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By W. A. Dickinson, H. F. Hendershot

THIS paper is a brief discussion of the past and present methods employed by the Huntington Works of The International Nickel Co., Inc., in the production of nickel and high nickel alloy seamless tubing. The various operations for both hot and cold processing will be considered in their natural sequence, together with the processing characteristics of the high nickel alloys and some descriptions of the equipment used. The tools and lubricants currently in use will be described. This discussion will relate primarily to nickel, Monel,† and Inconel,† since these are the most common of the many alloys processed into tubing at the Huntington Works. The nominal compositions of the materials are shown in Table I. CONVERSION FROM SOLID BILLETS TO TUBE SHELLS History The commercial production of seamless nickel and high nickel alloy tube shells is a comparatively recent development, the first nickel shells having been produced in 1922, Monel in 1930, and Inconel in 1931 on rotary-type piercing mills. Rolled or forged billets, ranging from 3 ½ - to 7 ½ in. diam, were pierced to produce shells ranging' in size from 4 3/8 in. OD X 0.180 in. wall to 8 3/8 in. OD X 1.0 in. wall. After piercing, the shells. were further processed by hot rolling, reeling, and sizing. Subsequent to these operations the shells were either supplied to the trade as "hot finished" tubes, or were processed by cold drawing to smaller sizes at the Huntington Works of the International Nickel Co. The extrusion of nickel and high nickel alloys also may be classed as a relative newcomer to the field of hot-forming methods, for it was not until 1928 that the commercial extrusion of these alloys was begun on a 600 long ton vertical extrusion press installed at Zenith Works of Henry Wiggin and Co., Ltd., Glasgow, Scotland. This press did considerable pioneer work and the results were so favorable that in 1937 a -2200 long ton horizontal press was installed. The quality of the inside surface of the tubing produced on this press was superior to that produced by piercing on a rotary-type mill and, as a result of this experience, a 4000 ton horizontal extrusion press was installed at the Huntington Works in 1943. Billet Preparation The first step in the extrusion, process is the selection of ingots with good hot malleability, as indicated by the test described by Martin and Bieber.1 Ingots then are forged into rough rounds which are machined to the desired billet diameter on a "bar peeler." This machine consists of a rotary head which carries the cutting tools and is driven by a 200 hp, dc motor. The feed mechanism consists of hydraulically driven input and output carriages on the respective sides of the cutter head. The diameter of the forgings used and the machined size or "billet diameter" that corresponds to the four different sizes of

Jan 1, 1951

By Cyril Wells, Robert F. Mehl

The practical importance of a knowledge of the rates of diffusion of carbon and of alloying elements in steel has often been pointed out.l,13 This importance lies chiefly, though by no means only, in the study of carbufizing and in the study of reactions involved in the eutectoid inversion in steel. The present paper is one of a series in which the rates of diffusion of carbon and of alloying elements in ?-Fe and their mutual effects are measured with precision. The present paper reports the results of measurements of diffusion coefficients D of manganese in ?-Fe over wide ranges of temperature, and concentration, and of the effect of carbon and impurities and of grain size upon these diffusion coefficients.‡ Data on the rate of diffusion of manganese in ?-Fe have been reported by Fry2 and by Paschke and Hauttmann.3 Claussen4 calculated the diffusion coefficient D from Fry's data as 3 X 10-10 sq, cm. per set. at 960º, which will be shown to be incorrect by many orders of magnitude. Paschke and Hauttmann gave a rough value of 9.6 x 10-8 Sq. cm. per set. at 14000. Neither of these workers considered the variation of D with concentration and with temperature, and neither studied the effect of carbon. Method and Materials Method.—The method employed is identical with that used earlier.5 Owing to the volatility of manganese and the consequent loss of manganese from the outer surfaces of the welded diffusion bars, these surfaces were discarded. The diffusion anneals were performed in argon, except One (test 18) in which hydrogen was employed for purposes noted below. The temperatures reported are accurate to about 3" and constant within 1°C; the diffusion times are reported to the nearest half hour. The specimens were furnace-coo1ed after the diffusion ation, at about 2° per min. Layers, usually 0.004 in. thick, parallel to the welded interface, were machined from the specimens after the diffusion anneal and analyzed for manganese to 0.I Per cent Mn; the distances of these layers from the interface was measured to ±0.0002 in. The concentration-penetration curves obtained were analyzed by both the Grube and the Matano solutions.8 The D values calculated by these two methods do not differ appreci000. The Grube solution was used except in tests in which the effect of concentration upon D was greater than so per cent; in such cases the Matano method, which explicitly provides for the variation of D with concentration,' is the more reliable. In general, the number of layers machined from the zones of variable composition were large enough to permit the use of the average layer composition as that of the center of the layer. In 3 of the 3' tests, however, this is not justified, and the D values

Jan 1, 1941

By Cyril Wells, Robert F. Mehl

The practical importance of a knowledge of the rates of diffusion of carbon and of alloying elements in steel has often been pointed out.l,13 This importance lies chiefly, though by no means only, in the study of carbufizing and in the study of reactions involved in the eutectoid inversion in steel. The present paper is one of a series in which the rates of diffusion of carbon and of alloying elements in ?-Fe and their mutual effects are measured with precision. The present paper reports the results of measurements of diffusion coefficients D of manganese in ?-Fe over wide ranges of temperature, and concentration, and of the effect of carbon and impurities and of grain size upon these diffusion coefficients.‡ Data on the rate of diffusion of manganese in ?-Fe have been reported by Fry2 and by Paschke and Hauttmann.3 Claussen4 calculated the diffusion coefficient D from Fry's data as 3 X 10-10 sq, cm. per set. at 960º, which will be shown to be incorrect by many orders of magnitude. Paschke and Hauttmann gave a rough value of 9.6 x 10-8 Sq. cm. per set. at 14000. Neither of these workers considered the variation of D with concentration and with temperature, and neither studied the effect of carbon. Method and Materials Method.—The method employed is identical with that used earlier.5 Owing to the volatility of manganese and the consequent loss of manganese from the outer surfaces of the welded diffusion bars, these surfaces were discarded. The diffusion anneals were performed in argon, except One (test 18) in which hydrogen was employed for purposes noted below. The temperatures reported are accurate to about 3" and constant within 1°C; the diffusion times are reported to the nearest half hour. The specimens were furnace-coo1ed after the diffusion ation, at about 2° per min. Layers, usually 0.004 in. thick, parallel to the welded interface, were machined from the specimens after the diffusion anneal and analyzed for manganese to 0.I Per cent Mn; the distances of these layers from the interface was measured to ±0.0002 in. The concentration-penetration curves obtained were analyzed by both the Grube and the Matano solutions.8 The D values calculated by these two methods do not differ appreci000. The Grube solution was used except in tests in which the effect of concentration upon D was greater than so per cent; in such cases the Matano method, which explicitly provides for the variation of D with concentration,' is the more reliable. In general, the number of layers machined from the zones of variable composition were large enough to permit the use of the average layer composition as that of the center of the layer. In 3 of the 3' tests, however, this is not justified, and the D values

Jan 1, 1941

By R. Wachtell

IN order to study better the phenomena at work in various phases of diffusion of the Fe/Si system when compounded and alloyed by powder metallurgy methods, several attacks have been planned. Electrical, hardness and other measurements have been discussed e1sewhere.l,2 The metallographic phenomena will be considered here. Concerning the metallography of the ferrosilicon alloys, some initial discussion is in order. As this laboratory discovered to its chagrin, there are many traps that lie in wait for even the experienced metal-lographer when he deals with alloys of high silicon content. Chief of these is probably the anomalous behavior of these materials under conventional etching techniques. We have before us, for instance, Corson's paper" of 1928, wherein is mentioned and illustrated (probably for the first time) the peculiar "barley shell" structure sometimes found in these alloys. Again in 19412 he same author reports the structure in 5-14 pct silicon irons. Houghton and Becker mention its presence' but make only tentative effort to explain it. In 1943, Hurst and Riley6 discussed the "barley shell" and declared it to be a false structure, resulting from the peculiar and characteristic film-forming propensities of the alloy. At about the same time, Wrazej7 proved correct the contentions of Hurst and Riley, establishing pretty well the mechanisms of formation and identifying the constituents involved. Hurst and Riley6 a1so describe in their paper (1943) a "cracked film" structure, also a pseudo-morph, the precise nature of which they do not suggest. Careful examination of such a film reveals that it not only cracks but begins to curl away from the surface of the metal and peel, much in the manner of flaking paint. The careful microscopist will be able to focus on the topmost edge of the flake, and, by optical sectioning, follow it down to the metal surface. We have been able, by oblique illumination of such specimens, to observe the raised segment of the film, the shadow that it casts, and the mating segment on the metal into which it fits. As late as 1946, Hurst and Riley8 found occasion to correct misinterpretation of this "cracked film" structure in a work by others on a 12 pct Si/Fe alloy. The "barley shell" and "cracked film" pseudo-morphs are not the only ones encountered in studies of these materials. A third pseudomorph, which may, however, have some structural significance is a fine striation of the surface. Closely spaced and parallel striae extend entirely across single grains. Each grain shows a different direction for the striae, and different closeness of the spacing. The regularity of this structure, and the fact that the striae do not cross from one grain to another, suggest that the structure is a film cracking controlled in some way by the crystal plane orientation of the surface being etched. In general it is wise for the metallographer dealing with these alloys to cultivate a feeling of uncertainty not only of the more complex questions of interpretation, but also of the basic question of whether that which he sees is indeed a true representation of the structure. We have taken, as a first test of the validity of a structure, its reproducibility "in situ" after repolishing and re-etching of the samples. Thus we knew the "barley shell" to be false (fig. 1) even before encountering the definitive works on the subject. The Metallography of Silicon Diffusion in Laminate Bars: As a first step in the study of the metallography of the diffusion process, we have pressed a series of laminate bars. These bars, or "sandwiches" as we have termed them, were pressed with covering layers of iron powder, and a "filler" of the Fe/Si master alloy under study. Bar dimensions were approximately %, x 3 x 1/4 in. The total

Jan 1, 1951

By G. W. Healy, J. C. Schottmiller

Molten silicates were found to exist in the Cr-Si-0 system at temperatures above 1450°C. one atom of oxygen is readily removed from CrzOs in the presence of Si02 at 1700°C, forming a silicate melt. Steam-hydrogen ratio measurements made at this temperature indicate that the free energy of the reaction: Cr20s(c) + Hz = 2CrO (in Si02 -saturated melt) + H20 is approximately 5600 * 1500 cal. A deep-blue chromous silicate, probably Cr2Si04, forms from these melts at about 1400" to 1500°C, and is characterized by.its distinctive X-ray diffraction pattern and optical properties—distinct pleochroism and high refractive indices. THE question of the state of oxidation of chromium in slags has vexed metallurgists for many years The experiments of Koerber and Oelsenl suggested the probable presence of divalent chromium in silica-saturated slags equilibrated with high-chromium melts. Hilty and coworkers2 had also found chromium at lower valency, as Cr304, in inclusions formed from oxygen-saturated Fe-Cr melts with as little as 10 pct Cr. In both cases, disproportiona-tion of the lower oxide to CraO3 and chromium was found to occur to a greater or lesser extent, depending upon the rate of cooling from the high temperature. The work on Cr304 was sufficiently detailed for chipmans to derive its thermodynamic properties, but Oelsen's experiments in the silicate system were not extensive enough since most of his runs were made with slags containing large amounts of manganese oxide in addition to iron and chrome oxide and silica. The present study describes experiments carried out to map out an approximate liquidus diagram in the CrzOs, "CrO", SiOa portion of the Cr-Si-0 system, and to measure the partial free energy of solution of oxygen in the system. EXPERIMENTAL 1) Approximate Melting-Point Determinations. Preliminary trials showed that when an equimolar mixture of Cr20s and SiOa was treated with hydrogen in the temperature range 1500" to 1600°C, copious amounts of steam were evolved, and a low-melting liquid formed which could be quenched to a blue, crystalline, material having a distinctive X-ray diffraction pattern. It was found that the identical material could be produced by heating intimately mixed, finely divided Cra03, Cr, and SiOa, held in a tungsten crucible, under purified argon. Thus, it was possible to prepare mixtures containing any desired proportions of chromium, silicon, and oxygen, pel-letize them, heat to temperature in the furnace shown in Fig. 1, and observe, after cooling, whether the pellet remained unchanged or showed signs of incipient, partial, or complete melting. 2) Free Energy of Solution of Oxygen. This was studied by measurement of steam-hydrogen ratios for the reaction: H20 (gas) + O (dissolved in charge) + Ha (gas) The experimental method chosen was to prepare a

Jan 1, 1964

By Rollin E. Hook, Attwell M. Adair

The response of CrzO3 and C~304 to various heat treatments was studied in are-melted iodide chromizim over the temperature range 1000" to 1750°C. These oxides, which are present as impurity phases in this material, were identified by X-ray diffraction teclzniques which were supplemented by optical metallop-aphy. As a function of increasing temperature, Crs04 is first observable in samples annealed at 1300°C and coexists with Cr2O3 (the low-temperature oxide) over a temperature range exceeding 200°C. As the temperature decreases, Cr3O4 dissolves with the concomitant precipttation of Cr2Y2. Both oxides precipitate predominantly at pain boundaries. The reactions which occur are involved with at least ternary equilibria, possibly due to iron which is present as an impurity in arc-melted iodide chromium. HILTY, Forgeng, and Folkman' reported in their investigation of the Fe-Cr-0 system that Cr3O4 (with about 8 pct Fe substituted for chromium) is a primary phase found in alloys with 9 or more pct Cr. They reported that this phase is stable only at high temperatures and that below the liquidus Cr3O4 is disproportionated into Cr2O3 and chromium-rich metal for both Fe-Cr-O alloys and in oxygen saturated pure chromium. Further, they proposed that CrsO4 forms by a peritectic reaction between Cr2O3 and the liquid. On the other hand, Hook, Garrett, and Adair2 found in their investigation of impurity phases formed in "pure" chromium (material consolidated from iodide chromium crystals) that Cr3O4 forms intergranularly and is stable as low as 1500°C which is 375OC below the melting point of chromium. The purpose of the research described herein is to determine the temperature range of stability of Cr3O4, and to show the nature of its decomposition. This further investigation indicates that Cr3O4 undoubtedly occurs in this material as low as 1300°C. The chromium studied was consolidated and fabricated from iodide chromium crystals (ICr-5) and contained Fe r 135 ppm, Si = 20 to 100 ppm, and 0 = 35 to 137 ppm. A complete chemical analysis is given elsewhere.' Annealing was conducted in 1 atm of purified helium and all samples were rapidly cooled (-200°C per sec) by withdrawing them from the furnace hot zone under a high flow rate of helium. The details of the electrolytic-etching technique and electrolytic-digestion techniques for preparation of insoluble residues for X-ray examination are given elsewhere also.' EXPERIMENTAL RESULTS The Starting Material. The as-swaged rod (final swaging done at 900°C) had a wrought grain structure and contained a dispersion of CrzO3 inclusions of maximum particle size of about 2 or 3 p, Fig. 1. The microstructure also contained a dispersed

Jan 1, 1964

By T. J. Fabiniak, R. A. Dodd, R. Balow

ALTHOUGH the (111) slip direction in pure bcc metals is well established, the information on operative slip planes is less unambiguously interpreted. So far, (110) {112), and (123) slip planes have been identified, but it is not certain whether glide on (112) and (123) really occurs or if it is composite slip on non-parallel (110) planes. The second of these possibilities is supported by the work of Chen and Maddin on niobium and molybdenum, and a subsequent analysis by these same workers of slip in bcc metals generally.3 The alternative possibility is exemplified by the work of Opinsky and smoluchowsky4 who concluded that slip in Fe-Si crystals can occur on any one of the systems {110}(111), {112}(111), and {123)(111), depending on which system the resolved shear stress is highest. Allen et alS5 also found that glide in ar iron could occur on any of these three systems, the operative system being determined principally by orientation. By an analysis of crystal rotation, slip lines, and X-ray asterism Harris6 concluded that niobium also deforms on these same systems, but if one of these glide planes does not coincide with the plane of maximum resolved shear stress, composite slip on nonparallel (110) planes may occur giving a macroscopic high indices slip plane. Earlier work on iron by Vogel and Brick reached the same conclusion.7 The analysis of slip in bcc metals is made more difficult by the fact that the slip lines may be quite wavy. In fact, the generality of wavy slip lines suggests that screw dislocations slip readily from one plane to another in the (111) zone ("pencil glide") although, as noted, it is not certain whether planes other than (110) really contribute to the slip. If planes of higher indices than {110} do operate, there is a possibility they may do so more readily at higher temperature Argon and Maloof9 observed {100}{211}(111) slip in tungsten single crystals plastically strained at low temperatures, but the results were interpreted in terms of an orientation-dependence rather than temperature-dependence. Therefore, at the present time corroborative evidence for the operation of higher indices slip planes at higher temperatures is lacking. The present results were obtained during the course of an investigation into the effect of cathode and anode surface crystallography on the prebreakdown currents of vacuum insulated devices. In the experiment of particular interest, the 1/8-in.-diam anode and the in.-diam cathode were tungsten crystals (total impurities -230 ppm) with (110) and (100) faces respectively. The faces were electrolytically planed and examined for initial perfection by plastic/carbon replicas and a study of Kikuchi lines in reflection electron diffraction patterns. They were aligned precisely parallel in an insulating holder incorporated into the electron microscope, the measured microscope vacuum being 2 x 10-5 torr, and the electrode spacing 0.01524 cm. The anode structure shown in Fig. 1 was obtained

Jan 1, 1970

By P. A. Tucker, C. R. Hudgens, D. E. Etter, D. L. Roesch, D. B. Martin

The equilibrium phase diagram of the Pu-Cd system is presented based on data obtained by differential thermal analysis, metallography, and electron-microprobe X-ray analysis. Liquidus temperatures range from 320° to 934°C. The system contains one congruently melting compound, PuCd, (945°C), and three incongruently melting compounds, PuCd, (800°C), PuCd, (730°C), and PuCd11 (410°C). A liquid-miscibility gap extends from 2 to 60 at. pet Cd with the monotectic reaction isotherm at 910°C. INTEREST in the potential use of plutonium alloys as reactor-fuel materials has prompted investigation of the phase equilibria in plutonium binary systems. A cursory investigation of the phase equilibria in the Pu-Cd binary system was conducted by differential thermal analysis (DTA), metallography, and electron-microprobe X-ray analysis (EMX). Extensive solid solubility of cadmium in both e and 6 plutonium was predicted1 based on atomic radii and electronegativities. Liquid immiscibility between these two elements was also predicted based on Mott's extension of Hildebrand's method. In the only previous investigation of the Pu-Cd system,2 two intermetallic compounds, PuCd11 (incon-gruent melting point 406°C) and PuCd8, were identified. EXPERIMENTAL The plutonium metal used in this work had a total impurity content of 500 ppm; the major impurities were: carbon (215 pprn), silicon (75 ppm), iron (60 ppm), nickel (40 ppm), and aluminum (25 ppm). The cadmium was reagent grade with a purity of 99.99 pet. The DTA technique for the study of plutonium alloys was previously described in detail.3 The alloys to be studied were prepared in tantalum DTA specimen capsules which were sealed by inert-gas welding. The alloys were homogenized in the liquid state in these sealed capsules which prevented the loss of cadmium by vaporization. Only the thermal arrests in the DTA heating curves were used to define the transformation temperatures of the system since supercooling affected many of the results during cooling. After the alloys were analyzed by DTA, the same alloys were used for the metallographic studies. Metallographic examinations were conducted in the manner described for plutonium alloys., No reaction was detected between the alloys and the tantalum capsules. Alloys for EMX analysis were placed in metallographic mounts together with specimens of unalloyed plutonium and cadmium which served as standards. The samples were highly polished but unetched. No protective coatings were applied to the surfaces of these radioactive specimens. Such coatings are detrimental to the excitation conditions and have been found to be unnecessary for the control of radioactive contamination. RESULTS The results of the DTA studies are presented in Table I. The phase diagram, constructed from these data plus the metallographic and EMX results, is presented in Fig. 1. The congruently melting compound, PuCd2, was identified by the occurrence of a maximum melting point (945°C) at 33.3 at. pet Pu-66.7 at. pet Cd and by the presence of a single phase in this composition.

Jan 1, 1965

By B. D. Lichter

The lattice parameters of zirconium and zirconium-oxygen solid solutions (hcp) were determined from measurements of back-reflection X-ray photograms obtained at 29°C using a symmetrical focussing camera. The following linear equations between parameters (c,a) in angstrom units (10-8 cm) and atom ratio (m) of oxygen to zirconium were obtained: c = 5.14764 + 0.2077m a =3.23168 + 0.1099m. The linear equations given are valid over the range 0 to 5 at. Pct 0. The accuracy of individual parameter measurements approaches the limiting accuracy determined by the spectral broadening of the incident characteristic radiation, and exceeds the accuracy of previously reported values. THE present work was undertaken in order to determine the lattice parameters of zirconium-oxygen solid solutions with an accuracy that allows quantitative determination of oxygen in zirconium. The results indicate that this is possible if very careful measurements are made, since the parameter change is only a few hundredths of a percent per at. pct 0.1, 2 In the present investigation the desired accuracy was achieved with large-grained samples using a back-reflection focussing camera and maintaining good temperature control during exposure. In addition a digital computer was used for calculation of the parameters by means of an analytical extrapolation.37 Suitable diffraction photograms were obtained from large-grained samples by using a modification of the technique described by Graf and Monteil.5 This consists of simultaneous rotation and oscillation of the specimen about two mutually perpendicular axes during exposure. Whereas, normally the upper limit of grain size is about 50 µ for useable diffraction photograms, this technique allows extending the upper limit of grain-size to exposure of a single crystal. EXPERIMENTAL Preparation of Alloys for X-ray Diffraction—Zir-conium, designated as hafnium-free, Westinghouse "Grade 1," was swaged from l/2-in.-diam crystal bar to 3/8-in.-diam rods. Substantially all of the hydrogen was removed from the zirconium by annealing at 1200°C in a high dynamic vacuum. The rods were then swaged to 0.2 in. diam without intermediate annealing, and 2 in. lengths were cut for alloying with oxygen. Samples for chemical analysis were taken from portions of the rods between each 2 in. length. Chemical analysis of the dehydroge-nated zirconium is given in Table I. Commercial tank oxygen (99.5 pct 0) was condensed in a liquid nitrogen-cooled trap, and part of the condensate was slowly reevaporated into 5-liter storage flasks. Nitrogen remained as a reactive impurity, and the calculated maximum increase in nitrogen content after a 5 at. pct 0 addition to zirconium was 50 ppm by weight. However, chemical analyses of several of the prepared alloys indicated that the maximum increase in nitrogen content was 10 ppm. The storage flasks, a Sieverts-type gas burette and manometer, and associated traps, pumps, and pressure gauges were connected through a glass high-vacuum manifold to comprise the gas addition system. A fused silica tube, connected to the mani-

Jan 1, 1961

By E. A. Nesbitt

The important permanent-magnet alloys 15 years ago contained carbon and depended upon it for their permanent-magnet properties. In recent years great advances have been made in a number of new alloys substantially free of carbon. These include Remalloy,' an alloy of iron, cobalt, and molybdenum, the various iron-nickel-aluminum alloys of the Mishima2 type, and the more recent Alnico V3 in which the best properties are developed by heat-treating in a magnetic field. The Mishima and the Alnico types of alloys are very brittle and after casting must be ground to size. This article describes a permanent-magnet material4 that can be machined as cast, and when handled with some care can be rolled to thin sheet and drawn to fine wire. Optimum magnetic properties are developed by a simple heat-treatment, and at this time the ductility of the alloy disappears. If the cast alloy is heat-treated without cold-working the mag netic energy product is about 1.0 X 106. This material is called Vicalloy I (pronounced vicalloy, V for vanadium, I for iron, and C for cobalt). When the alloy is first hot-worked and then considerably reduced in area by cold-swaging, drawing or grooved rolling, it is found that after heat-treatment the magnetic energy product measured in the direction of previous extension can be increased to 2.0 to 3.5 X 106. These higher values have been obtained only after reductions in area of 75 to 95 per cent, and since the material hardens considerably during working, the reduction ordinarily can be accomplished only in fine wires, although larger sizes can be reduced by the use of powerful machinery. When the material has been cold-worked in such a manner as to improve its energy product substantially, it is called Vicalloy 11. Commercial use of Vicalloy has been made in the recording of speech. Tape 0.002 by 0.050 in. has been found superior in quality to all others tried, and is now used in the Western Electric Mirrorphone 5 In a variety of forms Vicalloy I or I1 is useful in many laboratory instruments, and in experiments in which the sizes and shapes required cannot be obtained with the other more brittle permanent-magnet materials. In 1936, during a study of other age-hardening magnetic systems, it occurred to the author that some of the iron-cobalt-vanadium alloys might be suitable for permanent magnets. The proportions of iron, cobalt, and vanadium were varied and a range of alloys of particular interest was found, as shown by the indicated area in Fig. I. The limits of this range of composition are 30 to 52 per cent iron, 36 to 62 per cent cobalt, and 4 to 16 per cent vanadium. The compositions indicated by points outside this area were also tested. Preparation and Properties OF Vicalloy I The alloys were usually cast in graphite molds into bars 3/4 in. in diameter and

Jan 1, 1946

By E. A. Nesbitt

The important permanent-magnet alloys 15 years ago contained carbon and depended upon it for their permanent-magnet properties. In recent years great advances have been made in a number of new alloys substantially free of carbon. These include Remalloy,' an alloy of iron, cobalt, and molybdenum, the various iron-nickel-aluminum alloys of the Mishima2 type, and the more recent Alnico V3 in which the best properties are developed by heat-treating in a magnetic field. The Mishima and the Alnico types of alloys are very brittle and after casting must be ground to size. This article describes a permanent-magnet material4 that can be machined as cast, and when handled with some care can be rolled to thin sheet and drawn to fine wire. Optimum magnetic properties are developed by a simple heat-treatment, and at this time the ductility of the alloy disappears. If the cast alloy is heat-treated without cold-working the mag netic energy product is about 1.0 X 106. This material is called Vicalloy I (pronounced vicalloy, V for vanadium, I for iron, and C for cobalt). When the alloy is first hot-worked and then considerably reduced in area by cold-swaging, drawing or grooved rolling, it is found that after heat-treatment the magnetic energy product measured in the direction of previous extension can be increased to 2.0 to 3.5 X 106. These higher values have been obtained only after reductions in area of 75 to 95 per cent, and since the material hardens considerably during working, the reduction ordinarily can be accomplished only in fine wires, although larger sizes can be reduced by the use of powerful machinery. When the material has been cold-worked in such a manner as to improve its energy product substantially, it is called Vicalloy 11. Commercial use of Vicalloy has been made in the recording of speech. Tape 0.002 by 0.050 in. has been found superior in quality to all others tried, and is now used in the Western Electric Mirrorphone 5 In a variety of forms Vicalloy I or I1 is useful in many laboratory instruments, and in experiments in which the sizes and shapes required cannot be obtained with the other more brittle permanent-magnet materials. In 1936, during a study of other age-hardening magnetic systems, it occurred to the author that some of the iron-cobalt-vanadium alloys might be suitable for permanent magnets. The proportions of iron, cobalt, and vanadium were varied and a range of alloys of particular interest was found, as shown by the indicated area in Fig. I. The limits of this range of composition are 30 to 52 per cent iron, 36 to 62 per cent cobalt, and 4 to 16 per cent vanadium. The compositions indicated by points outside this area were also tested. Preparation and Properties OF Vicalloy I The alloys were usually cast in graphite molds into bars 3/4 in. in diameter and

Jan 1, 1946

By J. S. Bryner

In the study of metallographic specimens in the electron microscope, there is need for a method of locating the same field in both the light microscope and the electron microscope. This need arises chiefly from the fact that in the electron microscope the magnification and degree of resolution are so much higher, and the field so much smaller than in the light rnicroscope that it is often difficult, if not impossible, to identify positively what is being observed. The difficulty is increased by the fact that, because a transparent film replica of the metal surface must be used in the electron microscope, micro-constituents can be identified not by their color but only by their texture and contours. For these reasons it is desirable to obtain a series of photographs showing the same field in both microscopes in order that the appearance of common microstructures and micro-constituents in the electron microscope may be identified and catalogued for future reference. The need for a method of locating the same field in both microscopes arises also when it becomes desirable to enlarge in the electron microscope for more detailed study a particular interesting structure observed in the light microscope. Using the standard polystyrene-silicalJ replica technique, in which the silica film replica is fished from the ethyl bromide on a 1/8 in. diam zoo-mesh specimen screen, the possibilities of locating a particular area on the film in the electron microscope are rather remote. The desired structure may be obscured by the wires of the specimen screen or unrecognizable at the high magnification. A solution to the problem would be provided if a specially designed specimen screen, containing an opening which could be absolutely identified and quickly located in the electron microscope, could be fastened to the silica film replica in such a position that the desired field on the specimen would be located at the identifiable opening in the specimen screen. The design for such a specimen screen, a method for producing it, and a technique for fastening it to the silica film replica are described below. Description OF Method The Specimen Screen A simple design for a specimen screen containing an opening easy to identify and locate in the electron microscope is one with two lines of openings at right angles in the form of a cross. Such a screen is shown in Fig I. The opening at the center of the cross is identified easily and can be located quickly in the light microscope and in the objective image of the electron microscope. The specially designed specimen screens for this work were produced in quantity by electroforming. On both sides of a polished strip of copper I X 3 X 1/8 in., twenty patterns of the cross of openings were punched with a diamond point micro-hardness tester, using a load of magnitude

Jan 1, 1949

By E. O. Kirkendall

THE investigation reported herein was undertaken to obtain data to supplement those presented in an earlier paper,' particularly for longer times at a higher temperature. This information may further develop our knowledge of the mechanism of diffusion in substitutional solid solutions. Diffusion of solute atoms interstitially dissolved is not difficult to visualize; it can take place without much disturbance of the solvent atoms. The mechanism of diffusion of solute atoms substitutionally dissolved is not so easily understood. Many theories have been advanced. Rosenhain,2.3 Frenkel,4 Smekal,5 Langmuir,3,6 Steigman, Shockley and Nix,7 and Johnson8 all proposed theories to explain diffusion. Langmuir's proposed mechanism consisted of a simple cyclic interchange of atoms involving an interchange in lattice positions of four or more atoms. This mechanism, accepted by the author at the time of his previous publication,' and apparently quite generally accepted, required a net exchange in positions of both solute and solvent atoms in equal numbers. In other words, the rate of diffusion of the solvent and solute atoms would be the same. That this cyclic interchange in lattice positions of solute and solvent atoms in equal numbers is the only true mechanism of diffusion is denied by the evidence presented in this paper. EXPERIMENTAL PROCEDURE This modification of similar procedure1 will be outlined briefly. The method consisted of the following steps: I. A pure Muntz metal (60.6 per cent Cu, 0.1 per cent total impurities) that was almost all beta brass at 780°C. was chosen. 2. The brass was turned between centers in a lathe to a diameter of 0.5965 inches. 3. After the brass was cleaned, it was electroplated with pure copper to a diameter of about one inch. 4. The sample was heated slowly to 400°C. under reduced pressure and held at that temperature for 4 hr. to remove occluded gases. It was then cooled to room temperature. 5. The sample was heated to 780°C. ±3°C. and held at that temperature for different lengths of time; then quenched. Samples were cut off each time after quenching. Metallographic samples 34 in. thick were removed at I hr., 6 hr., 24 hr., 96 hr. and 701 hr. After 96 and 701 hr. samples of about I in. were removed for X-ray analysis. 6. The metallographic samples were polished on the cross section and photo-micrographs were taken. 7. The I-in. samples were polished and etched on both ends. With the aid of a microscope each was carefully mounted in a four-jaw chuck in a lathe, so that they could be accurately bored for an arbor. 8. Turnings were taken for each X-ray sample. After each set of turnings, the sample was heated in an oil bath for about 3a hr. at 300°C. It was then etched in 25

Jan 1, 1942

By C. M. Schwartz, J. R. Bridge, D. A. Vaughan

THERMAL expansion coefficients of a uranium were originally reported' on the basis of X-ray diffraction measurement of lattice constants at 25°, 300°, and 650°C. These data have been reproduced by Katz and Rabinowitch.' CuK radiation had been used in this work, with consequent crowding of the patterns. Considerable overlap of the back-reflection lines was observed as the temperature was raised. Subsequent reexamination of the data led to the conclusion that errors had resulted from failure to obtain unequivocal indexing of the high angle reflections at elevated temperatures. The measurements have been repeated, using FeK radiation, which provided sufficient dispersion to assure proper indexing of the reflections, at each temperature level. The unit cell dimensions were re-determined at ten temperatures, from 25" to 650°C. Schuch and Laquer easured the macroscopic contraction from room temperature down to —253°C, and reported a negative value from —210" to —253°C; they suggested the possibility of the occurrence of a phase change. In the present work, the lattice constants of uranium have been measured down to —253°C, to test this hypothesis. Filings were prepared from a single piece of pure uranium bar stock. They were carefully cleaned with a magnet and pickled in nitric acid to remove traces of iron from the file. They were then annealed at 600°C in a sealed evacuated silica tube. The annealed filings were pickled in strong nitric acid to remove any oxide layer, washed in water and alcohol, quickly dried, and sealed in evacuated thin-walled silica capillary tubes. If properly sealed, the sample could be heated to the a-ß transforination temperature without significant buildup of the diffraction pattern of oxide. The high temperature X-ray diffraction camera was modified from the design of Hume-Rothery and Reynolds.' The thermocouple used to record the specimen temperature was calibrated from lattice-constant measurements of a standard silver specimen, using the Hume-Rothery and Reynolds values for silver over the temperature range from 25" to 700°C. Temperatures were reproducible to 210°C. Temperatures to —210°C were attained by passing precooled gas over the sample. The gas from the cooling train was directed over the sample capillary tube and thermocouple by means of a chimney of 1-mil polystyrene. The 36-gage Cu-constantan thermocouple had been calibrated by

Jan 1, 1957

By William R. Patterson

ACCORDING to the phase diagram for the Mn-Ni system,' the high-temperature, fcc y-manganese solid solution is stabilized to below room temperature, in the range approximately 22 to 28 wt pct Ni. However, pearson2 cites evidence in the literature showing that for manganese contents greater than about 75 wt pct the quenched phase in Mn-Ni alloys is fct. This is in keeping with zener's3 suggestion that in manganese-rich alloys the fcc high-temperature phase undergoes a diffusionless or martensitic transformation to a fct structure upon quenching. Work by Basinski and christian4 on manganese-rich compositions in the similar alloy system Mn-Cu established that in alloys of greater than about 82 wt pct Mn the y-manganese phase underwent a fee fct martensitic transformation upon quenching to room temperature. Striking evidence for this martensitic transformation was the highly twinned or banded microstructure, an example of which is shown in Fig. 1. Similar microstructures have also been found in quenched Mn-Cr5 and Mn-Au6 alloys. In the present investigation, we attempted to obtain similar evidence of a fcc — fct martensitic transformation in manganese-rich Mn-Ni alloys. Manganese alloys in the range 10 to 30 wt pct Ni were prepared by arc-melting, under argon, at atmospheric pressure. The alloys all were 50 g in size, and negligible weight loss occurred during melting. The starting materials were electrolytic manganese and nickel, both of 99.9+ pct purity. The alloys were subsequently homogenized 48 hr at 1750°F, hot-rolled 50 pct at 1700°F, annealed 2 hr at 1700°F, and water-quenched to room temperature. All heat treatment was done in purified argon. Both X-ray and metallographic techniques were used to examine the structures of the quenched alloys. X-ray diffractometer studies were conducted on powder specimens obtained from filings rean-nealed 2 hr at 1700°F in argon and water-quenched. Identification of the intensity peaks from the diffractometer counter traces showed that below about 10 to 12 pct Ni the y phase decomposed partially upon quenching to give an a- + ?-manganese structure. In the range approximately 12 to 25 pct Ni, the structure was found to be fct ? manganese with a c/a ratio approaching 1.0 at 25 pct Ni. Beyond approximately 25 pct Ni, the structure remained fcc. These results, including lattice-parameter determinations, are given in Table I. Metallographic examination. was carried out on specimens polished and etched after quenching, and also on polished specimens reannealed and quenched. In the first case, the distinctive twinning or banding so prevalent in Mn-Cu alloys was sought, while in the second, the surface relief effect generally regarded as being truly characteristic of a martensitic transformation was sought. The microstructure of representative alloys in the range 12 to 25 pct Ni is shown in Fig. 2. The structure of the Mn-15 pct Ni

Jan 1, 1965

By T. J. Woodside

Prior to 1927 the lead blast furnace charge at El Paso consisted principally of direct-smelting carbonate ores, very low in zinc, and the resulting slag seldom carried more than 4.0 pct. With the exhaustion of the mines in Northern Mexico which supplied these ores, they were supplanted with a much smaller tonnage of sulphide concentrates containing appreciable amounts of zinc, and the zinc content of the slag rose to 10.0 pct. The Anaconda Company's slag fuming plant at East Helena, Montana, had then been in successful operation for several years, and it was immediately recognized that, while at that time the production of high zinc slag was small, if the grade held, a plant for the recovery of zinc from the accumulated slag might some day be practical. The grade not only held but became increasingly higher so that by 1946 suffcient slag had been accumulated to warrant the construction of a fuming plant regardless of future slag production from the blast furnaces, and with the removal of Government restrictions on construction at the end of the war the project was undertaken. The general design of the plant follows that at Bunker Hill, with waste heat boiler, unit coal pulverizers and even more extensive instrumentation and automatic control. The area around the lead blast furnaces is rather congested, being cut off from the nearest feasible site for the fuming plant by the copper plant, so that the most practical route for hot slag transfer is through the converter aisle. For this reason and also to make use of the existing converter cranes to serve the fuming furnace, an unused reverberatory at the north end of the converter building was dismantled and the fuming furnace and boiler located in its place. A flue at right angles to the furnace and boiler runs northward to the U-tube coolers and baghouse (Fig 1). From the bag-house a steel flue runs eastward to an existing and long unused 300 ft con- Crete stack. The coal handling system and de-leading plant lie north of the furnace and east of the cooling tubes and baghouse. The furnace is conventional, 8 X 21 X 33 ft high inside and completely water jacketed (Fig 2). There are 21

Jan 1, 1950

By Charles S. Larkey

Numerous papers have been published on the use of graphic methods for determining the best curve for estimating the production decline of oil wells but, as far as the writer has been able to ascertain, nothing has been published showing how curves may be worked out mathematically that will conform most closely to the production data under consideration in any given instance; hence the writer has endeavored to show just how such application can be made. Among the valuation engineers, two types of curves are in current use for the representation of the decline in production of oil wells. One may be represented by the equation, y = krx; this is sometimes known as a percentage curve, for the production for any period is multiplied by a constant rate or percentage to obtain the production for the succeeding period. It appears as a straight line on semilogarithmic cross-section paper. The other curve may be represented by the equation, y = kxn, and is shown as a straight line on logarithmic cross-section paper. In each equation, y represents the number of barrels produced in a given period of time, and x the successive periods of time. The other letters are constants to be determined for each well, or group of wells considered in arriving at the most probable curve to represent the rate of production for a given property. From this the underground reserves may be estimated by extrapolation, or by extending the curve beyond the last known period of production to show the most probable production values for the future. Application to the Burbank Pool Fig. 1 relates to a property in the Burbank Pool, Osage County, Okla. The production is shown as an average per well per month, is plotted to the vertical scale of barrels on the left-hand margin and to the horizontal scale of months at the bottom of the chart. In column y, the number of barrels is listed beginning with May, 1922, as the first month on which to base a decline curve. The type of curve used is of the form, y = krx, or, expressed in logarithms, log y = log k + x log r, in which log k and log r are constants to be determined so that the curve will most closely approximate the production data given.

Jan 1, 1925

By Carl Samans

THE attention of physicists and metallurgists has been directed toward the study and explanation of the deformation textures in metals for the past 15 years. In 1920 N. Uspenski and S. Konobejewski1 were first able to show that the symmetrical X-ray diffraction effects that had been previously reported by E. Hupka2 and others in metal foils were caused by a directed arrangement of the crystallites. Since then, the systematic study of textures resulting from the application of the pure forces of tension or compression to polycrystalline materials hag been supple-mented by many investigations on deformed single crystals, which have greatly added to our knowledge of deformation. However, despite the valuable information secured from these comparative studies only four investigations upon cold-rolled single crystals of any of the face-centered cubic metals have been reported in the literature. This lack of quantita-tive data is especially unfortunate because of the much greater practical significance of rolling textures and their effects in both cold-rolled and annealed materials. This investigation was undertaken for the purpose of specifying the deformation of rolled single crystals in the hope that such information might later facilitate the explanation of polycrystal-line textures.

Jan 1, 1934

By CHARLES F. DEISS

The total pipe-line runs of petroleum in Indiana during 1945 were 4,114,000 bbl., a decline of nearly 17 per cent below the estimated 4,950,000 bbl. produced in 1944. Drilling activity during the year was centered in Posey and Gibson Counties, where seven new pools were discovered in the state. Four of the pools are in Posey County-Crunk, Farmersville, Jeffries and St. Wendells East-and the other three are in Gibson County-Johnson West, Lysle and Mt. Carmel East.

Jan 1, 1946

By K. P. Gupta

The Cb-rich boundary of the (Cb,Al) a phase field at 1250OC is near 41 pct Al. The Al atoms tend to occupy the C. N. 12 sites in this structure. A homologous (Ta,Al)a phase was identified. No a phase was found in the Mo-Al system at 1200°C. The first binary o-phase with a non-transition element as a major component was found1,2 in the Cb-Al system. The composition of this phase was reported2 as approximately 34 at. pct Al, based on X-ray diffraction patterns taken of alloys in the as-cast condition. Further study of the composition of this o-phase, therefore, appeared desirable. Since Si was previously found3,4 to occupy preferentially the lowest C.N. sites (I and IV) in the a phase, and preliminary resultsa indicated that Al may show similar ordering, one of the aims of the present work was to obtain more complete information on ordering in (Cb, Al) o. Among the binary systems of Al with Ti-, V-, and Cr-group elements, the Ti-Al, Zr-Al, V-Al, and Cr-Al systems are known to comprise no o-phase. In the present work a Ta-Al and a Mo-Al alloy were studied in an effort to find additional o phases with Al as a major component. EXPERIMENTAL PROCEDURES AND RESULTS An alloy with the intended composition of Ta + 40 at. pct Al was prepared by arc melting in He atmosphere. In both the as-cast condition and after annealing for 10 days at 1250°C and quenching in cold water this alloy consisted of two phases, as seen in the X-ray pattern and the microstructure. One of these phases was identified as the o-phase; the observed and calculated d-spacings are shown in Table I. The lattice parameters of this o-phase are a = 9.972 A, c = 5.214 A and c/a =0.5228, as determined from a Debye-Scherrer pattern using Fe K a radiation. The d-spacings for the unknown second phase are given in Table 11. The alloy contained approximately 25 pct of the unknown phase after annealing, as estimated on the basis of microscopic examination. A Mo-Al alloy was prepared by arc melting, with an intended Al-content of 35 at. pct. The alloy button was annealed for 7 days at 1200°C and water quenched. The X-ray pattern of the alloy in both the as-cast and the annealed state showed the reflections of Mo3Al (Cr30 type structure) and an unknown phase different from a. Six Cb-Al alloys were prepared in the composition range 30 to 50 pct Al. All alloys were arc melted in He atmosphere. After annealing for three days at 1175oC in evacuated silica capsules and quenching in water, the alloys with 30 to 40 pct Al contained three phases, namely the o-phase, Cb3Al (Cr3O-type structure) and an unknown phase. The alloys with more than 40 pct Al contained two phases, namely, what appeared metallographically, the o-phase and the same unknown phase. In the alloys containing less that 38 pct Al, the unknown phase was not present after annealing for 4 days at 1250°c,

Jan 1, 1962