Volume 13 - Corrosion Part 16 pps

The most common fiberglass-reinforced plastic curing system uses methyl ethyl ketone-peroxide (MEKP) with a cobalt- containing promoter an obvious source of cobalt ions. The resin manufacturers provide mixed recommendations regarding alternative curing systems, some indicating that increased fabrication difficulty more than offsets the benefit of eliminating the cobalt. The quality of fabrication is a most important factor in successful applications of fiberglass- reinforced plastic and should not be compromised. Most resin suppliers recommend synthetic veils. Synthetic materials should certainly be used for strongly alkaline solutions. Postcuring is also recommended and provides a more resistant fabrication. Full curing of all secondary joints is most important. Finally, thixotropic agents should not be added to resin systems, especially when used in surfaces exposed to hypochlorite. Glass-flake reinforced spray linings are also used in hypochlorite services. The problems encountered indicate that these applications should be limited to low-temperature services or applied where the environment is not overly aggressive to the substrate. Elastomeric lining is common in a wide variety of hypochlorite applications a result of typically low temperatures. Probably the most frequently used lining material is chlorobutyl, because of its good resistance coupled with moderate cost. Other sheet lining materials with good resistance include EPDM and chlorosulfonated polyethylene. Natural rubber also finds some useful low-temperature applications. Other elastomeric applications might use the fluoroelastomers, which are good in any hypochlorite service, or neoprene, which has limited range. Glass is unaffected by hypochlorite within a moderate range of alkalinity and temperature. Glass-tubed heat exchangers have been used to cool soda bleach during manufacture. Vitrified clay pipe and other ceramic materials show excellent resistance to hypochlorite. Under certain conditions, concrete is resistant and has been used for manufacturing and storage tanks. Calcium Hypochlorite Although produced as a solid, the reactions of Ca(OCl) 2 in solution are very similar to those of NaOCl. In general, the recommended temperature levels for Ca(OCl) 2 are slightly higher, probably owing to the higher decomposition temperature. Like NaOCl, the calcium product is unstable at lower pH, but it can be concentrated to a higher degree. The corrosion rates for some metals are shown in Table 49. Table 49 Corrosion of metals and alloys in Ca(OCl) 2 204-day test in 18-20% Ca(OCl) 2 at 20-24 °C (70-75 °F) Corrosion rate Material mm/yr mils/yr Pitting Titanium nil none Zirconium 0.025 1 (a) none Hastelloy C <0.0025 <0.1 none Chlorimet 3 0.025 1 none (a) Severe attack under spacer Plastics and elastomerics can usually be used in Ca(OCl) 2 to slightly higher concentrations and temperatures than in NaOCl. Virtually the same applications are served by these materials in both products. The solid Ca(OCl) 2 product is typically packed in polyethylene or polyethylene-lined containers. Epoxy-phenolic lining performs effectively for trucks and railcars. It is critical to keep the product dry and away from organic fluids. Aluminum is sometimes used in handling solid Ca(OCl) 2 because any corrosion residue does not discolor the product. Corrosion by Ammonia A.S. Krisher, ASK Associates Anhydrous ammonia, a major commercial chemical, is used in the manufacture of fertilizers, HNO 3 , acrylonitrile, and other products. Except for a sensitivity to SCC, carbon steel is fully acceptable in NH 3 service. Stress-corrosion cracking of carbon steel NH 3 storage vessels was first observed in the early 1950s. In most cases, the developing cracks have been detected by inspection before leakage or rupture. However, there have been a few catastrophic failures. For example, in France in 1968, a tanker ruptured, killing 5 people. A second case was in South Africa, where a large tank failed in 1973 with 22 fatalities. Ammonia is stored under three conditions. It can be stored by cooling it to a low enough temperature, (-34 °C, or -29 °F) to maintain it in the liquid state at atmospheric pressure. This method is frequently described as cryogenic storage. A second approach is to contain the ammonia under sufficient pressure (about 2070 kPa, or 300 psig) to maintain the ammonia in the liquid phase at ambient temperature. Cylindrical pressure vessels are often used for fairly small quantities. Spherical pressure vessels are used for larger quantities. The third condition involves some degree of refrigeration combined with pressurization. This is termed semirefrigerated storage. Most cases of SCC have occurred in ambient-temperature pressurized storage vessels, for the most part in spheres. A few problems have been observed in semirefrigrated storage. There have been no documented cases of SCC in cryogenic storage vessels. When SCC does occur, cracks are primary transgranular and progress at a relatively slow rate compared to other SCC phenomena. Laboratory Studies One investigation using statically loaded tuning fork type specimens and tensile bars showed that NH 3 SCC is accelerated by cold work, welding, applied stresses, and the use of higher-strength steels. It was found that air contamination promotes SCC and that water in amounts greater than 0.1% inhibits cracking (Ref 217). Other experiments using slow strain rate tests and a low-alloy steel also found that air contamination promoted SCC and that water at a level greater than 0.09% was an effective inhibitor. Electrochemical studies showed that the SCC involves an anodic chemical process (Ref 218, 219). Field tests were conducted using specimens stressed by residual stresses from welding (Ref 220). Results indicated that high-strength steels fail more rapidly than low-carbon steel and that hard welds (welds that are harder than the base material) tend to accelerate cracking. Thermal stress relieving was also found to be effective in preventing SCC. Another investigation using low-alloy steels and slow strain rate test methods produced SCC at temperatures as low as 0 °C (32 °F). Again, air contamination and low water content promoted SCC (Ref 221). Results of an industry-sponsored technical investigation that used both slow strain rate tests and fracture mechanics type specimens are documented in Ref 222. It was found that oxygen levels greater than 5 ppm are required for SCC. Levels as low as 1 ppm caused cracking if carbon dioxide was also present and water was absent. This work also suggested that hydrazine (NH 2 ·NH 2 ), ammonium carbonate [(NH 4 ) 2 CO 3 ], and ammonium bicarbonate (NH 4 HCO 3 ) might be inhibitors. The fracture mechanics test methods were not successful, possibly because of the slow rate of cracking. Other tests using low-alloy steel and the slow strain rate test confirmed again that oxygen as a contaminant is damaging, with indications that levels as low a 0.01 ppm might be sufficient to cause the cracking, at least in low-alloy steel (Fig. 85). Nitrogen also appeared to be a cracking accelerator in combination with oxygen. The lower limit of the required water content to inhibit cracking was found to be about 0.08 wt% (Fig. 86). This work showed NH 2 ·NH 2 to be an effective inhibitor at 0.025 wt% for a contamination level of 200 ppm O 2 . Fig. 85 Effect of oxygen content on apparent ductility observed in slow strain rate tests of low- alloy steel in liquid NH 3 . Source: Ref 223 Fig. 86 Effect of water content on apparent ductility observed in slow strain rate tests of low- alloy steel in liquid NH 3 . Oxygen content was 200 ppm, added as air. Source: Ref 223 This body of laboratory work (seven studies over a period of 19 years by six different investigators using three different methods in four different countries) is impressive in its consistency. All of the studies showed that the primary causes of the cracking are high stresses and air contamination. Nitrogen and carbon dioxide were suggested by separate investigators as promoting SCC. Cracking is accelerated by the use of high-strength steels, the presence of hard welds, and air contamination. The cracking mechanism can be inhibited by water above about 0.1%. Thermal stress relief, if done properly, reduces stress below the critical level. Field Experiences Some reports suggest that water is not always an effective inhibitor, especially when water is added after SCC is detected. The significance of these reports is clouded by a lack of evidence that adequate control systems were used to ensure that a sufficient level of water was maintained. The research studies discussed previously do not address the effectiveness of water addition in slowing the growth of pre-existing cracks. There is also a problem area with the vapor phase of NH 3 tanks. Water is considerably less volatile than NH 3 , resulting in a lower water content in the vapor phase than in the liquid. If NH 3 vapor condenses on the wall of the vessel, the water content will probably be inadequate for inhibition, and SCC in the vapor phase is possible. There are also reports of recracking of vessels that cracked, were repaired, and then were stress relieved. It is extremely difficult to repair vessels that have suffered SCC. There are many cracks in the equipment, including some of submicroscopic, size. It is extremely difficult to prevent these cracks from propagating later. Stress relief of a vessel that has suffered SCC is also very likely to be unsuccessful. The very small cracks are contaminated to some degree. When this metal is subjected to the stress-relief thermal cycle, such phenomena a nitriding and carburizing may occur and promote further cracking. Practical Operating Guidance It is apparent that SCC of carbon and low-alloy steel NH 3 storage vessels can be a problem if proper procedures in design, fabrication, operation, inspection, and maintenance are neglected. If the degree of such neglect is large enough, catastrophic failure is possible. However, it is also apparent that application of proper procedures will ensure satisfactory long-term storage. Reference 224 discusses such practices. General recommendations for design, fabrication, operation, and inspection and maintenance practices are presented below. Design and Fabrication. Normal design methods used for vessels to contain hazardous fluids should be followed, including all requirements of governing codes and agencies. Design should also be reviewed using fracture mechanics concepts to assess the risk of brittle fracture. Fabrication should be carefully inspected by a properly qualified engineering representing the end user. A low-strength (specified tensile strength not exceeding 483 MPa, or 70 ksi) grade of carbon steel should be used. The hardness of welds should be specified to be 255 HB maximum, and the weld hardness should be checked in the field. Postweld heat treatment (stress relief) at 595 °C (1100 °F) minimum should be specified for all pressure vessels. The lower temperature/longer time alternatives for such treatment allowed in some codes are less effective in reducing residual stress levels. Operating practices should minimize air contamination. Water content should be maintained at 0.2% minimum if water is not objectionable to the user of the NH 3 . Water (and, if feasible, oxygen) content should be checked by routine sampling and analysis. Inspection and Maintenance. All tanks in NH 3 storage service should be carefully inspected on a routine basis. A new tank should be carefully inspected by the wet fluorescent magnetic-particle method after 1 to 2 years service. If no cracks are found, a somewhat longer inspection interval may be appropriate. If cracks are found, their severity should be assessed and appropriate actions taken. These actions may involve simply recording location and size of cracks, grinding out the cracked areas, or grinding out and rewelding the cracked areas. Figure 87 shows guidelines regarding modifications of inspection frequency as a function of oxygen and water content. Fig. 87 Guidelines for changes in inspection freque ncy when oxygen or water content is outside preferred range. Source: Ref 224 Any existing tank that has not been so inspected and has been in service longer than 2 years should be inspected at the first opportunity. Stress relief after repairs is not recommended. As noted previously, it is unlikely to be beneficial and may be harmful. References 1. W.D. 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Lead for Corrosion Resistant Applications, Lead Industries Association, 1974 [...]... 0.3Cu-0.6Ti 0.5Ti + Nb 1.6Cu 3.3Cu-0.05(Nb + Ta) 2.2Cu-0.06Al-0.88Ti 2.18(Nb + Ta )-2 .07Co-0.79W 0.5(Nb + Ta )-3 .2Co-0.8W 0.12Al-0.24Ti-3.61(Nb + Ta) 1.13Co-0.2V-3.49W 1Co, 0.2V, 2.5W Table 3 Effect of alloy components on the corrosion resistance of stainless steels in bleach plant applications Element Effect Beneficial alloy additions Enhances resistance to initiation of pitting and crevice Chromium corrosion. .. Paper 16, presented at Corrosion/ 84, National Association of Corrosion Engineers, 1984 186 M.J McNallan, J.M Oh, and W.W Liang, "High-Temperature Corrosion of Metals in Argon-OxygenChlorine Mixtures," DOE/ER-12093-T1, Gas Research Institute, 1982 187 M.J McNallan, M.H Rhee, S Thongtem, and T Hansler, "The Effect of Temperature on the HighTemperature Corrosion of Superalloys in Argon-20% Oxygen-0.25%... Manganese-substituted austenitic, may be better value than type 317L; not common at present 2 9-4 -2 2 9-4 Not as tough as austenitics, particularly after welding thicker sections Special precautions needed for welding to avoid N2 pickup Corrosion resistance, related to alloy content, can be very good 2 9-4 C NYBY MONIT SEACURE 2205 Ferralium 0.02% C max versions Higher alloys have remarkable corrosion. .. Staehle, Corrosion, Vol 32 (No 4), 1976, p 139 -1 42 220 T Kawamoto, T Kenjo, and Y Imasaka, IHI Eng Rev., Vol 10 (No 4), 1977, p 1 7-2 5 221 F.F Lyle and R.T Hill, "SCC Susceptibility of High-Strength Steels in Liquid Ammonia at Low Temperatures," Paper 225, presented at Corrosion/ 78, National Association of Corrosion Engineers, 1978 222 K Farrow, J Hutchings, and G Sanderson, Br Corros J., Vol 16 (No 1),... presented at Corrosion/ 83, National Association of Corrosion Engineers, 1983 212 M Yasuda, F Takeya, and F Hine, Corrosion, Vol 39 (No 10), Oct 1983 213 S.R Seagle, Pulp Paper, Vol 53 (No 10), Sept 1979 214 Cabot Dig., Vol 36 (No 5), Sept 1985 215 "Resistance of Nickel and High Nickel Alloys to Corrosion by Hydrochloric Acid, Hydrogen Chloride and Chlorine," Corrosion Engineering Bulletin CEB-3, The International... Rolls The corrosion- related failures of suction roll shells represent the most serious materials and corrosion problem in modern paper machines A variety of alloys are used for suction roll shells, including bronzes and various grades of stainless steel (martensitic, austenitic, duplex, precipitation hardening) Failure are due to corrosion thinning, pitting, corrosion fatigue, and stress -corrosion. .. a type 317L corrugated deck from a C-stage washer that failed because of crevice corrosion Fig 12 Effect of molybdenum content on the crevice corrosion temperature of commercial stainless steels The more resistant steels have higher crevice corrosion temperatures in the FeCl3 test Fig 13 Effect of molybdenum content on the crevice corrosion temperature of nickel-base alloys Note the superior performance... electrodes, and compared gaseous and liquid exposure in C- and D-stage washers (Ref 1) Figure 15 shows the corrosion products covering stainless steel test coupons that were exposed to a D-stage washer environment Fig 15 Stainless steel coupons of type 316L, 317L, and 904L on a rack exposed below the incoming stock of a D-stage washer Profuse ferrous oxide corrosion products cover the coupons Two other exposure... example, residual ClO2 can be recycled with a D2-stage filtrate to the D1-stage washer showers; therefore, an increase from 50 to 150 ppm ClO2 has been measured in a D1-stage filtrate when D2-stage SO2 additions were cut off during high ClO2 usage Recycling of D 1- or D2-stage filtrate to the Cstage washer should be avoided completely, because the more acidic C-stage filtrate (pH 2) regenerates ClO2 from... Heat-affected zone Fusion line Precipitation of carbides at fusion line (knife-line attack) (a) With high-alloy steels close to their corrosion limits In niobium- or titanium-stabilized steels Ensure full penetration, and do not use stitchwelds on process side Use electrode with good flux detachment Use steel with 0.03% C max Use lower heat input on final pass A very rare problem Niobiumand titanium-stabilized . degree. The corrosion rates for some metals are shown in Table 49. Table 49 Corrosion of metals and alloys in Ca(OCl) 2 204-day test in 1 8-2 0% Ca(OCl) 2 at 2 0-2 4 °C (7 0-7 5 °F) Corrosion rate. Stress Corrosion Cracking During Shutdown of Refinery Equipment," RP-0 1-7 0, National Association of Corrosion Engineers, 1970 8. C.P. Dillon et al., Guidelines For Control of Stress- Corrosion. p 33 138 . "Sulfide Stress Cracking Resistant Metallic Materials for Oil Field Equipment," MR-0 1- 75, National Association of Corrosion Engineers, 1984 139 . F.A. Prange, Corrosion,