 been shown co be more prevalent on sensitized stainless steels. Numerous other alleys, ouch as ferritic aud duplesmstruccure stainless steels, aluminun-, nickel-, copper- and titanium-base alloys have shown susceptibility to intergranular corrosion under certain conditions. Again, adverse thermal history and the precipitation of intermetallic phases in these alloys give rise to intergranular corrosion. A list of alloys in which intergranular attack has been observed, together with corrosives which induce this attack, is presented in Table 29-2. It should be noted that this table is not complete, and concentration and temperature of the corrosive have a marked effect on IGA. Many of the corrosives listed caused inter- granular stress corrosion cracking (and are so marked) and may not necessarily attack non-ctreased alleye, Mowever, if cle curcusives are present, inter~ granular attack should be considered. eo Pocccccccsccceccedseee 7 Beso coooococcococoocess BRC.CORP 37-74.F 153 Vienal examination of wolde that have been im service will reveal « localized band of material adjacent to the weld with a corroded appearance. Under severe conditions the corrosion has been described as “sugaring" because the grains of metal are loose and easily dislodged with the finger by rubbing over the corroded region, ‘The special case of knife-line attack is harder to spot, but will be in the form of a very narrow line of corrosion immediately adjacent to the weld of a stabilized stainless steel, such as types 321 or 347. IE @ general type of corrosion du @ pisce vf equipment is suspected of being intergranular corrosion, specimens should be taken for metallographic examination, This procedure will usually confirm whether or not the wrought alloy is sensitized, and therefore eubject to intergranular corrooien; prict to its being placed in service. There are also a number of laboratory and field corrosion tests that can be conducted to determine an alloy's susceptibility to intergranular corrosion. : Methods of Eliminating the Problem Intergranular corrosion 18 commonly avoided by one of these method: (1) Applying a solution-annealing heat treatment after fabrication 2) Uelltetag low carbon alley gradee, ox (3) Utilizing stabilized alloy grades. There are other factors, however, which influence intergranular corrosion and that have led to reporting other prevention methods. They include homogenizing anneal (mentioned previously) cold working, and grain size control. These each have problems in practice and would only be used under unusual circumstances. Solution-annealing involves heating the fabricated equipment to an appropriate annealing temperature (depending upon the alloy) to dissolve the chromiua carbides, end then repidly cuvliug through che sensitizing temperature range. This procedure avoids sensitization by not allowing time for the chromium carbides to reprecipitate after annealing. Utilization of low carbon (<0.03%C) grades of austenitic stainles: steels (e.g. 304L or 316L) simply removes the source of the problem by eli- minating most of the free carbon that would form chromium carbides. Utilization of stabilized grades euch as Type 321 (titanium added) or Type 347 (columbium added ) is another common approach to avoiding inter— granular corrosion. Quite simply, the added elements are stronger carbide formers than chromium, so chromiun carbides do not have a chance to form.BRC-CORP 37-74.F Selecting low carbon or stabilized grades of stainless steel is the favored method of avoiding inrargranular correcien. olution enncaling ie used if low carbon or stabilized grades are not available, or if maintenance welding takes place on a piece of equipment generally not intended for welding. ‘There are pros and cons for using either the low carbon grade or the stabilized grades. As mentioned earlier, the stabilized grades can be Susceptible to kaife-line attack , but they are generally stronger and tougher than low carbon grades. On the other hand, the low carbon grades generally have better weldability and are less prone to sigma phase formation (see Section 35). Usually though, the selection will be most heavily influenced by the prevailing price and availability of the different grades. Pitfall Any welding or heat treatment (with slow cooling) of austenitic stainless steel equipment will result in sensitization unless the alloy used was a low carbon or stabilized grade. Re-welding or multipass welding of Stabilized grades can result in thin areas sensitized to knife-line attack. Solution annealing of austenitic stainless steel equipment to Prevent intergranular corrosion often is not practical due to warpage and loss of tolerances. If austenitic etainlece eteel equipment for chemical se:vice comes from the manufacturer in a solution-annealed condition, and no welding is intended before or after exposure in service, then the more expensive low carbon or stabilized grades would not be required for resistance to intergranulai corrosion, Additionally, if welded equipment will not be exposed to chemicals giving rise to intergranular corrosion, then it would not be necessary to use low carbon or stabilized grad Under some conditions even the low carbon and stabilized grades of austenitic stainless steels can be sensitized, and therefore be susceptible to intergranular corrosion. Multi-pass welding of Types 321 oF 347 can Fesult in areas (thin lines) sensitized to knife-line attack in certain chemicals. Extremely oxidizing corrosives and severe heat treatments can result in intergranular corrosion of the law carhan grade: For alloys other than austenitic stainless steels, care should be taken to discover what temperature ranges cause susceptibility to intergranular verrovion, and what temperature ranges and heat treatments elisinate the Problem. For instance, the sensitization and solution-annealing tenperature for ferritic stainless steels are just the reverse of those for austenitic etainlecs etecio. e e e e e e e e e e e e e e eBRC-CORP 37-74.F 165 0.03% Carbon Sensitization Time at 648.9°C (1200°F), minutes 0.086% Carbon ° 3 5 10 20 Sensitization Time at 648.0°C (1200°F), minutes Figure 20-1 Effect of Carbon Content and Exposure Time to Sensitizing Temperature fon Intergranular Attack of Type 304 Stainless Stee! Magnification: 1.7X. Conditions: Specimens heated for various time periods as listed. Exposed for 16 hours to a solution of 0.5 M hydrofluoric acid and 0.5 M cupric sulfate (an extremely aggresive intergranular corrosive). After exposure, the specimens were bent, which opened cracks186 BRC-CORP 37-74-F 2 Figure 29-2 Semple Muctating the Elimination nf Intargranilar Creracinn (Wald Oacey) by the Use of Low Carbon Grades (ELC now referred to simply as L) of Stainless Steet Note the corrosion on the bortam Type 304 etrinlnes steel base metal adjacent to the weld. Magnification: 1X, e Figure 20-3 Sample IMlustrating the Elimination of Intergrenuler Corrosion (Weld Decay) by the Use of Stabilized Stainlos: Steels Note the corrosion of the unstablized base metal to the right of the weld, grifiestion: 1X,BRC-CORP 37-74.F 187 ©0000 ECOOOOHOHOCOEOCOD Figure 294 Knife-Line Attack of Type 347 Stainless Steet ‘Note that the severity of knifeline attack has resulted in separation of the weld from the base metal Magnification: XX. eS COCCCOCOOCOE °°158 BRCCORP 37-74. Table 2941 Corrosives Which Can Induce Intergranular Corrosion in Austenitic Stainiess Steet Acetic Actd Acetic Acid + Salicylic Acid Anmonium Chloride Amnontun Nitrate Ammonium Fluoride Ammonium Sulfate Ammonium Sulfate + H2S0y Beet Juice Carbon Dioxide + Carbon Monoxide + Hydrogen Caletu Hicrate Chloride Salts Chromic Acid Chromium Chloride Citric Acid Copper Sulfate Grude 012 (rractionacing cower) Fatty Acids Ferric Chloride Ferric Sulfate Formic Acid Hydrocyanic Acid Hyarocyanie Acid + Suitur Dioxide Hydrofluoric Acid Hydrofluoric Acid + Ferrie Sulfate Lactic Acid Lactic Acid + Nitric Acid Maleic Acid Nitric Acid Nitric Actd + Hydrochloric Acid Oxalic Acid Phenol + Naphthenic Acid Ynospnoric Acid Phehalic Acid Polythionic Acid Potassium Hydroxide Silver Nitrate + Acetic Acid podium Bisultate Sodium Chloride (including salt spray, sea water) Sodium Hydroxide Sodium Hydroxide + Sodium Sulfide Sodium Hypochlorite Sulfite Cooking Liquor Sulfite solution Sulfite Digester Acid (Calcium Bisulfite + Sulfur Dioxide) Sulfamic Acid Sulfur Dioxide (wet) Sulfuric Acid Sulfuric Acid + Acetic Acid Sulfuric Acid + Copper Sulfate Sulfuric Acid + Ferrous Sulfate Sulfuric Acid + Methanol Sulfuric Acid + Nitric Acid Sulfuraua Aqta Water + Starch + Sulfuric Dioxide Water + Aluminum Sulfate o e Ld e e e e e e e e e e e e e e e e eo e e ¥. COCCOCOOHCOSOOOCEBRCCORP 37-74. 159 Table 29.2 Corrosives Which Have Caused Intergranular Attack of Various Alloys ce (oterganular Corrosion 8 a al rms pst ‘Ammonia, Pure ° =t one te me a } Oriorides aaa me woes aes ee ase a Ree —— Pa na Lead & High Pressure Water tncoet 600] “Teo old Mosresom Brovre Nicht ‘Aviom ‘Moret wae Coorer Hf rie acid en Tae Aad, ‘lus Manganese Chloride ream = [Organi Cries, lus Water Fotassam Myaronse Potassium Permanganate = “Sut Water, plus Oxypen Sodium Hyioxde = ‘Seon Butte Compound Uranyt Suttae Zine, Moan . 1 ncergranulr Sire Corrosion Cracking Reporte 1 loerganuae Corrosion Reported 2) High Temperature (Greater than 318°C (600°F)) 1} Molten Sat