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I I/=C 1 Materials of
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Nickel and High Nickel Alloys by A. J . Marron, International Nickel Co., New York, N.Y .
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Nickel-base alloys will continue dominating the 1000° to 2000' F. service range until oxidation problems have been solved for more reactive metals
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Advantages of duplex nickel plating under chromium are becoming increasingly apparent
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Because of its resistance to chloride-ion stress corrosion, nickelchromium alloy continues to be favored for service in naval nuclear reactors
C O R R O S I O N resistance is a major factor in the selection of alloys for service in the chemical and process industries. Although testing in the specific environment is required for final choice of a material, relative resistance to attack serves as a means of screening possible alloys from those that are unsuitable. The relative resistance of 18 materials to electrochemical attack in 86 corrosive chemicals has been reported in tabular form. Included are nickel, Monel nickelcopper alloy, Inconel nickel-chromium alloy, a number of stainless steels, and two cupro-nickel alloys (2). In another study, Turner and others (59) have determined the corrosion rates of Ni-o-ne1 nickel-iron-chromium alloy, Monel alloy, Hastelloy alloys B and C, Chromel-A, Carpenter 20, and a number of stainless steels in a variety of metallurgical plant environments including an HIP01-HzS04 slurry, SO*, fluorides, and (NH4)$304. Monel nickel-copper alloy and Hastelloy alloy C are suggested as pump and valve materials for handling chlorine mixtures (19). The Qualiweld and Chlorecon processes for welding aluminum use atmospheres composed of mixtures of inert gases and chlorine. Kasen and others (38) state that the check valve on the Clz gas cylinder should be made of Monel alloy; copper parts of the flowmeter should be nickelplated. Nickel and Inconel alloy are recommended for handling nitrosyl chloride, one of the more reactive components of aqua regia; nickel-clad steel is approved by the Interstate Commerce Commission for shipping nitrosyl chloride in tonnage quantities ( I d ) .
to the nickel tubes by heat treatment at 1800" F. Corrosion tests in 30y0 NaOH and in 9y0 HC1 show that the restored tubing is suitable for other applications
Nickel tanks are used to store 73Y0 caustic a t 230" F. and 43y0 caustic at 300" F. to withstand corrosion and protect the purity of the caustic (75). Weyermuller and Swandby (63) predict that Kanigen nickel-lined tanks will last from 10 to 20 years in continuous immersion service with 7470 caustic at 260" F. ; organic coatings have a life of only 1.5 years in the same service. Embrittlement of nickel heat exchanger tubes occurs when coke accumulates on the internal surfaces. Under the same conditions, Inconel nickel-chromium alloy tubes are not embrittled. Ductility can be restored
(58). Corrosion results obtained during a study of 229 pulp and paper mill alkaline digesters, lined or clad with carbon steel, stainless steel, or Inconel alloy, were discussed by Canavan (73). Based on four digesters, the average corrosion rate for Inconel alloy was 11.5 mils per year, median 3 mils per year; for eight stainless steel digesters, the average rate was 8.5 mils per year, median 5 mils per year. Hastelloy alloy C digester
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valve gates have served for 2.5 years in paper mill service involving sulfuric acid in the cooking liquor under 100 p.s.i. pressure with temperatures ranging u p to 345' F. (62). Jacoby and Lankenau (36) cited several corrosion problems associated with pulp mill black liquor evaporators having components constructed of Inconel alloy, Types 304 and 316 stainless steels, and carbon steel. Pioneering work on the production of ground wood pulp for newsprint from hardwood chips: using a mild cold caustic treatment without pressure, was reported by Bugg and Pearson ( 7 7 ) . Type 304 stainless steel was used for all parts coming into contact with the pulp or process liquors; barrel rings, clamping bars, pressure bars, and keeper knife bars were plated with Alcoplate containing 93yGnickel. T h e applications of high nickel alloys in the petroleum industry were reviewed bb- Swales (57). Included in his discussion were Monel, K Monel, and S Monel nickel-copper alloys and Inconel nickel-chromium alloy for various parts in drilling equipment and in the handling of corrosive crudes. H e discussed also the use of Monel, K Monel: and S Monel nickel-copper alloys, Ni-o-Ne1 and Incoloy nickel-ironchromium alloys, Inconel and Nimonic DS nickel-chromium alloys, Corronel B, the Hastelloy alloys, Carpenter 20, nickel, and various stainless steels for combating specific corrosion problems in a variety of refinery processes. Experience with Monel alloy, components clad with Monel alloy, and K Monel alloy bolts in refinery alkylation units was reported by Bennett (8). I t was noted by Fincher (27) that corrosion problems associated with sour
gas condensate production are minimized by use of inhibitors and careful selection of equipment. J-55 grade tubing is used for producing wells; N-80 grade for injection wells. I'alve stems of K Monel alloy have been used successfully. Inconel alloy springs are essential for most valves and controls. ,4nickel tank truck containing a heating coil made of nickel tubing !vas used to prevent contamination of phenol by iron and to keep the material liquid during cold weather ( 2 0 ) .
Fabrication, Welding, and Brazing For nuclear power applications, Incone1 alloy will be used primarily for heat exchangers in pressurized-water systems. I n an investigation of Tvelding problems associated with the fabrication of heat exchangers for this service, Fragetta and Pease ( 2 9 ) found that TiM n modified Inconel wire, deposited by the inert gas-shielded consumable electrode process, yields high quality overlays on carbon steel as well as transition welds between Inconel alloy and stainless steel. The submerged arc process is not suitable for overlaying with titanium modified Inconel wire. T o maintain high ductility in the overlay deposit, postweld heat treatment must be limited to temperatures below 1200" F. when titanium modified wire is used. Metallurgically sound Inconel alloy tube to tube-sheet welds can be obtained by the inert gas-shielded tungsten arc process. The inert gas-shielded tungsten arc process was used by Slaughter and others (52) to investigate the properties of welds in Hastelloy alloy B and INOR-8
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17 Rlo-7 Cr-4 Fe-balance Ni using plate and filler wire of these alloys; Hastelloy alloy 1%' filler wirc was used also. Alloys were readily weldable and welds were free from porosity, cracking, or other defects. Room and elevared remperature properties in the as-welded condition were adequate for molten salt nuclear reactor service. The mechanism of ultrasonic welding was reviewed by -4ntonevich and Monroe (5). Practical application of the process at present is limited to the welding of aluminum sheet u p to 0.090 inch thick and to thinner gages of other metals. During the investigation of the welding of various dissimilar metal combinations, no intermetallic compounds \\-ere noted. Joint strengths for a number of dissimilar metal combinations were reported, including niobium LO Inconel alloy and niobium, molybdenum, or titanium to Type 316 stainless steel. The nickel-base filler metals were briefly discussed by Barnett (7). H e suggested welding processes for Monel and K Monel nickel-copper alloys, Nimonic 75 and Inconel nickel-chromiurn alloys, nickel: and Hastelloy alloys B and C. I n a comprehensive revicw of the welding of stainless steels and high temperature alloys, Skelron (57) pointed out rhe factors influencing the \veldability of various alloy types. Included were the Inconel, Incoloy, and Ximonic alloys. Discussion included the selection of proper welding tcchniqucs and joint design. Special consideration was given to Inconel X nickel- chromium alloy as an example ol the problems met in Lvelding the age-hardenable super alloys. Simulated brazing cycles were used by Hoppin and Bamberger (35) to investigate the effect of hydrogen brazing on the properties of eight hightemperature alloys. Alloys were exposed for 1 hour a t 2000" to 2240" F. Properties 01' the high-nickel alloys Inconel 702, Rene 41, and 5-1570 and a number of stainless steels are tabulated. Two new methods were reported by Kinelski and Adamec (40) for overcoming brazing. difficulties encountered with nickel-base age-hardenable alloys, such as Inconel X alloy. One of the developments is a palladium-nickel brazing alloy which is self-fluxing and does not attack the base metal. The other recommends placing nickel powder on the surface to be brazed before introducing molten brazing alloy; no flux is required if brazing is done in an argon atmosphere. According to Perry (46),addition of palladium to established types of copper, copper-silver eutectic, and 85 silver-
a -n ) 15 manganese brazing alloys markedly improved brazing quality, corrosion resistance, and strength. Compositions, melting ranges, and recommended brazing temperatures for these modified alloys are tabulated. T h e alloys were developed for joining high-nickel alloys to themselves and to other materials such as cupro-nickels, steels, molybdenum, and tungsten. Electronics T h e behavior of materials under irradiation was reviewed by DeBiasi (27). Most promising material for high temperature is rhodium, possibly with a nickel underlay. Behavior of a number of magnetic alloys, including nickelzinc ferrites, was discussed. Clark and Fritz (76) reported the effects of temperatures ranging from -60' to 250' C. on the a x . magnetic properties of the 50-50 nickel-iron alloys Hypernik, Hypernik V, and Deltamax, and on 80-20 nickel-iron alloys. Coefficients of linear expansion were reported for over 100 electronic materials including metals, plastics, ceramics, and natural insulators. Nickel, nickel alloys, and stainless steels were included (25). I n a discussion of the design of precision brazing jigs for microwave tubes, Hanfmann (34) covered, inter alia, selection of jig materials. Temperature limitations, coefficients of expansion, machinability, and hardness values were given for Inconel and Inconel X alloys, six types of stainless steel, and molybdenum. A graph showing the total expansion of materials used in electron tube manufacture includes data on Monel, Inconel, Inconel X alloys, and nickel. T h e American Society for Testing Materials (ASTM) has proposed a tentative specification covering materials and physical and chemical requirements for miniature electron tube leads. Outer lead materials may be nickel-plated mild or copper-coated steel, Grade A nickel, nickel-clad copper, and silverplated or silver-clad Grade A nickel. Inner leads may be nickel-plated mild or copper-coated steel or Grade A nickel ( 4 ) . The influence of composition of cathode nickel on the thermionic life of electron tubes was discussed by Acker ( 7 ) ; control of cathode nickel for improving electron tubes was covered. Bowe listed the chemical compositions, thermal, physical, and mechanical properties of 11 types of cathode nickel for receiving, power, industrial, and other types of electron tubes (70). ASTM has proposed a standard specification covering nickel-chromium and nickel-chromium-iron alloys for electrical heating elements. Alloys
covered are 80 nickel-20 chromium, 60 nickel-16 chromium-balance iron, and 35 nickel-20 chromium-balance iron. Composition ranges, forms, physical condition, and various electrical properties are discussed ( 3 ) . Plating T h e results of tests involving thousands of copper-nickel-chromium plated panels exposed under accelerated, roof, and service conditions were discussed by DuRose and Pierce (24). DuRose and McManus (23), in a review of recent tests on copper-nickel-chromium coatings, concluded that copper undercoating prior to dull nickel or sulfur-free nickel had no practical advantage; copper undercoating prior to sulfurcontaining bright nickel may give protection equivalent to a n equal thickness of the bright nickel. Northrup (44) reviewed the corrosion problems encountered with electrical installations in chemical plants and other corrosive environments. H e stated that nickel plating was the best protection for copper parts. T h e results of the American Zinc Institute research program on electroplated zinc die castings were reported by Safranek and others (49). I n these tests, bright, crack-free chromium received higher ratings than regular chromium. For the same total thickness duplex nickel was more effective in improving corrosion resistance than increasing the thickness of a single layer of bright nickel from 0.8 to 1.0 mil. Poll (47) noted that the Guide L a m p Division of General Motors has adopted duplex nickel plating and thicker chromium deposits to improve the durability of automotive zinc die castings. Caldwell (72) reported that duplex nickel plating is superior to regular bright nickel €or protecting zinc die castings from corrosion. A review of the literature on the codeposition of tungsten or molybdenum with other metals was presented by Safranek and Vaaler (50). Nickel, cobalt, and iron are the only alloying elements that make it possible to codeposit substantial quantities of tungsten or molybdenum. I t was reported by Handova (33) that conductive coatings are produced on titanium in a series of plating operations during which nickel, copper, silver, and gold are deposited successively. Nickel is deposited by a n electroless method to obtain a base coating with good adhesion to the titanium. Stewart (56) discussed the Kanigen electroless nickel process and its application to wire products. West (67) described a method of depositing electroless nickel on carbon prior to flame plating with tungsten. I
Materlals of Construction Review Spraul (53) summarized corrosion data for Kanigen nickel plate in numerous chemicals and under varied atmospheric conditions. Pretreating of the steel base in a high-temperature salt bath and postplating heat treatment for 4 hours a t 1400" F. gave best resistance to outdoor atmospheric exposure. Russian engineers have developed a process for producing hard, bright nickel deposits from oxalic acid electrolytes (55). Geneidy and others ( 3 7 ) measured the effects of magnesium salts in chloride-type nickel plating baths. Addition of magnesium salts increased cathode current efficiency, improved throwing power, and reduced porosity. At high concentrations of magnesium salts, deposits were harder and more brittle than deposits produced in baths containing no magnesium salts. The composition and applications of nickel anodes were reviewed by Fishlock (28), emphasizing the significance of various factors affecting anodic reactions in plating processes. Newman (43) discussed the principal sources of insoluble particles in plating solutions that produce roughness in nickel or copper deposits. An adherent film of nickel can be obtained on zirconium by heat treatment after plating; without heat treatment the deposit is nonadherent. Other metals can be deposited on the nickel (42). Cook and Vollmuth (78) described techniques for nickel plating copper nose cones for the Atlas and Thor missiles; a Watts-type bath was selected. Dubpernell (22) published a comprehensive review of 100 years of nickel plating; included was a list of United States and Canadian patents on primary and secondary brighteners.
Coatings Development of a process for nickel deposition by thermal dissociation of nickel carbonyl was discussed by Owen (45). Included were details of the variables controlling the process and the properties of the coatings. Nickel carbonyl is used to deposit a metallic coating on glass fibers in a newly developed process (26). I t was reported by Aves ( 6 ) that flamesprayed laminated coatings have solved the corrosion and erosion problems of re-entry of missiles into the atmosphere. Nickel has been used as one of the constituents in the preparation of layers having unique properties for specific applications. Keeler and Terminello (39) noted that electrophoresis and electroosmosis are employed for applying various coatings on steel and nonferrous metals; included are nickel-bonded silicon carbide on mild steel and nickelchromium on molybdenum. VOL. 52, NO. 11
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High Temperature The high temperature properties of a series of modifications of the 79 Ni8 Mo-6 Cr-6 Al-l Zr alloy were investigated (30). The strongest alloy (basic 1.5 T i 0.125 C) had a stress alloy rupture life, as cast, of 384 hours a t 1800' F. and 15,000 p.s.i.; after homogenization, the alloy had a life of 574 hours. According to Betteridge ( 9 ) . the high temperature properties of the Nirnonic alloys depend on the production method and heat treatment. Tensile and creep data were given for Nimonic 80A, Nimonic 90: and Nimonic 95 alloys. Conrad (77) developed a n equation for predicting the stress rupture properties of Nimonic 80A and Simonic 90 alloys. T h e equation permits prediction of stresses for rupture periods u p to 34,000 hours from test data of less than 3000 hours with accuracy equal to that of the Manson-Haferd method. T h e mechanisms for strengthening alloys to improve high temperature properties were reviewed by Jahnke and Frank (37). I n their discussion of various alloy systems, they concluded that nickel alloys will continue to dorninate applications in the 1000" to 2000' F. range until the oxidation problems have been solved for other systems. Wood (65) reviewed the data on thermal properties of high temperature materials including nickel and nickel-chromiumiron alloys. Levy (41) published a table giving the tensile properties, density, and modulus of elasticity of various metals from 70' to 2200' F. Included were Inconel X and Inconel 700 alloys, Hastelloy X and Hastelloy R-235 alloys: Udimet 500, N-252: and Rene 41. The mechanical properties of aircraft structural materials were studied by Preston and others (48) a t high temperatures, after rapid heating. Tensile, fracture, and short-time creep properties were reported for A-nickel and a number of other materials. Gregory and Epner (32) developed a technique of producing high density materials based on a n 80 nickel-20 chromium matrix with dispersions of 17.570 (volume) of titanium carbide or alumina. Stress-rupture properties of the matrix a t 1500' F. were improved considerably. \Yood (64) reviewed the production and properties of investment cast alloys for high temperature service. Included were the nickel alloys, Nimocast 90, 242, and 258, G39 and GMR-235, and a number of ironbase and cobalt-base alloys. Corrosion experiments are in progress in the AEC molten salt reactor program on Inconel nickel-chromium alloy and INOR-8 (nickel-molybdenum alloy). Inconel alloy showed low corrosion
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rates in 1000-hour tests. No attack occurred on welded INOR-8 plates in sodium or in a fuel-salt mixture during 500-hour see-saw furnace tests a t 1200' F. Precious metal brazing alloys 82Au18Ni and 80Au-20Cu were unattached after 2000 hours in static tests or 500 hours in see-saw furnace tests a t 1200 O F. in fuel salt mixtures (60). The corrosion of structural materials by liquid metals and fused salts was reviewed by Stang ( 5 4 ) . Included were nickel, Inconel alloy, and austenitic stainless steels. Although many materials have satisfactory resistance to lithium in static tests a t temperatures u p to 1500" F., none has been found that is resistant in dynamic nonisothermal systems. An investigation of container materials for fuel-bearing fluoride salts a t 1200' F. indicated that both Inconel alloy and INOR-8 had excellent resistance. literature Cited (1) Acker, J. T., Western Electric Engr. 3, 32-5 (April 1959). (2) A m . hfachinist 103, 153, 155, 157 (September 21, 1959). (3) Am. SOC. Testing Materials, Philadelphia, Pa., Preprint No. 10 (1959). (4) Ibid., No. 64 (1959). (5) Antonevich, J. N., Monroe, R. E., Battelle Tech. Rez. 8 , 9-13 (March 1959). (6) Aves, W7. L., Metal Progr. 75, 90-4, 189c, 190 (March 1959). (7) Barnett, 0. T., TVeldzng Design 3 Fabrication 32, 60-1 (September 1959). (8) Bennett, H. H., Corrosion 15, 237t240t (1959). (9) Betteridge, W., M e t a l Treatment and Drop Forging 26, 45-52 (February 1959). (10) Bowe, J . J., Electronic h d s . Tele-Tech. 18, 84-89 (April 1959). (11) Bugg, E. J., Pearson, A. J., Paper Trade J.142, 18-24 (Dec. 22, 1958). (12) Caldwell: M. R., Iron Age 183, 132-3 (June 11, 1959). (13) Canavan, H . M., T a p p i 42, 129-4132'4 (1959). (14) Chem. Promwing 22, 51 (December 1050)
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(15) Idid., 23, 111 (January 1960). (16) Clark. J. J.. Fritz, J. F., EleL. h l f g . ' 64,152-7 (December 1959). (17) Conrad, H., J . Inst. Metals 87, 347-9 (1959). (18) Cook, G. H., Vollmuth, L. P., Iron Age 184, 83-5 (Aug. 13, 1959). (19) Corrosion 15, 355t-357t (1959). (20) Corrosion Prevent. C8 Control 6 , 32 (August 1959). (21) DeBiasi, V., Aviation Age 30, 72-4, 76-80 (Augtlst 1958). (22) Dubpernell, G.: Plating 46, 599- 616 .L
(1 9.59). \----,-
(23) DuRose, A. H., McManus, R. T. F.: EleLtropEating and M e t a l Finishing 12, 409-1 5 (1959). (24) DuRose, A. H., Pierce, W. J., M e t a l Finishing 57, 44-50, 54 (March 1959). (25) Flectronics 32, 95 (May 29, 1959). (26 Engrs. Digest20, 232 (1959). (27{ Fincher, D. R.: Corrosion 15, 41%416t (1959). (28) Fishlock, D. J., Metal Finishing 57, 48- 51 (February 1959) ; 55-9 (March 1959). (29) Fragetta, W. A , Pease, G. R., Welding J. ( N , Y.)38, 347-56 (1959).
INDUSTRIAL AND ENGINEERING CHEMISTRY
(30) Freche, J. E., Waters, W. J., Natl. Aeronaut. Space Admin. Memo 4-1359E (May 1959). (31) Geneidy, A., Koehler, W.A , , Machu, W., .J. Elrctrochem. SOC. 106, 394-403 (1959). (32) Gregory, E., Epner, M., Summary Report by Sintercast Corp. of America (PB 131,846) (December 1956). (33) Handova, C. W.,Prods. Finishing (Cincinnati) 23, 40-2 (February 1959). (34) Hanfmann, A. M., Western Flectric Engr. 3, 32-5 (April 1958). (35) Hoppin, G. S., 111, Bamberger, E. PUT., Welding J. (117. Y.)38, 194s-201s (1959). (36) Jacoby, H. E.. Lankenau, H. G., T a p p i 42, 168A-171A (1959). (37) Jahnke, L. P., Frank, R . G., M e t a l Progr. 74, 77-82 (November 1958); 86-91 (December 1958). (38) Kasen, M. B., Allen, G., Baysinger, F. R., Weldin,? E q r . 44, 44-7 (1959). (39) Keeler, R. A , , Terminello, 1,. C., A m . Machinzst 103, 138-9 (May 18, 1959). (40) Kinelski: E. H., Adamec, J. B., Welding J. ( A T . Y.)38, 483s-486s (1959). (41) Levy, A. V.: ".Aviation Age Research and Development Technical Handbook," Vol. 2, pp. 110-1, Conover-Nast Publications, Inc., S e w York, 1958-59. (42) Murphy, N. F., Prods. Finishinp (Cincinnatz) 24, 76, 78, 82 (October 1959). (43) Newman, D. K., Electrqlding and Metal Finishing 12, 296-8 (August 1959). (44) Northrup, R. P., Corrosion Technol. 6, 344-6 (1959). (45) Owen, L. W., Metallurgia 59, 165573, 227-33, 295-301 (1959). (46) Perry, E. R., Australasian En,yr. 1959, pp. 53-6 (May 7). (47) Poll, G. H . ? Jr.: Prods. Fznzshing (Cincznnati) 23, 138-43 (June 1959). (48) Preston, J. B., Roe, W. P.: Kattus, J. R . , WADC Tech. Kept. 57-649, pt. 1 (PB 131,664) (January 1958). (49) Safranek, W. H.:Miller, H. R., Faust, C. L.: Automotiue Znd,s. 120, 70-4, 114 (June 15, 1959). (50) Safranek, W. H., Vaaler, L. E., Plattng 46, 133-43 (June 1959). (51) Skelton, H. A,, Can. Metalworking 21, 48, 50, 54: 56, 58, 60 (October 1958); 38, 40, 42, 44, 46 (Kovember 1958). (52) Slaughter, G. M., Patriarca, P., Clausing, R. E.: Welding J . (.V. Y.) 38, 393s-400s (1959). (53) Spraul, J . R., Plating 46, 1364--9 (3,-' 959\. - - ,(54) Stang, J . H., Reactor Ccre Materials 2, 30-3 (February 1959). ( 5 5 ) Steiger, A . J., M e t a l Finishing 5 7 , 52-3 (January 1959). (56) Stewart, D. E.. W i r e and W i r e Produds34. 1013-15 (1959). (57) Swales, G. L., C&roszon Technol. 6 , 81-4, 119-23 (1959). (58) Szymanski, W. A , , Corrosion 15, 112 (1 959). (59) Turner, A,. M'ellington, J . K . , Williams. L., Can. J. Chem. Erie. 37, 55--64 (1959). (60) U . S. Atomic Energy Comm. ORNL2474 (1958). (61) West. H. J.. M e t a l Finzshine., 57.. 64 ' (February 1959). ~
(62) Westein Metalzuorking 17, 39 (May 1959). (63) Weyermuller, G.? Swandby, R., Chem. Processing 23, 108-9 (February 1960). (64) Wood, D. R., Foundry Tradr J . 106, 663-8 (June 4, 1959). (65) Wood: N.: Wrstern iMetalzcorki?2g 17, 40-5 (March 1959).
