Nickel and HighaNickel Alloys H. 0. TEEPLE The International Nickel Co., Inc., New York 5, N . Y .
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Although nickel is still under government control and hence is available only in limited quantities, the commercial importance of nickel and its alloys prompted a continuing large number of studies and investigations which were reported in the literature during the past year. About 40% of the literature references pertained to the various physical properties; about 16% pertained to the various fabrication processes and techniques; and about 36% pertained to the various applications of nickel and nickel alloys. These studies point up the fact that the many favorable properties of nickel and its alloys can be used to achieve reasonable success in solving many industrial problems.
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HE current annual review of published references relating
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to nickel and nickel alloys is similar to the previous one (838). Alloys containing about 40% or more of nickel or appreciable quantities of cobalt comprise the materials considered for this review. The subject matter is divided into three general classifications: development of new alloys or improvements in present ones and studies of their physical properties; development in the fabrication and working of these alloys; and developments in the application of these alloys with particular reference to the chemical and process industries. Although nickel is still under government control, additional supplies are being developed which probably will relieve the tight situation to some extent. These newer developments are described in several articles. Davis (61)reviewed the nickel output, U. S. consumption, imports and exports, and developments of Falconbridge nickel mines, Nicaro, Hanna Development Co., Cobalt-Nickel Reduction Co., and Sherritt-Gordon. It was mentioned that gains in nickel consumption were most pronounced for the stainless steels, nonferrous metals and anodes and that the use of nickel in engineering steels and cast irons was about the same as in 1951. During 1952 Inco undertook prospecting for copper-nickel ores in northern Minnesota. Two nickel discoveries were reported in the Yukon territory, and permits were granted by the Bureau of Land Management to prospect for nickel-copper ore in the Superior National Forest, Lake County, Minn. The supply of nickel is discussed (%), and it is reported that the Defense Materials Procurement Agency signed an agreement with M. A. Hanna Co. for developing nickel deposits a t Riddle, Ore. Riddle ore is low grade and too expensive to produce under peacetime economies. National Lead Co. is building a plant to separate the nickel-copper-cobalt concentrate that is a by-product of its lead production, and a sizable addition to normal supply comes from the Nicaro plant in Cuba owned by the U. S. Government. Messner (170) presented an historical review of production, refining, fabrication, and price of nickel. World production from 1941 to 1950 and estimated ore reserves are tabulated. Flow sheets are presented showing the refining of nickel. Cormwall and Burbank (47) presented a discussion of the history of nickel industry, development of nickel and its forms, uses and properties, geology and mineralogy of nickel, world resources, economic factors of nickel ores, mining, milling, and metallurgical processes used in producing nickel and methods of marketing. A brief description of cobalt is presented (62)which includes a
history of its development and uses, a description of ita minerals, metallic forms and salts, and an outline of methods of marketing. A survey is presented (88) on new developments in metals extraction. Among the various developments described are Inco’s matte flotation process as well as other processes for recovery of nickel from some of the more recently found deposits. Downie (69) described researches on nickel converter practices that include differentconverter procedures, variations in handling nickel and nickel-copper matte, and electrically heated converters. Downie (60) gave a brief account of practical engineering details necessary for operating furnaces for a specific nickel smelting capacity. Electrical circuits, associated stack dimensions, foundations, and pumping features for specific ground and water supply conditions and designs of equipment selected are discussed. He also compared the efficiency of electric hearth and blast furnace practice in the smelting of nickel ores (61). After a discussion of constructional details in connection with air blast, the author draws the conclusion that, provided reliable air blast conditions exist and a straight run of the same briquet are used, the total cost of air blast practice remains less than those incurred by electric smelting. Rasmussen (808) described a cooperative research program on the production of ferronickel from nickel silicates that provides data for the planning of a production smelter in southwestern Oregon. It was found that the ratio of nickel to iron in the ore is high enough to produce alloy pig iron of about 15% nickel grade without recourse to selective reduction smelting. Such nickel pig iron, which also contains chromium, should be useful in the manufacture of low alloy constructional steels. Hammond (100) described the installation of an 8-ton steam forging hammer, which is successfully working in the Huntington Works of Inco. The hammer has a fully vibration-controlled mounting and is used for the hot forging of nickel alloy ingots. This installation was the first that was fully analyzed for shock, vibration, movements, and loads in all directions and the first in which prestressed concrete was employed for inertia blocks. Diagrams and photographs are shown. Hunter and Vergnano (113) reported in Aberdeenshire that crops are seriously affected by nickel toxicity, resulting from abnormally high nickel content of the soils. These soils and plants and certain aspects of nickel toxicity in plants grown under controlled conditions were examined, and the more general features of the investigation are described. Most corrective treatment for nickel toxicity is the application of lime with nitrogenous and potassic fertilizers. Nickel toxicity symptoms and nickel content of plants are given. GENERAL PHYSICAL PROPERTIES
There were a few discussions in the literature pertaining to various general physical properties of nickel and nickel-containing alloys.
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Uhlig (246) studied the metal surface phenomena and pointed out that valence forces a t the surface of a metal lead to a state of tension of the surface atoms and account for adsorbed films of substances bonded to metal surface in varying degrees, Such adsorbed layers account in a major part for friction and lubrication phenomena, catalytic activity, passivity and corrosion resistance, particularly of the transition metals. In the discussion, comments are presented on the behavior of the Hastelloys, Stellites, Monels, and Inconels. Tables and graphs are presented. Gay, Hirsch, and Kelly (88) carried out recent work showing that substructures are formed within the grains of a cold-worked polycrystalline metal. The methods used are described, and the methods can be extended to give estimates of excess and total dislocation densities within the particles and the densities in annealed metals. The metals investigated were aluminum, copper, gold, lead, nickel, tin, and zinc. Low expansion nickel alloys are described (162), and mention is made of the fact that the most widely used are 36% nickel for low expansivity up to about 400"F., 42% nickel for temperatures u p to 650" F., and 4 i to 50% nickel up to 1000" F. Physical, mechanical, and fabricated properties, thermal treatment, corrosion resistance, available forms, and uses are outlined in tabular form for these alloys. Trumpler and Meyer (2.45) studied the anodic behavior of nickel. The description of the apparatus and technique for these studies is presented. A critical potential was found, characteristic of an intermediate electrode state, leading either to passivation or activation, and from which, for sufficiently small potential adjustments, transition to either end-state slowly ensues. This critical potential is sensitive to hydrogen ion concentration and strongly affected by the presence of chloride ions. Austin (7) presented a table giving the composition, state, elastic and mechanical properties, specific damping capacity, and corrodibility in fresh and sea water for a number of materials of construction including nickel and nickel-base alloys. Johnson, Swikert, and Bisson (124-126) studied the wear and sliding friction properties of those nickel alloys retaining mechanical properties above 600" F. when operating against hardened SAE 52100 steels. Alloys tested were cast beryllium nickel, heat treated beryllium nickel, cast Inconel, Nimonic 80, Inconel X, Refractalloy 26, and Discaloy. On the basis of these tests of wear and friction properties, cast Inconel performed very well and compared favorably with nodular iron. Nimonic 80 also showed promise as a possible material. Graphs, photomicrographs, and tables are also presented. The properties are listed (161) of comnionly used spring materials including nickel and nickel-base alloys. Tables are presented which include tensile, hardness, and torsional properties. Dismant, Hamilton, Fassell, and Lewis (67) in a study of the decarburization of high carbon cobalt reported that an effective method of reducing the carbon content of the cobalt that is prepared in the arc furnace makes use of the fact that the cobalt metal is decarburized by carbon dioxide a t the temperature of the molten metal. Two methods were used: ( a ) the carbon dioxide was bubbled up through the molten cobalt, and ( b ) the molten cobalt was maintained in a carbon dioxide atmosphere. A high frequency induction furnace was used to keep the cobalt molten in both of these experiments. Tabular results are presented. COMPOSITION OF ALLOYS
During the year there were several investigations reported on the properties of alloys from the standpoint of composition. Taylor and Hinton (236) studied order-disorder and precipitation phenomena in nickel-chromium alloys. The electrical resistivity, specific heat, and x-ray measurements on NiaCr and NilsCr4Al show that both alloys undergo an order-disorder type of transformation at approximately the same temperature and an additional high temperature transformation occurs in NiI6Cr4A1 consistent with precipitation and resolution of a second phase.
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Taylor and Floyd (235) discussed in detail the constitution of nickel-rich alloys of the nickel-chromium-aluminum system. The equilibrium relationships in nickel-chromium-aluminum alloys containing more than 50 atomic % nickel were studied a t 750" to 1150" C. A newly developed coating alloy is described ( 7 S ) , and many applications for high temperature use are described. The alloy is nickel-base and contains chromium, aluminum, and molybdenum as well as other minor additions. I t is claimed to resist oxidation at all temperatures up to 1250 C. It is also reported that, provided the iron content of the alloy is kept below 1%,the alloy is highly resistant to lead oxide and lead oxybromide at temperatures up to 800" C. Poulignier and Jacquet (205) gave a detailed account of basic investigations on alloys of the Kimonic 80 type after simple aging a t high temperatures and after creep. Methods used were mechanical polishing followed b y chemical attack, including a special reagent developed b y C. Buckle and described in Compt. rend., 233, 869 (1951). The authors discussed the results dealing with relationship of structures a t high temperatures to creep properties. Data are presented on the advantages of the Buckle method for examining evolution of solid solution during heating, applications of methods described to investigation of phenomena relating to cold-work sensitivity, and the evolution of structure during high temperature oxidation in air. Ornitz and English (192) discussed the properties of a new alloy (46% nickel, 23% chromium, 5.28% tungsten) and compared this alloy NA22H with other heat resisting alloys. Graphs and tables are presented. Development is reported (227) of a heat resisting alloy (NA22H) that permits practical engineering applications at tempei atures u p to 2200" F. Tensile strength, tensile creep, and rupture properties, thermal expansion, oxidation tests, and welding characteristics are discussed. Applications are reported including the installation of 44 radiant tube assemblies in a continuous furnace for the annealing of strip and fabrication of retorts for endothermic gas generators. Analysis of the sample used in tests was 0.44% carbon, 26.3% chromium, 46% nickel, 1.36y0 manganese, 0.99% silicon, and 5.28% tungsten. A new alloy, Hastelloy X, is announced (160, 1'79) for high temperature service. The alloy contains 45% nickel, 9% molybdenum, 22% chromium, 0.15y0 carbon, and balance iron. Tests show the alloy has excellent forming characteristics, good high temperature properties, and high resistance to oxidation. A comparison of the wrought Hastelloy X and Multimet (N-155) is given in tabular form. An article is presented (228) indicating the demand for materials of superior strength and durability and the need for conservation of critical metals. Such a situation has sped the search for new improved alloys. High nickel alloys and nickel allow containing appreciable quantities of cobalt are discussed. It is mentioned that Hastelloy X is designed to replace strategic cobalt- and columbium-bearing alloy and also some high nickel alloys. The composition of the Haynes alloy No. 99, which uses high temperature scrap, is given: 20 to 22% chromium, 2 to 3% tungsten, 11 to 13% cobalt, 17 to 19% nickel, 3 to 4% molybdenum, 0.03 to 0.08% boron, 1% silicon, 1% manganese, and balance iron. A new alloy, developed by the Haynes Stellite Co. (40) is called Hastelloy F. The alloy is designed to be intermediate in price, workability, and corrosion resistance between the austenitic stainless steels and the nickel-molybdenum alloys. Information pertaining to its corrosion resistance, its mechanical and physical properties, and its welding characteristics are given. The only industrial use to date is for the lining of a sulfite pulp digester fabricated by A. 0. Smith Corp. (Figures 1, 2, and 3). Taylor and Floyd (234) studied the constitution of nickel-rich alloys of the nickel-titanium-aluminum system. They found that over the range 750" to 1150' C. micrographic and x-ray @
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COURTESY HAYNES STELLITE CO.
Figure 1. Hastelloy Alloy F Used as a Lining in Top Vapor Zone of Sulfite Pulp Digester A view of largest alloy-lined digester ever made being assembled for field erection
diffraction techniques (1) show that a t 750" C. the face-centered cubic primary nickel solid solution holds more than l2-atomic yo titanium and aluminum in solution. The y phase is in equilibrium with the intermetallic compound, q Ni3Ti, and the extensive face-centered cubic ordered phase, 7' based on NiaAl. A brief survey of alloys with 50 atomic % nickel revealed a ternary Ni2TiAl phase, p3, with a Cu2ZnAl type of structure, in equilibTium with the plNiAl and p2NiTi phases, which have CsCl type structures. The boundaries of the y- and 7'-phase fields in the nickel-aluminum system have been revised.
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The binary nickel-chromium and nickel-titanium systems were re-examined by. Taylor and Floyd (833)using x-ray diffraction and micrographic techniques. New equilibrium diagrams are presented. Isothermals for nickel-rich nickel-clymium-titaaium alloys were constructed corresponding to 750 , lOOO", and 1150' C. Isoparametric contours were drawn for the nickelrich primary solid solutions. The boundary separating magnetic from nonmagnetic ternary ?-phase alloys a t 20' C. is indicated in the nickel-chromium-titanium diagram. Margolin, Ence, and Nielsen (166) investigated the titaniumnickel phase diagram up to 68% nickel. Methods used were metallographic, x-ray, and melting point. Alloys from 68 t o 90% nickel were made by examination of as-cast structures of sponge titanium-base alloys. Several features of the phase diagram are given along with photomicrographs and graphs. Das, Rideout, and Beck (60) studied the intermediate phases in the molybdenum-iron-cobalt, molybdenum-iron-nickel, and molybdenum-nickel-cobalt ternary systems. I n these three ternary systems a t 1200' C. the p-phase forms narrow, elongated hernary solid solution fields. If the electron vacancy numbers assigned to molybdenum, iron, cobalt, and nickel are 4.66, 2.2, 1.71, and 1.6, respectively, then the eloqated p-phase fields in the above ternary systems correspond quite well to a constant electron vacancy range of about 2.95 to 3.25. The alloying behavior of the p-phase is entirely analogous to that previously found for the u-phase. Phase diagrams and photomicrographs are presented. Metcalfe (174) investigated thermal and dilatometric characteristics of alloys of cobalt with chromium and molybdenum. Temperature observations were used to investigate the phase changes above 1100" C. in alloys containing more than 50% cobalt. The nonsuppressible transformations in cobalt above 1120" C. and in the intermetallic compound Co2Cr3were studied. The liquidus and solidus surfaces were determined. Insufficient data were obtained to complete the constitution diagram. Kieffer and Kolbl(188) $iscussed in detail the development and properties of heat- and scale-resistant hard alloys based on titanium carbide with nickel-cobalt-chromium binders. The results of important researches are tabulated for titanium-rich sintered carbides, with end without binders. The chemical compo-
sition of the various nickel-base alloys used as binders is given; the performance of one of the materials is described as a turbine rotor, which gave satisfactory service a t 30,000 to 35,000 r.p.m. with a blade temperature of 1020" C. Reynolds, Freeman, and White (811) studied the influence of chemical composition on rupture properties a t 1200O F. of forged chromium-cobalt-nickel-iron-base alloys in solution-treated and aged conditions. They found that the use of careful control over processing conditions in this investigation showed that for forged alloys containing chromium, nickel, cobalt, iron, molybdenum, tungsten, and columbium it was possible to correlate the stress rupture properties a t 1200' F. with systematic variations in chemical composition and, further, that wide range in properties can be obtained by such variations. Rupture strengths were a function of the effect of composition modifications on both the inherent creep resistance and the amount of deformation the alloy would tolerate before fracture. Tables, graphs, and photomicrographs are shown. Hagg and Kiessling (98) studied ternary metal-boron systems which included cobalt-manganese-boron, cobalt-iron-boron, and nickel-manganese-boron. In such terna ry systems-Mel, Mea-B-where Mel and Me2 both belong to the first series of transition metals, the distribution of the metals between the two phases Mel, Men-B and (Mel, Me2)2-B in equilibrium with each other, x-ray methods show that the metal with the lower atomic number is always concentrated in the phase richest in boron. This indicates that the transition metals in the first series are more btrongly bound to the boron, the lower their atomic number. Beattie and VerSnyder ( 1 4 ) studied the x-ray diffraction and microstructural characteristics of experimental iron-base, cobalt-base, and nickel-base alloys. The alloys studied were 50% iron, %yonickel, and 16% chromium for the iron-base alloys. The cobalt-base materials were 5001, cobalt, l6Y0 nickel, and 19% chromium. The nickel-base materials were 50% nickel, 19% chromium, lOyo cobalt, 10% molybdenum, and 3% titanium. The high temperature alloys show the effects of titanium and molybdenum as alloying additions; formation and occurrence of TiCN and NbCN; intermetallic compounds M2Ti and Fe2Al; a new phase CrMoN,; and the second Brillouin zone of MeC and M2& has a capacity for approximately seven electrons per metal atom. The deoxidation technique is described (38)in the melting of copper and nickel-base alloys. The oxidation-reduction technique is the best means of securing clean, gas-free, high fluidity
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metal. With high conductivity copper, calcium boride, calcium copper, or lithium metal are recommended as deoxidants. For commercial copper, a mixture of phosphorus and silicon gives excellent results. Magnesium or a combination of magnesium, boron, and manganese are used as deoxidants for nickel and the nickel-copper alloys, such as nickel bronzes, nickel silvers, and Monel. Vacher (247) described a twin-boundary method found to be useful for determining the orientation of crystals in annealed Monel. The results indicate a qualitative relationship between crystal orientation and the extinctions of polarized light reflected from the crystals. The optical anisotropy of etched Monel metal surfaces probably was caused by parallel furrows formed by the tendency of the etching reagent to develop etch pits whose facets were parallel to cubic planes. Tables and photomicrographs are also included. Ellwood ( 6 8 ) studied lattice vacancies and porosity in coppernickel alloys and found that vacancies occur in such alloys when they contain less than 80% nickel, the maximum being about 2% at 45% nickel level. Alloys were melted and solidified in vacuo, annealed in a vacuum for 7 days at 900" C., reduced in thickness by 50% by hammering a t room temperature, and then annealed in vacuo at temperatures between 700' and 970' C. for periods u p to 4175 hours. .4lloys grow progressively, the amount of growth depending on temperature of annealing and the number of lattice vacancies. Considerable microporosity developed during the heat treatment, x i t h the porosity occurring in the crystal boundaries. Hayes, Roberson, and Paasche (102) developed the diagram for the zirconium-rich portion of the zirconium-nickel system. The diagram shows a very limited solubility of nickel a-zirconium a t room temperature. The maximum solubility of nickel in p-zirconium is 1.9% a t 961" C. Eutectic reactions occur at 17% nickel and 961 O C. and 27% nickel and 985 C. Photomicrographs and diagrams are presented. Floyd (79) found that the rapid formation of the Ni3AI phase during solidification of alloys of nickel and aluminum rendered difficult the interpretation of results of investigations of this part of the phase diagram. As a consequence of this difficulty two different reactions were proposed. The present work demonstrates that the &AI phase is the product of a peritectic reaction between the melt and the p (NiAl) phase. This was established by a comparison of microstructures of small ingots of a series of binary nickel-aluminum alloys containing 20 to 30 atomic % aluminum u-ith those of a corresponding series in which 2'/2 atomic yo of nickel was replaced by chromium. Chemical analyses of the alloys are given in table form. Pearson and Hume-Rothery (196) studied the constitution and structure of nickel-vanadium alloys in the region 0 to 60 atomic weight yo vanadium. A rather complete discussion of the phase diagram is given. Ellwood and Bagley (69) found anomalies in lattice spacing and density in the solid solution of gold and nickel. They concluded that the Brillouin-zone overlaps occur in the solid solution, accompanied by the formation of vacant lattice sites. Nickel has a valency of 3.2 when dissolved in gold up to 60 atomic %. Seigle, Cohen, and Averbach (218) studied thermodynamic properties of solid nickel-gold alloys. The free energies, enthalpies, and entropies of mixing of nickel-gold solid solutions containing 5 to 95 atomic yo nickel were determined b y the electromotive force method a t 700' to 900' C. The thermodynamic activities exhibit large positive deviations from Raoult's law, and the entropies of mixing are almost twice those of ideal solutions. The enthalpies of mixing are positive (heat is adsorbed) and are attributable to the lattice distortional energy resulting from the size difference between nickel and gold atoms. This factor appears to be responsible for the miscibility gap a t lower temperatures. Equations, graphs, and tables are presented. Masing and Nickel (157) discussed the formation of nuclei O
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during transformation in the irreversible iron-nickel alloys. A review of the data relating to the course of alpha-gamma'and gamma-alpha transformations, with special reference to thermodynamic results and to results obtained aftei extended heating periods in constitutional studies. Data on the nature and occurrence of martensite transformation, diffusion effects and comments on composition of precipitated gamma phase as related to requirements of diagram, and confirmatory data on the diffusion of molybdenum and iron and on behavior of nickel-silicon and nickel-gold alloys are included. Oriani and Jones (191) studied the disordering reaction in Xi3Pt. Their experiments fixed the disordering temperature of NisPt a t 580" zt 5 " C. The resistance of the ordered phase increases rapidly a t temperatures just below the critical. Dehlinger (55)reported that a number of alloys, classified into close-packed (face-centered cubic and Laves phase) and open structures (Hume-Rothery and Zintl-types) are distinguishable by atom conc'entration and course of heat formation, I n closepacked alloys the curve is invariably parabolic; in open-structure alloys it is made up of straight-line sections. The various systems discussed include nickel-phosphorus, nickel-antimony, nickel-silicon, nickel-tin, aluminum-nickel, chromium-nickel, cadmium-platinum, copper-platinum, and mercury-platinum. Lander, Kern, and Beach (156) studied the solubility and diffusion coefficient of carbon in nickel. Experimental values for the solubility of carbon in nickel in the range 700' to 1300" C. yield thesquation Ins = 2.480 4880/T, where S is the solubility in grams of carbon per 100 grams of nickel. Values obtained for the diffusion coefficient in the same range fit the equation InD = 0.909 - 20,20O/T, where D is in square em. per second. These results are of interest in the problem of the activation of thermionic oxide-coated cathodes, and the experimental method used to measure the diffusion coefficients is related to phenomena occurring in vacuum tubes. T o extend the usefulness of these results in this direction, rates of reaction between diffused carbon and barium oxide coatings on nickel were also measured. The rates of diffusion are limited over a wide range of conditions of interest. A report is given by Cimino and Parravano (44) on some data on the production of Ni& by decomposition of normal hexane a t nickel surfaces. Carbide formation occurs through the following steps: (a)dissociative adsorption of n-hexane a t nickel surfaces and production of atomic carbon; and ( b ) reaction to NiaC and material transport by diffusion through it.
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Planner (200) discussed powder metallurgy, its historical development and applications. Among the alloys discussed were the Hastelloys, the Stellites, and Inconel X. Consideration is also given to meta1,ceramic materials, and many illustrations are presented. Berg ( 1 6 ) described the use of sintered porous nickel lates in the construction of nickel-cadmium and nickel-iron alkaEne batteries. The plaques are prepared in graphite molds by sintering carbonyl nickel powder. A grid, of commercially pure nickel wire, is packed about in the middle of the powder and sintering is carried out for 10 minutee a t 1600' to 1700" F. in a dissociated ammonia atmosphere. MAGNETIC PROPERTIES
As has been the case in the previous years, a number of studies were made pertaining to the ferromagnetic properties of nickel and nickel alloys. Hoselitz (111) discussed ferromagnetic properties of metals and alloys. Kominal compositions, including the nickel content, averaged magnetic, physical, and mechanical properties, and heat treatment of a number of magnetic alloys are presented. Brockhouse (16)described a considerable amount of work on the initial magnetization of nickel under tension. The study was made in an attempt to resolve discrepancies appearing in the literature, and the initial susceptibility and the Rayleigh constant of pure nickel wire were measured between room tempera-
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ture and the Curie point under various tensions. Illustrations are presented. Fukuroi and Yasuhara (84) presented the results of a study wherein pure nickel sheets were cold rolled to varied degrees of reduction up to 77%, and the magnetic properties were measured by means of a torsion magnetometer in the directions parallel and perpendicular to the roll direction, before and after the heat treatments a t temperatures below and above the recrystallization temperature. Anisotropies were found for all magnetic properties; the magnetic pfoperties and their anisotropies varied somewhat regularly with the reduction in thickness by cold rolling. The annealing a t a temperaCOURTESY HAYNE8 STELLITE CO. ture below the recrystallization temFigure 2. Half-Section of Smithlined Hastelloy Alloy F Top Head Knuckle perature increased the value of the after Sandblasting for Final Inspection of Alloy Surface initial susceptibility and its anisotropv _ " of the cold Eolled specimen. The variations in the initial susceptibility and coercive force are disThere is a large effect of cooling rate on anisotropy for comcussed in terms of fiber structure and internal stress. Tables and positions near FeNia where atomic ordering occurs. There is graphs are given. a definite but small effect of cooling rate on the magnetostricDehlinger and Scholl ( 6 4 ) compared internal stresses detertion. A special study was made of the alloys containing 74 t o mined by x-rays and ferromagnetic methods. Freely drawn 68% nickel. nickel wires were used in the experiment, and it was found that a t Ireland ( 1 1 7 ) discussed the magnetostriction in Alnico 5. higher degrees of deformation the magnetically determined value In the development of Alnico 5 magnets for use in vibration pickof internal stress is lower than the x-ray line-broadening value ups operating on magnetostrictive principles, an investigation and hence cannot be used. The ferromagnetic effect is effective was made of the effects of production processes on the magnetic only in the region between the ultimate tensile limits of a single and magnetostrictive properties of Alnico 5. crystal and of polycrystalline material. This is probably due to Lee (139) described a simple apparatus, comprised of a double unilateral slip of grains over lattice vacancies in this region. roller and mirror system, capable of giving accurate measurements Broom and Barrett (18)studied the effect of deformation on of magnetostriction of ferromagnetic rods. The apparatus was used to study the magnetostriction of some alloys, including the the electrical resistivity of some cobalt-nickel alloys. The renickel-cobalt system. The temperature coefficients of magnetosistivity determinations on annealed and deformed wires of some striction of four nickel alloys-Mangonic, W6, 36% nickel-iron, cobalt-nickel alloys coniirmed the fact that stacking faults can make a large direct or indirect contribution to the increase in and 42% nickel-iron. The compositions of the various alloys resistivity due to cold work. Graphs and tables are presented. studied are tabulated. Backofen and Hundy ( 1 1 ) carried out a study of mechanical Crawford (49) discussed the factors governing the design of anisotropy of some ductile metals. Fracturing test specimens in ultrasonic generators for metallurgical applications which include tension after prestraining in torsion showed that a fibrous crackmagnetostriction of the ferromagnetics, power units, and translike structure, causing a considerable degree of mechanical anisotducers. Materials considered for ultrasonic transducers include pure nirkel, nickel-iron alloy, and Permendur, an iron-cobalt ropy, existed in 70:30 brass, nickel, Monel, and Armco iron. A similar structure was observed in high purity aluminum but, for alloy. It is reported that the subjection of a metal to ultrasonic reasons that are not clear, not in 25 aluminum. vibrations in a solid state makes it more active in the presence Lee (140)discussed magnetostriction and mentioned that the of chemical reagents. phenomenon is divided into three parts-the form effect, the Metcalfe (176)studied the allotropy of cobalt, and a dilatoforced magnetostriction, and the spontaneous linear magnetometric investigation of 99.9% pure cobalt showed that on heating striction. Each part is discussed and the magnetostriction of, a transformation occurs between 1119' and 1145"C., which is unsome ferromagnetic metals and alloys, such as 42% nickel-iron, affected by the rate of heating. On cooling considerable hystere30% nickel-cobalt, and nickel, is given. sis occurs, so that althoughtransformation is veryrapid a t 800' C., Fine (78)investigated fundamental factors controlling modulus 20 hours heating is required to complete the transformation a t 1050" C. All the available evidence presented indicated that of elasticity in metals and its variation with temperature. The the allotropic transformation is a reversion to hexagonal cobalt investigation developed an alloy called Vibralloy, containing 43% nickel, 9% molybdenum, and balance iron. Its temperaabove 1145' C. The two allotropic transformations in cobalt are compared, and a theory is advanced to explain the range of ture coefficient of elastic modulus may be controlled over a wide range, and it has substantial ferromagnetic permeability and high temperature over which the transformation takes place. Graphs mechanical strength. It is used for the feeds of vibrating reed and photomicrographs are included. selectors. Graphs of Young's modulus versus temperature are Welch and Cametti (967) made a series of torsional hysteresis included for nickel-iron compositions and the effect of adding and creep tests on several alloys, including K Monel, Inconel X, molybdenum and of cold-working is also discussed and illustrated. SAE 4140 and SAE 1015. The nonmagnetic alloys, K Monel and Inconel X, proved to have exceptionally low hysteresis and Bozorth and Walker (29) described studies on magnetic crystal anisotropy and magnetostriction of iron-nickel alloys. Sincreep for shearing stresses up to 24,000 pounds per square inch. gle crystals of iron-nickel alloys were prepared, and measurements Both values were only O.Ol%, even for reverse loading. The were made of the magnetic crystal anisotropy and magnetostricapparatus used in this investigation is described and shown in tion a t saturation in different crystallographic directions, as dediagram form. The physical properties of the specimens tested are also given. pendent on the rate of cooling of the specimen after annealing.
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The physical properties of a new high permeability nickel-iron alloy, known as Permalloy F, is presented (72). The alloy has a markedly rectangular hysteresis loop and a low value of coercive force. It is suitable for core material for all forms of saturable reactors. A discussion is presented (173) with respect to the extensive use of nickel-iron magnetic alloys such as Permalloy C or Mumeta1,which is 76 to 80% nickel. Permeability figures are quoted in a table, and i t is stated that with the use of these data i t should be possible to reduce the amount of magnetic material in cores, without lowering in any way performance standards, by comparing the performance of silicon-iron alloy as alternatives. The investigation and evaluation of various configurations of core materials for optimum transformer design were made by Hughes and Salt (112). The commercially available materials are listed as silicon steels; nickel alloys, Nicaloi, 45 Permalloy, Monimax, Hipernik, 78 Permalloy, and Orthonik; cobalt alloys, Permendur and Riperco; and the Perminvars and Copernik. The nickel alloys have lower saturation flux densities than the silicon alloys, making them most useful at the higher frequencies where lower flux densities are ordinarily used in order fo keep core losses within bounds. The resistivity and normal permeability for some of the materials mentioned are given in table form. Johnson (125) described a high speed magnetic amplifier wherein grain-oriented 50% nickel iron is used as a core material. This alloy has an essentially rectangular hysteresis loop and a reasonably high saturation density making it satisfactory for use in the design of these amplifiers. Littman (144) studied ultrathin magnetic alloy tapes having high permeability and a relatively high resistivity to minimize eddy-current effects, The alloys investigated included 3 % silicon, balance iron; 4870 nickel, balance iron; and Permalloy, 79% nickel, 4% molybdenum, balance iron. The soft magnetic alloys were rolled to thicknesses between l/g and 1 mil and fabricated into toroidal cores. The properties of these alloys are tabulated. Wakelin and Yates (261) studied the order-disorder transformation in iron-nickel alloys in the region of FeNi3. Iron-nickel alloys of high purity v,-ere studied by measurement of electrical resistivity, x-ray analysis, and by examination of the magnetic properties in both low and high fields. Maximum change in structure-sensitive properties occurred at 75 atomic % of nickel. Formation of order is extremely sluggish and takes place at 494" to 500' C. Low field magnetic measurements showed that maximum and initial permeabilities of FeNi3are considerably decreased by the annealing process known to produce the ordered alloy. Data on the effects of additions of small percentages of aluminum, copper, molybdenum, and manganese to pure FeNia and notes on the mechanism of action of iron and nickel atoms are included. Piercy and Morgan ( 1 9 9 ) carried out an investigation on ferromagnetism in a nickel-manganese alloy containing up to 40 atomic yo manganese. Twenty alloys within this composition range were subject to heat treatments such that the atomic arrangement within the alloy varied from disorder to a high degree of longrange order. Graphs are presented. Ebeling and Burr (63) discussed the effects of macrostructure on the performance of Alnico permanent magnets. The effects of casting texture, grain orientation, and grain size on the performance of Alnico permanent magnets are described. Single crystal specimens were produced and used in the study. The results indicated that permanent magnet performance is impaired by a refinement of the grain size. Compositions are given for cast Alnico 5 and 6. Polgreen (201) described the production and application of various magnetic powders; the many powders discussed (with their respective properties) include a number of nickel-containing materials. Ziegler (269) reported on a number of investigations conducted
Vol. 45, No. 10
by the Signal Corps engineering laboratories, which uncovered results that greatly assisted in overcoming the difficulties associated with the variation of the slope of the minor hysteresis loops. Materials used in this investigation were Alnico 5, 6, and 7. Yamamoto (268) studied the ferromagnetic behavior of nickelcobalt alloys. The magnetization curves for magnetic fields up to about 900 oersteds were measured ballistically for the whole composition range of nickel-cobalt alloys. Also measured were the magnetization for various constant fields, saturation magnetization and field, magnetocrystalline anisotropy constant, and initial and maximum susceptibilitiej as functions of composition, Data indicate that the two-phase range in the nickel-cobalt system extends from 68 to 78 cobalt a t ordinary temperatures, contrary to the prevailing opinion. Graphs are provided. The mechanism that enables Alnico 5 to respond to heat treatment and the merhanism that causes the alloy to have a high coercive force of 60 oersteds were investigated by Nesbitt and Heidenreich (183). Simplified permanent magnet structure showing domain orientation is illustrated and discussed. RIcCaig (148) carried out an investigation on the preferred direction in a magnetically hardened permanent magnet alloy, Alcomax I11 (28% cobalt, 14Y0 nickel, 7.8y0 aluminum, 370 copper, 0.870 niobium, and balance iron) was cut so that the columnar axis was along a diameter. Using a torque magnetometer, the easy direction of magnetization was determined. The angles between this direction and the direction of the hardening field and columnar axis, respectively, are tabulated, and the effect of various cooling rates are discussed. It is reported by Geisler ( 8 9 ) that many transformations are nucleated wholly or in part at preferential sites in the microstructure. Sites for accelerated transformations are generally lattice discontinuities or interfaces such as grain boundaries, slip bands, twin boundaries, and subgranular boundaries. Localized formation of particles of the new phase at grain boundaries of the parent phase may produce a susceptibility to intergranular corrosion and brittle fracture. Precipitation at interfaces is considered responsible for the initial hardening of some alloys. Photomicrographs show the grain boundary recrystallization reaction in a 29% copper, 21% cobalt-nickel alloy and the precipitation in a single crystal of Alnico 2. Wolf ( 2 6 7 ) discussed the heat treatment of magnetic materials. Equipment is described and mention is made of the fact that boxes or canisters of a high-nickel alloy, such as Inconel or Incolog, are necessary. Rules and precautions necessary to commercially anneal magnetic parts for uniform magnetic and physical properties are given. Kerry and Lynch ( 1 2 7 ) described the Bell Laboratory planartype diode and outlined a method for determining cathode emission and conditions of life testing the diode. The initial emission ofthe diode is related to the effective reducing agent content of the cathode nickel. I n general, as effective reducing agent content of nickel is increased, initial emission also increases but not without limit. The increase of the reducing agent content above a certain level causes no further increase in initial emission. The relationship between tube life and effective reducing agent content indicates that maximum tube life is obtained over a very narrow range of effective reducing agent values and that this maximum is apparently limited to a region in which effective reducing agent content is approximately chemically equivalent to the total oxide coating content. A method is given for calculating the effective reducing agent content of a cathode nickel. Ogawa and Watanabe (185) studied the electron diffraction of nickel surfaces tarnished in the course of heat treatment in hydrogen. It was found that when nickel plates for vacuum tubes were annealed in hydrogen gas a t 900' to 1000' C. their surfaces often tarnish and show milk-white appearance. A greater part of the diffraction rings of the milk-white surfaces were due to magnesium-calcium silicates. It was concluded that the tarnishing was due to silicates of light metals. Tables and photomicrographs are included. Steinberg and Oliver (250) reported that the shock resistance of proximity fuse type tubes was improved by switching from an oxide-coated nickel cathode to an oxide-coated tungsten material
October 1953
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which proved less shock sensitive. The solution to the problem of insufficient emission after long periods with no plate current ffassing, but with heaters on, was t o use a passive cathode with ess than 0.15y0 silicpn in the nickel. Nichrome wires were used for the filament in place of tungsten t o obtain constant current over the range of battery voltage. Loofbourrow and Morris (148) described a stable oscillator for UHF television receivers. A new triode tube used in the receiver has a cathode of nickel tubing and a plate of carbonized nickel. An announcement is made (169) of a new nickel cathode alloy series known as the Cathaloys. A numbering system is presented wherein the alloys will be numbered consecutively starting with 30 for the active alloys group and 50 for the passive materials. Properties of the various alloys in this series are presented. An announcement is made (210) of three new composite metaIs which will provide an economical alternative material for pure nickel in many vacuum tube applications. One composite consists of aluminum alloy clad to both sides of low carbon steel. Another consists of low carbon steel clad on one side with aluminum and on the other side with nickel. The third consists of low carbon steel with nickel on each side. The double nickelclad steel can be used as an alternative for pure nickel strip where neither of the other composites is suitable. Doelz and Yathaway (68) discussed the use of mechanical
I-F filters. Included is a discussion of service tests, applications, analysis, and design performance characteristics of mechanical I-F filters. Mention is made of the use of nickel for coupling elements as well as the use of pure nickel wire for transducer material for use a t the filter terminations. Klass (131) described a mechanical filter for intermediate-frequency radio circuits which consists of eight nickel-iron alloy disks, two of which function only as end supports for the six center resonators. All eight disks are connected to each other. The use of a nickel wire attached to the first resonator disk and another to the last resonator disk is reported. HIGH TEMPERATURE PROPERTIES
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A number of studies were made during the year on high temperature properties of nickel and nickel alloys. Many of the studies concerned fatigue, stress rupture, and creep properties. Several studies were made on the formation and composition of high temperature oxides. Jenkins and Digges (121) described the results of tension tests made a t temperatures ranging from -320' to 1500" F. on high purity nickel in the annealed condition. The results are summarized i n the figures given in the report. Strain aging occurred in specimens tested in the temperature range 80" to 300' F., but recrystallization and recovery predominated in specimens fractured a t 1200' and 1500' F. Kopelman and Compton (132) studied the spontaneous combustion of metal powders. The pyrophoric behavior is attributed to the amount of free surface of metal powders and results from the powder's inability to dissipate its heat of oxidation rapidly enough. The degree of pyrophoricity depends on particle size and particle sizes of 100 to 300 A. units make iron, nickel, and copper pyrophoric. The ignition control of such powders and their uses, such as nickel powder in fuses of hand grenades, are discussed. Shahinian and Lane (220) investigated the influence of grain size on high temperature properties of Monel. Specimens of Monel having grain sizes of 0.024 to 0.78 mm. average diameter obtained by cold-working and annealing a t 1300" to 2300" F. were tested in creeprupture a t 700" to 1300" F. and stresses of 7000 to 65,000 pounds per square inch. The results are presented numerically and graphically. The influence of grain size on total elongation and reduction of area was small below the equicohesive temperature and increased with decreasing grain size above the equicohesive temperature. Reduction of area was higher than elongation a t lower temperatures and lower than elongation a t higher temperatures. Grant and Bucklin (94) in a study of creep-rupture and recrystallization of Monel used annealed, 30% cold-worked and 75%
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cold-worked specimens for creep-rupture studies and 4 to 75 % cold-worked specimens for recrystallization studies. The various values found are given and it is reported that the Grant and Bucklin method of graphically extrapolating and interpolating short-time creep-rupture data was satisfactory. Hardness, electrical resistivity, x-ray and metallographic studies showed that recrystallization begins a t approximately 1145" F. for 75% coldworked material and a t 1650" F. for 4% cold-worked material. Recrystallization occurred during creep-rupture testing a t lower temperatures and shorter times than was predicted from hardness tests and reduced strength because of the formation of fine grains along original grain boundaries. Manson and Haferd (155) described the determination of a linear time-temperature relation for the extrapolation of creep and stress rupture data. The time-temperature parameter was based on an examination of published stress-rupture data for a variety of materials. The proposed form is (T - Ta)/(log t log t,) where T is temperature in " F., t is rupture time or the time tolobtain a given total creep elongation, and T, and log t , are material constants which appear to be determinable from suitable rupture data in the time range between 30 and 300 hours. This parameter is used in conjunction with 40 materials with experimental data involving rupture times below 300 hours. The results extrapolated appear to agree quite well with longer rupture times up to 10,000 hours where data were available. Stressrupture curves are given for a number of heat resisting alloys including Inconel X. Lohberg (146) surveyed the relationship between the temperatures a t which creep begins and the melting point of the alloys and discussed various means by which creep resistance can be increased. Among the numerous alloys studied were Monel and Inconel, Nimonic 80A, and various cobalt-base alloys. Graham and Walles (93) studied the relationship between the creep and tensile properties at elevated temperatures of Nimonic 80. The authors described an experimental and theoretical attempt to formulate a quantitative phenomenological theory of inelastic deformation in metals, under uniaxial loading, with particular reference to creep. Nimonic 80 was chosen for this investigation. Equations, tables, and graphs are shown. Johnson and Frost (122) studied the rheology of metals a t elevated temperatures. They investigated general stress, time and temperature dependence of creep, plastic strain, and relaxation properties of a number of different metals and alloys, including Nimonic 75. Detailed description of apparatus for compression creep tests on small specimens is given. The investigation involves simple tensile, torsion, and combined stress-creep tests and similar varieties of short period plastic strain tests and relaxation tests. Herbert and Armstrong (104) carried out a series of creep tests on Nimonic alloys under varying stress and temperatures. The tests were carried out using a cycle in which two levels of operation were used; the stress a t the lower level was 90% of that a t the higher level, and temperatures of 780" and 640"C., respectively, were used. The materials tested were Nimonic 80A and Nimonic 90 in bar form. The results of the tests are presented in numerical form as well as in creep curves. A report is presented (169) on the large scale test program in the laboratory of International Nickel Co. a t Huntington, W. Va., on high temperature creep characteristics of nickel alloys. One phase of the material testing program is being conducted by means of more than 40 creep test machines which apply loads ranging from 2800 to 100,000 pounds per square inch a t temperatures ranging between 700' and 1800" F. Vidal (249) studied high temperature fatigue limit in ordinary and controlled atmospheres of a number of high temperature alloys. The original work was done on French alloys that were reproductions of Nimonic 80. Atmospheres studied were normal atmospheres, petroleum gases in oxidizing atmospheres, kerosine containing sulfur under conditions of alternately oxidizing and
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reducing atmospheres. Other alloys were also tested, and the results were compared with values for Nimonic 80. A new alloy, Nimonic 95, has been announced (171), and i t is reported to be similar to Nimonic 90, but the creep resistance at elevated temperatures has been improved by increasing the content of the hardening elements. I t s creep properties for relatively short periods, which are of interest for aircraft jet engines, show improvement over those for Nimonic 90. Properties are tabulated. It is reported that tests to extend the knowledge of its creep resistance and to determine other properties are now in progress. MacGregor and Walcott (149) investigated the tension creep to-rupture properties of the alloy steel K-155. Rupture times in the 10- to 1000-hour range were considered and tests were made at 1200' F., 1350 O F . , and 1500' F. The effect of stress concentration in the form of transverse circular holes was investigated under the same conditions. Comparisons of the effects of simple combined stresses (as in torsion) were made with torsion creep-torupture properties. The composition of N-155 is 21% chromium, 19% nickel, 19% cobalt, 3% molybdenum, and 2% tungsten. Tables, diagrams, and graphs are presented. Lazan and Demer (137) investigated the damping, elasticity, and fatigue properties of several temperature-resistant materials, such as Inconel X, low carbon N-155, and 5-816. Cantilever beam testing equipment was used. Diagrams are presented to facilitate comparison of the elasticity properties among metals tested a t a given temperature. Morral and Lazan (f78)reported the continuation of earlier metallographic studies on heat-resistant alloys which included metallographic studies on N-155 specimens exposed to static and dynamic stress at elevated temperatures. The effect of the variables (time, temperature, static stress, and alternating stress) were determined. Visual and macroscopic classification of the fractures were attempted, and microscopic structure and microhardness data were reported. Graphs, photomicrographs, and tables are included. White (264) discussed high temperature metals and the determination of properties and operating temperatures and pressures of various metals and alloys for use a t elevated temperature in the power, petroleum, automotive, and aviation industries. Among the alloys discussed are superalloys including N-155. Vidal and Loupoff (26260)described an original method for interpolation and extrapolation of data (time, stress, and elongation) relating to creep of high temperature gas turbine alloys. An account is given of creep and stress-rupture experiments on Rateau machines. Data are given for a number of nickel-containing alloys including Per 2 (70% nickel). Wilterdink, Holms, and Manson (266) carried out short-time spin tests on parallel-sided, 10-inch diameter Inconel X disks, subjecting the disks to temperatures from 70" to 1440" F. Agreement between theoretical and experimental results was good. Temperature gradients produced little reduction in the burst speed of the disks which had a high ductility. Illustrations are provided. Freeman, Ewing, and White (85)studied the influence of chemical composition on rupture test properties of 62 alloys a t 1500" F. The alloys studied were forged chromium-cobalt-nickel-ironbase alloys, and they were tested in both the solution-treated and aged conditions. The elements can be varied individually between quite wide limits without significantly changing the rupture properties. The results of these tests were similar to those previously obtained at 1200' F. (Nutl. Advisory Comm. Aeronaut. Report 1058) except that increased chromium was not beneficial a t 1500" F., and the saturation effect for molybdenum and tungsten did not occur at 1200 O F. Numerous tables and graphs are presented. Chevenard and Wache ( 4 1 )presented a detailed discussion and description of techniques for determining the physical, chemical, and structural effects in high temperature materials. The struc-
Vol. 45, No. 10
tural hardening austenitic materials and their thermal properties were studied. There also is included a discussion on the thermoelectric methods of examination, x-ray examination, and micrographic and chemical techniques used. The data presented relate to a series of high-nickel, nickel-chromium-iron alloys, and austenitic nickel-chromium steels. Data on the creep of material containing o.3yO carbon, 36y0 nickel, 11% chromium, and balance iron a t 750" C., after various heat treatments, are included. The purpose of a project described by Preston (807) was to determine the high temperature mechanical properties of several materials available in sheet form. The materials investigated included three iron-base strain-hardened type alloys and three cobalt-base alloys which are used in the fully annealed condition. Microstructures are discussed and creep and stress-rupture, short-time tension, and yield data are presented for these alloys from room temperature to 1800' F. Moore and Lee (177) studied the rate of growth of the layer of nickel oxide on nickel from 400 to 900 C. at 10-em. oxygen pressure. It was found that the film thickness, y, increases according to the parabolic law d y / d t = k/y, the rate constant k being, in theory, equal to 40, where D is the self-diffusion coefficient of nickel in nickel oxide. The entropies and heats can be satisfactorily interpreted in terms of the formation, dissociation, and migration of cationic vacancies in the oxide. Tables and graphs are also presented. Pfeiffer and Hauffe (198) studied the influence of alloy elements and of treatment with metal oxide vapors on the rate of oxidation of nickel and titanium. Data are presented on the effects of addition of a variety of atomic per cent of chromium and a variety of atomic per cent of silver addition to pure nickel. A discussion is presented on the possible influence of oxide vapors on the growth of oxide films. A number of vapors, such as oxygen, lithium oxide, tungsten oxide, and others are discussed. Preece and Lucas (W06)studied the high temperature oxidation of some cobalt-base and nickel-base alloys and described the oxidation characteristics of cobalt and nickel and their alloys a t 800" to 1200" C. Of the various reactions noted, spinel formation is shown to be detrimental to the formation of a protective oxide layer. The effects of vanadium, boron, niobium, beryllium, titanium, zirconium, calcium, tantalum, aluminum, cerium, silicon, and thorium on the oxidation of 32 cobalt-chromium alloys are described. Thorium and silicon increased the resistance to oxidation, whereas vanadium and boron were highly deleterious owing to the formation of low melting point oxide. Bryan ( 5 1 ) made an x-ray diffraction analysis of Inconel scale on combustion tube inner liners and revealed that i t is composed of nickel oxide and lesser amounts of chromium oxide and iron oxide. Metallographic examination demonstrated that heavy scale is associated with precipitation and possible carbides a t the grain boundaries, a fact that can explain intergranular corrosion of scaled Inconel in acid solutions. Several acid solutions were found which removed most of the scale without seriously attacking the base metal. A full scale test with the nitric acidferric chloride solution was performed with satisfactory results. Buckle, Jacquet, and Poulignier (SW)described a metallographic method for determination of service temperatures with application to the 80% nickel-20% chromium high-temperature alloys. The colored film metallographic technique was applied to a study of surface temperatures experienced in service of a Nene rotor blade made of Per X alloy, described as an improved Nimonic 80. The temperature to which the blade is exposed is determined by polishing and etching the surface and comparing the appearance of different areas with that of surfaces of the same material that had been submitted to known temperatures. The authors verified that various high-nickel alloys undergo structural changes on heating which are reproduced in colored films obtained in the present technique , Economos ( 6 4 ) studied the behavior of refractory oxides in O
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October 1953
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contact with metals a t high temperaturea. Oxides such as alumina, magnesia, beryllia (BeO), zirconia, titania, and thoria were used, and the metals used were titanium, beryllium, silicon, niobium, nickel, molybdenum, and zirconium. Nickel and molybdenum were the only metals of those tested which were stable in contact with the oxides a t all temperatures. The results are summarized in chart form. Hauffe (101)gave an account of experience on nickel, iron, titanium, silver, and silver-cadmium alloys. He included data on the beneficial results obtained with evaporated lithium oxide coatings on nickel. Azcona (IO) presented a progress report covering the effect of heat treatment of electrodes on the spectrum emitted by sample. Emission anomalies were observed in certain ranges during both the heating and cooling of the electrodes. Haynes Stellite No. 30 was used in the study, which is a cobalt-base alloy containing nickel, chromium, molybdenum, and iron. As the temperature of deformation is lowered, Ellis and Geiner (67) found that the flow strength and ultimate strength of a number of metals and alloys at room temperature are increased. Materials used in this investigation were oxygen free-high conductivity copper, a high purity and 25 grade aluminum, and grade A nickel. Likewise, in materials in which lattice scattering predominates, electrical conductivity is decreased to a greater degree as the temperature of deformation is lowered. These effects are attributed to a decrease in simultaneous recovery during deformation as the temperature is lowered. Ziegler (270) discussed properties of metals below -300" F. giving mechanical properties, specific heat, thermal expansion, and electrical and thermal conductivities. Among the various materials considered are the stainless steels, constantan, Monel, and certain aluminum-magnesium alloys. FABRICATION
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Welding and Brazing. Chyle (43)discussed the selection of the most suitable welding processes and mentioned that the factors involved in the selection of the welding process depend upon engineering design and service requirements of the product as well as the inherent characteristics differentiating the various welding processes; the characteristics of the welds made by the various processes; composition of the metals to be welded; welded joint design; production rate, and power availability. Recommended welding processes for different materials including nickel and nickel-base alloys are given in tabular form, and the best processes for different joint designs are presented also. Berryman (17) discussed the inert-gas metal arc process and its application to various materials of construction, including stainless steels, nickel, copper, and copper-base alloys. Techniques used for each material are given. Mueller and Root (182) discussed inert-arc welding technique for elimination of backing rings in piping. The use of inert-arc welding for thin-walled tubing proved to be quite successful for fabricating nickel, Monel, Hastelloy, and austenitic stainless steels. Serefian (819) surveyed modern theory on welding and weldability of a large number of metals and alloys including nickel, Monel, Inconel, and Nichrome. The discussion included the welding of cast iron dealing with effect of composition of filler rods. Gill and Simons (91) discussed the welding of nickel, Monel, S Monel, K Monel, and Inconel by metallic arc, atomic hydrogen, resistance, and carbon arb welding methods. Nippes and Gerken (184) described the seam welding of 0.005inch Inconel sheets using a short on-off cycle using a welding machine incorporating the feature of low moving head inertia and low friction. Conditions were determined for welding Inconel in both the annealed and hard conditions. Photomicrographs are presented.
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COURTESY HAYNES STELLITE CO.
Figure 3.
View of Smithlined Hastelloy Alloy F Top Vapor Zone after a Year's Service
Fullerton (86) reported that improved weld quality and increased welding speeds may be achieved by modifying the drive mechanism of standard seam welders. This results in accelerated performance in the welding of stainless steels, Inconel X and Inconel W, Haynes Stellite No. 25, and other crack-sensitive alloys used in the fabrication of afterburners, variable nozzles, exhaust cones, tail pipes, and high temperature jet engine components. A new indexing device is discussed. The successful spot welding of O.OO6inch Monel sheet was achieved by the use of electronically controlled spot welder. The technique and operations of the machine are presented (268). The Monel is used in the form of diaphragms of expansion type thermostatic elements incorporated in steam traps. Halliday (99) discussed the welding of stainless steels wherein the problems are reviewed and mentioned that the successful production of strong, durable, and clean welded joints with Monel metal or stainless steels present difficulties for the welding engineer. Fullerton (86) described equipment used in the aircraft industry for resistance welding of a number of different alloys including Inconel, Inconel XI and N-155,as well as a number of austenitic stainless steels, aluminum, and magnesium alloys. A report is presented (881) of the successful welding of a diaphragm made up of two pressings from 0.006-inch Monel sheet as being accomplished by spot welding. Lyall (147) discussed the welding of nickelclad steels by shielded metal-arc process. Mention is made of the fact that nickelclad evaporators for the alkali industry are welded by the inert-gas shielded metal-arc process without iron pickup in the weld. The use of uncoated welding wire and an inert gas blanket to protect the weld zone accounts for the clean welds which require no slag removal. Welded Inconel tanks for storing rye or scotch whisky, gin, rum, and other spirits are superior to glass-lined containers, because the Inconel units will not crack or chip (116). Wallace and Vanderveer (852) discussed brazing vacuum-tight joints in high-nickel alloys. Several consecutive brazing opera-
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INDUSTRIAL AND ENGINEERING CHEMISTRY
tions are required to join relatively large parts produced from Inconel and other high nickel alloys; however, by the method described a clean, oxide-free, vacuum-tight assembly was made. Diagrams are presented. Van Natten (248) discussed joint design for brazing and listed many factors that require consideration. A table is presented showing base materials versus brazing filler metals; nickel and nickel alloys are included. Burt (84) discussed brazing equipment, modern methods for copper brazing, and the use of conveyor belts of nickel-chromium alloys. Bertossa (18) discussed the development of a system of vacuum brazing wherein sound and continuous high strength bonds were readily obtained throughout areas of virtually unlimited size without the use of introduced furnace atmospheres and without contamination from fluxes. This high strength brazed bond, which averages from 40,000 to 60,000 pounds per square inch shear strength, could be attained without difficulty between low and medium carbon steels and pure nickel, Monel, and Inconel. Special techniques are necessary in the vacuum brazing of nickel and high nickel alloys to carbon steels due to the high solubility of copper brazing alloys in the nickel and high nickel alloys. Three major classifications of stainless steels can also be brazed by the described system. Photomicrographs, graphs, and illustrations are included. Peaslee and Boam (196) reported that the brazing of stainless steel for high temperature work can be successfully accomplished by the dry hydrogen process using Nicrobraz stainless brazing alloy. Nicrobraz has satisfactory physical properties and oxidation resistance for high temperature applications through 2000" F. Joints brazed with Xicrobraz and those brazed with copper and silver-manganese are compared on the basis of data obtained for the tensile, shear strength, impact strength, oxidation, and stress rupture characteristics. Elonka (70) described the hard surfacing of alloys to achieve abrasion and impact wear, corrosion resistance, as well as hardness. Reference is made to a number of metals and alloys, including nickel and nickel-base materials. Klain and Croisant (180) discussed the resistance welding of dissimilar metals to magnesium for electrical connections. The method of resistance welding is used for attaching wires to magnesium dry cell batteries and to other magnesium parts where electrical contact is necessary. Among the wires used for welding is nickel. Tremlett (248) discussed the resistance to scaling and the effects of alloy elements-such as chromium, nickel, silicon, and titanium-on the oxidation-resistance strength at high temperai ture of a number of alloys. The creep results of chromium, highalloy nickel-chromium, and nickel-chromium-tungsten steels are recorded. Various features affecting suitability for welding chromium, chromium-nickel-tungsten steels. and details for welding techniques were covered also, Mechanical Forming, Machining, and Castings. Sherman (222) traced the development of new forming techniques in which metals can be rolled to thicknesses of 0.0005 inch and to tolerances as close as zkO.0001 inch. The metals processed in this close tolerance, thin gage strip include nickel and various nickelbase alloys, high-nickel permanent magnet alloys, precious metals, and cobalt-nickel-iron alloys. The availability and typical applications of high-nickel alloys, rolled to precision tolerances and ultrathin gages, have been listed (14.9). Canzler (39) described the production of clad steel plate by hot rolling, Copper, nickel, copper-nickel alloys, Monel, silver, and various corrosion and heat resisting steels are used for the cladding. Physical properties of clad plate, welding of clad plate, and chemical plate design are discussed. Ottmar (194) reported that the use of metallurgically bonded
Vol. 45, No. 10
metal combinations would overcome many of the engineering limitations of single metals and would conserve critical and high cost materials. At present aluminum-base composites, iron and steel composites, stainless steel clad metals, rare metal and precious metalclad materials, and leadclad metals are available. Additional combinations produced are molybdenumclad cupronickel, platinumclad steel, copperclad magnesium, copperclad nickel, and nickelclad copper. Properties of all these combinations are discussed. Watson (658) gave a detailed description of the heat and pressure method for clad steels. Developments in Monel-, Inconel-, and stainless clad steels are reviewed, and the properties of clad products are included. The production lines a t Ryan Aeronautical Co. (8) have been streamlined to fabricate thousands of inner and outer combustion chambers and transition liners for General Electric 5-47 jet engine. The inner combustion chambers are made of Inconel. The sheets are blanked and pierced in precision dies by huge presses, rolled into circular form, and welded along their seams with automatic heliarc machines. Other details of the fabrication of the combustion chambers are presented. Close (45) described experiments with toothless bandsaw blades that point the way to fast, economical methods of cutting ferrous metals. Various sheet materials now being sawed with the toothless tapes include mild steel, stainless steel, as well as Superalloys including nickel-base materials. Holub (109) presented a brief picture of oxygen cutting processes for removing metal and described some of the new developments. Powder cutting is commercially practical for stainless steels, high temperature alloy steels, cast iron, and many of the nonferrous materials, such as bronze, nickel, aluminum, concrete, and certain refractories. The drilling of various Ximonic alloys is discussed ( S ) , and production figures are given that weie obtained in the machining of three of the high nickel alloys, Ximonic 80, 808,and 90. -4 slom automatic feed was used for drilling turbine blades in these three alloys. The tools were high speed steel containing 20 to 22% tungsten, 6 to 7% cobalt, with molybdenum, chromium, and vanadium, and were designed for heavy duty at fast speeds and heavy feeds. Tables are included. The casting of the Superalloys developed for high temperature applications is outlined briefly by Dickinson (55). Comparative properties of a number of alloys are tabulated. Tedds (287) described the investment casting of Nimonic 75 to form turbine burners, fuel nozzles, and flame tubes. Levoe (141) described various parts for gas turbine motors which are investment cast using Hastelloy B. This method of production, when Superalloys are used, reduces cost, improves design, and saves strategic alloys. A brief outline of the inve'tment casting process is given. A report is presented (668) aherein shell molded castings of Inconel, Hastelloy C, N-155, Haynes No. 36 and many of the AIS1 300 and 400 series stainless steels are given. The foundry can produce castings from 1 ounce to 350 pounds with a capacity of 3000 pounds of castings per day. A 900-pound electric induction furnace supplemented hy all other necessary foundry equipment is used. Spindler (265) discussed the problems of temperature control and metal losses during melting and mentioned that the solution involved the use of induction furnaces. Closely controlled, high quality castings of nickel-base alloys and stainless steels were produced. Most heats are made with 60% scrap, consisting of gates and risers from previous heats, and 40% steel, ferroallov, or special ingots. Nominal compositions of the various alloys, such as Worthite, nickel, &Ionel, Inconel, AIoyco N-2, and Aloyco N-3 are given in tabular form. Coatings, Brenner, Zentner, and Jennings (65) accumulated data on those mechanical properties of nickel electrodeposist
October 1953
4
INDUSTRIAL AND ENGINEERING CHEMISTRY
that are of immediate value in engineering applications. The study involved measurements or determinations of cathode current efficiencies, internal stress of the deposits during deposition, chemical composition of deposits, structure by optical microscopy, electron-microscopy, and x-ray diffraction, mechanical properties, ' density, thermal properties, electrical resistivity, magnetic properties, and effects of heat treatment. The authors report that the type of solution used is the most important factor in determining the properties of the deposits. According to Thews (239) the chief factors in the success of the electrolytic nickel plating process are the composition, physical state, and the treatment of the anodes. Impurities present in nickel solutions, the pro and con of cast &odes, the affinity of fused nickel for gases and its adsorption capacity, the use of scrap anodes, melting and deoxidizing, casting anodes, and cleaning the anodes are all discussed. Richards ($12) presented several notes on the peeling of nickel deposits, including means to avoid or to counteract the difficulty. Factors that influence the peeling and flaking tendencies are the adsorption of hydrogen during cleaning, pickling, and plating; faulty cleaning and rinsing; metallic impurities in the nickel baths; chromic acid additions; organic acids in bright nickel plating; solution pH; organic impurities in nickel solutions; temperature and concentration of the solution; and the current density. A tabulation of symptoms and causes of nickel deposit failure completes the study. Hogaboom (108) discussed processes, equipment, and operations used by platers in 1903. The cleaning cycle used then is the same as the one used now. Formulas for nickel and other plating solutions are given and the difficulties encountered in the working of nickel solutions-such as pitting of steel or iron-and their remedies are briefly outlined. Anodes used were approximately 90 to 92% nickel with about equal amounts of iron and carbon and in general were cast in sand molds. Due to the high melting point of nickel, iron and carbon were added to obtain a good anode. A simple change is described (118) in the method of dumping nickel plating solution storage tanks which results in a considerable saving of money. A diagram of the method is shown, Surface preparation, plating processes, and applications are described by O'Keefe (190)for the light metals, aluminum and magnesium. One application is illustrated by an airplane propeller blade of Duralumin coated with nickel. The largest article produced in nickel by the electroforming process is described (162) as being a giant mold made by the Bone Engineering Corp. for the Goodyear Aircraft Corp. The mold is employed for low pressure molding of plastic domes for radar installations on U. S. Navy Aircraft. Electroformed shell, only '/4 inch thick, is reinforced with steel ribbing welded to the outside surface, thus effecting extremely lightweight construction. The story is presented (66) of a large nickel-plated drum dryer used in the manufacture of machine-glazed paper. The application of a nickel deposit on the cast-iron drum gave good resistance to corrosion and a superior glaze to the paper, Korbelak and Okress (1%) described a method using electrodeposits of nickel to facilitate manufacture of large size intricate designs of stainless steel. A tabular summary illustrated with photomicrographs outlines the use of varying thicknesses of plated coatings for different brazing temperatures. APPLICATIONS
High Temperature. Rose (616) discussed in general high temperature alloys in service which include plain carbon steel. low alloy steel, stainless steels, high alloy steels, and nickel-base alloys, such as Incoloy and Inconel. Properties and applications for each metal are discussed. Kinsey (129) discussed high temperature alloys available for use as combustion chambers, nozzle guide vanes, turbine blades,
2225
and rotors or disks. Composition, tensile, creep, and rupture properties are given in tabular form for a number of alloys. Other typical alloys are classified according to their major constituents and hardening means. Nominal compositions for a number of alloys, including the nickel-base Nimonics, Inconel X, and others are listed. An account is presented (1)of a visit to Mond Research Laboratory and Henry Wiggin Works in Birmingham, England, and a review of the various types of Nimonic alloys now available is presented along with indicated fields of application and present state of research. Reference is made to a laminated sheet of Nimonic 75 on either side of a copper sheet. This sheet is of principal interest as a flame-tube material. Products of this type are being developed under the name of Nimoply. Brown ($9) discussed defects in high temperature alloys leading to failure in forming or welding. A table is presented which lists alloy designation and composition of high temperature alloys, including Inconel and the Hastelloy alloys. Bruckart (SO) described the results of research on materials for use in engines a t temperatures above 1600' F. References are made to the ceramics, the cermets, the stainless steels, and cobalt-base alloys as well as Vitallium. Comments are offered with respect to the fact that siliconized molybdenum can be used a t temperatures up to 3300" F. The cladding of Monel by the rolling-on method was found to be successful when nickel and nickel-base alloys were used. Alloying was found to improve the strength of molybdenum a t room and a t elevated temperaturesfor example, a properly protected molybdenum, 0.25% silicon alloy developed a t Battelle was tested a t 1800' F. and 25,000 pounds per square inch stress. It lasted nearly 300 hours with a minimum creep rate of 0.014% per hour. Maxwell and Sikora (16'7) studied the stress rupture and creep testing of brittle materials. They reported the development of a convenient technique for determining long-time properties, stress-rupture strength, and creep of ceramics and ceramals for use in high temperature applications. The method uses a comparatively short specimen completely in the furnace and held in the grip of a material having sufficient plasticity a t the test temperature to ensure alignment. The gripping mechanism, whose parts are machined from annealed Inconel X, is described. Hicks (106)studied a number of ceramic coatings in order to establish techniques of applying heat resistant films for jet engine use. A number of materials were used in the investigation, includin Inconel and Multimet N-155. I n addition to the nickelbase afioys, a number of stainless steels were also studied with respect to the applicability of various ceramic coatings. Jackson (120) discussed cast alloys for salt-bath heat treating and determined the resistance of high alloyed materials to attack in various salt-bath media operating a t 1600" F. Most of the samples represented alloys of the iron-nickel-chromium system. However, one of the materials was a nickel-base al]oy--60% nickel, 12% chromium. The effect of operating variables on intergranular corrosion, effect of bath oxidation and rectifiers, the effect of salt type, effect of cast alloy grain size, effect of pretreatment of cast alloys, and the effect of cyanide additions to salt bath are all discussed. Pray, Peoples, and Boyd (206) studied the corrosion of a number of metals and alloys by molten bismuth. Among the mai terials tested were Inconel, Nimonic 80, and the Hastelloys. The test temperatures were 750' and 850' C. It was found that corrosion appeared to be most severe a t or near the liquid-vapor interface, and only the 2.9% silicon transformer steels and Duriron were considered to exhibit good corrosion resistance in this temperature range. Tables and photomicrographs are presented. A discussion of the corrosion of materials by liquid low melting alloys is presented (164). Corrosion data for ferrous and nonferrous alloys (the latter including nickel-base alloys) by sodiumpotassium alloys, bismuth-lead eutectic alloys and eutectic bismuth-lead-tin alloy from 200' to 1600' F. are presented in graphical form.
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INDUSTRIAL AND ENGINEERING CHEMISTRY
Brasunas (84)discussed liquid metal corrosion in considerable detail. Liquid metals are described as those that melt below 400" or 500" C. Since alloys behave differently than pure metals the behavior of each is discussed a t some length with specific examples of each presented. Photomicrographs are shown of the intergranular solution of nickel by lead a t 1000" C. and the leaching of nickel from the surface of Type 304 stainless by molten lithium at 1000" C. in 40 hours. Other examples are included. Imhoff (114) described various types of pot designs used and discussed their progressive changes doiw to the present time. iin investigation of the action of molten zinc upon commercial metals and alloys, including Monel, nickel, chromium-nickel, iron, Thermalloy, and various types of steels showed that firebox steel and flange steel were the best practical metals to be used for galvanizing pots. The use of Incoloy (115) is described in the manufacture of a new type of thermocouple-protection tube. This new nickel alloy has similar physical properties to Inconel, the material which was used previously for these protection tubes, but the new alloy contains only half the amount of nickel as does Inconel. Healy and Andrews (103) carried out a study of the enameling of nickel sheet. The tremendous formation of bubbles and the apparent lack of adherence of porcelain enamels to nickel sheet are attributed to carbon oxide gases. Changes occurring at the enamel-nickel interface were studied by the use of coarse-grained particle technique, and the effects of various heat treatments of the sheet nickel before enameling were considered. Orr (195) discussed the use of a number of alloys including Hastelloy C and Inconel as rings that are welded to the ends of lengths of low carbon steel tubing. When such tubing is subsequently glass-lined the glass terminates at either end on the alloy ring, thus enablihg corrosion resisting joints to be achieved. The effect of high temperature steam attack at 2200" F. was investigated by Ogden and Scorah (186) on a nickel-chromiumiron alloy known as Chromel-C. The attack results in the formation of a thin, hard film of chromium oxide which has special properties in the field of steam generation, Within the interior, high temperature steam attack leads to chemical reactions with metallic oxides, carbides, etc. These phenomena become more and more critical as the operating temperature approaches the melting point. Photomicrographs, tables, and graphs are included. Hildebrand (107) made a comparison of iron-chromiumaluminum alloys and 80% nicke1-20'% chromium alloy for use as electrical resistance material. The iron-chromium-aluminum alloys constitute an excellent substitute for the nickel-chromium since their properties make them, in many cases, superior to the nickel-chromium alloys. The iron-chromium-aluminum materials can be used up to 1350" C. where the maximum working temperature of the best nickel-chromium is 1150' C. The life and electrical properties as well as the mechanical properties at room temperature are better for the iron-chromiumaluminum type, but from the corrosion- and heat-resisting points of view the nickel-chromium material has the advantage. Farber and Ehrenberg (76) determined corrosion rates a t temperatures above 1000" K. for several metals including Inconel, nickel, and a number of other materials in atmospheres of hydrogen sulfide, sulfur dioxide, and carbon monoxide. This was done by an increase in the electrical resistance of the metals in the form of filaments 0,010 inch in diameter, The metals most easily corroded in hydrogen sulfide were Inconel, iron, copper, and stainless steels, whereas tungsten, molybdenum, and tantalum offered the most resistance. It was found that Inconel is very resistant to sulfur dioxide, whereas tungsten, tantalum, and molybdenum are easily corroded. Carbon monoxide increases the corrosion rate of nickel in hydrogen sulfide, whereas the corrosion rate of iron is decreased in the presence of carbon monoxide. Two ceramic coatings, L-7C and A-417, developed by the National Bureau of Standards, were tested by Morse (180) to see
Vol. 45, No. 10
which was more suitable as a protective coating for gas turbine blades. Cast Vitallium turbine blades, two of each coated with each of the ceramics, were installed in the turbine wheel of a turbojet engine and subjected to 20-minute cycles consisting of 5 minutes at idle and 15 minutes at rated speed. The results indicated the coating A-417, after showing no evidence of fusion during 100 operating cycle!, was superior to the ceramic coating L-7C. A technical description of the Rover turbocar and the Rover T.8 gas-turbine engine is presented by Bell (15). The combustion system of the T.8 is a film-cooled flame tube of Nimonic 75. H. R. Crown Max is used for compressor-turbine nozzles, and the compressor turbine rotor is machined from solid Nimonic forging. Power turbine rotors are made quite satisfactorily from IYimonic 80, and aluminum sprayed mild steel is used for the combustion chamber and exhaust collector duct. Robertson (214) presented a survey of high temperature mateiials for the use of metals a t high temperatures in steam and gas turbines. Among the alloys discussed are nickel and cobaltbase alloys. Graphs and photographs are included as well as the compositions of representative alloys used for stressed parts in the temperature range 45 O to 950 C. Moffatt (176) reported that measurement of temperatures of gases a t very high temperatures is important for the development of gas turbines and guided missiles. High temperature probes were designed that reduced velocity, radiation, and conduction errors a t 1000" F. and 2000 feet per second. Data for selecting probes and estimating these errors under various conditions are presented. Inconel and 18-8 stainless steel are used in the construction of these robes. Rowley and Strotzki &16) gave a report on gas turbines that included principles and performance, applications in aircraft, marine, automotive, and railroad industries and in stationary installations. Tables of materials of construction consisting of three groups of superalloys with their compositions and stress rupture properties are also presented. A tabulation of the second world-wide engineering features of stationary gas turbine installations in all arts of the world is also presented. Graphs, diagrams, and t a b e s are also provided. Reeman and Buswell (309) described an experimental air cooled turbine and described the design and the manufacture of the turbine. I n the lengthy description, mention is made of the use of a number of nickel-base alloys for critical parts of the turbine. Everhart ( 7 4 ) discussed jet engine blades and mentioned that service performance of the blades, vanes, and buckets were influenced by the production method. Nickel- or cobalt-base alloys are used for turbine buckets, although work is in progress which ma lead to the application of ceramic-metal mixtures and mogbdenum-base alloys for this purpose. Various production methods are discussed, and characteristics of jet engine blades made by various methods are tabulated. Mannin (164) surveyed Russian views and designs in the gas turbine field, outside of aviation. Some details of their achievements in this development are described. O
-4new composite sheet material is described (269) which has high heat conductivity and serves to boost jet engine service life and performance. This material is fabricated of copper and stainless steel sheets welded at the edges to seal the sandwich. The use of Inconel electrodes or 80% nickel-20% chromium electrode is described as being used regardless of the type of composite sheet material being welded. I t is reported ( 6 ) that experiments are being carried out testing the high temperature behavior of Rosslyn metal, a clad metal, in combustion chambers and afterburner vanes for jet engines, It is stated the substitution of Rosslyn metal for high strength chromium-nickel alloys would save 30% of the scarce materials. 4 t present combustion chambers, transition liners, and tail cones are fabricated from stainless steels, Inconel, and other nickelchromium alloys that have high corrosion resistance but inherently poor heat conductivity. To test the high temperature behavior of Rosslyn metal, which is a copper core clad with stainless steel, combustion chambers are being fabricated (150) of Type 321 stainless and 1010 mild steel clad for comparison with standard Inconel chambers. The low thermal conductivity of Inconel and other chromium-nickel alloys and temperature differentials of Inconel X, N-155, and Hastelloy C are considered. Stone (232) discussed materials used in afterburners of jet engines which include Type 321 stainless steel for tail cones and injectors, Inconel W a n d K-155 for the outer shell of the tail cone,
October 1953
B
r,
INDUSTRIAL AND ENGINEERING CHEMISTRY
and stainless steel for the clamshell nozzles. The pneumatic section of the actuator is fabricated of stainless steel and aluminum. A detailed description is given ( 2 ) of the Morane-Saulnier 755, which is powered by two Turbomeca Marbore jets. Welded, hollow sheet-metal blades form the static nozzle msembly of the turbine and are fabricated from a French heat-resisting steel, which has properties similar to those of Nimonic 75. A rather detailed discussion is presented by Lee (138) on the power plant for the Russian MIG. It is stated that the materials used are similar to those used in a Rolls-Royce Tay and the Pratt and Whitney 5-48. Turbine blades are made of a stainless steel alloy known technically as Nimonic 80, while the burner liner and swirl vanes are of Nimonic 75. Titanium stabilized stainless steels are also used. Each of the combustion chamber assemblies consists of a combustion chamber cover of cast aluminum and an inner removable liner made of high temperature resistant alloy. The link chute adapter is made of stainless steel sheet, formed and spot welded. Diplock, Lofts', and Grimston (56) discussed performance of alloys in liquid propellant rocket motors. With nitric acidkerosine or liquid oxygen-kerosine motors, where maximum temperatures in gas generators reach 1000' C., Nimonic turbine blades would be used. Reference is also made to the use of stainless steel and aluminum as materials of construction. The use of K Monel is described (165) for liquid oxygen tanks. Such tanks are used on some guided missiles and must withstand high pressures a t temperatures as low as -325' F. K Monel is used for this purpose as the ductility and toughness of the alloy are unaffected by low temperatures. Bucknall and Ball (33)described research during World War I1 qn the improvement of materials and methods of production of exhaust valves for airplane engines. Nickel-chromium alIoys (80:20) and an alloy of 74% nickel, 20% chromium, and 6% iron as well as some other alloy steels were studied. The mechanical properties (shock resistance and hardness) were studied. The data are tabulated. The use of Monel as root bolt, nut, and bolt heads in the assembly of air-screw blades is described (4). Other details concerning finishing operations, manufacture of heating elements, and construction and manufacture of de-icing elements is also presented. Blank, Hall, and Jackson (20) evaluated commercially available alloys for suitability as superheater and reheater tubes a t metal temperatures up to 1350' F. Test materials consisted of various nickel-base alloys, such as Inconel and Illium G. Austenitic stainless steels were also tested. High sulfur, high alkali, and high vanadium content fuels produce combustion products which are often extremely corrosive. Photomicrographs, tables, and graphs are presented. Brooks and Rosenblatt (27) discussed nuclear power plants including the design and performance of liquid metal heat exchangers and steam generators. Mention is made of the use of L-nickel in connection with sodium and sodium-potassium alloys for coolants. It is mentioned that the high thermal conductivity made nickel desirable for the tubing material. Wellons (261) discussed the need for reliable bearings that will be large in diameter and operate at high delta amplitude ( d n ) values, temperatures, and thrust loads. Consideration is given the problems of operating a t high temperatures, and the best solution is t o use materials for cages that are inherently nonwelding. Materials classified as nonwelding are phenolics, cast iron, bronze, Monel, Nichrome, and beryllium-copper. New steels are investigated which will be satisfactory in applications where outer race temperature exceeds 350' F. Petroleum. Caldwell (36) reported that corrosion in oil wells producing hydrogen sulfide has been a serious problem for years. Subcommittee TP-1D of the National Association of Corrosion Engineers was organized in 1950 for the study of sour oil well corrosion. This subcommittee has as its objective the accumula-
2227
tion and analysis of data on sour oil well corrosion with a view to determining the extent of the problem and disseminating information as early as possible on likely methods of control. Various remedial measures, such as the use of inhibitors, and the use of K Monel or 9 to 1201, nickel steel are suggested. Bradley (25) described the use of formaldehyde and oil-soluble inhibitors as being effective in reducing the well servicing frequency in wells producing sweet crude where corrosion is probably caused by the acidic nature of the produced brine which contains dissolved carbon dioxide and organic acids. These inhibitors also were effective in sour crude where corrosion is caused by the action of hydrogen sulfide in the presence of the produced brine. Control measures include the testing of high alloys such as aluminum bronze and nickel-copper rods, nickel tubing with two-step square type thread couplings, and a stainless steel pump. Robbins and Kelly (H3) discussed common practices for determining the presence of corrosion in oil well tubing including internal caliper surveys. The best method in any given well a t any particular time to discover or determine the presence of corrosion is the use of the internal caliper. The instrument is described and charts representing the condition of the tubing are interpreted. In an effort to ensure maximum life of subsurface equipment 18-8 stainless, R Monel, K Monel, and Type 416 heat-treated stainless steels are being used. An account is presented (73) on work carried out t o establish cause of failures occurring in mild steel pipelines. Pipes were commonly subject t o resonant vibrations and suffered fatigue fractures. A section is presented on fatigue limits of pipe materials and terminations include data for fatigue limit and damping factor of mild steel, hard nickel, soft nickel, half-hard Monel, soft Monel, and Everdur. Full details of the testing technique are presented. The American Petroleum Institute Interim Advisory Committee on Alloy Steels (187) presented a discussion of creep, alloy steel development, and materials for piping, tubing, forging, pressure vessels, and catalytic cracking and reforming processes. Materials discussed include Monel, Hastelloy B, nickel, Stellite, various austenitic and ferritic stainless steels, aa well as other alloyed steels. Specific recommendations involving conservation of nickel and molybdenum in the ferritic steels used in oil refineries for high and low temperature service is included by the committee. Prange ($04) presented a general discussion of the problems of designing for corrosive processes, and mentioned three ways to control corrosion. One of the methods found useful for controlling corrosion involved the use of more corrosion resisting materials of construction, such as stainless steel, nickel, Monel, and Inconel. Hafsten and Groth (97) described the corrosion of refinery equipment by sulfuric acid and sulfuric acid sludges. Among the many metals and alloys discussed are the Hastelloy alloys and Monel. Many illustrations, graphs, and tables are presented. A number of corrosion case histories are presented (189),and mention is made of the use of Monel linings, nozzles, trays, and bubble caps. Type 410 stainless bubble caps, Inconel, and Type 316 stainless steel bubble caps were tested in a depropanizer tower over a 5-year period. The performance of these several materials of construction are compared. A discussion is presented (197') of corrosion occurring in refinery vessels as a result of various refining processes. Special materials that are resistant to corrosion are discussed, and they include Monel and nickel. Mention is made of the fact that Monel has proved to be quite useful for resisting attack by hydrogen chloride or by hydrochloric acid, occurring in the various refining processes. Farrar (77) discussed the chemical cleaning of refining equipment in considerable detail and mentioned that nickel and its alloys may be cleaned with nonoxidizing acids. A number of case histories are cited for the cleaning of refining equipment.
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INDUSTRIAL AND ENGINEERING CHEMISTRY
Chir, Colenutt, and Turner (42) described some corrosion problems encountered in the Mina-Al-Bhmadi refinery. These problems mere encountered in the Kuwait refinery during the actual processing of crude oil. Applications of various metals and alloys are given and mention is made of the use of Monel for wearing rings and spacer sleeves in pumps. Isotopes. The description is presented (826) of the technique employed for harnessing the energy of cobalt-60 in nondestructive testing. This technique is effective as it includes precise exposure calculations and safe operator procedure. The isotope costs less, is more powerful, and extremely portable; its life span is relatively long for practical use. The effective life of the isotope is 5.3 years. It has been employed to inspect a 2I/2-inch thick girth weld in a pressure vessel. Trout and Vlach (244) described a new tool for medical research. Cobalt-60 is used as an irradiator in a teletherapy unit used for medical research. The unit is loaded with 200curie cobalt-60 source and studies of shielding, Ra-beam characteristics, depth dose, and biological effects are under way. When these are completed, the unit will be reloaded with a 1000-curie source from Canada's Chalk River atomic pile. Blomgren, Hart, and Markheim ( 2 1 ) described the features of two cobalt-60 irradiation chambers. Up to 100 curies of cobalt activity may be housed in this chamber. The double-cavity irradiation chamber is provided with a single 400-curie cobalt-60 source that may be lowered into either of two irradiation cavities. One of these cavities is a thermostated well that may be maintained a t temperatures ranging from -30" to +130° C. Eisler (65) described the solution of the problem of measuring the level of chromic acid solution in a glass-lined kettle, which is part of a deionizing unit for removing contaminants from chromium plating solutions. The problem was solved by the use of an external radioactive level gage. Irradiated cobalt wire was used in this installation. It is reported (217') that Southern Pacific Railroad used cobalt-60 for exploring the quality of metal parts. The use of the isotope provides a nondestructive method of testing castings and weldments. When not in use the cobalt capsule is kept in a spherical lead container 6 inches thick. It is reported (161) that among the first practical industrial applications for nuclear fission is the examination of steel castings for internal defects with radioactive cobalt. When used with photographic film, the rays produce a picture of any defects in the steel. The gamma rays are capable of penetrating steel from l/z to 6 inches thick. Chemical Processing and Miscellaneous. Mott (181) discussed the corrosion resistance of cast nickel. Also considered are applications, composition, machinability, heat treatment, weldability, and mechanical and physical properties of nickel. A table showing the ratings of the corrosion resistance of nicker t o acids, alkalies, salts, gases, organic materials, and various other materials is indicated, Nickel is reported by Fontana (81) to be the best material for handling caustic at all concentrations and temperatures including fused material up to 900" F. The only limitat#ionis that severely stressed nickel may show cracking in strong caustic at temperatures of 600' F. and higher. The rate of corrosion of steel by caustic at very high temperatures (550" to 600' F.) is quite rapid, and nickel or nickel alloy materials are required. It is reported (143, 229) that difficulties in transporting hot caustic soda solutions can be eliminated by the use of a 10,000foot long wrought nickel piping system that will carry the solutions at temperatures around 600" F. Even a t these high temperatures, the rate of corrosion for nickel h y caustic soda is less than 0.020 inch per year. Further, more than 2700 feet of Heliarc welding is done on the entire operation. The use of nickel-plated pipe and fittings is described (224) in connection with soap processing. The nickel-plated pipe has performed satisfactorily both in hot caustic soda and in fatty acid service. Tice ( S 4 l ) discussed the effect of operating factors such as aeration or the presence of oxidizing agents, velocity or flow of corrosive, or agitation and temperature on the corrosion resistance of metals and alloys. These various factors were illustrated by the performance of Monel in sulfuric acid.
Vol. 45, No. 10
In a report by Dunn and Liedholm (62) of a new process for the production of nitration grade aromatics, the problem of maintaining product purity is discussed, and the suitability of nickel and a number of other materials is described. Hader, Waldeck, and Smith (96) discussed the principal materials of construction used for the production of carboxymethylcellulose. Among the various metals and alloys used for corrosion resisting applications are lMonel and Hastelloy alloys. Tables and a flow sheet are presented. Bice, Prange, and Weis (19) discussed various alloys in liquid hydrogen sulfide service. A surge tank is described as being constructed of firebox quality steel of ASTM specification A-70, It is mentioned that corrosion problems with carbon steel in service with anhydrous hydrogen sulfide have not been severe. Among other metals and alloys discussed are nickel and nickelbase alloys and Ni-Resist. Bqueous hydrogen sulfide is much more corrosive than anhydrous hydrogen sulfide, and the various metals act differently in the two media. Embrittlement failures were reported in valve trim and Bourdon tubes made of carbon steel and Type 304 stainless. Type 316 stainless makes satisfactory Bourdon tubes. Glitsch and Fowler (98), in a two-part article, discussed bubbletray design, pressure surges, and truss-type design for bubble towers as well as materials used to construct bubble caps and ti ays and their resistance to wet corrosion and corrosion caused by a number of specific corrosives. Among the many materials considered are Monel, Inconel, nickel, and Hastelloy alloys. Potts and White (202) discussed the fractional distillation of fatty acids and discussed materials of construction and important design factors. Mention is made of the use of Inconel as well as Type 316 stainless steel for fatty acid service. LaQue (156) summarized the corrosion resistance of titanium and compared those results in sea water with tests made on Monel, Inconel, and stainless steel. Tables, graphs, and illustrations are presented. It is reported (860) that Monel-clad is used on extensible radio and radar masts for snorkel-equipped submarines with a resultant saving in money to the Navy. Instead of seamless tubes of 18-8, the new design uses low alloy steel tubing ~5 ith a clad surfacc of llonel. These tubes must withstand salt water corrosion. The use of Rfonel is reported (188) as protection against salt water and spray on oil derricks in the GulI of Mexico. Monel is used as sheathing for the piling. Thornton (240) described the successful use of water from the Gulf of Mexico, both as a coolant and process raw material. Procedures are described for obtaining the sea water, measures to prevent corrosion, application of cathodic protection, and methods of protecting condensers. For intermediate heads, 100 to 150 feet of water, cast-iron casings, and Rfonel impellers are used. For still higher heads, Ni-Resist or Rlonel casings, Monel impellers, and K &lone1 shafts are used. Cathodic protection is extensively used in water boxes of condensers a t the powerhouse and throughout the process area. Bamforth (12) described a modern plant for salt production; the evaporator was fabricated entirely of solid nickel and is among the largest solid nickel vesseIs ever constructed in Great Britain. The application of other materials of construction are also presented and mention is made that liquor circulating lines are of nickel and the pumps are of Ni-Resist. Cornish (48)described the action of metallic nickel on bismuth trichloride. He reported that nickel reacts with dilute aqueous solutions of bismuth trichloride resulting in the deposition of elementary bismuth. There is a range of concentration of the salt within which nickel has no action a t 25" C. At higher temperatures other factors intervene and smooth reaction occurs. Tables and references are presented. Landau (134) reported that the ability of metals to resist fluorine is due to the formation of a protective film. Materials of construction, such as Monel and nickel, are useful in the handling
October 1953
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INDUSTRIAL AND ENGINEERING CHEMISTRY
of fluorine. Indications of their limitations as t o concentration, heat and thickness, and specific recommendations on general design factors are itemized. As with fluorine, Monel is more applicable to the handling of aqueous hydrofluoric acid over a wide range of temperature and concentration than any other common metals. Nickel and copper show somewhat greater corrosion rates, particularly a t high temperatures and lower concentrations. Hastelloy A has been used with dilute hydrofluoric acid. The results are presented in tabular form. Wilkes (666) discussed the use of a number of metallic materials, including Monel and Hastelloy C and a number of nonmetallic materials in ion exchange systems. Jackson (119) discussed corrosion problems in steam-jet vacuum equipment. Mention is made that steam nozzles, in order to withstand erosion, are made of either stainless steel or Monel. Many materials used in ejectors range from nonmetallic to metallic materials, including Hastelloys, Illium, tantalum, and beryllium-copper. Herbolzheimer (106) discussed the use of stainless steels and Monel for bars in pulp-beating equipment. These materials replace steel and bronze which are susceptible to corrosion. Barker (13) discussed chlorine bleaching in the pulp and paper industry. Mention is made of Monel stems and Hastelloy C trim for chlorine valves. I n the handling of wet chlorine, Hastelloy C is used. Several plastic materials have been developed that show great promise; stainless steels are useful for low concentrations of chlorine but are apt to be rapidly attacked under some conditions. Horigan (2 10) discussed the use of corrosion resistant metals in the pulp and paper industry including Monel, nickel, and Inconel. An exhaustive analysis of corrosion problems was made, and some solutions to these problems were indicated. Graphs and photomicrographs are included. Morrison (179) in studying the corrosion of soda-pulping steel digesters has found that these digesters can be used for from 15 to 20 years before a dangerous condition will exist. For those mills that have encountered trouble, a plan t o alleviate the difficulty is to line the top third of the digester with Inconel plates welded to the steel shell. Most of the wear in a digester seems to occur at the top point where the chips settle during cooking. Giacobbe and Bounds (90) reported the use of precipitation hardened beryllium-copper, K Monel, Ni-Span C, and Inconel X for Bourdon tubes. These alloys have good corrosion resistance and can be joined readily by brazing or welding. Masing and Roth (158) have made a fundamental examination of chemical, electrochemical, and corrosion resisting behavior of molybdenum. Alloys considered are various nickel-base alloys containing molybdenum, iron, copper, chromium, and tungsten. Data are presented on the influence of molybdenum and nickel on current density potential curves of the alloys, on passivating influence of nickel a t higher current densities, and on the addition of chromium to produce a passivating effect a t lower current densities. A literature review is appended, and results of the exposure of three of these nickel-base alloys in hydrochloric acid and potassium chloride were outlined along with the comparative results of Hastelloy Alloys B and C. Weisert (266) presented data in chart form on the corrosive behavior of the nickel-molybdenum alloy, Hastelloy B, in acids, alkalies, and organic chemicals, Observations on the mechanical properties, applications, and forms available for the alloy are added. Fabrication, applications, and availability of Hastelloy C are discussed by Weisert (864). Mechanical properties and chemical composition covering the nickel content are tabulated. Temperature concentration charts indicating the corrosion resistance of Hastelloy C to over 150 corrosives are given. Weisert (266) also has presented in chart form the corrosion resistance of Hastelloy D, a nickel-silicon alloy, to a number of corrosives with data on mechanical properties and applications
2229
of the alloy. Hastelloy D is best known for its exceptional resistance to sulfuric acid a t all concentrations and a t all temperatures. Werner (262) reviewed, to a large extent, German literature on corrosion in a chemical plant. Various types of corrosion are explained; a technique for protecting nickel kettles during heat treatment against sulfur pickup is outlined. Gray (96) discussed methods of preventing corrosion including metallic and organic coatings, such as nickel-chromium, nickel, copper-nickel-chromium, zinc, aluminum, cadmium, chromium, copper-chromium, phosphate, and resins, The use of corrosion resistant metals, cathodicprotection, and corrosion inhibitors were also included. Maxey (166) presented a corrosion inhibitor checklist covering representative liquids and metals. Admiralty, aluminum, copper, and brass, magnesium, Monel, steel, stainless steel, and tin plate are the metals listed. In the selection of valves and fittings knowledge of operational conditions-such as corrosion, pressure, temperature, and contamination-are required (37'). Applications of cast iron, NiResist, Type 316 stainless steel, and Monel are discussed. Fangemann (76) reported the development of temperature compensated alloys of the Elinvar type to eliminate the thermostat type compensators. The two materials of this type are Iso- , Elastic and Ni-Span C. A table gives the composition, physical, and mechanical properties of these two nickel alloys. Copson (46) discussed the influence of corrosion on the cracking of pressure vessels and mentioned that serious damage can occur when stress and corrosion combine, taking the form of stress corrosion cracking, involving static tensile stres~es,or corrosion fatigue involving cyclic stresses. The effects of corrosion on pressure vessels may be minimized by design, by reduction of internal or applied stresses, and by choice of materials suitably resistant to their expected service environment. Among the various metals and alloys discussed are nickel and nickel-base alloys; corrosion fatigue data is given for a number of these materials. Tables, graphs, and photomicrographs are presented, The bursting of disks was the subject of a symposium (80) by the Institute of Chemical Engineers in London. Almost all the requirements of disk materials can be met by the use of nickel, aluminum, silver, platinum, palladium, copper, and gold, Although pure metals are generally desirable, the presence of a small amount pf cobalt in nickel appears t o be no disadvantage, and with fully annealed Monel a relatively complex alloy has given very consistent results. Simonds (283) discussed the use of steel, nickel, Inconel, Durrlr nickel, Ni-clad, and various stainless steels in the plastic industry. Today's metal requirements in the plastic industry are 70% steel, 10% cast iron, 15% stainless steel, and 5 % other metals. An announcement is made (166) of a porous nickel sheet material silicone-treated through which water will not pass a t less than 3 pounds per square inch differential, but through which air will pass freely. The material can be cut to the size and form required and can be subjected to mild forming operations. It is permanent under ordinary service conditions. The use of Monel is described (163) in the fabrication of a radar screen, Square Monel tubing was used t o construct a small, compact parabolic radar antenna lens. About 2000 pieces of seamless Monel tubing were cut to exact lengths, flash nickel plated, tin plated, and coated with soft silver brazing alloy and then furnace brazed. Mayer (168) discussed current trends in miniature relay design. This included the performance objectives for applications in airborne electronic circuits, with description of specific relays developed under military contracts. The use of various materials of construction, including high nickel content alloys and beryllium-copper, is outlined. Fyffee and Arobone (87) described the use of Advance, Copel,
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INDUSTRIAL AND ENGINEERING CHEMISTRY
or constantan wire, having a composition of 45% nickel and 55% copper for both static and dynamic testing applications. Isoelastic wire with a composition of 36% nickel, 8% chromium, and 0.5% molybdenum is used for dynamic testing only. Gages of t,his wire provide about six times the voltage output of the copper-nickel gages. Among the various materials of construction used for Bourdon tubes are KR Monel, various st,ainless steels, phosphor bronze, and Haynes Stellite Alloy No. 605. In corrosive atmospheres, 18-8 st’ainlessparts are used in the pressure transducer. Tables and diagrams are provided. Stevens (631) discussed materials of construction applications on the U.S.S. Illusiue, the first of a new class of minesweeper, which is a wooden-hulled ship ~vit’li metal parts and fit,tings made of nonmagnetic alloys. llent,ion is made of t,he use of Alone1 for tanks and the addition of nickel t o austenitic iron t o retain the austenite or nonmagnetic structure at ordinarj- t,emperatures. Considerable use is also made of austenitic stainless steels. In connection with the latter materials, powder cutt,ing was used. A discussion of frett.ing corrosion is presented (6) and methods for preventing this type of corrosion are evaluated. Among the various mat,erials of construction discussed are Inconel, K Monel, annealed nickel, and electrodeposited nickel. Bell Aircraft C o r p . ’ ~X-2 rocket-powered, swept,-wing research plane that is being prepared (9)for supersonic flight tests has a K Monel fuselage and stainless steel wings and t,ail. Lewis and Underwood (142) described a project of producing precision surface-finished specimens that was carried to the point where standard specimens are now available commercially; t,hese cover most of the commonly encountered surface roughnesses. The problem of obtaining, in quantity, highly accurate replicas of the original gold surfaces was solved by using pure nickel, which in turn was used for the production of further nickel replicas. BIBLIOGRAPHY
Aeroplane, 84,122-4 (Jan.23, 1953). Ibid., 84, 258-61 (Feb. 27, 1953). Aircraft Prod., 15, Xo. 172, 38 (February 1953). Ibid., pp. 68-74. A l l e n Eng. Rez;., pp. 12-15 (January 1953). Am. M a c h i n i s t , 96, No. 12, 157 (June 9, 1952). Austin, G. W., Brit. Ministry of Supply, Aeronaut. Research Council, A . S R e p t . (1952). Automotive I n d s . , 107, No. 3, 40-1 (Aug. 1, 1952). Aviation W e e k , 57, No. 5, 70 (Aug. 4, 1952). Ascona, J. M. L. de, Spectrochim. A c t a , 5, No. 1/2, 18 (July
1952). Backofen, W. .4.,and Hundy, €3. B., J . I n s t . Metals, 81 (Pt. 9), 433-8 (May 1953). Bamforth, A. W., T i m e s Reo. of Ind., 7, 25-9 (May 1953). Barker, E. R., Jr., Paper Trade J . , 135, S o . 20, 253-4, 256-7 (Xov. 14, 1952). Beattie, H. J., Jr., and VerSnyder, F. L., T r a n s . A m . SOC. Metals, 45, 397-424; Disc. 424-9 (1953). Bell, F. R., Autocar, 97, 810-15 (July 4, 1952). Berg, C., Precision Metal Molding, 10, No. 8 , 49-50, 83 (1952). Berryman, J. H., Product Eng., 24, No. 4, 171-3 (1953). Bertossa, R. C., Welding J . (&Y. Y.)S z ~ p p l . 31, , S o . 10, 441s-is (1952). Bice, W.O., Prange, F., and Weis, R. E., IND. ENG.CHEM.,44, 2497-500 (1952). Blank, H. A., Hall, A. L I . , and Jackson, J. H., T r a n s . A m . SOC. Mech. Engrs., 74, No. 5, 813-19 (July 1952). Blomgren, R. A , , Hart, E. J., and Llarkheim, L. S.,Ret. S c i . Insty., 24, N O . 4,298-303 (1953). Bozorth, R. R I . , and Walker, J. G., Phys. Ret., 89, 624-728 (Feb. 1,1953). Bradley, B. W., W-oild O i l , 135, No. 7 , 214, 216, 218, 226 (December 1952). Brasunas, A. de S., Corrosion, 9, No. 3, 78-84 (1953). Brenner, A , , Zentner, V., and Jrnnings, C. \I7.,Plating, 39, S o . 8,865-94,899-927,933 (1952). Brockhouse, B. X., Con. J . P h y s . , 31, S o . 3, 339-55 (1953). Brooks, R. D., and Rosenblatt, -4.L., Mech. Eng., 75, No. 5, 363-8 (1953). Broom, T., and Barrett, C. S., Acta Metallurgica, 1 , KO. 3, 305-9 (May 1953).
Vol. 45, No. 10
(29) Brown, H., I r o n A g e , 17, No. 16, 121-5 (ilpril 16, 1953). (30) Bruckart, W.L., Battelle Tech. Rea., 2, No. 2, 19-29 (1953). (31) Bryan, G. M., Wright A i r Development Center, Tech. Rept. No. 52-100 (August 1952). (32) Buckle, C:, Jicquet, P: A., and Poulignier, J., Rev. mdtal, 50, 105-14; Disc. 114 (February 1953). (33) Bucknall, E. H., and Ball, F. -4., Ibid., 49, 249-61; Disc. 261 (April 1952). (34) Burt, F. &I., W e l d z n g Engr., 37, 30.7 , 30-4 (1952). (35) Business W e e k , No. 1227, 146, 148-9 (March 7, 1953). (36) Caldwell, J. 9., Corrosion, 8, No. 8 , 291-4 (1952). (37) Can. Chem. Processtng, 36, KO. 9, 38, 40 (1952). (38) Can. Metals, 16, No. 4,38 (1952). (39) Cansler, H., Chem. & Process Eng.,33, No. 10, 544-6 (1952). (40) Chem. Eng. A-ews, 31, 1232 (March 23, 1953). (41) Chevenaid, P., and Wache, X., Schwezz. A r c h . angew. W i s s . u. Tech., 18, 127-36 (April 1952). (42) Chir, V. J., Colenutt, F. H., and Turner, K . , Inst. Petroleum Rev., 7,159-64 (May 1953). (43) Chyle, J. J., Mochine Design, 24, KO. 8 , 182-5, 265-6, 268 (1952). (44) Cimino, A., and Pallavano, G., J . Phys. Chem., 56, No. 6 , 706-7 (1952). (45) Close, G. C., Modern Nachzne S h o p , 25, No. 3, 136-40 (August 1952). (46) Copson, H. R., Welding J . (-T. Y.)Suppl., 32, No. 2, 75s-91s (February 1953). (47) Cormwall, H. S.,and Burbank, W.S., “Materials Survey on h-ickel,” National Security Resources Board, E.S. Dept. of Interior, Bureau of Mines (1952). Cornish, E. H., J . A p p l . Chenz., 3, P t . 3, 106-9 (1953). Cramford, A. E., Metallurgiu, 47, S o . 281, 109-13 (March 1953). S. --., K ~.~ Rideout. S.P.. and Beck.’ P. A. J . IMdoZs -~ _ R_ ,-n ~ - - (Trans. ---. AIME), 4,KO,10,’1071-5 (1952). Davis, H. W., Eng. Mining J . , 154, NO. 2, 98 (1953). Davis, H. W., and Moore, P. N., “Cobal t Materials Survey 1950,” National Security Resources Board, U. S. Dept. of Interior, Bureau of RIines, Geological Survey (February 1952). Dehlinger, U., Z . Metallkunde, 43, 109-11 (April 1952). Dehlinger, U., and Scholl, H., Ihid., 44, 136-8 (April 1953). Dickinson, T. A., Foundry, 80, No. 6 , 255-6 (1952). Diplock, B. R., Lofts, D. L., and Grimston, R. A., J . Roy. Aeronaut. SOC.,57, 19-28 (January 1953). Dismant, J. H., Hamilton, J. H., Fassell, W.M., and Lewis, .T. R.. J. Metals (Trans. AIbIE). 4. KO. 8. 884 11952). Doelz, M. L., and Hathaway, J. C., Electronics, 26, No. 3, 138-42 (1953). Downie, C. C., Mining J . ( L o n d o n ) , 239, No. 6098, 13-14 (July4,1952). Ibid., No. 6110,342-3 (Bept.26,1952). Ibid., No. 6123,738-9 (Dec. 26, 1952). Dunn, C. L., and Liedholm, G. E., Oil Gas J . , 51, No. 5,68-70, 96 (1952). Ebeling, D. G., and Burr, A. A , , J . Metals (Trans. AIME), 5, NO.4,537-44 (1953). Economos, G., IXD. EKG.CHEX.,45, 458-9 (1953). Eider, S. L., Chem. Eng., 59, No. 9, 172-3 (1952). Electroplating & Metal S p r a y i n g , 5, Xo. 7 , 229 (1952). Ellis, W.C., and Geiner, E. S.. J . Metals (Trans. A I N E ) , 4, 648-50 (June 1952). Ellwood, E. C., N a t u r e , 170, KO. 4327, 580-1 (Oct. 4, 1952). Ellwood, E. C., and Bagley, K. Q., J . I n s t . Metals, 8 0 , Pt. 11, 617-19 (July 1952). Elonka, S.,Power, 97, No. 3, 107-22 (1953). Engzneer, 193,775 (June 6,1952). h i d . , 195,628-30 (May 1,1953). Engineering, 175,248 (Feb. 20, 1953). Everhart, J. L., Materials & Methods, 37, No. 2, 92-6 (1953). Fangemann, A l , G., Mnchzne Design, 24, KO, 11, 154-8 (1952). Farber, M., and Ehrenberg, D. RI., J . Electrochem. SOC.,99, NO. 10,427-34 (1952). Farrar, G. L., Oal Gas J., 51, No. 46, 211-12, 215, 219, 223-4, 226,230,232,235 (March 23,1953). Fine, R I . E., Bell Labs. Record, 30, S o . 9, 345-8 (1952). Floyd. R. W.. J . Inst. Metals, 80, Pt. 10, 551-3 (June 1952). Fluid Handling, No. 37, 39-44 (February 1953). Fontana, hl. G., IND.EXG.CHEM.,44, No. 6, 81 A-2 A, 84 A (1952). Fortune, 47, No. 4, 152-7, 208, 211-12, 214, 216 (1953). Freeman, J. W., Ewing, J. F., and White, A. E., iVatl. Adzisory Comm. Aeronaut. Tech. Y o t e 2745 (July 1952). Fukuroi, T., and Yasuhara, K., Science Repts. Research Insts. TGhoku L’nic., S e r . A3, S o . 6, 687-97 (December 1951). ?~
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October 1953
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I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
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2231
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Vol. 45, No. 10
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