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By F. A. Forward, A. H. Ross, J. Halpern

Application of the carbonate leaching process to carno-tite ores has often been limited by the difficulty of obtaining simultaneous high recoveries of uranium and vanadium. The chemical aspects of this problem are discussed and the effect of prior roasting procedures on this discovery is described. IN treating carnotite ores by carbonate leaching it is often necessary to subject the ore to a prior roast. Among the advantages that may result from roasting are: 1) improvement in settling and filtering characteristics of the ore; 2) destruction of carbonaceous impurities that would otherwise contaminate the leach solution and consume carbonate reagent; and 3) substantial increase in extraction of vanadium, which is usually low when the un-roasted ore is leached. Recovery of vanadium may be an important factor in processing carnotite ores, and the fact that vanadium is usually recovered in good yield by acid leaching has often been an economic advantage over results obtained with carbonate leaching. It has been found that response of an ore to carbonate leaching, following roasting, depends primarily on its composition and on the conditions of the prior roast treatment, particularly with regard to the roasting temperature, the atmosphere maintained above the charge during roasting and cooling, and the presence of certain reagents. These factors, especially the last, virtually determine the extractions of uranium and vanadium attainable by carbonate leaching, as well as the reagent consumption on leaching, whereas adjustment of the leaching conditions has only a limited influence. These variables were examined systematically to elucidate roasting and carbonate leaching of carnotite ores and to establish a treatment yielding high recoveries of both uranium and vanadium. Tests were conducted on samples of four different Colorado Plateau ores, described in Table I. Roasting Procedure: The roasting tests were conducted in an electrically heated furnace in which the temperature was controlled to ±15°C. The ore (usually a 500-g charge) was ground to —100 mesh, mixed with the desired reagent, and spread in a silica tray to a bed depth of about 1/2 in. During the roast the charge was rabbled at intervals of 15 min. To provide free access of air the furnace was usually ventilated; however, in a few experiments a controlled atmosphere such as carbon dioxide or hydrogen was maintained above the charge. Leaching Procedure: The pulp, generally comprising 500 g of ore and a 2000-cc solution containing 80 g per liter of Na2CO8 and 20 g per liter of NaHCO3, was agitated in an autoclave at 120°C, under 30 psi 02. Samples were withdrawn periodically, and the solution and ore residue were analyzed. Under the conditions employed, maximum attainable extractions were generally achieved in 4

Jan 1, 1959

By J. J. Stokes

Literature on the electrolysis of aluminum from cryolite melts and on the structure of these melts is surveyed critically. Data on density, freezing point, and other properties are reviewed. Theories of the electrolysis are examined in the light of these data. Two theories are presented which account equally well for the observations. ALTHOUGH the production of aluminum is a large-scale industrial process, consuming approximately 3 pet of all of the electric current generated in this country, the mechanism of the Hall Process remains a 70-year-old mystery. It is a remarkable fact that the aluminum industry, which was established largely through research and owes much of its growth to research, still employs as its basic process the one developed by Charles Martin Hall while he was still a young man working in a woodshed. There are, of course, modifications in detail and a tremendous expansion of the size of the units used, but basically the process employs carbon anodes and a carbon-lined iron vessel as a cathode for the electrolysis of alumina dissolved in molten salt. Of the almost infinite variety of salts available, the relatively minor Greenland mineral, cryolite, 3NaF.A1F3, is still the only one which gives good performance in the electrolysis. In the early days, the process was thought of as a simple one. The dissolved alumina dissociated and, during the electrolysis, the aluminum was carried to the cathode where it was discharged and collected in a pool of metal. The oxygen was carried to the carbon anode where it reacted to form primarily carbon dioxide together with some carbon monoxide. About the only virtue that can be claimed for this hypothesis is that of simplicity. The actual mechanisms must be tremendously more complex. This paper is devoted to a rather narrow part of the whole subject, namely, what ions are present in the bath, and by what mechanism the current is carried. The complexity of the literature on this system is demonstrated in Table I, which shows the ions postulated as being present during the process. This system is not easy to investigate. Cryolite melts at about 1000°C, so that all the investigations are at relatively high temperatures. Molten cryolite fumes in air, particularly if excess aluminum fluoride is present. The cryolite changes composition on heating at 1000°C, principally by reaction with moisture in the air, but apparently also by reaction with oxygen. Cryolite reacts with most of the customary materials of construction, and those that are not attacked by cryolite seem inevitably to react with molten aluminum. Graphite is the only common material that is inert to the electrolytic bath. Pure cryolite can be held in platinum. There is hope that some of the newer refractories will stand up in bath, and their development for this purpose would be a major advance in the field. The techniques to be discussed, then, are not the most advanced ones. Rather, they are examples of old standardized methods applied under difficult conditions. The principal methods that shed real light on the mechanism are density, electrical conductivity, freezing-point lowering, transport number, viscosity measurements, and reactivity of bath with carbon dioxide. The first measurement to be discussed is density. This procedure is relatively straightforward. A hollow platinum bob is suspended by fine platinum wire from an analytical balance into the melt being investigated. Density1-4 of the system sodium fluoride-aluminum fluoride is shown in Fig. 1. There is a maximum in the density near the cryolite composition, but actually the maximum is on the NaF-rich side of cryolite, close to the composition NaF - Na3AlF8. Density measurements are also useful in giving a clue to the nature of cryolite-alumina melts.1, 4 On the first addition of alumina, density decreases, Fig. 2, although the density of alumina, either solid or liquid, is higher than that of cryolite. These density results indicate that the systems are not simple. A great deal of effort has been spent in measuring the electrical conductivity of molten cryolite and of cryolite with various additives. Conductivity measurements are quite easy for fused salts that can be measured in a dip cell, but no successful dip cell has been made available yet for cryolite. Recourse is had

Jan 1, 1959

By K. G. Gorling, S. J. Wallden, N. B. Lindvall

It is the policy of The Metollurgical Society to provide, in the TRANSACTIONS OF THE METALLURGICAL SOCIETY OF AIME, a prompt and accurate medium for publication of reports of significant new research in both the scientific and engineering aspects of metallurgy. Papers submitted to the Society are judged by competent reviewers according to established criteria for technical merit, accuracy, originality, and presentation. STAFF: Editorial Director, Rixford A. Beals; Associate Editor, James J. Burke; Assistants, L. Capria and R. K. Larkin. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: A. W. Thornton, Choirmon; Dennis Carney, John Chipman, J. C. Fulton, J. H. Hollomon, H. tl. Kellogg, A. E. Lee, R. Maddin, J. D. Sullivan, and O. Swan. Review and selection of manuscripts is under the supervision of the following Publications Committees: Extractive Metallurgy Division T. B. King. Cha~rmon; S. J. Dickenson, R. P. Hermsdorf, R. Schuhmann, Jr.. and P. T. Stroup. Institute of Metals Division: Robert Maddin, Chairman. F. Lincoln Vogel, Jr., Vice-chairman, W. A. Backofen, R. W. Balluffi, J. H. Bechtold, M. B. Bever, R. S. Busk, C. G. Goetzel, Paul Gordon, C. D. Graham. Jr., Robert F. Hehe-mann, R. I. Jaffee, F. E. Jaumot, Jr., lrving R. Kramer, A. J. Leno, Horold Margolin, C. J. McHorgue, Russell A. Meussner, J. 6. Newkirk, H. W. Paxton, G. E. Pell~ssier, I. S. Servi, Alan U. Seybolt, A. J. Sholer, and Sack Wahsburn. Iron and Steel Division: J. C. Fulton, Chairman; T. B King, F. C. Langenberg, W. O. Philbrook, and T. B. Winkler. Published bimonthly by the American Institute of Mining Metallurgical and Petroleum Engineers Inc., 29 West 39th Street, New York 18, N. Y. Telephonne pennsylvania 6-9220.Petroleum Subscription Engineers$20 per year for non-AIME members in United States and North South and Central 6-9220.SubscriptionAmerica $25 toreign; $5 for AIME members. Single copies, $4.00, iinalo copies Southfpr;ign,andCentral $5 00. The AIME 'is $25not responsible for any statement made or opinion expressed in its publications Copyright 1958 1958 by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc. . Registered coble address, AIME New York . . . Indexed in Engineering Index, Industrial Arts Index, ...and Chemical Abstracts . . . Application for second class mail privileges IS pending at New Yark, N. Y. Volume 212, Number 2.

Jan 1, 1959

By T. D. McKinley

Theory, operational characteristics, and indicated precision and accuracy of analytical methods based on vacuum extraction, equilibrium pressure, and combustion approaches are reviewed. At the present time vacuum extraction at 1400°C and the equilibrium pressure method are recommended for determination of hydrogen in titanium and titanium-rich alloys. UNTIL a few years ago the role of hydrogen in titanium was an unknown factor with regard to its effect on the physical and mechanical properties of the metal. However, following the work of Jaffee and othersa-" it is now generally acknowledged that hydrogen has a degrading effect on titanium and its alloys. The chief manifestations are a decrease in impact strength in -systems and delayed cracking in a-ß systems. Since hydrogen does have a de- grading effect on titanium it is essential to control it within tolerable limits. It then follows that procedures for quantitative estimation of hydrogen are a primary requirement for the industry. For greatest benefit these methods should be simple, rapid, and precise. In addition to having these virtues, methods must be easy to duplicate in both equipment and technique to gain widespread use. After inherent accuracy has been established, the, required precision to make a method acceptable is dependent largely on the nature of the work at hand. Ability to obtain a representative sample has a pro-

Jan 1, 1959

By J. D. H. Strickland, K. J. Jackson

IN previous papers' ' details were given of the constructlon and use of an apparatus to study the rate of chlorine consumption and the rate of sul- fate and sulfur production when dilute aqueous chlorine solutions were allowed to react with pyrite and galena in acid solutions at or near room temperature. The reaction with pyrite was very rapid, and hence entirely transport-controlled in its kinetics, and produced only ferric and sulfate ions. The behavior of galena was much more complex and was studied in some detail. Sulfur monochloride could be detected as a reaction product and both

Jan 1, 1959

By N. F. Neumann, A. W. Schlechten

Metal chlorides were formed by reacting metal oxides and calcium chloride; the effect of additions to the reaction mixture was studied. It was found that by use of proper additions, metal chlorides could be prepared from mixtures that were not reactive under ordinary conditions. ManY recent metallurgical developments involve the use of chlorine or chlorides as primary reagents; good examples are found in the production of ductile zirconium and titanium by reduction of their chlorides with magnesium. Various methods of preparing metal chlorides are used and many others have been proposed. Some chlorides are formed by the direct combination of a metal or alloy with chlorine. Other processes react chlorine and metallic oxides; carbon or other reducing agents are usually employed to reduce the metal oxides and so promote chlorination. Metallic chlorides have also been produced by the exchange of chlorine between metal oxides and a chloride, such as sodium chloride. This type of reaction was the basis for the old process of chloride roasting in which metal ores were roasted in the presence of salt. Soluble chlorides thus formed

Jan 1, 1959

By S. Senderoff, D. E. Couch

A PROCESS for the electrolytic preparation of molybdenum from molten salts has been described previously. This previous work centered on electrowinning and electroplating characteristics of the process. In this paper the properties of the process as a refining medium are discussed. In producing metals from ores, it frequently has proven most economical to obtain a comparatively impure metal by smelting, and to purify the product by electro refining. Direct electrowinning from molten salts is rather difficult when a porous diaphragm is required in the process, as in the case of molybdenum, since satisfactory refractory materials for such a diaphragm in molten salts have not yet been developed. In electrorefining, however, a soluble anode is used. By suitable control of anode and cathode current densities, the lower-valent molybdenum compound used in the electrolyte is not oxidized, and a diaphragm is not needed, thus avoiding difficulties which are encountered with other electrowinning processes. Electrorefining may result from two different processes in the cell: Dissolution of the molybdenum and the less noble impurities with a separation of the more noble impurities as an anode sludge; the electrodeposition of molybdenum and the more noble metals at the cathode, leaving the less noble metals in the electrolyte. The amount of separation which occurs in each process is determined by the potential of the operating electrode and the relative concentration of the various species at (or in) that electrode. Since molybdenum has a comparatively noble position in the EMF series in molten alkali halides,2 most refining would be expected to occur at the cathode. In this work only the cathodic process was studied. The objective was to determine to what extent various metallic ions, if they dissolve from the anode or are otherwise introduced, were concentrated in the electrolyte. The necessary conditions for the separation of each and the limiting concentration which may be tolerated in the electrolyte for effective refining were studied. The deposits were chipped from the cathode and analyzed spectrochemically for metallic impurities. Besides determining the major contaminant, a general qualitative analysis was obtained to be sure that other metallic ions were kept at a very low level during each series of runs and to be sure that the baths were not being contaminated accidentally. Samples of the bath, for analysis, were taken at the temperature of operation so there was no chance of selective crystallization during cooling. In this way the ratio of molybdenum in the bath to the other metal could be determined readily. These data permitted a check on the anode efficiency and any volatilization that took place during the electrolysis. Experimental Apparatus—The apparatus as shown in Fig. 1 was used to determine the effect of the various foreign ions upon electrodeposited molybdenum. The entry chamber A allowed the cathodes to be removed without cooling the bath and without allowing oxygen or moisture to enter." The cathodes were made Prom 0.25-in. tungsten rods and were rotated during the electrolysis. The balloon in the lower arm B was inflated with helium after the cathode was drawn up into the upper section for removal. A new cathode was then placed into the entrance chamber A after which the chamber was flushed

Jan 1, 1959

By H. K. Najarian

This paper describes recent development work on the Wheaton-Najarian Vacuum Condenser for Zinc at Josephtown Zinc Smelter, wherein, to dissipate the heat of condensation, the "airlift" action of gases bubbling through the molten zinc in the condenser is utilized to circulate the zinc through an outside "cooling well" and cooling it continuously. AN earlier paper1 gave an account of initial development of the Wheaton-Najarian Vacuum Zinc Condenser at the Josephtown Zinc Smelter of the author's company. This paper is a progress report of further development work over the years directed toward improving the efficiency and increasing the capacity of the condenser. In this type of zinc condenser, zinc vapor with accompanying noncondensable gases from electro-thermic zinc smelting furnaces is passed upwardly through a mass of molten zinc confined in a refractory-lined U-tube. The zinc vapor condenses in the molten zinc and the noncondensable gases are drawn out of the condenser by suction applied over the surface of the molten zinc. The heat of condensation of zinc, amounting roughly to 1000 Btu per lb of zinc condensed, is absorbed by the molten zinc and, in turn, is dissipated continuously to keep the temperature of molten zinc in a range to permit effective condensation. At the time of publication of our first paper, we had at Josephtown Smelter five units of 69-in.-bore metal furnaces and one larger metal furnace having 96-in. bore. Each 69-in. metal furnace had a condenser with 22-ft overall length. The 96-in.-bore furnace had a condenser with overall length of 31 ft. Condensers were of circular cross section, with corrugated steel outer shell and carborundum lining. Diameter of these condensers was 32 in. inside the refractory lining. Molten metal in the con- denser was kept cool by spraying cold water on the outside of the condenser shell. Under good operating conditions, 22-ft condensers produced some 12 tons of metal per day; and the 31-ft condenser, about 22 tons. When the furnaces produced zinc vapor at higher rates, invariably the condenser temperature would rise to levels where excessive blue powder would form and accumulation of accretions in the condenser would be accelerated. We found that, with the system of cooling in use, we had to provide heat-exchange surface of some 150 sq ft to condense 1000 lb of metal per hr with reasonable efficiency. The wall of the condensers was made up of 5/8-in.-thick corrugated-steel shell having next to it several layers of mica and inner refractory lining of special carborundum shapes to fit the corrugation in the steel shell, and having a minimum thickness of about 2 in. Relatively low rate of heat transfer through the thick condenser wall and slow internal circulation of the molten zinc limited the rate of heat exchange between hot metal within the condenser and the cold water flowing over the outer steel shell. The thickness of the condenser wall was about minimum that we considered suitable for continuous operation. As we learned to operate the electrothermic furnaces with higher power input, producing zinc vapor at higher rates, it became apparent that we needed condensers having larger heat-exchange surfaces. Our 96-in.-bore furnace had 6 single-phase power circuits with transformers rated at 500 kva each and normally good for power input of 3000 kw.

Jan 1, 1959

By K. A. Semlak, F. N. Rhines

NFILTRATION is a term used to designate that i- process by which the pores of a metal powder are filled with a relatively low-melting liquid metal through the action of capillary forces. This is accomplished in practice either by heating the porous body in contact with the solid infiltrant metal above the melting point of the latter, or by preheating the porous body separately and then dipping it into the liquid metal. The liquid, as it sweeps through the porous body, replaces the gases progressively, thus yielding a relatively dense product in a short time.' Liquid-phase sintering, which is related to infiltration, is a process by which a mixture of two or more metal powders is sintered at a temperature between the liquidus and solidus of the ultimate alloy.' According to Cannon" liquid-phase sintering can be divided into three stages which he calls liquid flow, accommodation, and solid sintering. The largest density increase occurs during the first stage, where the lower melting component melts and, driven by capillary forces, flows among the particles of the higher melting component, where, after dissolution of the bonds between the solid particles, it moves them into close packing. This happens so quickly that little has yet been learned of its mechanism. A study of the rate of capillary rise of a liquid metal in a higher melting metal-powder compact may be expected, therefore, to contribute not only to a firmer understanding of the process of infiltration as such but also to a more extensive knowledge of what occurs during the initial stage of liquid-phase sintering. Theoretical Basis In order to derive a mathematical expression of the rate of infiltration, it has been assumed that a powder compact consists of a great many parallel capillary tubes and that the rate of rise of a liquid in an average capillary channel represents the rise in the entire compact. For a straight capillary, assuming that Poiseuille's law obtains for the non-stationary state and that wetting is very rapid, Ligenza and Bernstein' have derived the following differential eauation of motion where h is the height of rise of the column of liquid at time t, R, is the radius and 1 the length of the capillary, t) and 7, the viscosities of liquid and air, respectively, p and p, the density of the liquid and air, respectively, y the liquid-gas surface tension, 0 the liquid-solid contact angle, and g the acceleration due to gravity. The term on the left of Equation [I] represents the rate of change of momentum of the contents of the capillary tube. On the right the terms represent, respectively, the forces due to a) surface tension, b) viscous resistance, c) gravity, and d) end-drag effect. Equation [I] is not amenable to explicit solution, but for a tube of sufficiently small radius, the rate of rise may be slow enough so that the rate of change of momentum and end-drag terms may be neglected. The validity of this simplification was established by Ligenza and Bernstein' by graphical differentiation of observed data obtained from organic liquids rising in glass tubes. The solution of this simplified case is:

Jan 1, 1959

By E. R. Macgregor, J. Halpern

The kinetics of the reduction of cupric salts in aqueous solution by molecular hydrogen to metallic copper are described. The rate of reduction appears to be homogeneously determined and shows a marked inverse dependence on the hydrogen-ion concentration. Precipitation of copper is more rapid and complete in sulfate than in per-chlorate solution. A mechanism is proposed which accounts for this behavior. IN recent years a number of important hydro-metallurgical processes have been developed in which metallic salts in aqueous solution are reduced by gaseous hydrogen, usually at elevated temperatures and pressures, and thereby precipitated either in metallic form (e.g. Ni, Co, Cu) or as an oxide or salt of lower valence (e.g. VO, and VA).1 ; In connection with applications such as these, most of which involve heterogeneously catalyzed reactions, recent demonstrations"-" that salts of certain metals, e.g., Cu", Ag' , Hg" , and Hg,+ can activate molecular hydrogen homogeneously and thus catalyze hydrogenation reactions in aqueous solution, are of considerable interest. For example, cupric salts catalyze the otherwise slow homogeneous reduction of dichromate and ceric salts by hydrogen, i.e. Cr,O; + 3HL. + 8H1 ? 2Cr'- -- 7H,O [1] 2Ce ' ! H.. ? 2Ce" | 2H . [2] In perchloric-acid solution, where Cu" is not appreciably complexed, the kinetics have been found" " to be of the form -d [H,] _- k,[HJ [CU"]' dt -LCu+' l+ (k ,/k,) [H] [3] where, K = 1x10"' exp [—26,600/RT] 1, mole-' min-' ... [4] and (k ,/k,) - 0.25 at 110°C. This kinetic behavior suggests that the reaction proceeds by a mechanism involving the following sequence of steps kt Cu" +H1CuH' 4-HA [51 k., CUH + CU" ? + 2Cu f H' [GI 6Cu'+ Cr,07 + 14H'+ 2Cr- (¦ 7H,O + 6Cu" ['i] fast The catalytic activities of the undissociated cupric-sulphate and cupric-acetate complexes are somewhat greater (by factors of 6.5 and 120, respectively) than that of the simple hydrated Cu" ion.'" These considerations suggest that, in contrast to the other hydrometallurgical hydrogenation reactions, referred to previously, reduction of cupric salts in aqueous solutions by molecular hydrogen, should proceed homogeneously, and in the absence of an extraneous catalyst. This has already been demonstrated" for acetate-buffered solutions where the product of the reaction is a precipitate of cuprous oxide (Cu,O). In the present paper, an investigation of the reduction of cupric salts in perchloric-acid and sulphuric-acid solutions, leading to the precipitation of metallic copper, is described. Some results for the sulphate system, which is of considerable hydrometallurgical interest, have been reported previously by Ipatieff",' " and by Schaufel-berger' but these do not give a quantitative account, of the kinetics and mechanism of the reaction. Experimental The reduction experiments were conducted in the 1-gal, titanium-lined autoclave described in connection with earlier related investigations," " and using a similar procedure. The solutions were made up by dissolving known amounts of CP grade Cu(ClO,), and HC10, (or CuSO, and HISO,) in dis-tilled water. While in the autoclave, the solution was stirred and maintained at a constant temperature (±loc) and under a constant partial pressure of hydrogen gas. It was ascertained that the agitation (provided by two 3-in., four-bladed stirrers, rotating at 900 rpm) was adequate so that at no time was the rate of reaction limited by solution of hydrogen. During each experiment, samples of the solution were withdrawn periodically, allowed to cool, and the concentration of copper remaining in solution was then determined electrolytically. Some Cu' is formed during the reaction, but undergoes disproportionation when the solution is cooled to room temperature. For purposes of kinetic calcula-

Jan 1, 1959

By A. P. Young, L. I. Marsh

HE relationship between microstructure and *- fracture is of interest in many metals and alloys. This relationship is sometimes established by examining the fracture surfaces and the flat surfaces near the fracture path in tensile samples. However, it is often difficult to tell from examining the fractured sample whether the fracture is intergranular, intra-granular, or a mixture of both. Also, it is often of interest to follow the progress of slip, twinning, or crack formation along the fracture path before fracture occurs. The ambiguity concerning the type of fracture generally can be resolved if the area along the path of ultimate fracture can be photographed at inter-

Jan 1, 1959

By R. H. Atkinson, R. N. Rhoda

An improved technique has been developed for the deoxidation of palladium with aluminum which is especially suitable for use in making small castings with an induction-melting and casting machine. The effect of various crucible linings on the efficiency of the residual deoxidizer and accompanying oxide film in protecting palladium against oxidation during remelting also has been examined; the preferred crucible lining consists of zirconia cement. THE objective of this work was to develop a simple method of deoxidizing induction-melted palladium which would be suitable for use by manufacturers of jewelry and other small castings. In a common method of deoxidizing torch-melted palladium a piece of aluminum foil is dropped on the surface of the molten metal. If a film is present, which is usually the case, it must first be removed by oxidizing the molten metal thoroughly because it would interfere with the entry of the aluminum into the melt. Removal of the film is probably facilitated by a mild fluxing action of the silica crucibles which are used for torch-melting. However, removal of an alumina film from molten palladium in the crucibles normally used for induction melting is a much slower process and it became necessary to modify the de-oxidation procedure. In the modified procedure the charge is simply melted and the desired amount of aluminum, crimped to one end of a tungsten wire, is plunged through the film into the palladium and the wire immediately withdrawn. The trace of tungsten which dissolves along with the aluminum can be avoided, if considered objectionable, by using a palladium wire. In view of the persistence of the alumina film under the conditions of induction-melting it also was decided to ascertain the efficiency of this film in protecting palladium against oxidation during repeated remelting and casting. Melting Equipment and Materials The equipment used for melting and casting consisted of an Ecco GC:6, 6 to 8-kva high-frequency converter and an Ecco M34B centrifugal casting machine. This unit is being increasingly used for making jewelry and dental castings and it also has been found useful in making exploratory melts of a variety of nickel alloys, for which purpose it is well suited on account of its speed of melting and economy of material. A description of the machine and its operation will be published elsewhere.' A common palladium jewelry alloy, 95.5 palladi-um-4.5 ruthenium (referred to as "palladium" in the trade), was selected for the deoxidation tests. It was available as melting stock which had been melted in air to free it from oxidizable impurities, and also as clean scrap from previous melts which had been deoxidized with aluminum. The latter was thought to be typical of clean "palladium" scrap to be found in a manufacturing jeweler's establishment and it is also similar to one brand of "casting palladium." By the same token, the oxidized melting stock corresponds to "casting palladium" after the latter has been melted and thoroughly oxidized: Pure aluminum wire (99.9 pet), 0.032 in. diam; 1 in. = 0.036 g. Scrap tungsten wire, 0.014 to 0.020 in. diam. Argon, commercial water-pumped; 99.9 pet pure Experimental Procedure Samples of about 50 to 75 g of the palladium alloy were melted in a crucible lined with a proprietary refractory alumina cement. Some charges were melted in air, others in argon. The oxidized melting stock was melted and solidified a number of times in order to remove as much oxygen as possible before deoxidizing, but this treatment was unnecessary in the case of scrap. In either case the metal was deoxidized with aluminum (0.01 to 0.05 pet) by the

Jan 1, 1959

By R. B. Roof, J. J. Lombardo

DURING the course of investigations on U-Cb alloys by X-ray diffraction techniques, an impurity or an additional phase was observed in severa1 alloys of various compositions. The X-ray dif-

Jan 1, 1959

By R. G. Hudson, H. W. Paxton

The activities of iron and chromium in their binary system have been measured by the Knudsen orifice technique. The system is close to ideal at 1200- 1250 C with slight positive deviations. The effect of this on the liquidus and solidus is discussed and these are calculated for two limiting assumptions. The vapor pressure of pure iron, pure chromium, and one alloy is compared with that obtained by the Langmuir free-evaporation technique. The results agree, indicating a vaporization coefficient close to 1. HERE are no reported data on the thermody-A namic activity of iron and chromium in the solid portions of the phase diagram. It is generally assumed'.' that the liquid solutions of iron and chromium obey Raoult's law. Chen and Chipman" have inferred that the liquid solution obeys Raoult's law. The minimum' in the solidus-liquidus curves for the iron-chromium system shows that there are deviations from ideality in either the solid or liquid or both. Because of the importance of developing reliable techniques for obtaining activity data in alloy systems at high temperatures and of the data so obtained, an investigation of the activity of iron and chromium in the binary at 1200-1250 C was undertaken using the Knudsen cell. Experimental The apparatus and experimental procedures used in this investigation were described in a previous paper." The various materials used for the construction of the Knudsen cell are listed in Table I. The metal used for the determination of the vapor pressure of chromium was 99.9 pet pure, obtained from A. D. Mackay, Inc. The iron was obtained as electrolytic grade from Fisher Scientific Company. The Fe-Cr alloys used are shown in Table 11. The largest error and controlling factor in the accuracy in the experiments reported here are introduced because of temperature uncertainty, which is estimated to be ±3 deg C. This introduces an uncertainty of 26 pet in the measured pressure. Experimental Results and Calculations The vapor pressures of pure iron and pure chromium were calculated from the measurements by the Knudsen equation3 on the assumption that only Cr or Fe atoms were present in the gas phase. For metal vapors, at the high temperatures and low pressures involved in these measurements this should be a reasonable assumption. Whitman" corrections for the cells were made. The data and results of pressure calculations are presented in Table I, and are plotted in Fig. 1. In addition the heat of vaporization at the absolute zero, ?E°°, has been calculated for chromium. These calculations are summarized in Table 111. The data used in these calculations are as follows kelley13 (F° - E°°/T ) Speiser, et al H (F° - E°°/T ) 010 where F" — standard free energy at temperature T It was necessary to calculate the total pressure above the alloys from the total weight loss W of the cell during a run, because of the fact that all attempts to collect and analyze the chromium and iron vapor effusing from the cell in the apparatus available failed. The failure resulted from the re-

Jan 1, 1959

By R. Haynes

ON the basis of compositional changes of a phase observed in a eutectoid Cu-Al alloy1 it has been suggested that mechanisms for the decomposition of the ß phase proposed by earlier workers2-5 were incorrect. These data are reinterpreted in conjunction with lattice parameter data obtained on an alloy containing 12.2 pet Al, whose isothermal transformations have been reported elsewhere.5 The a Lattice Parameters of a 12.2 Pet A1-Cu Alloy—~iffraction patterns of completely transformed specimens were obtained in a back reflection camera using copper Ka radiation. Lattice parameters of

Jan 1, 1959

By C. Chiou, M. E. Fine

While Gunier-Preston zones are growing in Al-4.2 pct Cu at room temperature, Young's modulus, measured dynamically, increases about 0.4 pct. From the change in modulus with time the exponent of time in the rate equation for growth of the zones was deduced to be %. From a comparison of the rates of increase of modulus at 1, 28, and 42°C an activation energy of 12 to 14 Kcal per mole is computed. These findings support the idea that copper atoms are supplied along dislocation channels to growing zones. In alloys the elastic constants will be functions of the distributions of the atoms. If the degree of ordering or clustering is changed, one expects a corresponding change in the elastic constants. During age-hardening of aluminum-copper alloys at room temperature, the copper atoms cluster on 100-type planes in the aluminum lattice forming

Jan 1, 1959

By A. S. Nowick, W. A. Goering

INspite of considerable interest in the kinetics of ordering of the alloy Cu3Au there is no direct information available on the activation energy for atom movements in this alloy, such as that obtainable by radioactive tracer-diffusion studies or by internal friction measurements. Accordingly, this alloy was examined to find out whether it displays an internal friction peak resulting from stress-induced ordering, similar to that studied extensively in other alloy systems.1-3 Measurements of the internal friction as a function of temperature were made in a torsion pendulum similar to that described by Ké.8 Wire specimens 0.032 in. diam and 11 in. long were used. The wire, obtained in the cold-drawn condition,* was annealed at 900C in a quartz tube to obtain a large grained sample, and then mounted in the torsion pendulum furnace. Internal friction is reported here as the lag angle, 4, which is equal to the logarithmic decrement divided by .ir. Fig. 1 shows the internal friction at three frequencies (the frequency given for each curve is the value measured at the peak). The data for these curves were obtained on cooling one specimen from 460C to just above the critical temperature for long-range ordering, which is about 390C for this alloy. In this way, the internal friction is measured under conditions where the alloy is in the disordered condition throughout the run. The curves obtained at frequencies of 2.15 and 1.29 cps show peaks in the range of measurement. The corresponding peak for the 0.78-cps curve is estimated, from the shift of this curve relative to the others, to be located slightly below the critical temperature (at 385C). The fact that the peak can be observed above the critical temperature is good evidence for the belief that it is a stress-induced ordering phenomenon similar to that which is observed in other disordered alloys. The fact that the peaks in Fig. 1 are not the same

Jan 1, 1959

By P. A. Beck, S. Kohara, M. N. Parthasarathi

IT has been shown1,3 that many observed phenomena related to annealing textures in f.c.c. metals can be adequately accounted for, at least in a qualitative way, by considering the orientation dependence of the boundary mobility, without any hypotheses concerning preferred orientation of nuclei. It was noted1 that this approach is particularly successful in the common cases of primary recrystallization in highly cold-worked polycrys-talline metals, where nuclei occur in great abundance, and that in the other extreme case, where the number of nuclei is very limited, or even only a single crystal is grown, the orientation dependence of boundary mobility has only a small effect, or none at all, on the orientations resulting from annealing. Recently Dunn described examples3-6 where observed secondary recrystallization textures apparently cannot be accounted for on the basis of oriented growth alone, but also require oriented nuclei, or at least the absence of nuclei in certain orientation ranges. In general, the great difficulty in correlating the preferred orientation of recrystallized grains with that of nuclei is inherent in the fact that nuclei are by nature very small, and that they are usually identifiable as "nuclei" only after growth, i.e., after they have already been subject to growth selectivity. An investigation was carried out by Liebmann and Lücke,' and also a very similar one by Graham and Cahn,' to obtain quantitative information on the orientation depend- ence of boundary migration rates in the recrystallization of slightly deformed aluminum single-crystal rods or plates, in which artificially nucleated recrystallized grains of predetermined orientation were grown. Liebmann and Lücke foupd maximum boundary mobility for boundaries across which the misorientation corresponded to a rotation of 40 deg around a common [Ill] axis, in accordance with earlier conclusions.9,1 Also, they confirmed that such an orientation relationship predominates among crystals growing into slightly extended single crystals from presumably random artificial nuclei. On the other hand, Graham and Cahn found no preferred orientation among crystals grown in a similar manner. It is not as yet known how these observations may be reconciled with each other. The view has been expressed in various papers5'10,21 that selective growth based on the orientation dependence of boundary mobility is not in itself sufficient to account for the formation of sharp re-crystallization textures, such as those often observed in highly deformed polycrystalline metals after annealing. The present work was undertaken to ascertain whether or not it is possible to obtain a sharp re-crystallization texture in a case where random nuclei are assuredly present in large numbers. It was previously found1' that high-purity aluminum crystals rolled 80 pct on the (110) plane in the [1T2] direction, when suitable precautions are taken, may be annealed for periods of about 1000 sec at 350°C without recrystallization. It was also found that the reluctance to recrystallize in this case is due to the scarcity of material in sufficiently deviating orientations to serve as nuclei. By using such a matrix,

Jan 1, 1959

By J. C. McDonald

A DDITIONAL experimental data are presented in this note on a phenomenon which has been touched on but lightly in the literature. The common magnesium base rolling alloy (AZ31B) contains about 3 pet A1 and 1 pet Zn. When cold rolled, it hardens until it starts to break up in the rolls at 30 to 50 pet reduction. When it is heated after rolling to full hardness, it softens. However, other magnesium alloys have shown themselves capable of being cold rolled indefinitely, provided the ratio of roll diameter to starting gage is sufficiently high. As measured by the tensile test, these alloys actually soften when the reduction becomes large (60 to 90 pct). A subsequent heating at 300' to 500°F can produce hardening of this metal. Heating at higher temperatures (600' to 800°F) causes recrystalliza-tion and softening. Menzen' has shown that a magnesium base alloy can be cold rolled without intermediate anneals as much as 90 pet. The alloy studied, Mg-1.5 pet Mn, softened considerably between 20 and 90 pet reduction, as measured by tensile properties; a decrease in yield strength of 30 pet, and an increase in elongation from 3.2 to 16.7 pet (longitudinal direction of the sheet). However, Menzen gives no data on the reaction of this metal. to heating. Ansel and Betterton2 and Hurst and Hatch3 report a similar effect in Mg-1.5 pet Mn-0.1 pet Ca. Their data show an initial hardening, followed by softening. The former authors also show that the alloy softened by cold rolling will harden when heated at low temperatures, and that these effects are absent in Mg-3 pet Al-1 pet Zn. In the course of work4, 5 some years ago, the author observed similar effects with alloys containing cerium, thorium, or zirconium; but not with elements like aluminum, silver, or zinc. Table IA contains the results of an experiment which shows these effects rather well. A binary alloy with 0.3 pet total rare earths (Mischmetal* added) was rolled hot to 1/16 in. and then annealed to full softness by heating 30 min at 800°F. Rolling was continued at 1.5 pet per pass to 80 pet total reduction on 8 in. diam rolls. The metal was harder after 20 pet work than initially but, at 80 pet reduction, properties were back to their original values. Heating for 1 hr at 450°F produced about the same hardness whether the reduction was 20 or 80 pet. At intermediate reductions, the metal hardened, but not to as high values. Extensive cold rolling may also be carried out on metal hot rolled at temperatures sufficiently low to produce a semihard temper. Mg-0.6 pet Zr was rolled to 0.1 in. at 700° to 800°F, 30 pet per pass. As shown in Table IB, a further cold reduction of 85 pet, at 1.5 pet per pass, definitely softened the metal.

Jan 1, 1959

By M. V. Nevitt

THE Cr,O-type, or P-tungsten, structure having the space group (Oh2— Pm,n) is one of the most widely occurring structures found among the intermediate phases involving transition metals. Including the phases reported here for the first time, the total number of these A,B phases now known is 39. Greenfield and Beck' have correlated the lattice parameters of these phases with the Goldschmidt radius of the close-packed chains of A atoms. Laves' discussed the apparent size of the A and B atoms in this structure. Gel1er" proposed a scheme for reproducing the lattice constants of the phases by the use of a list of effective C.N. 12 radii for the component elements. Reported here is a survey of the A,B combinations which appeared favorable for the stability of the Cr,O-type phase but which, at the time the investigation was begun, either had not been reported upon or had conflicting reports as to the existence of the structure. Seventy systems were investigated, and 8 Cr,,O-type structures were found. Six of these also were reported by other investigators in the interval between the start of this investigation and its completion. This survey yielded information as to the influence of the relative sizes of the A and B atoms on the stability of the phase and, for the various families of Cr,O-type phases, the effects of the sizes of the A and B atoms on the lattice constant. Likewise, a somewhat clearer picture of the connection between the position of the A and B elements in the Periodic Table and their Cr,O-type phase-forming tendencies has become apparent. Experimental Procedure Alloys were prepared in the form of arc-melted 3-gram buttons in all cases where the vapor pressure of neither component was high enough to cause

Jan 1, 1959