Nickel alloys, 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). 

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. 

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. 

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. 

Flange face areas experience stagnant conditions. Additionally, some gasket materials, such as asbestos fiber, contain leachable chloride ions. This creates crevice and stress corrosion cracking problems on sealing surfaces. Where necessary, flange faces that are at risk can be overlaid with nickel-based alloys. Alternatively, compressed asbestos fiber gaskets shrouded in PTFE may be used. 

Nickel-chromium alloys can be used in place of austenitic stainless steels where additional corrosion resistance is required. These alloys are still austenitic but are highly resistant to chloride-induced stress corrosion cracking when their nickel content exceeds 40 per cent. 

In tests lasting for 14 days, Copson found that the susceptibility of steel to stress-corrosion cracking in hot caustic soda solutions increased with increase in nickel content up to at least 8-5%. Alloys containing 28% and more of nickel did not fail in this period. In boiling 42% magnesium chloride the 9% nickel-iron alloy was the most susceptible of those tested to cracking (Table 3.38). Alloys containing 28 and 42% nickel did not fail within 7 days. 

Table 3.38 Resistance of iron-nickel alloys to stress corrosion cracking in boiling 421 0...

The corrosion rate of nickel in sodium hydroxide is adversely affected by heat transfer by small amounts of oxidisable alkaline sulphur-containing salts, e.g. Na2SOj, NajS Oj, Na S and, at high temperatures, by alkaline oxidising agents, viz. NaClOj and NajOj. In the former circumstance Alloy 600 is more resistant than nickel, but not in the latter. When Alloy 600 is used for service in caustic alkalis, it should be stress relieved after fabrication to minimise the possibility of stress-corrosion cracking. 

As with alloys of other metals, nickel alloys may suffer stress-corrosion cracking in certain corrosive environments, although the number of alloy environment combinations in which nickel alloys have been reported to undergo cracking is relatively small. In addition, intergranular attack due to grain boundary precipitates may be intensified by tensile stress in the metal in certain environments and develop into cracking. Table 4.28 lists the major circumstances in which stress corrosion or stress-assisted corrosion of nickel and its alloys have been recorded in service and also shows the preventive and remedial measures that have been adopted, usually with success, in each case. 

With regard to stress-corrosion cracking in the Ni-Cr-Fe system, including both nickel-base alloys and stainless steels, a vast number of papers has been published. A detailed review of work published before 1969 is available and the authors have since published additional data . 

The fracture mode of stress-corrosion cracks in austenitic stainless steels can be transgranular, intergranular or a mixture of both. One of the earliest environments found to cause problems was solutions containing chlorides or other halides and the data due to Copson (Fig. 8.30) is very informative. The test solution for that data was magnesium chloride at 154°C the alloys contained 18-20alloy with a composition of approximately 18Cr-8Ni has the least resistance to cracking in this environment. 

For aggressive conditions it may be advantageous to use one of the many high-nickel alloys available. The high cost of such alloys may be economically beneficial although some of the alloys are subject to stress-corrosion cracking, but in a more restricted range of environments than the lower nickel alloys that they would replace. 

Alloys of high nickel content also have improved chloride stress-corrosion cracking resistance and Incolloy 825 has replaced type 321 stainless steel for steam bellows on some plants. Occasionally cracking of the latter was experienced due to chloride-contaminated steam condensing in the convolutions on shut-down and being re-evaporated at start-up. 

Low-carbon and chromium-nickel steels, certain copper, nickel and aluminium alloys (which are all widely used in marine and offshore engineering) are liable to exhibit stress-corrosion cracking whilst in service in specific environments, where combinations of perhaps relatively modest stress levels in material exposed to environments which are wet, damp or humid, and in the presence of certain gases or ions such as oxygen, chlorides, nitrates, hydroxides, chromates, nitrates, sulphides, sulphates, etc. 

Replacing some of the nickel with iron produces a family of alltws with intermediate corrosion resistance between stainless steels and the Ni-Cr-Mo alloys. Alloys such as Incoloy 825 and Hastelloy G-3 and G-30 are in this family. Incoloy 825 has 40 percent Ni, 21 percent Cr, 3 percent Mo, and 2.25 percent Cu. Hastelloy G-3 contains 44 percent Ni, 22 percent Cr, 6.5 percent Mo, and 0.05 percent C maximum. These alloys have extensive applications in sulfuric acid systems. Because of their increased nickel and molybdenum contents they are more tolerant of chloride-ion contamination than are standard stainless steels. The nickel content decreases the risk of stress-corrosion cracking molybdenum improves resistance to crevice corrosion and pitting. Many of the nickel-based alloys are proprietary and are coverecf by the following specifications ... 

Monel, the classic nickel-copper alloy with the metals in the ratio 2 1, is probably, after the stainless steels, the most commonly used alloy for chemical plant. It is easily worked and has good mechanical properties up to 500°C. It is more expensive than stainless steel but is not susceptible to stress-corrosion cracking in chloride solutions. Monel has good resistance to dilute mineral acids and can be used in reducing conditions, where the stainless steels would be unsuitable. It may be used for equipment handling, alkalies, organic acids and salts, and sea water. 

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