Stainless steels stress-corrosion cracking

Stainless steel alloys show exceUent corrosion resistance to HCl gas up to a temperature of 400°C. However, these are normally not recommended for process equipment owing to stress corrosion cracking during periods of cooling and shut down. The corrosion rate of Monel is similar to that of mild steel. Pure (99.6%) nickel and high nickel alloys such as Inconel 600 can be used for operation at temperatures up to 525°C where the corrosion rate is reported to be about 0.08 cm/yr (see Nickel and nickel alloys). 

Duplex stainless steels (ca 4% nickel, 23% chrome) have been identified as having potential appHcation to nitric acid service (75). Because they have a lower nickel and higher chromium content than typical austenitic steels, they provide the ductabdity of austenitic SS and the stress—corrosion cracking resistance of ferritic SS. The higher strength and corrosion resistance of duplex steel offer potential cost advantages as a material of constmction for absorption columns (see CORROSION AND CORROSION CONTROL). 

Many instances of intergranular stress corrosion cracking (IGSCC) of stainless steel and nickel-based alloys have occurred in the reactor water systems of BWRs. IGSCC, first observed in the recirculation piping systems (21) and later in reactor vessel internal components, has been observed primarily in the weld heat-affected zone of Type 304 stainless steel. 

Materials of Construction. GeneraHy, carbon steel is satisfactory as a material of construction when handling propylene, chlorine, HCl, and chlorinated hydrocarbons at low temperatures (below 100°C) in the absence of water. Nickel-based aHoys are chiefly used in the reaction area where resistance to chlorine and HCl at elevated temperatures is required (39). Elastomer-lined equipment, usuaHy PTFE or Kynar, is typicaHy used when water and HCl or chlorine are present together, such as adsorption of HCl in water, since corrosion of most metals is excessive. Stainless steels are to be avoided in locations exposed to inorganic chlorides, as stainless steels can be subject to chloride stress-corrosion cracking. Contact with aluminum should be avoided under aH circumstances because of potential undesirable reactivity problems. 

Sulfide inclusions have been identified as the origins of pits and stress-corrosion cracks in stainless steel stmctures under some conditions (see... 

Virtuallv evety alloy system has its specific environment conditions which will prodiice stress-corrosion cracking, and the time of exposure required to produce failure will vary from minutes to years. Typical examples include cracking of cold-formed brass in ammonia environments, cracking of austenitic stainless steels in the presence of chlorides, cracking of Monel in hydrofluosihcic acid, and caustic embrittlement cracking of steel in caustic solutions. 

These alloys have extensive applications in sulfuric acid systems. Because of their increased nickefand molybdenum contents they are more tolerant of chloride-ion contamination than standard stainless steels. The nickel content decreases the risk of stress-corrosion cracking molybdenum improves resistance to crevice corrosion and pitting. 

Coupon tests involved a number of metallurgies and were done to evaluate precipitator-plate alloys. Test stainless steel plates failed, not only because of pitting but also because stress-corrosion cracks developed. 

Microstructural examinations revealed that the cracks originated on the external surface (Fig. 9.15). The cracks were highly branched and transgranular. The branched, transgranular character of these cracks is typical of stress-corrosion cracking of austenitic stainless steels. The thick-walled fracture faces are also typical of cracking by this mode. 

Remedial measures include reduction or elimination of chlorides or replacement of the 304 stainless steel with a metal that is resistant to chloride stress-corrosion cracking. 

Other examples of metallurgy decisions are red brass versus admiralty tubes with fresh water on the tubeside and suspected stress corrosion cracking conditions on the shellside, and stainless steel versus carbon steel with chlorides present. A good metallurgist should be brought in when these kinds of decisions are needed. 

Austenitic stainless steels (the 300 series) are particularly su-sceptible to stress-corrosion cracking. Frequently, chlorides in the process stream are the cause of this type of attack. Remove the chlorides and you will probably eliminate stress-corrosion cracking where it has been a problem. 

Straight chromium ferritic stainless steels are less sensitive to stress corrosion cracking than austenitic steels (18 Cr-8 Ni) but are noted for poor resistance to acidic condensates. 

Acetic 31 6 L stainless steel Excess acetic anhydride in glacial acetic acid can accelerate corrosion chloride impurities (ppm levels) can cause pitting and stress-corrosion cracking... 

Eliminate unfavorable environments. The presence of oxygen and other oxidizers is a critical factor in stress corrosion cracking. For example, the cracking of austenitic stainless steel in chloride solutions can be reduced or completely eliminated if oxygen is removed. 

The corrosive environments which cause SCC in any material are fairly specific, and the more common combinations are listed in Table 53.2. In the case of chloride stress corrosion cracking of the 530 series austenitic stainless steels it is generally considered that the risk is... 

Boiler salts can contain chloride ions. When carried over into the steam (e.g. during priming) this can result in chloride stress corrosion cracking of austenitic stainless steel expansion bellows. In steam systems where freedom from chloride cannot be guaranteed, bellows... 

Steel is the most common constructional material, and is used wherever corrosion rates are acceptable and product contamination by iron pick-up is not important. For processes at low or high pH, where iron pick-up must be avoided or where corrosive species such as dissolved gases are present, stainless steels are often employed. Stainless steels suffer various forms of corrosion, as described in Section 53.5.2. As the corrosivity of the environment increases, the more alloyed grades of stainless steel can be selected. At temperatures in excess of 60°C, in the presence of chloride ions, stress corrosion cracking presents the most serious threat to austenitic stainless steels. Duplex stainless steels, ferritic stainless steels and nickel alloys are very resistant to this form of attack. For more corrosive environments, titanium and ultimately nickel-molybdenum alloys are used. 

The shape of a vessel determines how well it drains (Figure 53.7). If the outlet is not at the very lowest point process liquid may be left inside. This will concentrate by evaporation unless cleaned out, and it will probably become more corrosive. This also applies to horizontal pipe runs and steam or cooling coils attached to vessels. Steam heating coils that do not drain adequately collect condensate. This is very often contaminated by chloride ions, which are soon concentrated to high enough levels (10-100 ppm) to pose serious pitting and stress corrosion cracking risks for 300-series austenitic stainless steel vessels and steam coils. 

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