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By T. R. Graham, R. S. Dean. J. R. Long

Although considerable information has been published concerning manganese additions to the aluminum bronzes, these data refer principally to the two-phase alloys containing 8 to II pet aluminum, with some incidental information on the single-phase alpha solid solution alloys. Straussl gives an excellent review of the literature on aluminum bronzes up to 1927 and a bulletin2 of the Copper Development Association brings the bibliography up to 1938. The most extensive work on manganese addition is that of Rosenhain and Lantsberry,3 who investigated alloys ranging up to 10 pct aluminum and up to 10 pct manganese, and presented data on the physical properties of sand-cast, chill-cast, and several wrought alloys. The greater portion of the work, however, concerns alloys ranging from 7 to 10 pct aluminum in the cast condition and sheds little light on the properties of wrought single-phase alloys. Corson4 notes that alloys containing 10 pct manganese and 4 pct aluminum are not hardenable by heat-treatment, while one with 15 pct manganese and 5 pct aluminum can be hardened, but he gives no tensile data on it. In fact, no systematic study of the properties of single-phase wrought alloys containing substantial amounts of manganese has been reported. It should also be noted that most of the investigators worked with alloys containing significant amounts of iron and silicon, and that these impurities, whether intentionally added or accrued from the raw materials used in the preparation of the alloys, may be expected to have a direct bearing on the resultant properties. In the work on alloys made with electrolytic manganese, the Bureau of Mines has undertaken an investigation of the copper-manganese-aluminum system for the purpose of establishing the constitution and properties of high-purity alloys. In a recent paper6 the authors reported a metallographic investigation of the alpha solid solution area and the adjoining fields of the copper-manganese-aluminum system up to 50 pct manganese. This study established the alpha-phase boundaries at 50" temperature levels from 400' to 850°C. It was found that the addition of manganese to copper-aluminum alloys decreases the solub%ty of aluminum in the alpha phase (Fig I), curving the boundary toward the copper-manganese base line. The greatest change occurs in the first 20 to 25 pct manganese, which decreases the solubility of aluminum to approximately 4 pct. With larger amounts of manganese the alpha boundary tends to parallel the copper-manganese binary. At 13oo'F and higher,

Jan 1, 1947

By T. R. Graham, R. S. Dean. J. R. Long

Following the development of electrolytic manganese production by the Bureau of Mines, an extensive program was planned to study the character of this high-purity product and its possible utilization in various alloy combinations. Previous work reported in the literature concerning alloys containing substantial amounts of manganese dealt largely with material prepared from relatively impure grades of the metal, and in many instances the impurities thus introduced did not permit true evaluation of manganese as an alloying element. One phase of the Bureau's program included a general review of the system and the establishment of the physical properties of copper-manganese-zinc alloys, using electrolytic manganese, and with particular emphasis directed to compositions within the alpha solid solution area. A number of reports of the work on alloys in this system, giving specific data concerning the equilibrium system and some of its alloys, have already been published. One study' established the alpha solid solution area at various temperature levels and composition ranges up to 50 pct manganese. Other investigation reports presented the properties of selected alloys; namely, a 65 pct copper, I0 pct manganese, 25 pct zinc alloys;1 a sensibly white manganese brass composed of 70 pct copper, 20 pct manganese, 10 pct zinc,3 and a series of alloys with a constant copper content of 60 pct and 5 to 25 pct manganese, balance zinc.4 In these reports tensile properties as influenced by cold-working and subsequent annealing were given in detail. Additional data are now available on other alloys of the alpha region up to 50 pct manganese, and these, together with previously published information, are sufficiently complete to establish the relationship between properties and composition for this portion of the ternary system. The present report is a summary of the tensile properties of wrought alloys in the form of sheet and rod stock. The summary is necessarily limited to data for only one condition of cold-work and a single annealing temperature, since a complete exposition of all the data available would be too extensive for this presentation. Nevertheless, it is possible to make a reasonable approximation of the tensile properties in other conditions of cold-worki"g and annealing by a correlation of the data previously presented on specific alloys and the data given here.

Jan 1, 1947

By Michael B. Bever, John R. Anderson

Carbon may affect the alloys of copper in several ways. Provided an alloying element does not oxidize preferentially, even minute quantities of carbon dissolved in liquid alloys of high copper content will form insoluble carbon oxide gases under oxidizing conditions. Gas porosity in castings of high-copper alloys can originate in this way. In certain alloys of low copper content carbon may have considerable solubility and may be an effective deoxidizer. In these alloys carbon will tend to suppress porosity. Carbon that is dissolved in the molten alloy is likely to be retained in the solidified metal. The effects of carbon on the physical properties of the metal are determined by the form in which it is present. Depending on the alloying elements and also on the cooling rate, carbon may precipitate as graphite, may form a carbide or may remain in solid solution on cooling. As solid copper does not dissolve a measurable amount of carbon, a carbon-bearing solid solution can occur only if the copper is alloyed with a large excess of an element that forms such a solution. The effect of graphite or of carbides on the properties of an alloy will depend on the size and distribution of the precipitated particles. As Hensel pointed out in discussion,' the formation of an alloy carbide may interfere with the age-hardening properties of a copper alloy. One would also expect that the presence of carbides or of graphite will under certain conditions promote corrosion or high-temperature failure in nonferrous alloys. Since carbon has an effect on the soundness of castings and affects the structure and behavior of solid copper alloys, its solubility in the liquid alloys is of practical importance. The isothermal change of carbon solubility with alloy composition is of interest from a theoretical standpoint. The binary alloys of copper with manganese and with nickel are used industrially and serve as a base for more complex alloys. The solubility of carbon in each of these metals is known, but its solubility in their alloys has not been determined. Earlier Data The solubility of carbon in molten pure copper is about o.oooi pct at II00°C and 0.0004 pct at 1475°C.l Various authors2""6 have published data on the solubility of carbon in molten manganese. There is agreement on a value of about 6.7 pct in the temperature range r2170 to 1245°c This solubility value corresponds to the formula Mn3C. It increases very little with increasing temperature. Corson7 states that carbon is soluble in copper-manganese alloys and that the

Jan 1, 1947

By E. O. Karenna, A. D. Smigelskas

This is the third paper in a series on the diffusion of zinc in alpha brass.' At the time of the first paper it was accepted that diffusion in a substitutional type of solid solution depended upon an equal interchange of solute and solvent atoms across the diffusion interface (or past a given lattice reference point). Discrepancies in the size of the areas under the diffusion curves on each side of the interface, if observed, were explained on some other basis than the fact that the solute atoms might cross the diffusion interface without an equal number of solvent atoms diffusing across the interface in the opposite direction. The second paper presented evidence indicating that zinc atoms in alpha brass diffuse across the interface more rapidly in one direction than the copper atoms diffuse across the interface in the opposite direction. This phenomenon forced the interface to move in the opposite direction of the diffusion of zinc atoms to provide space for the additional zinc atoms dissolved in the alpha brass. That the interface and columnar grain structure on one side would remain intact during this mass movement was not expected; how ever, it is gratifying that they did. While the evidence was sufficiently satisfying to the author, it was decided that additional experiments were in order to prove that zinc diffuses more rapidly than copper in alpha brass. It is the purpose of this paper to present the results of these experiments. Procedure A bar of 70-30 wrought brass was selected, to avoid the relatively large volume change in going from beta to alpha brass as in the previous investigation. A bar 7 in. (18-cm.)* long and about 3/4 in. (1.9 cm.) wide was surface ground and polished with abrasive paper on plate glass to 0.4184 0.0002 in. (1.062j + 0.0005 cm.) thick. Six0.00j-in. (0.013-cm.) diameter molybdenum wires, chosen because of their very low solubility in coppcr and alpha brass, were strctched lengthwise along each of the two plane surfaces. Glass tubes placed at right angles to the wires every 1/2 in. held the wires tightly against the brass. The sample was then emersed in an acid copper sulphate plating bath and electroplated to a depth of about 0.020 in. (0.050 cm.) copper on all sides. The glass tubes were no longer necessary to hold the molybdenum wires in place and were removed. The sample was then electroplated to a depth of

Jan 1, 1947

By C. Ernest Birchenall, Robert F. Mehl

Application of diffusion laws in the customary form to experimental studies in binary metallic solid solutions has shown the diffusion cocfficient to vary with concentration for all systems investigated. The factors determining this variation have not been ascertained. However, the question of whether the diffusion coefficient would become a constant, independent of concentration throughout a single phase if the concentration gradient in the diffusion equation were replaced by an activity gradient has been an attractive subject for speculation. Wagner¹ derived an expression for the force acting on a diffusing particle in terms of the chemical potential. This was also the approach chosen by Jost2 in his monograph. From a somewhat different point of view, Eyring3 and his co-workers have used activity gradients when dealing with diffusion in concentrated nonideal solutions. The only actual test with experimental data is that given by Darken,4 though this is more qualitative than quantitative. Many others opposed the application in any way of thermodynamic concepts to kinetic phenomena, including diffusion processes. A rigorous examination of this principle requires good data expressing the relationship between activity and concentration for solid solutions for which reliable diffusion work has been done. The literature provides such information only for the interstitial solution of carbon in gamma iron (austenite) and for the substitutional copper-zinc solutions (alpha brass). Activity data for carbon in austenite at 800°C and 1000°C are available from the recent work of Smith5 on the equilibrium of hydrogen-methane and carbon monoxide-carbon dioxide mixtures with gamma iron. Combining these with the diffusion studies of Wells and Mehl6 makes possible a quantitative test for this interstitial solid solution. The vapor-pressure determinations for zinc over brass by Hargreaves7 allowed the calculation of activities in this system over a wide range of temperatures and concentrations. Extensive investigation of diffusion in this substitutional solid solution has been carried out by Rhines and Mehl.8 Activities in Brass9 If the vapor phase of zinc is assumed to behave as an ideal gas, any solid or liquid solutions that are in equilibrium with the same partial pressure of zinc at the same temperature have the same thermodynamic activity of zinc. In order to assign a numerical value to the activity azn, it is necessary to choose some standard reference state to which an activity value of unity is arbitrarily assigned. It is customary to choose the liquid or solid state of the pure material. Then azn is defined numerically by

Jan 1, 1947

By C. Ernest Birchenall

AS a basis for further progress in several branches of metallurgy, particularly the study of physical properties of solid solutions and the kinetics of solid-solid reactions, a more complete understanding of the structure of solid solutions and the nature of the metallic bond is- necessary. Any investigation contributing to this understanding should be of primary interest to the metallurgist. Since the metallic bond is characteristic of an assemblage of atoms, it can be studied only where this assemblage exists. One of the most promising approaches to this study of the interactions in metals is through the general problem of binary metallic solutions. Although crystal structures of many solid metallic solutions have been determined and solubility limits for many systems are given in phase diagram studies, progress beyond this is irregular. Electromotive force and vapor pressure determinations have provided thermodynamic activity data for small concentration and temperature ranges in the amalgams and a few other systems.' In two systems, however, copper-zinc and iron-carbon, data are available for the calculation of activities over wide ranges of temperature and concentration. This activity data for the brass system is summarized in the preceding paper.= A detailed study of the solubility and distribution of carbon in iron is given by Smith and Darken.3 Their treatment of interaction energies is applicable only to dilute interstitial solutions. The objectives here will be to derive from activity gats given in the previous paper for the brasses and structural considerations as much new and detailed information as possible about the interactions between copper and zinc in metallic solid solution and the effect of these interactions in determining the short range structure of the equilibrium phases; that is, we shall investigate the energy of interaction between pairs of atoms of the same and different kinds, the deviations of the distribution of nearest neighbors from complete randomness, and show that the conclusions found are consistent with the observed behavior of the brass system. The method of treatment is fairly general for substitutional metallic solid solutions and will be applied to other systems. The determination of vapor pressures of the components of alloy systems is being undertaken in this laboratory to supply more data for this purpose. The information obtained from solid solutions may be extended by careful analogy to liquids as long as the metallic type of bonding is preserved. Since it will be necessary to employ the language of thermodynamics, a brief summary defining the terms used extensively in solution theory is given below. Solution Theory4 An ideal solution is one in which the vapor pressure of the constituent molecules

Jan 1, 1947

By Tedsen L. F., Dorn J. E., A. E. Flanigan

since aluminum-alloy sheet may be used occasionally at moderately elevated ternperatures, the effects of temperature on the mechanical properties are of interest. Recently the short-time tensile properties of several high-strength materials have been studied at temperatures up to 3750°F.l This paper deals with stress-rupture and creep properties at the same temperatures. The work was done at the University of California as a portion of the project NRC-548. It was financed by the War Production Board and was supervised by the Office of Production Research and Development. This paper has been released for publication by the latter agency. The following materials were studied, all in the form of 0.040-in. sheet: Alclad 24s-T Alclad 24s-T8I Alclad 24s-T86 Alclad 75s-T R3oI-T (clad) Specimens were loaded in tension in the cross-grain direction. Testing temperatures included 94°F., 2II°F., 300°F., and 375°F. Stress levels were selected to cause rupture in times ranging from several minutes to 1000 hr. In each test the following data were obtained: (I) fracture time, (2) elongation at fracture, (3) the complete strain-versus-time curve (creep curve), (4) creep rate (defined in a later section). Materials Materials for specimens were obtained from the manufacturers' commercial

Jan 1, 1947

By A. H. Geisler, F. Keller

Although the subject of precipitation from solid solution appears to be one of the more profitable fields in metallurgy for study with the electron Microscope, few comprehensive studies have yet been made. Occasionally electron micrographs have been published that illustrated alleged precipitation in various alloys, but frequently the apparent size, shape and distribution of the particles do not fully agree with those expected from theory or from observations of the Precipitate when the particles have grown to a size resolvable with the light microscope. The presence of a Widmanstatten pattern for submicroscopic precipitate particles has been demonstrated for only a few aged a1loys.l The initial problem has been the development of suitable techniques for applying the transmission-type instrument to a field that has been inherently associated with reflection-type microscopes. The various techniques have been the subjects of numerous publications, and instead of describing them individually here it will sufficc to say that the oxide film method has proved to be the most satisfactory method yet found for studying the microstructure of aluminum alloys with the electron microscope. This method has the definite characteristic advantage that the actual surface layer of the specimen is examined and not a plastic or silica replica. Doubtless suitable methods for forming and removing the oxide film could be developed for alloys of other metals. The purpose of this report is to point out the characteristics of the oxide film method that have been observed during the studies of numerous aged aluminum alloys and to present the results of these studies. Preparation OF Specimens The oxide film method for preparing specimens of aluminum alloys for examination in the electron microscope has been described in detail previously,¹,² Briefly, the procedure consists of preparing the metallographic specimen, forming the film by anodic oxidation and removing the film from the prepared surface of the oxidized specimen, The specimen is polished accordillg to the usual procedure for microscopic examination.³ he specimen may then be etched to remove flowed metal but etching to attack the alloy constituents or to leave them in relief as in the replica processes is not necessary. Electrolytic polishing is not generally recommended, Deep-etched specimens are used frequently, however, since they provide information that is not revealed by polished specimens and frequently present the same information more clearly than do the polished specimens, The surface preparation of specimens to be deep-etched is not important, since specimens that have been subjected to the first wet PoliShing operation are generally used, but frequently the as-rolled surface is Suitable. These specimens are then etched using a suitable macroetching reagent.

Jan 1, 1947

By James T. Kemp

Some interesting and, to American eyes, rather unusual processes for refining impure aluminum derived from scraps were found by American and British investigators who went into Germany in 1945 for the Technical Industrial Intelligence Committee of the Joint Chiefs of Staff. What was found was recorded in a series of reports (see page ), many of which have been released for general reading. This paper gathers under one title and summarizes the German work in refining light metal scrap. Reference must be made to the original reports for greater detail. Basically, the occasion and stimulus for the German developments in treating light metal scrap were hard necessity. Germany needed the metal for a rapacious war industry. Adequate supplies of new aluminum from reduction works were not assured. Great quantities of airplane and other light metal war scraps were forecast. It was evident that the scrap metal would have to be reabsorbed by the producing industry and would have to be kept of good quality. The normal current production of manufacturing scrap was being and could be consumed as generated. It offered no technical problem. The mixed scraps, especially those arising from crashed and decommissioned airplanes, however, presented problems of another kind. Airplane Scrap The recovery of usable aluminum alloy from the mixed assemblies that made up the piles of airplane scrap was attacked in different ways by different groups and with differing degrees of success. Three procedures actually were used on a commercial scale, one was in pilot-plant stage and another had come to a halt in the laboratory a year before Germany collapsed. Four of these five processes actually involved "refining"; that is, some measure of purification of the metal after melting. Sorting and Separation on a Sloping Hearth The simplest procedure for utilizing airplane scrap involved no refining in the strict sense of the word. This was the practice adopted by two representative plants visited by the author, the Leipziger Leichtmetalle Werke, Rackwitz, Saxony, and the Vereinigte Leichtmetalle Werke, Hanover. These firms did essentially the same thing that was done in England but not with equal success, to judge by their shorter experience, the smaller tonnage handled and by the number and quality of alloys produced. The two German firms named rough-sorted scraps by their easily recognizable alloys, essentially by part and shape. They used hand labor to chop and hack and tear apart. The easily separated heavy metal and nonmetallic scraps were discarded as they were found. Steel and the higher-melting-point metal parts riveted to aluminum or built into

Jan 1, 1947

By C. S. Barrett, C. T. Haller

Twinning in magnesium is known to occur profusely under certain conditions, and when it occurs in polycrystalline materials it brings about a partial or even a complete change in the preferred orientation. The amount of research on this subject, however, has not been in proportion to its importance as a mechanism of deformation and reorientation. Much of the research has been limited to twinning in single crystals. The present study1 concerns polycrystalline sheet, and is an investigation of the twinning produced by plastic deformation as a function of the following variables: 1. Direction and type of deformation. 2. Amount of deformation. 3. Speed of deformation. 4. Temperature of deformation 5. Composition and temper of the sheet. 6. Twins previously produced. 7. Twins previously produced, then annealed. By proper control of these variables it is shown that, on a laboratory scale, samples can be produced that are free from preferred orientations. The materials used were samples of commercial magnesium-alloy sheets with nominal compositions given in Table I. X-ray diffraction was used in most of this work to detect the twins and to estimate the amount of twinning. Since twinning on (102) planes causes a re-orientation of the crystal lattice by 86", it is very easy to study with X-ray diffraction patterns, particularly if one notices the diffraction ring from the basal plane— the 002 reflection. By properly directing the X-ray beam, it is possible to produce 002 reflections from twinned material at, say, the 6 and 12 o'clock positions on the 002 ring, with the untwinned material reflecting to 3 and 9 o'clock positions; and by judging the relative intensity of the arcs on the diffraction ring at these positions, it is possible to judge the amount of twinned material relative to the untwinned. This X-ray method of estimating the amount of twinning is generally superior to metallo-graphic observation, for it was found

Jan 1, 1947

By R. S. Busk, E. G. Bobalek

The relation between gases and metals has been a subject of increasingly active investigation during the past years, principally devoted to the study of metal-hydrogen systems. It has been found that hydrogen is soluble in most molten metals to an appreciable extent and somewhat soluble in most solid metals.l,2 In every known case there is a sudden decrease in solubility at the melting point. Thus a freezing mass of metal containing hydrogen in excess of the solid solubility must in some way expel that excess during the freezing process. This leads to internal blowholes, and such effects as pinhole porosity. Gas trapped in metal that is to be fabricated by a working process such as extrusion or rolling may be the cause of blisters. For some cases, notably in copper and iron alloys, the presence of hydrogen can lead to extreme embrittle-ment of the metal. The aluminum-casting industry has long recognized the importance of hydrogen in its techniques. Excess gas in molten aluminum alloys often leads to the formation of "pinhole porosity" in the solid casting.= To prevent this hydrogen pickup it is necessary to avoid overheating the melt and to protect it from such sources of hydrogen as water. In spite of all precautions, it is sometimes necessary to extract hydrogen from the melt just before pouring by bubbling with a gas such as chlorine or nitrogen. Reccntly it has been found that somewhat similar effects are possible with magnesium alloys, in that the presence of hydrogen can induce or aggravate micro-p~rosity.4-6 This paper is primarily concerned with a presentation of some facts concerning the solubility of hydrogen in magnesium and its alloys, with some discussion of the significance of these facts in a practical sense. In any study of gas-metal systems it is important to bear in mind a clear distinction between adsorption on surfaces and absorption within the lattice.' Considerable attention has been directed toward determining whether hydrogen is truly soluble in any solid metal, or whether the gas extracted from a sample was present at surfaces (external and internal) only.7 Most present day evidence supports the idea of true solution in addition to adsorption. A second important factor when dealing with gas solubility is the dependence of such solubility on external pressure. For diatomic gases such as H², solubility in both liquid and solid metals apparently is proportional to the square root of the pressure, indicating a breakdown to a monatomic gas before diffusion into the lattice.= For true equilibrium values of solubility, therefore, the pressure at the the surface must be constant and, preferably, known. Very little has been published concerning the hydrogen-magnesium system. Winterhager has presented the most

Jan 1, 1947

By William E. Shaw, Louis A. Carapella

Magnesium and its alloys have long been characterized as possessing limited capacity for mechanical forming at atmospheric temperatures prior to rupturing despite their outstanding performances in this respect at elevated temperatures. Responsible for this behavior are the fundamental facts that these hexagonal-type metals have comparatively few slip elements at low temperatures for any extensive deformation and that, at high temperatures, additional slip elements become operative, thus enhancing greater plasticity under strain. The transitionai point has been set at 2 25°C by Schmidl for single crystals, and at 250°C by Morel1 and Hanawalt² for extruded magnesium metal. In a recent X-ray investigation on poly-crystalline magnesium-alloy sheets, Barrett and Haller3 have revealed that, below the transitional tempelature, the initial plastic deformation proceeds mostly by a twinning action; that, above such a temperature, the action is mostly by slip. The deep-drawing performance of the magnesium + 1.5 pct alloy sheet† over a wide range of temperatures has been investigated by Weber and Vanden Berg,' and their results are presented in Fig I. It should be noted from this work that a maximum drawability of about 25 pct at room temperature has been obtained on this alloy under the conventional deep-drawing operations. For the same alloy, it is now possible to augment the cold drawability to about 40 pct by a process to be disclosed. Hitherto, this value has been obtained only by deep-drawing the alloy at around 230°C. That greater plastic flow is attainable at atmospheric temperatures on magnesium under certain deformational techniques was discovered by the authors6 in their analyses of plastic-deformational behaviors of pure magnesium. This fact is best illustrated in Fig 2 from the Har-greaves analysis6 performed by the authors under two different modes of loading. For direct test, a separate unstrained specimen was used for each load duration, whereas for the integrated test the same specimen was employed for all the five intermittent loadings so that the load duration was made additive throughout the investigation. The higher plastic flow-rate at room temperature, as designated by the Har-greaves constant S, was obtained by the integrated or intermittent loading procedure. The authors6 in further tests showed that, under such a procedure greater plastic flow was also realized with a progressive increase in deformatione 1 loads. These findings have been applicd

Jan 1, 1947

By J. P. Doan, G. Ansel

The important literature concerning zirconium in magnesium-base alloys is predominantly contained in patent references. Sauerwald, Eisenreich, and Holubl-4 discovered the profound grain-refining influence of small amounts of zirconium on cast magnesium and the attendant increases in strength and ductility. They extended their work to reveal that limited amounts of certain other elements, including zinc, could be added for further improvement in strength and hardness. British Patent 5111375 relates to the parent discoveries of Sauerwald, Eisenreich, and Holub. All of these references deal primarily with casting characteristics and properties in the cast state. Minor mention is made of desirable tensile strength, ductility, and toughness of wrought Mg-Zr alloys* modified by one or more additional elements. No extensive reference in the literature5. has been found to the particular characteristics of wrought blg-Zn-Zr alloys, with which the present paper is concerned. The work to be discussed represents essentially an extrusion study of the blg-Zn-Zr alloys and indicates that this system is highly interesting in the wrought state both academically and commercially. Accordingly, an important aim of this paper is to describe the hot-workability, tension and compression properties, metallography, and toughness of these alloys. Compositional variations are limited to the ranges 0 to 7 per cent Zn and 0 to I per cent Zr. Experimental Procedure Alloying and Casting Alloying ingredients were cell magnesium, commercial zinc (intermediate grade), and a chloride salt containing approximately 50 per cent ZrCl² and 50 per cent alkali chlorides. This salt is produced by Titanium Alloy Manufacturing Company. Melting, alloying, and pouring procedure essentially followed the crucible process as described by Nelson.6 The magnesium was melted using Dow No. 310 flux, and the temperature raised to 1350° to 1400°F for the alloying operations. After alloying of the zinc, the zirconium containing salt was added in small portions with vigorous stirring. This is an adaptation of the method described in British Patent 533264.7 The alloying efficiency of zirconium was approximately 30 per cent. During the alloying of zirconium, fluorspar was added in amount required as a flux-inspissating agent. Next the melt was refined with Dow No. 310 flux and held quietly for 15 min. Finally billets were cast in a book-type permanent mold

Jan 1, 1947

By J. W. Hickman, E. A. Gulbransen

One of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film. A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film. A comprehensive program has been undertaken to study these phenomena. This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C. Before the introduction of the electron diffraction technique, it was necessary to use either direct chemical analyses or X-rav diffraction analyses to determine the nature of the oxide film formed on the metal or alloy. Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry. In special cases the information obtained may be identical, but in general both viewpoints are necessary. Much of the early work was carried out on the oxidation of bulk samples where thick films were obtained. The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses. Although much useful information has been obtained in this manner. little could be learned about the character of the protective oxides during the period when the films were actually protective. Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique. In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective. Literature The oxidation of iron has been extensively investigated by X-ray and electron diffraction. Jackson and Quarrelll found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature. The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe³O4; between 515° and 900°C. the stable film was FeO. Above the upper change point of iron the oxide was found to be Fe³O4. From 400' to 515°C., FeO, Fe³O4 or a mixture of the two oxides was found. Recrystallization of the air-formed film below 400' and above 900°C. led to the formation of Fe3O4. In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described.

Jan 1, 1947

By J. W. Hickman, E. A. Gulbransen

In a previous paper' the authors have investigated the structure of the oxide films formed on most of the metals that make up the alloys of this study. The metals were studied in order to provide basic information on the structures, both physical and chemical, of the oxide films and to determine how these structures are effected by the temperature, time of oxidation, and surface preparation. It was felt that an understanding of the physical and chemical structure as well as the stability of the oxide film might furnish clues as to the nature of the reaction process and the protective quality of the film. The oxidation of the metals was studied over the temperature range 300' to 7o0°C. except for copper, wherc the range selected was 100' to 500°C. The results of these studies were presented in graphical form as existence diagrams of the oxides on a time-temperature scale. For some of the metals the existence diagrams were simple and showed few chemical transitions, but there were numerous cases where the physical state of the oxide surface was a function of time and temperature. In general the physical state of the oxide surface changed with increasing temperature so as to increase the sharpness of the diffraction patterns and to cause orientation effects to be more pronounced. Deviatiois in lattice Darameters from X-ray values were noted. In general these deviations were of positive nature and may be due to solid solution of the metal in the oxide lattice. This effect might be expected in thin oxide films. In a study of the oxidation of alloys containing two or more metals, there may arise the complicating factor of identification of the oxides formed. A thorough understanding of the oxides formed on the pure metals, therefore, was, essential before investigation of the oxidation of alloys. In this paper it is our purpose to present a study of the following problems: 1. The existence diagrams of various alloys. 2. The effect of the structure of the alloying metal on the existence diagram of iron. 3. The effect of the percentage of chromium on the oxides formed on Fe-Cr alloys. 4. The relationships, if any, between the oxides formed and the protective quality of the oxides. The following alloys are included in this study: alloys of iron with body-centered cubic, face-centered cubic and other metals, 13 Cr-Fe, 18-8 stainless steel, K4²B, Nichrome V, Hipernik, Inconel, Stellite "²I," Refractaloy, Kovar, mild steel, a series of Cr-Fe alloys and a series of Co-Fe alloys. Since many of the commercial alloys in this list contain more than two metals, various complicating factors in the identification of the oxides formed may arise.

Jan 1, 1947

By J. W. Hickman, E. A Gulbransen

The physical and chemical structure of the oxide films formed on metals and alloys is of interest in our understanding of their protective properties. According to Pilling and Bedworth,¹ if the specific volume of the oxide is equal to or greater than that of the metal, a compact or continuous structure results; if the volume of the oxide is less, a cellular or porous structure forms. With the cellular type of coating the surface layer of oxide offers no impedance to oxidation; at a given temperature the rate of oxidation is quite constant. On the other hand, the compact type of coating acts as an effective barrier to oxygen and the rate of oxidation will follow a parabolic law. The recent work of Gulbransen2 and of Leontis and Rhines3 on the oxidation of magnesium indicates that it is not necessary for the volume of the oxide to be greater than that of the metal in order that the oxidation may follow a parabolic rate law. One exception to the rule of Pilling and Bedworth¹ is noted by Scheil;4 namely, tungsten. At 500° and 700°C long-time oxidations indicate a linear rate law with time. However, Dunn's6 0xidation measurements from 700°to 1000°C indicate that a parabolic rate law is followed. The oxide is mainly yellow WO a with a thin layer of the blue oxide. Preliminary results on the oxidation of tungsten6 in the temperature range 400° to 500°C indicate that the oxidation does proceed according to a parabolic rate law. Irrespective of the actual rate law that tungsten may obey, it is of interest to compare the results obtained on the oxidation of tungsten in the thin film region with those found when the metal is scaling. A time-temperature study of the oxides formed on both molybdenum and tungsten may indicate whether there exist any peculiarities in the oxide structures of the thin film region compared with those of the scaling region of oxidation. In a recent paper the authors7 presented an investigation of the structures of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper. The results of these studies are presented in graphical form as existence diagrams of the oxides on a time-temperature scale. The existence diagrams of the oxides occurring on some of the metals are simple and show few chemical transitions, but there are many cases in which the physical state of the oxide surface changes as a function of time and temperature, as evidenced by the appearance or disappearance of orientation effects and sharpness of patterns. In general an increase in temperature results in an increase in

Jan 1, 1947

By Otto H. Henry, Edward L. Badwick

Up to the present time, according to Hansenl and Haughton,² the constitution of the bismuth-indium system has not yet been published. The generally accepted value for the melting point of indium, as listed in most scientific journals and textbooks, is 155°C. Recently, however, H. M. Davis3 has determined a new melting point for indium of 157.3²C O.l°C. Since bismuth has been used in preponderance as an alloying element in the majority of low-melting alloys, and indium has been used with considerable success in lowering the melting points of low-melting alloys, 4,6 an interest has been developed in the application of these two metals, making a complete knowledge of the constitution of its alloys desirable. In this investigation, the melting point of indium reported by H. M. Davis has been found to be substantially correct. A value of 157. ²°C ± O.5°C was determined. The two eutectic compositions have been placed at 34 and 50 pct bismuth with their respective eutectic temperatures as 72.4°C ± 0.5°C and 90°C ± 0.5°C. The bismuth-indium phase diagram has been determined by thermal and microscopic analysis and is shown in Fig I. Thermal Analysis Granulated bismuth and indium shot, having a guaranteed purity of 99.99 and 99.95 pct, respectively, were melted in a carbon crucible by means of a laboratory heater. To minimize oxidation of the alloys, a heavy mineral oil (Nujol) having a high- flash point was used. A platinum-platinum rhodium thermocouple of fine wire encased in a thin-walled Pyrex glass tube, about 1/8 in. in diameter, was connected to a type K potentiometer for temperature measurements. The thermocouple was calibrated against the melting points of tin, bismuth, and the silver-copper eutectic and the boiling point of water. Since the temperature readings could be reproduced to 0.²°Cl and the accuracy of the temperature standards in this range is slightly better than 0.5°C, it scems reasonable to assume that the temperature readings are reliable to approximately 0.5°C. The cooling rate could be controlled by varying the amount of insulation surrounding the crucible. Three or four layers of asbestos paper, 1/16 in. thick, sufficed to give a cooling rate of from I° to ²°C per minute. Undercooling was slightly noticeable. This condition was minimized by vigorous stirring, since the advantage of using slower rates was too small to justify the greater expenditure

Jan 1, 1947

By B. D. Cullity

Gold and beryllium form an intermediate phase composed of the two metals in equal atomic proportions and having the formula AuBe. According to Winkler,' this phase probably exists in two modifications: beta, stable below about 600°C, and alpha, stable between 600°C and the melting point, about 740°C. Only the low-temperature beta form will be considered in this paper. Experimental Procedure The gold used had a fineness of 999.75 to 999.85, balance mainly silver, and the beryllium purity was better than 99.8 pct. AuBe was prepared by melting the constituents in a beryllia crucible in an evacuated induction furnace. After melting and thorough mixing, the alloy was allowed to solidify in the crucible. No difficulty was encountered in obtaining a homogeneous ingot. Both chemical analysis and microscopic examination of the ingot showed that the alloy was essentially one phase, containing 50 at. pct gold. The alloy was quite brittle and powder samples could easily be prepared by grinding in an agate mortar. The X-ray diffraction patterns were made with CuK-alpha radiation in a Debye-Scherrer powder camera 57.3 mm in diameter. The film was placed unsym-metrically in the camera in order to afford a basis for film-shrinkage corrections. A sample homogenized at 500°C gave the same diffraction pattern as a sample taken from the as-melted ingot. General Results The diffraction pattern of AuBe was readily indexed on the basis of a simple cubic lattice with ao = 4.659 + 0.001kX. If the unit cell is assumed to contain four AuBe "molecules," the calculated X-ray density is 13.46 grams per cc as compared with the measured density of 13.55 gm per cc. The only missing reflections in the diffraction pattern are (100) and (220) (see Table I). Since these missing reflections are not those characteristic of body or face centering, the lattice of AuBe must be simple cubic. To locate the positions of the atoms within the unit cell, two possibilities had to be considered: I. The structure was disordered and there were eight positions to be filled by an LCaverage" gold-beryllium atom. That the structure was disordered seemed unlikely since the lattice parameter did not vary with composition in alloys containing sornewhat more and somewhat less than so at' pet gold, indicating a fixed composition for AuBe.

Jan 1, 1947

By J. R. Long, R. S. Dean, D. C. Root, E. T. Hayes

The U. S. Bureau of Mines has recently reported on the development of a process for preparing pure ductile titanium in substantial quantities1 and on the physical properties that may be attained in the metal, when consolidated by powder metallurgy methods and fabricated by certain hot and cold-working procedures.2 The high physical properties (Table I), combined with excellent corrosion resistance and light weight, will lead no doubt to appropriatc applications of the metal. In any application, methods of joining will be of considerable importance. The relatively high activity of the metal toward the common gases raises the question of weldability and conditions that might be required for successful welding. Since hydrogen, oxygen, and nitrogen embrittle the metal, it should be protected from these gases at elevated temperatures. This was demonstrated by a few preliminary trials of arc, gas, and resistance welding. In these trials only the resistance method proved to be immediately- applicable. While atomic: hydrogen welding of titanium may be successful in some instances, a considerable amount of development work will be required to prove its worth. In addition, it would be suited only to small assemblies that could be heated subsequently in a high vacuum to remove embrittling hydrogen. Heli-are methods likewise would be limited to small assemblies, which could be completely protected by a helium atmosphere. It was quite apparent that titanium required more protection than was afforded by the normal flow of helium gas used for welding magnesium and aluminum. The hot metal is attacked by oxygen and nitrogen, and the rapid diffusion of the oxide into the metal prevents the formation of a protective coating and requires the helium atmosphere to be maintained until the weld has cooled nearly to room temperature. The preliminary work indicated that titanium could be successfully spot-welded without deterioration of the metal and that the microstructures of the welds were normal, exhibiting good bonding, and no oxidation. The high resistivity of titanium (53 microhms per cu. cm.) suggested that it would behave somewhat like stainless steel and allow considerable latitude in the several welding variables. The results reported here are intended to give a general picture of the effects of varying welding current, welding time, and tip pressure on single spot welds made on several different thicknesses of titanium sheet. The work was undertaken to demonstrate the feasibility of welding titanium rather than as an exhaustive study of spot welding. There are, therefore, a number of factors that will require further investigation to establish the specific controls required for actual applications.

Jan 1, 1947

By John Wulff, Steinberg Morris, Robert Kamm

In powder metallurgy it has often been observed that shrinkage may occur in one direction and growth in another during sintering. Even in long-time sintering experiments the rate of shrinkage may be different in different parts of the compact. In the fabrication of some parts requiring a constant permeability it is even questionable in some cases whether pressing from one direction should be attempted. These observations require for their interpretation a more detailed study of green or pressed density than has heretofore been available. Usually average density measurements of the whole compact are made and in some cases carefully cut sections are measured. A different approach to the problem was first mentioned by Rakowskil and also used by Balshin.2 Balshin's diagram is reproduced in Fig I and schematically shows the result of pressing three layers of metal powder with fine intervening layers of graphite. The retarding effect of the die walls and a qualitative example of the density distribution is evident. More quantitative information about the distribution of density within a cold-pressed powder compact would be useful in showing the variation in density in as as influenced by the type of poKder, shape of die, lubricatioll during the process, and other variables. Furthermore, information about the cracking of cold-pressed compacts may be obtained from an analysis of the stress distribution within a, powder compact, and some information about the stress distribution can be obtained in turn from the derlsity and strain distributions. A more detailed report on some of the present experiments appears in reference 3. Present Investigation In order to ascertain the density gradients in cold-pressed metal powders, a deformable lead grid within the powder was employed. After pressing in cylindrical di" the ejected compact was radiographed, giving a pattern of the deformed grid. From the radiograph density and deformation from point to point is readily measured. From the radiograph strain distribution and stress trajectories were also determined. The latter also permits the determination of the coefficient of friction at the die wall. This technique indicates that the densest Part of a compact pressed from one side is at the top outer circumference and the least dense region at the bottom circumfercnce near the stationary plunger. For Some heights of compacts the density at the axis is such that the lower density is at the top rather than at the bottom. SO irregular a density distribution is due primarily to die-wall friction. As the ratio - diameter to height of compact is increased the die walls play a correspondingly smaller role. More uniform density

Jan 1, 1947