an ~ ] M a t e r i a Zofs Construction Review
Nickel and High Nickel Alloys by A. J. Marron and J. 1. Everhart, International Nickel Co., Inc., New York, N. Y.
Galvanic coupling of Ni-Cr alloys to steel does not accelerate corrosion of either member in nuclear power plant boiler water
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MAJOR DEVELOPMENT in the past year was the start of commercial production of refined nickel at the Thompson project in Manitoba, Canada. Another significant development is the use of nickel alloy electrical resistance probes in petroleum refineries for monitoring corrosivities of streams and for corrosion control. Duplex nickel coatings were cited as the first big breakthrough in improving corrosion resistance and durability of automotive bright metal trim. This review covers the period March 1960 to March 1961.
Chemical and Process industries According to Nelson (37), a survey of eight chemical plants and nine petroleum refineries indicated that there are 60 possible causes of metal failure under the severe conditions involved. Most failures can be traced to metallurgical phenomena, outstanding categories being connected with temperature and corrosion. Discussion included the problems encountered in the use of austenitic stainless steels, Incoloy alloy 800, and Hastelloy alloy B. (Check the box on p. 91 5 for new nickel alloy designations.) I n a review of the use of nickel and high nickel alloys as construction materials for chemical plants, Hinde (27) published isocorrosion curves for Monel glloy 400 in H z S 0 4 and for nickel, Monel alloy 400, and nickel-molyb.denurn alloys in HCl. Schilmoller and LaQue (47) discussed the behavior of a number of materials in HzS04 solutions encountered in the refining of nickel, copper, and cobalt. Materials included Monel alloy 400, Ni-o-ne1 alloy 825, Illium G , and various Hastelloy alloys. According to Turnbull (57), an investigation of the effects of operating
conditions in multieffect NaCl evaporators showed that corrosion rates depend on the p H of the solution. Data are presented on a number of materials including nickel, Monel alloy 400, Monel alloy 410, Inconel alloy 600, Incoloy alloy 800, and Hastelloy C. I n a comprehensive discussion of inorganic fluorine compounds, Leech (29) covered the occurrence of fluorine compounds in minerals, production of H F which is the principal source of fluorine compounds used industrially, and the production of fluorine. Aqueous H F above 70% concentration can be handled in steel, but more dilute solutions require use of nonferrous metals, particularly nickel and nickel alloys. I n the production of fluorine, although mild steel can be used in cells and piping, nickel or Monel alloy 400 is preferred. Materials for use in the recovery of nuclear fuel elements, clad with zirconium, by fluoride volatilization were evaluated by Miller and others (34). Among materials investigated were nickel, Inconel alloy 600, Monel alloy
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400, Hastelloy alloy R , INOR-1, and INOR-8. T h e latter, a 71Ni - 16Mo 7Cr - 5 Fe alloy, was the most promising material. Gordon and Holloway (75) recommend Monel alloy 400 valves, tees, and fittings for handling fluorine in the laboratory. A survey of alkaline digester corrosion in 22 pulp and paper mills was reported by Morrison and others (35). Corrosion data based on 172 carbon steel digesters and 34 digesters clad with stainless steel or Inconel alloy 600 showed average corrosion rates of 36.2 mils per year for carbon steel, 3.3 mils per year for steel clad with Inconel alloy 600, and 6.1 mils per year for steel clad with stainless steel. Harris and Park (79) discussed sulfate digester construction based on They experience with 61 digesters. reported that Inconel alloy 600 and Type 316 stainless steel are not attacked by sulfate liquor but are slightly attacked by the vapor driven off during the cooling cycle. Effects of aeration, pH, and conductivity on the corrosion of bronze Four-
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drinier wire were discussed by Gerhauser (73). H e concluded that the only preventive measure for mills with extremely high conductivity is the use of nickel-plated, tin-plated, or plasticcoated wire. Materials for handling natural gas and condensate containing aqueous H2S were evaluated by McGuire and others (37). Included were carbon and low alloy steels, Monel alloy 400: Monel alloy K-500, and Inconel alloy 600. Components requiring high tensile strength should be made from Monel alloy K-500 or heat-treated C-Mn-hlo and AIS1 4140 steels. Monel alloy 400, Monel alloy K-500, Inconel alloy 600, and Hastelloy alloys are excellent for valve trim, springs, flow beams, and pressure controls. Electrical resistance probes are now being widely used in petroleum refineries for monitoring corrosivities of streams and helping to solve corrosion problems (38). Materials suggested for probe specimens include nickel, Monel alloy 400, and Hastelloy alloys. Small quantities of water can transform relatively innocuous dry halogenated chemicals into aggressive corrosives by hydrolysis, according to Gladis (74). Performance of a metal in wetted and hydrolyzed chlorohydrocarbons depends on its resistance to corrosion by HC1 under process conditions. Results of laboratory and plant tests are reported for a number of metals, including Monel alloy 400, Inconel alloy 600, Ni-o-ne1 alloy 825, and Hastelloy alloys B and C. Developments in corrosion-resistant materials for use in the production, transportation, refining, and chemical processing phases of the petroleum industry were discussed by Swales (56). Included in a broad range of materials were nickel-molybdenum, nickel-chromium, nickel-chromium-iron, and nickel-chromium-molybdenum-iron
alloys. Tables of compositions, properties, and corrosion resistance in acids and sea water are included. Nuclear power plant steam generator tubing materials were tested for susceptibility to chloride-ion stress corrosion cracking by White and Johnson (67). Inconel alloy 600, nickel, and titanium were completely free of cracking or pitting. Copson and Berry ( 9 ) studied the behavior of Inconel alloy 600 in simulated primary and secondary nuclear power plant boiler water. Inconel alloy 600 forms tightly adherent tarnish films in these waters and corrodes a t rates comparable with those of Type 347 stainless steel. Galvanic coupling of Inconel alloy 600 to steel or to stainless steel does not accelerate attack on either member of the couple. The corrosive effects of sludge accumulation on pressurized water reactor tubing alloys were studied by Howells and McNary (24). Inconel alloy 600 was the most resistant of alloys tested; Type 347 stainless steel was next. Carbon steel and Monel alloy 400 were corroded severely.
High Temperature High temperature corrosion phenomena in refinery and petrochemical service were reviewed by Skinner and others (52). Corrosion resistance and mechanical and physical properties of common engineering alloys were discussed. Included were Inconel alloy 600, Incoloy alloy 800, Monel alloy 400. and nickel. A study of carburization and oxidation in C O atmospheres was reported by Hopkinqon and Copson (22). Rates of carburization and oxidation reached a maximumin thc range 1500'to 1750' F.; attack was slight a t 1330' and 1830' F. Nickel-chromium alloys resisted carburization and oxidation in all
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INDUSTRIAL AND ENGINEERING CHEMISTRY
atmospheres included in the test. Eberle and Wylie (10) reported that corrosive attack in a gas generator, in which methane was burned with oxygen to produce C O and hydrogen, varied with the temperature. Above 1650" F. the attack was straight oxidation; at lower temperatures heavy carburization occurred in addition to oxidation. The most resistant materials were those resisting carburization including Monel alloy 400, Inconel alloy 600, and nickel. Sliding characteristics of metals a t temperatures up to 1600" F. were investigated by Peterson and others (40). Friction and surface damage of nickel were high initially and diminished above a transition temperature (1200" to 1400" F.); transition temperature appeared to be associated Tvith continuous reformation of an oxide film. Johnson and others (26) reported that gaseous halogenated methane derivatives may solve high temperature lubrication problems. Materials tested included Inconel alloy 600, Inconel alloy X-750, and Hastelloy alloy C. The corrosion resistance of a number of alloys in the boiler of a simulated pressurized water nuclear power plant was discussed by Howells and McNary (23). Materials tested included nickel. Monel alloy 400, and Inconel alloy 600. Hale and others (77) studied the corrosion of nickel and Monel alloy 400 in gaseous fluorine a t pressures u p to 1 atm. absolute and temperatures to 1500O F. I n an evaluation of coolants for the maritime gas cooled reactor program, Bokros and Wallace (5) studied the oxidation of reactor materials in high pressure (1000 to 2000 p.s.i.) and high temperature (1100" to 1740" F.) CO2. Materials included stainless steels, nickel: Inconel alloy 600, Inconel alloy X750, Nichrome V, and Hastelloy B. Inconel alloy 600 and Type 316 stainless steel were suggested for high strength fuel-cladding service. Corrosion tests on construction materials for the processing plant of a liquid metal fuel reactor were discussed by Susskind and others (5'5). Materials included Inconel alloy 600, INOR-8, Hastelloy alloy C, and various stainless steels. Mass transfer tests indicated that high nickel alloys may be superior to other materials for this service. Corrosion of super alloys by fused salts was investigated by Moskowitz and Redmerski (36). Thin coatings of KCl and LiF caused severe corrosion of the alloys in air a t 1600' to 1900" F. by preventing formation of a protective oxide film. Included in the tests were Inconel alloy X-750, Inconel alloy 702, RenC 41, and M-252 alloy. According to Sibley (50). heating elements made of a new modification of the 80Ni - 20Cr alloy operate satis-
a n m d Materials of Construction Review factorily for long periods in gaseous atmospheres. The alloy is recommended for service in all controlled atmosphere furnaces operating up to 2150' F.
I The Huntington Alloy Products Division, producer of the alloys listed below, has recently adopted a new numbering system covering its various proprietary alloys. The new and old designations for the alloys mentioned in this review are as follows:
Plating
Old
New
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Finishing and plating technical developments during 1960 were covered in a comprehensive review by Hall (78). In a discussion of the contribution of nickel and chromium to the durability of decorative plating, Sample (46) noted that bright nickel is more variable and generally inferior to buffed dull nickel of the same thickness, when plated with conventional chromium. Duplex nickel under the same conditions provides corrosion resistance equivalent to that of dull nickel. Seyb (49) pointed out that bright crack-free chromium is not dependent on the sacrificial corrosion of nickel under the chromium, whereas duplex chromium does depend on sacrificial nickel corrosion. Outdoor corrosion resistance of chromium-plated polished Watts nickel was compared with that of duplex nickel by Brown and Millage (6). According to Safranek ( 4 4 , duplex nickel, crack-free chromium, and duplex chromium provide long life to decorative and functional zinc die castings, particularly in automotive service. Safranek and others (45) summarized three research programs on methods of improving the corrosion resistance of zinc die castings. Duplex nickel coatings perform effectively only when plated with 0.02 mil, or more, chromium. A composite of bright nickel and 0.055mil chromium was effective in preventing corrosion during accelerated tests and outdoor exposure. As the result of atmospheric exposure tests for one year in Miami, Detroit, and Pittsburgh, Bigge ( 4 ) reported that buffed Watts nickel or duplex nickel gave superior performance to bright nickel on zinc die castings. Duplex nickel also was superior to bright nickel on steel panels. The American Society for Testing Materials (ASTM) has issued a tentative recommended practice as a guide to the production of adherent nickel electrodeposits on nickel (7). The suggestions include methods of cleaning, etching. and electrodeposition. Investigation of methods for the codeposition of nickel and other metals continues. Sree and Rama Char (53) codeposited nickel and cobalt from a pyrophosphate bath using anodes containing 32 and 74% nickel. Optimum conditions were evolved to obtain satisfactory alloy plates containing 10 to 91% nickel. Russian research on the codeposition of nickel and cobalt from H 2 S 0 4 baths was discussed by
Monel alloy 400 Monel alloy 4 7 0 Monel alloy K-500 lnconel alloy 600 lnconel alloy X-750 lncoloy alloy 800 Ni-o-ne1 alloy 825
Monel nickel-copper alloy Monel nickel-copper alloy castings K-Monel age-hardenable nickel-copper alloy lnconel nickel-chromium alloy lnconel X age-hardenable nickel-chromium alloy lncoloy nickel-chromium-iron al!oy Ni-o-ne1 nickel-iron-chromium alloy
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Steiger (54). Separate nickel and cobalt anodes were used in developing thick (3 to 4 mm.) nickel-cobalt deposits of controlled composition. Using nickel and zinc anodes, Rama Char and Panikkar (43) codeposited nickel and zinc from pyrophosphate baths. Optimum plating practice was developed to obtain alloys containing 21 to 84y0nickel. Electrodeposition of nickel, copper, and bimetal sheets on an industrial scale was reported by Carrington (8). Sheets were uniform in thickness and had smooth, nonglossy surfaces. They were highly ductile and cheaper than rolled sheets of comparable thickness (9.5 mils). According to Beck and Jankowsky ( Z ) , use of copper and Watts nickel undercoats substantially reduces the hydrogen embrittlement of AIS1 4340 steel caused by chromium and cyanide cadmium electroplating. The use of disodium m-benzenedisulfonate as a hardening agent in a Watts nickel bath was discussed by Metzger and others (33). This agent increased deposit hardness to a maximum of 350 Vickers and reduced stresses in the deposit. Recent developments in chemical and electrochemical polishing were discussed by Pinner (41) in a comprehensive review. Included were procedures for polishing nickel and stainless steels. A fairly satisfactory chemical polishing solution for nickel contains "01, H2S04, and glacial acetic acids. In Russian practice, H s S O ~ - H ~ P soluO~ tions are used for electropolishing nickel.
Coatings Development of sprayed metal coat.ings for abrasion, corrosion, and oxidation resistance was reported by Bell ( 3 ) .
Xi-Cr-B-Si alloy powders are sprayed on the surface and reheated to form a bond with the basis metal. Corrosion resistance of these coatings was discussed. Modified coatings are being developed for abrasion and oxidation resistance. Wear resistance of automobile camshafts is improved by flame spraying a coating of Ni-Cr-B alloy (60). Hard surfacing with a nickel-base material containing chromium borides improved the abrasion resistance of feed ports and conveyor blades of a centrifugal coal filter (58). According to Schwarzkoff (48), flamesprayed nickel-chromium or cobaltchromium coatings have excellent hot hardness up to 1400" F. New techniques for cladding by gasshielded welding were discussed by Engel (72). High quality okerlays at high deposition rates are obtained with nickel alloys, stainless steels: and copper alloys. The use of electrodeposited nickel as an undercoat for organic enamels was reported by Carlin (7). Oleoresinous enamels do not adhere to freshly plated nickel. Formation of an oxide, sulfide, chromate, or phosphate film is required to obtain good adhesion.
Electronics According to Wenny (59), recent developments have shown the necessity of refining to extremely high purity and working to very small dimensional tolerances. For example? special transformer cores of high purity Supermalloy (79Ni - 15Fe - 5Mo - 0.5Mn - 0.5Co) require holding metallic impurities to less than 20 p.p.m. and holding the strip thickness to a tolerance of 10 millionths of an inch. Other illustrations are cited. A chemical etching procedure has been developed by Koontz and others VOL. 53,
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(28) to produce ultraclean electron tube components. Standard etching and cleaning methods have been established for a number of materials used in modern electron tubes, including electronic Grade 21 nickel and 999 nickel. The relation between the thermionic emission from oxide cathodes and the glass envelope composition was discussed by Kern and Graney (27). High purity cathode nickel was used to increase the sensitivity of the oxide coating to contamination. I n a study of hydrogen absorption by tube parts, Lichtman (30) determined that nickel parts were more easily ou,gassed than cold rolled steel regardless of the firing procedure. The third of a series of reports on transformer materials covered evaluation of magnetic materials for extreme environments ( 7 7 ) . Included in a table summarizing the results are nickel and nickel-base alloys of the following proprietary designations: Permalloy, Perminvar, Supermalloy, Monimax, Sininiax, Mu-metal, Invar, and Deltamax. Gourash (16) discussed materials for toroidal cores for high temperature magnetic amplifiers. Included were Hipernik and Hipernik V. The effects of high temperature on the magnetic properties of core materials were discussed by Pasnak and Lundsten (39). Among materials tested from room temperature to their Curie points were 4-79 Permalloy and 7-70 Perminvar. I n a comprehensive report on electronic materials for environmental extremes, Sideris (51) discussed the requirements for service under the high temperature, radiation, corrosion, and stress conditions encountered in space vehicles. Nickel and nickel-base alloys were included. The electrical resistivity, temperature coefficient of resistance, and stability requirements of alloys for precision resistors were discussed by Jackson and Dunleavy ( 2 5 ) . The listing of electrical properties and trade names of commercial alloys generally used for resistor windings included nickel-chromium and modified nickel-chromium allovs.
Fabrication and Welding Ultrasonic welding of dissimilar metals was reviewed by Potthoff and others ( 4 2 ) . Joints produced by ultrasonic welding are generally free of intermerallic compounds, interdiffusion, and brittleness in contrast wirh joints produced by fusion bonding. Present limitations of the process for nickel-base alloys is a maximum thickness of 0.040 inch. Development of new nickel-chromiumiron welding materials (MIL Type 4N85 covered electrode and EN87/
916
RN87 inert gas filler wire) was reported by \\Titherell (62). These materials were developed for the fabrication of Inconel alloy 600 components for service in nuclear power station applications. Tests to determine the properties of as-deposited nickel-base alloys containing 64 to 97y0 nickel were discussed by Heuschkel (20). Tests were run at temperatures ranging from -452’ to 2200 F. Evaluation tests of BP-85 nickelchromium covered electrodes were reported by McKittrick and Owczarski ( 3 2 ) . This electrode is suitable for joining Inconel alloy 600 to itself, dissimilar metal welds, and carbon steel overlays.
literature Cited (1) Am. SOC. Testing Materials, Philadelphia, Pa., Preprint No. 12, 1960. (2) Beck, W., Jankowsky, E. J., Tech. Proc. A m . Electroplaters’ Sac. 47, 152 (1960). (3) Bell, G. R., Brit. Weldzng J . 7, 305 11960). (4)’ Bigge, D. M., SOC.Automotive Engrs., New York, N. Y.. Preprint No. 147 A, I_ 9_ m
(5) Bokros, J. C., Wallace, W. P., Corrosion 16,73t (February 1960). (6) Trans. ~, Brown, H., Millage. D. R.. Znst. M e t a l Finishing 37,’Pt. 1, 21 (Spring 1960). (7) Carlin, F. X., Tech. Proc. Am. Electroblaters’ Sac. 47. 59 11960). (8j Carrington,’ E., ‘EZect&lating and ‘2rietal Finishing 13, 80 (March 1960); 126, 143 (April 1960). (9) Copson, H. R., Berry, W. E., Corrosion 16,79t (February 1960). (10) Eberle, F., Wylie, R. D., Zbid., 15, 622t (December 1959). (11) Elec. M J g . 65,76 (May 1960). (12) Engel, R. D., Welding J . 39, 1222 (1960). (13) Girhauser, 3. P., Tappi 43, 207A (April 1960). (14) Gladis, G. P.. Chem. Eng. Progr. 56, 43 (October 1960). (15) Gordon, J., Holloway, F. L., ISD. ENG.CHEM.52,63A (May 1960). (16) Gourash, F., Elec. MJg. 66, 10 (September 1960). (17) Hale, C. F., Barber, E. J.; others, U. S.At. Energv Comm. Reut. AECD4292, July 1959:’ (18) Hall, N., Metal Finzshing 59, 36A (January 1961). (19) Harris, H. B., Park, L. H., Tappi 43, 226A (May 1960). (20) Heuschkel, J., Weldzng J. 39, 236s (June 1960). (21) Hinde, J., Chem. Process Eng. 41, 295, 297, 301 (July 1960). (22) Hopkinson, B. E., Copson, H. R., Corroszon 16, 608t (December 1960). (23 Howells, E., McNary, T. A., White, E., Zbid., 16,241t (May 1960). (24) Zbid., p. 571t (November 1960). (25) Jackson, C. M., Dunleavy. J. G., Materials in Design Eng. 52, 121 (August
A.
1960).
(26) Johnson, R. L., Swikert, M. -4., Buckley, D. H., Corrosion 16, 3 9 3 (August 1960). (27) Kern, H. E., Graney. E. T., i\STM Spec. Tech. Publ. No. 246, p. 167,1959. (28) Koontz, D. E., Thomas, C. O., others, Zbid., No. 246, p. 136, 1959.
INDUSTRIAL AND ENGINEERING CHEMISTRY
(29) Leech, H. R., Chem. @ Znd. (London)
1960, p. 242.
(30) Lichtman, D., ASTM Spec. Tech. Publ. No. 246, p. 120, 1959. (31) McGuire, W. J., Vollmer, L. \V., others, Trans. Can. Znst. Mining M e t . 63,
425 (1960). (32) McKittrick, G. F., Owczarski, W. A., U. S. .4t. Energy Comm. KAPL-MGFM-8, June 1959. 133) Metzger, W. H., Jr., Krasley, P. A.. Ogburn, F., Plating 47, 285 (March 1960). (34) Miller, P. D., Peterson, C. I,. others, U . S At. Energy Comm. BMI1348. June 1959 (35) hiorrison, J. J.’ B., Canavan, H. M., Blanchard, 2. S.,Paper Trade J . 144, (Nov. 7 , 1960). (36). Moskowitz. A., Redmerski, L., WADC I\ ADC TR 60-115, 60-115,March 1960. ((3? 3 7 ) Nelson: Nelson. G. A,, A., Metal Progr. Progr 77. 80 (May 1960). (38) Oil Gas J . 58. 135 iMav 16. 1960’1. (39) Pasnak, M.; Lundsten, ’R., Trans. Am. Inst. Elec. Engrs. 78, Pt. I: 1033 (January 1960). (40) Peterson, M. B., Florek, J. J., Lee, R. E., Metal Progr. 77,194 (May 1960). (41) Pinner, R., Electroplating and Metal Finishing 13, 205 (June 1960). (42) Pottoff, W. C., Thomas, .J. G.. Meyer, F. R., Welding J . 39, 131 (February 1960). (43) Rama Char, T. L.; Panikkar, S. K., Electroplating and Metal Finishing 13, 405 (November 1960). (44) Safranek, W. H.: Metal Progr. Pro,gr. 78, (Julv 69 (July 1~- 960). , 1960\. (45) (45) Safranek. ’ W. H., Miller, H. R., others, Plating 47,405 (April 1960). (46) Sample, C . H., Zbid., Zbid.. 47, 297 (March I w,n\ ,_(47) Sdhilmoller, C. M.. LaQue, F. L.. Chem. Eng. 67, 170 (April 4, 1960). (48) Schwarzkoff, 4. J.. Prod. En,?. 31, 70 (Sov. 14, 1960). (49) Scyb, E. J.? Tech. Proc. A m . Electroplaters’ Sac. 47, 209 (1960). (50) Sibley, F. S.,Iron Age 185, 74 (May 5, 1960). (51) Sideris, G.: Electronics 32, 81 (Dec. 3. 1959). (52) Skinner. E. N., Mason. J. F., Moran. J. J., Corrorion 16, 593t (December 1960). (53) Sree, V., Rama Char. T. L., J . Electrochem. Soc. 108, 64 (1960). (54) Steiger, A. J., .Wetal Finishin? 58, 53 (December 1960). (55) Susskind. H., Hill, F. B., others. Chem. Eng. Progr. 56 (March 1960). (56) Swales, G. L., in “Corrosion Problems of the Petroleum Industry.“ Soc. Chem. Ind. Monograph No. 10. 184,1960. (57) Turnbull, J. M., Corrosion 16, 11 (.July 1960). (58) Welding J . 39, 813 (1960). (59) Wenny, D. H., Jr.; Bell Labs. Record 38, 130 (.4pril 1960). (60) Western Metalworking 18, 40 (July 1960). (61) White, D. E.: Corrorion 1 6 , 320t (July 1960). (62) Witherell, C. E., Welding J . 39, 473s (November 1960). ~~
After November 1962 the complete annotated bibliography can be obtained from the AD1 Auxiliary Publications Project, Library of Congress, Washington 25, D. C . , as Document No. 6849, at $1.75 for microfilm and $2.50 for photostat copies.
