Nickel and igh-Nickel Alloys Y.
T
H I S annual revieLv, like r,he previous one ( I l l ) , deals principally with nickel and alloys containing more than about 40% of nickel or of nickel plus cobalt. The subject matter is divided into three general classifications: developments or improvements in alloys and studies of the physical properties of alloys; developments in the fabrication of nickel alloys including welding and forming; and developments in the application of the alloys including uses for high temperature and corrosion resistance, particularly as applied to the chemical and process industries. A L L O Y S A N D PROPERTIES T h r search for neK alloys having unique corrosion resistance or phj-sics1 properties has resulted in a considerable study of the basic metallurgy and the phase changes in alloy systems of nickel with a number of other metals. Long et al. (155) presented data on titanium-nickel d l o y i with nickel contents up to 40%, including preparation and treatment of allo:-c, effect of oxygen, determination of solidus, and structure of solid phases. Koster and Rauscher (146) constiucted a nickclmanganese diagram from thermal, microscopic, x-ray, and magnetic data. PIIoduli of elasticity a t room temperature to 800" C. are given for nicltel-manganese alloys containing up to 50% manganese. Paul and Beard (181) determined t,he liquidossolidus points of nickel-manganese alloys from 35 Mn-65 S i to 80 1In-20 Xi. Microscopic and x-ray data on experimental a l l o p containing 76 to 16% copper, 59 to 0.9% nickel, and 80 to 10% aluminum, annealed for periods up t o 4 weeks, were used by Iiocter, Zn-icker, and Moeller ( 1 4 6 ) to construct isothermal tliagrams a t 500°, 600°, 700", and 900" C. Epremian and Harker (94)reported work with the nickel-tungsten system, piving clats on the hardness, electrical resistivity, and microstructures of the alloys. Preparation of nickel-beryllium alloys was described in a FIAT report ( 3 7 ) . The process consists in preparing a master alloy of 10% beryllium and 90% nickel by melting beryllium flakes and nickel together in an atmosphere of hydrogen, u-ing sodium acid fluoride as a flux. This master alloy is brittle. Alloys containing 1 to 2% beryllium are prepared by melting the rmster alloy with pure nickel. These alloys are ductile, and have a hardness of u p to 550 Brinell hardness number. Alloys for rmtch springs containing titanium and in ssinie cases beryllium, developed under the name of Nivarox, are corrosion-resistant and nonmagnetic. A typical analysis of X v a r o s is 37% nickel, 8% chromium, 1% beryllium, 1% titanium, 0.8% manganese, 0.2% d i c o n , remainder iron. Raub and Engel (186) made a study of the constitution and structure of the ternary system, gold-nickelcopper. I n order to extend the knowledge of the chemical behavior of gallium and indium in alloys, the crystal structures of twenty intermetallic phases were determined by Hellner and Laves (126). Equilibrium diagrams were presented for the nickel-gallium and nickel-indium systems. A silver alloy ronraining 20 to 30% nickel appeared to have outstanding electricd contact properties (115). Hibbard (128) reviemd current fundamental research in nonferrous physical metallurgy. I n describing the production of magnetic materials i c Germany, Both (68) discussed factors governing the achievement of LI rectangu1:ir hysteresis loop in a 50% nickel-iron alloy, including
the effects of impurities, mechanical stresses, cold ieduction, UICI annealing temperature. A review (172) of the Gelman trani former industry referred to the use of a number of nickel-iror, alloys. Lord (157) disclosed a pulse transformer of a hi+permeability and high-reqistivity allov such as a 42y0 niclLcl-3% silicon-55% iron alloy. Bouchard (69) determined the influence of magnetization upon the thermoelectiic force of ferromagnetic. materials including nickel, cupronichels, Permalloy, and nicshtliron alloys containing 72, 58, and 48.5% nickel. T h e collectivc treatment of ferromagnetism was applied by Wohlfarth (235) t o the magnetic and thermal properties of nickel and nickel alloys Keel (176) reviewed modern theories of magnetism and some or their applications, including relative sensitivities of nickel and 0' iron to various defects such a9 heterogeneity. Rocard (188) rucorded experimental data on the direct and indirect magnetustriction of nickel and Koster (244) diqcussed the delta-E effew and magnetostrictive properties. Shaiv (205) explained r,iagnetic characteristics of Curie temperature with magnetic data on a number of alloys including 80% nicke1-20% chromium allo\ , 30% nickel-70% copper alloy, 60% nicke1-40% copper allov. I< Monel, and Inconel. Van Duwn and Dah1 (e&) determined the freezing poiiita UT nickel and of cobalt on the international scale to be, respectively, 1455" * 1' and 1495" =t1 " C., also summarizing freezing point determinations from various sources. Diuyvesteyn (88) d e t u mined yield and tensile strength, elongation. and hardness number of a number of polycrystalline metals including nickel a t hi> temperatures d o m to - 183" C. Siesle and Bricb (205),revic \ving the literature on mechanical properties of various motalincluding nickel a t subatmospheric temperatures concluded tlia t only face-centered cubic metals retain their ductility as t hi deformation temperature approaches zero. Welcer (626, 227) used gradually increasing longiLudina! impii t loads to obtain information on the elastic limit and microplastic deformation of aircraft matrrials including None! and K 1Iorwi under dpnamic stresses. Kuozynski (149) found that the elwtrical resistivitj of nickel decreases u i t h elastic elongation at constant temperature, differing from many of the other metals in thirespect. Williams (651)reviewed mechanical, phrsical, theimal and corrosion-resistant properties of nickel, llonel, K Monri nickel-copper alloys, and Inconel. Davis et a2. (86),in determining the roughness factor of sample3 of flat silver foil and of RIoriel ribbon b r absorption of several different gases including krj pton butane, and Freon 21, found the ratios of surface areas as mecisured b j adsorption and the geometric surface area to be 0.83 for silver and 0.97 for hfonel. Inasmuch as the true roughness factomust be a t least unity and probably 1.3 or more, it seems n e c ~ sari to use somewhat larger cross-sectional areas for the adsorhit+ molecule. -1 revicn- of the properties and applications of corrosion inhibitors by RIisch and hlacDonald (170) included their use mith several materials including XIonel. Fontana (99, 101) and Iieating (140) discussed stress corrosion and correctiv- mrasure5, n ith examples of stress corrosion of nickel. Fontana (100) a h discussed genpral corrosion, intergranular corrosion, and pitting iiith esamples including intergranular corrosion of nickel, Evans (9L)presented the results of fundamental studies of the in2126
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INDUSTRIAL AND ENGINEERING CHEMISTRY
fluence of residual stress on chemical behavior of metals. Transfer of oxide films from nickel to a vaseline base indicates that a state of constraint existed during attachment to metal. Causes of stress-corrosion cracking and corrosion fatigue cracking are exp l a i n d and correct,ive measures suggested. Albert ( 6 ) discussed fretting corrosion. Luc.~:( 159) summarized the corrosion-resistant properties of Chlnrimet 2 (63% nickel, 32% molybdenum, 3% iron, 1%silicon, ant1 1'; manganese) and Chlorimet 3 (60% nickel, 18% molybdenum, 18% chromium, 37, iron, 1% silicon, and 1% manganese). A series of Langalloy alloys produced in England (36) is somen-hat similar t o Hastelloy alloys in corrosion resistance. Langalloy 4R (63% nickel, 30% molybdenum, 5% iron, 0.75% silica, and 0.75% manganese) is similar to Hastelloy B and Langalloy 5R (56% nickel, 17% molybdenum, 15% chromium, 5% iron, 0.75% silicon, and 0.75% manganese) is similar to Hastelloy C. Baker and Parsons ( 5 7 ) described a nickel-base a,lloy comprising 3% iron, 0.04 t o 0.10% carbon, 17-1870 molybdenum, 17 t o 18% chromium, 1.5% silicon, 0.75% manganese, balance nickel. In reriewing certain aspects of corrosion of various alloys, including those of nickel and of cobalt, Kaidu (17 5 ) referred to several nciv alloys including a nickel-tungsten alloj- tvith 18% tungsten which is resistant to sulfuric acid, a nickel-tant,alum alloy with 307; t a ntaium, resistant to aqua regia, and a nickel-copper-tungsten alloy with 15% copper and 10% tungsten, especially resistant to sulfuric acid. Some further work has been done on the determination of nuclear properties of nickel. Ewald (96) described a method for the photometric determination of the relative abundance of nickel isotopes and the atomic weight, of nickel. I n work d o scribed by Parmley and Moyer (178) the bombardment of isoproduced a 1.75 =t 0.05 hour half-life. topes of Nie1 and Si6* Chemical extractions showed this activity belonged t o cobalt. Barschall et al. (60) measured total cross sections of nickel, iron, and bismuth for neutrons. Shaw (206) measured the packing frs,ctions of nickel isotopes. Among present uses (SO) of radioisotopes in the metal working field is the study of diffusion of nickel in nickel-aluminum alloys. A summary of nuclear data for nickel was presented by Way ( 2 2 3 ) . High Temperature Alloys. There were several reviews of the high temperature mechanical and physical properties of the numerous alloys considered for use in stress applications a t high temperatures, as for jet engine and gas turbine construction. Among the high-nickel or cobalt-nickel alloys included in one or more of these reviews were Inconel, Inconel X, Hastelloy B, Vitallium,. 5-816, S-590, K-42-B, Refractalloys 26 and 70, X-40, 422-1B(HS 30), 6059(HS 27), iY-155, and the Kimonic alloys 75, 80, and 80A. Freeman and co-workers (107, 108) gave stress rupture properties of sheet materials at, 1700" and 1800' F. and tension, rupture, and creep properties at 1200°, 1350°, and 1500" F. Phillips (182)gave stress rupture properties a t 1500" F. Grant, Frederickson, and Taylor (120) gave ductility characteristics a t 1200" to 1800" F. and creep and stress-rupture properties a t 1200" to 1600' F. Dunlop (89) discussed British, American, and German developments including the above alloys, the 60% nickel-20% chromium-20% iron and 80% nickel-13% chromium-7% iron alloys, and a new cast cobalechromium alloy called J alloy. Additional properties of the J alloy, a modified Vitallium containing 60% cobalt, 23% chromium, 6% molybdenum, 2% tantalum, and 1% manganese, were given by Grant (119). -4dditional data were given by R o d e y and Skrotzki (19Y),Woodhouse (256), Chisholm ( 7 9 ) ,and others (5,40). Kimonic alloys are used for gas turbine blading for generation of electricity in England (63). Materials used in the English Mamba (21,SB) gas turbine propeller aircraft engine and in the Turbo-Wasp engine (206) include Nimonic 80 for blades and Nimonic 75 for flame tubes. Adderley (1) reviewed German gas turbine developments during the period 1939 to 1945, including projects for power generation,
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marine, armored fighting vehicles and &craft, compoiieIit design, materials, manufacture, test equipment, and administration of g:ts turbine development. The alloy used for turbine blades was Tinidur (30% nickel, 15% chronlium, 1.77, titanium, 0.8% ma,nganeFe; o,570 silicon, 0.2% aluminum, 0.15% carbon, bnlance iron). The best creep-resisting nllcys were the DCL Heraeus alloys; a typical one DT'L 42 contained 30 to 35"/;,nickel, 22 to 25% cobalt, 12 to 17% chromium, 4 to 654 molybdenum, 4 to 6% tungsten, 1.5 to 2.5% titanium, 0.6 t o 1.0% manganese, 0.4 to 0.8% silicon, and 0.1% carbon. Schempp (196) also reviewcd German dcvelopments. Burns ( 7 2 )discussed the phenomenon of crecp and the application of creep data t o the design of high t; mperature parts. Physical and corrosion data were given (26) for :I number of alloys used for high temperature thermocouples including 80% nickel-l4% chromium-6% iron, 60% nirkel--14\% chromium-26% iron, and 32% nicke1-20% chromium-48Cjo iron alloys. Edlund, Oberle, and Strauss (93) described an alloy conFiiting essentially of 5 to 4Oy0 chromium, 1 to 40% of at least oiie metal of the group tungsten, molybdenum, and uranium, 0.05 to 7.0% beryllium, 0.25 to 7.0% boron, 0.01 to 3.0% carbon, ::nd 25 to 65% cobalt' plus nickel. Hickman and Gulbransen continued their investigation of the oxide films formed on metals and alloys a t elevated temperature? using electron diffraction techniques. In a study of the coppernickcl system (130) it was found t h a t copper oside forms the outer layer a t lower temperatures, while nickel oxide occurs on 311 alloys ahove 1300" F. A study of the nickel-chromium alloys (129) provided an explanation for the improvement in high temperature oxidation effected by additions of silicon to these alloys. The alloy with the longest life showed only the presence of chromic oxide in the surface film while smaller quantities of silicon permit formation of SiO.CrzOa. The presence of manganese and absence of zirconium, calcium, and aluminum result in chorter life which is correlated with the appearance of Ni0.Cr203. The 617, nickel-l6% chromium-Z3yo iron series of alloys does not show the same correlation of lifetime and oxide strrictures as the 80% nickel-20% chromium alloys. In a study of the reactions of metals in high vacua a t elevated temperatures, Gulbrnnsen and Andrew (121) included the vacuum oxidation of zirconium: tungsten, molybdenum, and 12% chromium-iron, and formation of carbon monoxide by reaction of carbon in metal with surface oxide on the 80% nickel-20% chromium alloy. Mahla and Nielsen (164) described an oside replica method technique for the electron microscope examination of the surface films on stainless steels, nickel, and nickel alloys. Shirai (204)found a single crystal film of nickel to be completely oxidized in 20 minutes by heating in air a t 400" C. RIeijering (168) studied some aspects of internal oxidation of alloy5 of nickel, copper, silver, and iron with small amounts of other metals. Rhines (186) found that internally precipitated oxides appear to influence the modes of recrystallization and grain growth. A 30% nicke1-70% copper alloy retained a fine grain size when annealed for a long time at high temperature in vacuum, whereas the same treatment in air produced a very coarse grain size. ZnpEe (237) made t'hermodynamic calculations for reactions of metals and alloys including nickel with moisture at 2730" to 3090' F., intermediate temperatures, and room temperatures. Wagner and Zimens (a21) determined rates of osidation of pure nickel and of nickel containing 0.3, 1.0, 3.0, and 10.0% by weight of chromium or manganese in pure oxygen a t 1 atmosphere pressure and temperature of 1000" C. Champeix ( 7 7 )found t h a t the spectral emissivity of nickel increases rapidly with temperature rise. Sintered Alloys. Miller (l69), Toerge (215), Langhammer (160), Franks (104), and Schwarzkopf (199) reviewed powder metallurgy processes including the preparation of metal ponders, compacting, sintering, and application of the products. Examples include nickel and several high-nickel alloys. 4 formula developed by Weinbaum (225) gives concentration of metal a s
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function of space, time, temperature, and particle size using 1-to-1 atomic proportions of nickel-copper alloy as an example. Duwez and Martens ( 9 1 ) described a method for producing porous metals and alloys having controlled permeability using nickel and 80% nickel-20% iron alloy as examples. Goetzel (118) produced high temperature-resistant materials by powder metallurgy, especially the infiltration technique for making refractory materials and hard metallic compounds. Examples include a chromium boride-nickel alloy and a hot-forged tungstennickel alloy. Duwez and Wheeler ( 9 2 ) made an experimental study of cooling by injection of a fluid through porous materials including nickel. Schlecht ( 1 9 7 ) described the production and properties of carbonyl nickel powder and nickel-iron powders in Germany. Hausner (126) dealt with metal ceramics, a new field in powder metallurgy. The ceramals, or combinations of ceramic materials and metallic powders, find a useful field in production of high temperature-resisting materials. Examples include mixtures of titanium dioxide and nickel powder and mixtures of alumina or silicon carbide and nickel powder. A sintered alloy of tungsten, copper, and nickel known as Hevimet ( 9 , 39) has a density 50% greater than that of lead, and is applicable to the design and construction of moving parts possessing maximum inertia and minimum size. Combining high tensile strength and good machinability, i t is highly resistant to atmospheric salt water corrosion. The average product has a density from 16.8 t o 17 grams per cc., tensile strength of 85,000 to 118,000pounds per square inch, and Rockwell hardness of 30 t o 40 C. Kramer (148) described the development of the modern version of the Hametag mill for production of metal powders including nickel. Sheath rolling of powdered metal compacts was investigated by Long and Hayes (164). FABRICATION
Considerable use now is being made of inert-gas shielded arc welding of high-nickel alloys. Herbst and Pilia ( 1 2 7 ) dealt with the Heliarc welding of nickel, Monel, cupronickel, Inconel, and the Hastelloy alloys, including discussion of joint constructions, limitations on thickness of mateiials, weld strengths, and other design data. A review ( 2 5 ) of technological advances in welding during 1948 includes discussion of developments in inert-gas shielded arc welding of Inconel, Monel, and other alloys. Reviews by Schreiner and Tippett ( 1 9 8 ) , Strutz ( d l f ) , and others (48) of fabrication methods for railroad equipment, described both inert-gas shielded arc welding and submerged melt welding of Monel, nickel, and other nonferrous alloys. -4bulletin of the International Nickel Company gives procedures for inert-gas shielded arc welding of Monel, nickel, and Inconel (156). Chyle (81) discussed factors to be given consideration in the design and fabrication of welded lightweight pressure vessels, including selection of material, operating stressesand safety factors, selection of welding processes, inspection, heat treatment, proof testing, and final qualification of product. Nickel, Monel, and Inconel are among the materials included. How (133) developed charts to permit quick estimates of the cost of plate cutting, rolling, edge preparation, welding labor, welding rod, and flux for butt and fillet welds of U-69, U-70, and A.P.1.-A.S.M.E. vessels of various materials including nickel-rlad steel. Maintenance welding of plant equipment in the heavy chemical industry was discussed by Fuchs and Godfrey (114). Colwell and Cummings ( 8 2 ) and Chisholm (80) discussed problems of welding the high-temperature alloys used in jet engine construction. In a review of spot welding as a production process, Bolz ( 6 7 ) included nickel and hlonel in tables of weldability ratings. Seam welding of Monel vapor-tight evaporators in industrial refrigerating lines was described ( 2 4 ) . Lardge (152) described the application of spot, stitch, and seam welding to jet engine parts including spot welding of Inconel, Nimonic 75, and other high temperature materials. Miniature resistance welding and appli-
Vol. 41, No. 10
cation of spot and projection welding t o nickel strip in the radio tube industry were discussed by Freedman (106). Nickel welding electrodes are used in repairing castings and machining errors ( 2 3 ) . A welding electrode ( 1 71 ), suitable for uniting nickel-chromium or nickel-chromium-iron alloys, contains 76 to 80% nickel, 16 to 20% chromium, and 0 to 4% iron in the mire a i t h silicon and columbium preferably in the flux coating. An automatic butt welder is used for welding nickel ground wire t o spark plug shells ( 5 2 ) . A number of metals including nickel can be successfully “cold” welded ( 4 ) . Wakefield ( 2 2 2 ) , Rowan ( 1 9 2 ) , ilvery (55), and others ( 5 1 ) reviewed the application of metallic coatings by spraying or metallizing procedures. The discussions include the application of sprayed coatings of Monel, nickel, and other high-nickel alloys and of cobalt-base and nickel-base hard surfacing materials. Batsford (61 ) described applications of metallization to maintenance problems in petroleum refineries. Dickinson (87)gave recommended cutting speeds, feeds, and tools for machining sprayed coatings of Monel and nickel. A description (75) of a method of coating metals with metals and alloys includes examples of iron wire coated uith nickel and hlonel and molybdenum wire coated with a platinum-nickel alloy. A review ( 2 2 ) of brazing techniques and applications included an example of brazing molybdenum to nickel for Klystron parts. A comparison of techniques of brazing included torch, resistance bath, furnace, and induction brazing, and gave nickel and hlonel examples. Beatson ( 6 2 )gave procedures for the welding, brazing, and soldering of coated metals including nickel-plated steel. Tolley ( 2 1 6 ) reviewed electrolytic polishing methods and applications including nickel, Rlonel, and nickel-copper alloys. ilnother review (20) covered American developments in the electrolytic polishing of nickel. -4continuous method of electropolishing nickel and high-nickel alloys was described by Faust and Miller ( 9 7 ) . Renews by Durkin ( 9 0 ) and by hlacSair (163) covered the chemical surface treatment of metals including alkaline cleaning, solvent degreasing, pickling of ferrous materials, brass, and stainless steel, phosphate coatings, and chemical treatments of aluminum and magnesium. .4 description of the sodium hydride method of descaling nonferrous metals and alloys including hionel, nickel, Inconel, and their clad steels was given by Alexander ( 7 ) . Rosen and Black (191) gave methods for pickling Monel, including removal of grease, oils, fats, tarnish, reduced oxides, oxide film or scale, and embedded iron particles from the surface. A method for flash pickling of nickel and Monel was described by Pray and Igelsrud ( 1 8 5 ) . Manler (165) and Rosen (190) reviewed mechanical polishing and buffing of metals including nickel and hlonel. -4review ( 5 ) gave practical guidance on the machining of high-nickel alloys. Pattison (180) and Taylor (212) described the manufacture and applications of clad-steel plates including nickel, Monel, and Inconel-clad steels. A review discussed the forging of some of the high temperature alloys, including 5-155, S-590, S-816, Hastelloy alloys B and C, Refractalloy, and Yimonic 80. Information and data necessary to appraise the potentialities of investment casting as a means of reducing costs or impioving peiformance are given by Wood and Von Ludwig (254). Among the nickel or cobaltnickel alloys obtainable in this form are Vitallium, Multimet, Hastellov C, Monel, H Noriel, S Monel, nickel, Inconel, Msco 20, S-590, S-816, 61 HS 23, and 6059 HS 27. hlethods of identifying alloys by spot testing were described by Kirtchik (14.2). Zeeh (639)compiled a data sheet from library and laboratory research, giving quick methods of identification for corrosion-resistant alloys including use of the electrograph. hIonel and nickel are among the materials included in a summary ( 5 3 ) of simple tests for identifying metals by appearance, chip tests, and blowpipe tests. Wrought Bastelloy and Multimet alloys now are available (14) in the form of drawn wire for such applications as metal spraying, welding wire, wire screen, wire cloth, and springs.
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Blair (65) described the production electroforming of intricate shapes or articles of high design from nickel. Electroforming can be done at the rate of 0.010 inch per hour. Nickel tubing with 0.005-inch wall can be electroformed cheaply and with high prccision. Examples (8) of nickel electroforming include fountain pen caps, electronic parts, and fine-mesh screens. Mechanical properties of plated nickel deposits were summarized by Roehl (189). Wernick and Willetts (228) discussed heavy nickel deposition as a manufacturing operation. Several authors (15,28,34, 58, 117, 177, 208-210) discussed the application of metallic coatings, including nickel, by high vacuum distillation of the metal. Such coatings appear to provide good surface and uniformity with comparatively high speed production. A method for plating nickel by chemical reduction on the receiving surface was rccrntly developed by the Bureau of Standards (44). APPLICATIONS
High Temperature. Applications of high-nickel and highcobalt alloys at the high temperature associated with jet engine and gas turbine operation have been referred to in the previous section on high temperature alloys. Because of their good mechanical and physical properties, there has been continued increase in their use for other high temperature applications including heat treating and chemical processing equipment. Glick and Harlepp (116) described the use of Inconel and S i chrome fixtures in induction heating furnaces. Littlejohn ( 153) rderred to the use of nickel-chromium and nickel-copper alloys in the manufacture of resistors in high-current control instruments. Ivanso (137) summarized some of the applications of wrought Inconel in heat treating equipment. Inconel sheet is used for construction of annealing hoods (10). Weber (224) described the use of Inconel flatwire brazing trays. A preheated furnace ( 4 7 ) operating with a wide operating range of 400" to 18.50 F. uses nickel-chromium alloy heating elements. Equipment described by Sanderson (195) for heat-treating stainless steel in a molten sodium carbonate bath uses immersed Inconel heating electrodes for the bath. A new highly sensitive nickelnickel-molybdenum thermocouple that will stay on calibration in reducing atmospheres a t temperatures as high as 2100" F. was announced ( 3 8 ) . A gas turbine thermocouple ( 6 7 ) combining high rate of response x i t h excellent life expectancy uses Inconelsheathed lcad wires and Chrome1 terminals. Inconel-sheathed tubular electric heating units arc used in a new line of all-metal electrical infrared radiant heaters ( 5 3 ) . Hammerquist (122) described materials used including nickel alloys in the construction of equipment for production of high purity manganesc. A4thermoflex blanket material used to insulate jet plane parts against evhaust cone heat is sandwiched between layers of Inconel wire mesh ( 2 ) . Bvehinsky (74) discussed materials currently used in heavy-duty spark plugs including a iiickel-chromium-beryllium alloy. Binsey (141) described materials used, including nickel, in the construction of a high temperature creep testing machine. Main (149) referred to the use of nickel containers to hold molten brazing fluv. According to Kautz (139) the use of a nickel flash on steel to be coated u-ith 1300O F. enamels promotes adherence, Ion-ers bonding temperature about 50" F., and produces white coats with greater opacity. .4 time fuse element described by Fraser and Bennett (105) utilizes a finely divided nickel produced by distillation from a mercury-nickel amalgam. Crede (85) described a number of alloys used for glass-to-metal seals, including iron-nickel alloys containing 42 to 48% nickel. Inconel is among the materials suitable for application of a ceramic coating having resistance to high temperature oxidation (124). Petroleum Refining. Morton ( 17 4 ) reviewed metallurgical means of combating corrosion and abrasion in petroleum refining including current applications of nickel alloys. Fragen et al. (103) found that corrosion by the aluminum chloride-hydrocar-
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bon complex in the liquid phase isomerization of light hydrocarbons causes penetration of carbon steel a t the rate of 1 to 5 inches per year in the reactor and may reach 15 inches per year at points of high turbulence. To prevent corrosion, reactors were lincd with gunited Lumnite cement and nozzles with flanges and valves of Hastelloy B. Evering and d'Ouville (95) referred to the use of Hastelloy B liners in similar reactors for production of neohexane. Treseder and Wachter (218) pointed out t h a t thc addition of 0.2% antimony chloride to the aluminum chloride-hydrocarbon complex in a similar isomerization proccss at 80' C. would reduce corrosion of nickel from 0.17 to 0.008 inch per year. Certain other chloride salts such as sodium, calcium, or potassium chlorides also appear to be effective corrosion inhibitors (217) in similar processes. Furth (115) described the application of Monel-clad stcel tube sheets to prevent corrosion in refinery heat exchangers using nonferrous tubes. Brown and Strong (71) described the applications of Monel for lower section of debutaniaer, reboiler, caustic stripper tubes, caustic heat exchangers, and channel head linings in a plant for removal of mercaptans from refinery products using a caustic methanol process. Rlumer (66) described uses of hIoncl for lining top sections of crude distillation towers and for other overhead equipment for resistance to hydrochloric acid conditions. .Inew type of helium liquefier described by Scott (201) has a thick-walled Monel chamber designed to withstand a pressure of 4100 pounds per square inch. After 9 months' service, thcre was no noticeable corrosion of nickel plating on a n A.P.1.-type pipe joint used in a corrosive distillate well (173). Brown (10)gave the results of corrosion tests made with cast nickel-silicon alloys and other materials in t,he reboilers of sulfuric acid concentrators. I n the commercial synthesis of basic orgariic chemicals by thc direct oxidation of aliphatic hydrocarbons, described by Foster (102), corrosion of equipment was prcvented by the use of stainIcss steels and Monel. Chemical Processing. I n a series of published symposia dcscribing the performance of matcrials of chemical plant construction with various common chemicals, Friend (109) dealt with nickel, Monel, Inconel, and Ni-Resist ; Chisholm (78) with the Hastelloy alloys; and Luce (168) with the Chlorimet alloys. The chemicals covered in these symposia include sulfuric acid, industrial alcohol, hydrochloric acid, and fatty acids. .I review (13) of const,ruction materials used for thc production and handling of various chemicals included refcrence to the use of Hastelloy alloys with acetic acid and acetic anhydride; Monel with cane sugar solutions; nickel and Monel with sodium hydroxide; >Ionel, nickel, and Inconel with fatty acids; Monel with hydrofluoric acid; Hastelloy B and nickel in the production and handling of synthetic phenol; t,he Hastelloy alloys and Illium with phosphoric acid; Monel and nickel with soap and glycerol; Monel and Inconel in manufacture of sulfate pulp; Chlorimet alloys in sulfuric acid manufacture; and Inconel in thc storage and bottling of whisky. -4symposium on modern metal protection included discussion of corrosion-rcsisting applications of Hastelloy alloys by Long (156) and of some high-nickel alloys by Tecple (213). A review of corrosion-resisting metals and alloys by Butterill (79) included applications of Monel in cyanide and other solutions in metal rcfineries. A reviety (214 ) of applications of corrosion-resistant materials in pulp and paper mills included those of Monel, nickel, Inconel, and Hastclloy C. Monel and the Hastelloy alloys were among the materials included by Richelson (187) in a survcy of eonstiuction matcrials for jct pumps. Compton and Mendizza (89) discussed corrosion of telephone outside plant materials including Llonel. Friend (210) reported the results of corrosion tests of nickel and high-nickel alloys in inorganic sulfates, including ammonium sulfate, aluminum sulfate, ferrous sulfate, manganesc sulfatc, nickel sulfate, zinc sulfate, chromium sulfate, and potassium persulfate. I n the description of a plant for the production of
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INDUSTRIAL AND ENGINEERING CHEMISTRY
various barium compounds, White (250) referred to the use of Monel pumps, piping, and filters in production of barium carbonate and barium chloride, Monel evaporators for barium carbonate and barium chloride, nickel-clad steel fusion pots, and Monel flakers in production of solid sodium sulfide. I n the description of three new plants for production of sodium hydroxide (11, 16, 1 3 , 232) reference is made t o the use of nickel-clad and Ineonelclad steel evaporators, Inconel and nickel piping, and Monel, nickel, and Inconel circulating pumps. I n a description of a new process for the semicontinuous deodorization of fats, Bailey ( 5 6 ) referred to the use of nickel for the deodorizer tower, trays, steam distributor, and heating coils. Ziels and Schmidt ( 2 4 0 ) ,in a study of the catalytic effect of metals and light on vegetable fats and oils, found that nickel and aluminum were the only metals among those tested which were entirely free of any pro-oxidant effect upon the fats. I n a discussion (46) of the trend to the use of corrosion-resistant alloys for soap plant equipment, reference is made t o the use of nickel or high-nickel alloys for soap kettles, crutchers, cutters, mixers, dies, piping, and saponifying tanks. Barnebey and Brown (59) described the use of Inconel for high-temperature fat splitting tower, fatty acid storage, and piping in a plant for continuous fat splitting by the Colgate-Emery process. A new plant for continuous soap production utilizes nickel and nickel-clad steel for sodium hydroxide tanks and circulating lines, for brine heaters and circulating lines. and for soap and lye lines, and forged Inconel bowls for centrifugm Friend and Mason (112) presented the results of plant corrosion tests including nickel alloys in the processing of soap and of fatty acids. Tests in soap plants were made in caustic storage, brine storage, soap kettle, acid and alkali treatment of spent soap lyc, crude glycerol evaporation, finished glycerol stills, and glycerol bleaching and storage, Tests in fatty acid processing were made in Twitchell splitting, continuous high temperature splitting, distillation, acid washing, and storage. A new plant ( 1 2 ) for the production of synthetic glycerol utilized nickel and nickel-clad steel for glycerol evaporators and finished glycerol storage. Sickel reactors were used for the polymerization of vinylidene fluoride, for polymerizations involving l,l-dichloro-2,2-difluoroethylene (161), and for the chlorination of ethane (160). A nickel-lined pressure vessel was used in the fluorination of carbon tetrachloride (76). Apparatus for the dehydrofluorination of polyfluoroalkanes includes a reactor of nickel or Inconel (162). In a discussion of industrial fluorine chemistry, Finger and Reed (98) referred to the use of Monel and nickel for handling hydrofluoric acid. Rudge (194) reviewed the preparation, properties, and handling of elemental fluorine including applications of nickel. A review (132) of the development of equipment for alkyd resin manufacture referred to the use of nickel, Inconel, and Rlonel resin kettles, I n describing a new process for the utilization of waste sulfuric acid pickle liquors and zinc waste, Kraiker ( 1 4 7 ) referred t o the usc of Monel in the handling, evaporation, and drying of zinc sulfate and zinc chloride, and of Hastelloy C with solutions containing chlorine. Monel pickling equipment is used for the sulfuric H C I pickling ~ of iron and steel (51) Corrosion tests (29) in brass and copper pickling solutions included nickel and nickel alloys. The selection of metals, including Monel, and of coatings for fan systems handling corrosive and abrasive fumes was discussed by Langlois (151). Sickel-plated brass was resistant to corrosion bl salicylanilide and 2-naphthol used as fungicide for cork ( 8 4 ) . In corrosion tests (229) to determine the effect of noncondensable gases in steam, nickel was corroded by water saturated with certain mixtures of carbon dioxide and air a t 35 pounds per square inch gage pressure. Inconel, tin, and stainless steel were completely resistant. Corrosion tests by Zarubina (258) in atmospheres containing sulfur dioxide included nickel plating. Pray et al. (184) studied the corrosion resistance of metals in the products of combustion of flue gases. Inglesent et al. (134, 135) investigated the corrosion of filters in
Vol. 41, No. 10
sugar refineries. The investigation included measurements of galvanic potentials between various common constructional metals, including Monel, in sugar liquors at several temperatures. Factors influencing corrosion of nickel alloys in the dairy indust r y were studied by Pattison (179). A long-term corrosion investigation (60) of corrosion in sea water, tropical fresh water, and marine atmosphere in the Panama Canal Zone incorporates 52 different metals and alloys including Monel and nickel. Bethon ( 6 4 ) reviewed the experience with various materials of construction in steam condensers on Navy vessels including the use of solder-coated Monel sea water boxes of sectionslixed type. Hansom (125) reviewed some applications of nickel alloys in marine engineering. Some miscellaneous applications are recorded for high-nickel alloys, including a hand-operated metal degreasing unit of nickelclad steel ( 5 4 ) ; a new pressure indicator using K Monel Bourdon tubes ( 4 1 ) ; a i i w flon. calorimeter developed by the Bureau of Standards using a >Ionel calorimeter tube (200); a large mass spectrometer using Sichroine V for central frames and guard rings (167); a device for producing mechanical vibrations of very high frequencies, incorporating magnetostrictive rings of nickel 1219); metallic asbestos-filled gaskets of nickel and Monel (49); and a corrosionproof motor using Monel for the outside shell and the fan cover ( 3 5 , 4 2 ) . Other applications include Monel panels on a Flakice machine (207); Monel cooling coils in an ice cream machine (18); a time capsule of Monel to be buried and opened in the year 2047 (46); a cadmium-nickel alkaline storage battery made in this countrv !19); and a hlonel expansion joint ( 1 7 ) . BIBLlOGRAPHY
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INDUSTRIAL A N D E N G I N E E R I N G C H E M I S T R Y
(48) Anon., Tool Engineer, 20, KO.5, 61 (1948). (49) Ibid., 21, No. 4. 56 (1948). (50) Anon., U. S. Panama Canal, Special Eng. Div., First Interim Report, No. 74, Appendix 1 (January 1947). Anon., Welding Engr., 33, No. 3, 62-4 (1948).
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