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By C. E. Armantrout, J. A. Rowland, D. F. Walsh

THE close-packed-hexagonal structure of mag-J- nesium is converted to a ductile and malleable body-centered-cubic lattice by the addition of lithium in excess of 10 pct. Further, the density of magnesium or magnesium-base alloys is decreased by additions of lithium. The practical possibilities of such alloys as a basis for uniquely light, malleable, and ductile structural materials were pointed out by Dean in 1944' and by Hume-Rothery in 1945.2 It was apparent to these investigators, however, that more complex compositions would be required if strengths sufficient for structural applications were to be developed in these alloys. In a search for strengthening additions, various investigators w have examined a number of the ternary and more complex alloys containing magnesium and lithium. An investigation of the fundamental characteristics of these alloys was undertaken by the Bureau of Mines. The investigation was initiated with a study of the magnesium-rich corner of the equilibrium diagram for the ternary system, Mg-Li-Al. The following data from published investigations of Mg-Li-A1 alloys were available: 1—a description of isothermal sections at 20" and 400°C through the Mg-Li-A1 constitution diagram by F. I. Shamrai;' 2—a diagram by P. D. Frost et al." showing approximate phase relationships at 700°F for a number of the Mg-Li-A1 alloys; and 3—diagrams showing the constitution at 500" and 700°F for the Mg-Li-A1 alloy system published by A. Jones et al.' Where compositions and temperatures permit comparison, these diagrams show disagreement. The 700°F isotherms of Frost and Jones differ only in the placement of the phase boundaries. But Sham-rai's 400°C (752°F) isotherm shows a variation in phases as well as in phase boundaries. Although rigid comparison of these different isothermal sections might not be justifiable, it seems impossible to reconcile Shamrai's construction with the isotherms of Frost or Jones. The isothermal sections presented in this paper were prepared to determine compositions which might be suitable for age hardening and to develop the general slope and placement of the various phase boundaries in the magnesium-rich corner of the diagram. Sections at 375", 200°, and 100°C were selected for investigation. In constructing these sections, the solubility of aluminum in magnesium, as reported by W. L. Fink and L. A. Willey Vn 1948, was used at the binary Mg-A1 boundary and the solubility of lithium in magnesium was obtained from the equilibrium diagram for that system as reported by G. F. Sager and B. J. Nelson" in the same year. The solubility of magnesium in lithium was determined experimentally and conforms in general to data reported by P. Saldau and F. Shamrai." Parameters for AlLi and MgI7A1, were taken from American Society for Testing Materials X-ray diffraction data cards. Experimental Procedures Although the isothermal sections presented in this paper are not unusually complex, the experimental techniques involved in their construction are made extremely difficult by the relatively high vapor pressure of lithium and the great chemical activity of both magnesium and lithium. Because of these characteristics, which make precise control of the composition of equilibrium-treated filings practically impossible, the disappearing phase method was used in preference to the parametric method in conjunction with metallographic studies. The alloys used in this investigation were melted and cast in an atmosphere of helium using a tilting-type furnace which enclosed a steel crucible and mold in a single unit. Each portion of the charge (500 to 600 g) was cleaned carefully just before placing it in the crucible; and the charge, crucible, and entire melting apparatus were evacuated and then washed with grade A helium while preheating to approximately 100°C. The alloys were melted and chill cast in an atmosphere of helium. Alloys prepared in this way were relatively free from inclusions and a fluxing treatment was considered unnecessary. The cylindrical ingots obtained were scalped and then reduced 96 pct in area by direct extrusion, yielding % in. diam rod. Sections of the rod, approximately 3 in. long, were given equilibrium heat treatments and then sampled for metallographic examination, X-ray diffraction study, and chemical analysis. The surface of each equilibrium-treated rod was machined to a depth sufficient to insure removal of contaminated material before samples for chemical analysis or X-ray diffraction study were obtained, and all decisions on microstructure were based on the examination of the central portion of the metallographic specimen. All specimens homogenized at 375°C were analyzed after this equilibrium heat treatment. When the composition of an alloy placed it in a critical area of the 200" or 100°C isothermal section, a check chemical analysis was made on a sample taken from the alloy specimen as-heat-treated at the particular temperature. Standard chemical procedures of gravimetric analysis were used in the determination of magnesium and aluminum; lithium, potassium, and sodium were determined by flame photometer methods

Jan 1, 1956

By A. M. Gaudin, D. W. Fuerstenau

IN concentration of certain ores by soap flotation, prevention of quartz flotation is desired; the contrary is true in treatment of some oxide iron ores. Experimental study of the flotation of quartz goes back at least a quarter of a century.' Clean quartz does not float with fatty acids or soaps but does float when activated by one of many metallic salts. Control of pH is important. Broadly speaking the problem of quartz flotation has been approached from the empirical side, as was the related topic of flocculation or dispersion of quartz suspensions? Empirical studies indicated the existence of critical relationships between the additions of collector and activator. These additions were not stoichiometric for the formation of soaps of the activator cation. For example, Gaudin and Rizo-Patrona found optimum quartz flotation at pH 10.6 using barium activation and oleate collection when the molar ratio of oleate to barium was 1 to 1 instead of 2 to 1, as would be called for formation of Ba(OL),. Cooke and Digre" ' found that if calcium is the activator, a minimum quantity of that agent is required for effective flotation when the pH is 11.5. In other words, if the concentration of Na' exceeds 10 -2.5 mols per liter or if the concentration of H exceeds 10-11 mols per liter, the concentration of Ca++ in solution required for quartz activation is increased. This suggests that H+ is much more effective than Na+ on 10-2.5 quartz, perhaps in the ratio ofp or 108. Schuh- mann and Prakash6 studied anew the activation of quartz by barium, calcium, aluminum, and ferric iron. Salts of these metals are activators provided they are in stoichiometric excess over the collector used with them. Alkaline-earth salts are effective only in alkaline circuits. Important as they are in giving data on the effect of various agents on quartz, all these studies fail to give information on the detailed structure of the quartz-solution interface. A beginning in this direction was made by Gaudin and Chang,? who measured the adsorption of radioactively marked barium and laurate ions at quartz surfaces, and by Gaudin. Spedden, and Laxen,8 ho measured the adsorption of radioactively marked sodium at quartz surfaces. Work has also been done by Bell0 n measurement of the adsorption of sodium ion and chloride ion at quartz-solution interfaces. In all these experimental measurements of adsorption, the solid was centrifuged or filtered from the bulk of the liquor with which it had been associated; and the composition of the solid surface was ascertained by analysis, after allowance was made for the ionic composition of the liquor included with the centrifuged solids on the assumption that it is identical to the bulk liquid. Adsorption measurements give only the total amount of collector adsorbed at the quartz-solution interface; they give no indication of the distribution of these adsorbed ions at the interfacial layer. It is the ionic structure of the solid-solution interface and its importance to flotation that is the subject of this paper. The structure of this interfacial layer can be investigated by means of electrokinetic methods so that by combining electrokinetic studies with adsorption measurements, a more complete picture of the quartz surface may be obtained. The following studies were made to ascertain how electrolytes used in the soap flotation

Jan 1, 1956

By D. J. Carney, E. Richard Randolph, E. Van Meter, J. J. Oravec, Stanley H. Ward, Gerald J. Anderson, Rolland L. 203-000-000-005 Blake

DURING the last 30 years the inductive electromagnetic method has been used chiefly in the search for massive sulphide mineralization. This application has met with varying degrees of success and in recent years has resulted in discovery of several large orebodies. Little has been written concerning its use in exploration for soft iron ores, but one of the present authors has reported on experiments with massive magnetic deposits.' To augment the exploration tools available to geologists in delineating iron orebodies, Cleveland-Cliffs Iron Co. and McPhar Geophysics Ltd. undertook in 1953 to apply the inductive electromagnetic method to Cleveland-Cliffs properties in the Lake Superior region. As a result of this project, equipment has been developed that enables simultaneous transmission of two audio frequency waves, and the field technique and interpretative procedure involved have furthered exploration in the district significantly. Thus far, inductive electromagnetic application in the Lake Superior region has been only a development tool, that is, it is used to locate obscured contacts and faults as a part of property expansion and development. However, its application to primary reconnaissance of unexplored areas may be feasible in the future. The method has assisted in placing drillholes efficiently, and the elimination of excess drilling foot-ages and/or actual elimination of unnecessary holes has amply justified the expense of the geophysical survey. Cost of the field work involved is comparable on a per station basis to the cost of a magnetometer or superdip survey. Since observations require no reduction, i.e., are directly interpretable, overall expenditure is low, and the scope and detail of the survey can be adjusted in the field as geological- geophysical correlation becomes evident. To a great extent, this eliminates the second-guessing so commonly arising after office calculations are completed on data obtained with other types of geophysical surveys. This unique feature of field interpretation and its associated intimate feel of the project area, is, perhaps, one of the most valuable aspects of the inductive electromagnetic method as applied to iron ore exploration. Basis of Method Fundamentally, the method involves transmission of an alternating electromagnetic wave, of a chosen audio frequency, which permeates the ground materials in the vicinity of a transmitting, or primary, coil, see Fig. 1. This wave, or field, induces an electric current in any conductor on which it is incident. The flow of an alternating current in a conductor sets up its own, or secondary, radiating electromagnetic field. These two fields form a resultant whose configuration depends on the following characteristics of the subsurface conductors: 1) size, 2) shape, 3) electrical conductivity, 4) magnetic permeability, and 5) frequency of the transmitted wave. To a lesser extent the resultant is also dependent on material adjacent to the conductor, topography, and surface conductivity. For illustrative purposes, the primary, secondary, and resultant fields may be represented by vectors. In operation, the direction of the resultant vector is measured by a small receiving coil tuned to the frequency of the transmitted wave. Generally speaking, the method can be compared to the transmission and reception of the familiar radio broadcast, with special variations permitting measurement of the effect on reception of intervening materials. Field Technique Mechanics of field operation are simple. The mast is set up in a vertical position and is then guyed in place. The transmitting loop then is raised by means of a sheave at the top of the mast and the coil connected to the motor-generator. A special plane table is clamped into position on the mast and the loop is plumbed. The plane table is oriented according to a grid system established over the project area. By means of this plane table it is possible

Jan 1, 1956

By K. B. Higbie

The quantitative separation of tantalum from columbium has been obtained through several liquid-liquid extraction processes. The valuable metals are separated by selective extraction from organic feed solution using a mineral acid or by selective extraction from aqueous feed solutions employing an organic solvent. The greatest degree of separation was obtained when organic ketones, particularly methyl isobutyl ketone, were used. Approximately 200 combinations of various organic solvents and mineral acids were tested as possible separation systems in which the tantalum or columbium content was extracted from organic solutions of the anhydrous pentachlorides.

Jan 1, 1956

By Y. C. Liu, W. R. Hibbard

An analysis of the relationship between the deformation and recrystallization textures in face-centered-cubic metals is presented. The analysis assumes that orientations of the secondary as well as the primary textures are related to the deformation texture. The effect of alloying elements on the recrystallization texture of copper-base alloys is also discussed. ROTATIONAL relationships based on prior orientations have been used to derive both the primary and secondary recrystallization textures."" This similarity suggests that, if the secondary texture arises from grains formed during primary recrystallization, as proposed by Dunn: and if primary recrystallization derives its lineage from the deformation structure, then the orientations obtained in secondary recrystallization .as well as those obtained in primary recrystallization should be related to the deformation texture. The following discussions are

Jan 1, 1956

By F. W. Wessel

This report summarizes Bureau of Mines laboratory tests of four tungsten¬-bearing materials of various grades, The test work has demonstrated that the dry reaction between sodium carbonate and scheelite is best conducted at 900° C. or a few degrees less. The sodium carbonate requirement, in addition to the stoichiometric equivalent of the scheelite, is in some inverse relationship to the grade of tungsten in the ore. Residence time and particle size exert a definite but minor control on the reaction. Pressure-digestion tests on an impure concentrate indicate the technical feasibility of extraction by this process. INTRDUCTION Over 100 years ago Oxland discovered that tungstic oxide could be removed from wolframite and converted to a soluble form by reacting the mineral with a soluble alkaline salt at elevated temperatures. He patented this discovery, and this patent 4/ since has been the basis for most tungsten extraction. Much literature exists on this process and its modifications, and the characteristics and possibilities of the reaction are quite well defined.

Jan 1, 1956

Jan 1, 1956

By W. E. Wickerham

THE Magnetic Storm Monitor is an instrument that continuously records variations in the earth's total magnetic field at a fixed location. It is intended for use in conjunction with airborne magnetometer surveys. There are stormy periods when changes in the earth's magnetic field are so violent that data obtained with airborne equipment would be of little value. The Monitor provides this information so that flights may be cancelled or terminated, thus eliminating useless flying. Moreover, when some unpredictable change in the earth's field occurs during an airborne survey, the Monitor record, showing a similar event, may serve to salvage the data. The utility of a base instrument is determined largely by its physical dimensions, power requirements, stability, and reliability. This instrument is small enough to be transported in any powered vehicle. It will operate from either a 110 v, 60 cycle power line or from an inverter powered by an automobile battery. The development of an electronic feedback circuit that measures the magnetic field strength and a fabricated buckout magnet having essentially zero temperature has contributed to instrument stability and reliability. A tripod supporting the magnetometer head, a chassis housing all electronic components, and an Esterline Angus Recorder comprise the equipment, shown in Fig. 1. The vibrator-type inverter shown is used when a 110 v, 60 cycle power line is inaccessible. Approxi- mately 60 w are required to operate the instrument and the circuit is insensitive to reasonable power line voltage changes or transients. The head unit contains a fluxgate-type magnetometer element and a special magnet mounted on a ceramic structure. Since this magnet is used to buck out most of the earth's field, adjustments are provided for properly positioning the magnet with respect to the element. This assembly is mounted in such a way that the element can be oriented into the total field. Fluxgate Element: The heart of the Storm Monitor is a fluxgate-type magnetometer element. The ability of this unit to detect changes in magnetic fields has been covered at length in the literature.1, 2 For this discussion it will suffice to say that the Gulf

Jan 1, 1956

By P. W. Neurath, R. E. Waite

INFORMATION is available on the effect of stress on permeability, coercive force, and hysteresis for a variety of materials' but for the technically important grain-oriented 3 pct Si-Fe' the stress effects are not adequately covered in the literature; in addition, most of the stress data do not permit estimation of what would happen to the 60 cycle watt losses of the material under stress. Direct measurement of these effects therefore has been made and appears to be of considerable theoretical as well as practical interest. Losses were measured on the central 25 cm portion of 40~3~0.035 cm samples which could be stressed in a small tensile machine built for this purpose. Under tension the following effects, illustrated in the figures by a particular example, were observed: 1—"Unstrained" material of commercially acceptable loss level shows no change or a small increase in loss at low elastic stresses. For the sample shown in the figures, this is illustrated during the initial run, where a 7 pct increase is observed (Fig. 1). 2—There is no additional change in loss when the sample is further strained up to the elastic limit (Fig. 1). Within that limit the loss-stress curve is reversible. This is not illustrated in Fig. 1. 3—Even in the plastic range only small increases in loss are observed as long as the sample is kept under stress (Fig. 2, point N); often no increase can be observed (Fig. 1). 4—A large increase in watt losses is observed after removal of the stress subsequent to plastic deformation (Figs. 1 and 2). 5—All, or nearly all, of the foregoing increase in loss due to plastic deformation can be eliminated by a reapplication of tensile stress but returns upon removal of this stress. This is illustrated in the third run (Fig. 3). This run remains within the elastic limit and shows the reversibility of the stress-loss curve under this condition. These findings have been confirmed on large Samples (approximately 200~10~0.035 cm and larger) except that under 1 no initial increase in loss was ever observed on these. The accuracy of the watt loss measurements is of the order of 1 pct. Neither bending of the sample in the tensioning device nor a redistribution of flux along the width of the sample accounts for these results. They therefore must be explained on the basis of either a change in the domain configuration due to stress or a change in the domain wall mobility. Acknowledgment The assistance of Mr. Robert L. TenBroeck with the instrumentation is gratefully acknowledged.

Jan 1, 1956

By Louis A. Panek

The practice of roof bolting or rock bolting to stabilize rock surrounding underground excavations has increased tremendously within a few years. This widespread application has led to many questions concerning the mechanics of bolting and has pointed up the need for a quantitative method of designing bolting systems. To answer these questions a research program was initiated to determine the principles of roof bolting. The first problem chosen for investigation was the use of bolts to reinforce bedded roof, since the great majority of bolts are used under these conditions. The attack employed is a combination of theoretical and experimental stress analysis. Centrifugal testing of models was chosen as the experimental method because it is particularly suited to the study of stratified roof. This report describes the models, the experimental method, and the model-prototype relations. By using dimensional analysis, a general expression for a roof-bolting design formula in terms of the structural variables has been obtained. Certain model-prototype similarity requirements have been relaxed, thereby minimizing the number of variables to be studied and extending the applicability of quantitative test data to a large class of full size structures.

Jan 1, 1956

By S. C. Sun

With the aid of emulsifiers, intense high-frequency sound waves are capable of emulsifying any collector in water. The data show also that ultrasonically emulsified collectors are more effective in floating minerals than the nonemulsified collectors. THE use of ultrasonics in forming emulsions is not new. As early as 1927 Wood and Loomis reported preparation of emulsions with ultrasonics. In 1935 Rschevkin and OstrawskyV escribed the use of great ultrasonic power in producing fine emulsions of various oils and paraffin in water. Recently Oyama and Tanaka3 employed ultra-emulsification to increase the effectiveness of sodium ethyl xanthate in flotation of chalcopyrite and galena. An emulsion is a two-phase system consisting of two incompletely miscible liquids, the one being dispersed as finite droplets In the other. The dispersed liquld is known as the internal or discontinuous phase, and the surrounding liquid is termed the external or continuous phase. There are two types of emulsions; one is oil-in-water (O/W) and the other water-in-oil (W/O). The word oil refers to the liquid other than water. Circumstances exist in which the emulsion type is not clearly defined, and the internal and external phases both contain portions of the opposite phase. This is said to be a dual emulsion. Among the many hypotheses, 5a, B proposed for the formation of emulsions, the Bancroft's adsorbed film or double interfacial tension theory is widely accepted. Bancroft 7, 8 deduced that in the process of emulsification the interfacial tension between oil and water is lowered by the formation of an emulsifying film, which contains the adsorbed molecules and/or ions from the emulsifying agent and the two liquids. This film has two interfacial tensions, one with the water and the other with the oil, which are not necessarily equal. The difference in interfacial tension between the two surfaces of the film is chiefly responsible for forming different types of emulsions. For example, if the interfacial tension between water and film is less than that between oil and film, the film will become convex on the water side, thereby tending to form an oil-in-water emulsion. On the other hand, if the interfacial tension between water and film is greater than that between oil and film, the film will become concave on the water side, thereby tending to make a water-in-oil emulsion. In line with this theory, emulsifying agents soluble in water have the tendency to form oil-in-water emulsions, while those soluble in oil form emulsions of the reverse type. Apparatus and Experimental Procedure: The ultrasonic apparatus shown in Fig. 1 consisted of a hypersonic generator (A), Brush Development Co. model Bu-204; a hypersonic transducer bowl (B) whose resonant frequency is 400 kc per sec; and a round-bottomed glass tube (C) of 2.2 cm ID and 21 cm in length. The acoustical output power of the hypersonic transducer bowl was standardized with a Hewlett Packard vacuum tube voltmeter, model 41 0B, across the hypersonic generator output. The glass tube, containing the materials to be emulsified, was placed 1 cm above the central surface of the transducer bowl, which was filled with water as shown in Fig. 2. Ultrasonic emulsification was performed in three steps, although a one-step method has been used: 1) emulsifying the predetermined amounts of col-

Jan 1, 1956

It has been established that molybdenum sesquisulphide, not molybdenite, is in equilibrium with molybdenum metal and sulphur vapor in the vicinity of 1100°C. The S2 pressure for this system has been obtained using the Knudsen orifice method and the standard free energy for the dissociation of S2. THIS work was undertaken to help in determining the thermodynamic properties of the molybdenum sulphide which is in equilibrium with metallic molybdenum and sulphur vapor in the temperature range 1025" to 1150°C. From the results of MontoroL and of Parravano and Malquori' molybdenite would be expected to be in equilibrium with molybdenum metal, while the results of Guichard indicate that a lower sulphide must be in equilibrium with the metal. Thus it was concluded that the problem warranted reconsideration, especially in view of the suspiciously low temperature independent term for the standard free-energy function for the reaction MoS² Mo + S,. The reaction was calculated and duly noted as being low by Richardson and Jeffes,' using the data of Parravano and Malquori.' Experimental Method The general method used in this investigation is that of the Knudsen orifice method for the determination of equilibrium pressure. The apparatus and technique are similar to those described for the determination of the vapor pressure of silver.% owever, a closed-end McDanel tube instead of fused silica was used to maintain the vacuum, a molybdenum effusion cell with a replaceable lid was employed instead of a silica cell, and a titanium getter maintained at run temperature was used to assure that no oxidation of the molybdenum or molybdenum sulphide was taking place. All runs were made at a residual pressure less than 10-5 mm Hg. The data are given in Table I. Runs 1 through 13 were obtained using molybdenite, analyzed 98.5 pct, from the Molybdenum Corp. of America. The remaining runs were done with a sample from the Climax Molybdenum Corp. which was their grade No. 3 and analyzed 59.87 pct Mo. The weight loss of the cell during heating up and cooling down was subtracted from the total weight loss of the cell during the run. Also, when the tem- perature was changed, the Knudsen cell was placed in the vacuum chamber and heated at temperature for several hours in order to allow the sulphide and the metal to adjust their compositions to the equilibrium values, to desorb or adsorb gases into or from the molybdenum cell itself, and to desorb any water from the molybdenum sulphide or molybdenum powder inside the cell. Water may have been adsorbed inside the cell because, after each run, the top of the cell was removed and the material in the cell was stirred to insure that a layer of molybdenum metal would not build up and obstruct the passage of sulphur vapor into the gas phase. It was established that the molybdenum cell alone decreased in weight an inappreciable amount when heated at the highest run temperature for long periods of time. There are two questions to be answered before the data in Table I can be used to calculate thermodynamic functions: 1—Which molybdenum sulphide is in equilibrium with molybdenum metal and sulphur vapor? 2—What sulphur species are present in the vapor phase? It can be assumed safely that no molybdenum is vaporized, since its vapor pressure is almost negligible at these temperatures. It will be shown subsequently that no sulphide of molybdenum is volatile. Question 1 was answered in the following way: The especially purified molybdenite, obtained from the suppliers mentioned previously, was charged

Jan 1, 1956

By C. B. Jordan

LAVES and Wallbaum' have described TiRu and TiOs as having the same structure as TiFe; they had previously described the latter compound as having the CsCl structure. On the other hand, a careful investigation of the structure of TiFe by Duwez and Taylor- ailed to reveal the ordered CsCl structure, finding instead a random arrangement of titanium and iron atoms on the points of a body-centered-cubic space lattice. Consequently, it is not clear whether Laves and Wallbaum proposed the ordered or the disordered structure for TiRu and TiOs. In order to settle this question as to the structural type and to obtain values of the lattice para- meters (thereby completely determining the structures), the present investigation was undertaken. Samples having the compositions TiRu and TiOs were weighed out accurately from iodide titanium supplied by the New Jersey Zinc Co., ruthenium powder from Goldsmith Brothers Smelting & Refining Co., and osmium powder from Wildberg Brothers Smelting & Refining Co. No analysis was made of any of these metals. According to the respective analyses of the suppliers, total impurities amount to less than 0.03 pct in the titanium and to less than 0.5 pct in the osmium. The purity of the ruthenium is not known. The alloys were prepared by arc melting in a furnace of the type described by Schramm, Gordon, and Kaufmann.9 pecimens for X-ray diffraction were obtained by crushing the ingots and passing the resulting powders through a 200 mesh screen. Diffraction patterns were made with a powder

Jan 1, 1956

The reduction of titanium tetrachloride to trichloride can be achieved by employing hydrogen and electric arcs. It is possible to produce melts containing up to 50% TiCk in the eutectic mixture of LiCl/KCl by striking a D.C. arc at the surface in the presence of hydrogen and TiCl. vapour. If the electrode IS made to just penetrate the surface of the salt mixture, a hot zone results from the' high resistance contact with both lower chlorides and sintered titanium may be produced. The sintered metal forms just below the melt surface while the trichloride forms at the gaslIiquid junction.The "hotspot cathode" appears to offer a solution to the problem of producing coherent deposits as the spong'e metal can 'be continuously withdrawn in a similar manner to the "calcium process".INTRODUCTIONConsiderable interest has been shown for some years in the possible development of a cheap electrolytic process for the extraction of titanium metal, since a method using simple materials and cheap electric power would materially reduce the cost of production. Even when cheap starting materials are used, however, there exist several general difficulties in the operation of plant which both limit the speed of production and increase the cost of the product. It happens that most of the techniques so far tried produce a powder as cathodic deposit, and when this is the case the following difficulties arise:1. The whole contents of the bath must be treated with solvent in order to extract the 'metal powder which may itself tend to oxidise, and thus become contaminated.2. Fine metal powders, which often contain residual entrained salts, are less easy to consolidate by arcmelting than metal sponge.

Jan 1, 1956

By S. Yukawa, M. J. Sinnott

A high resolution autoradiographic study of the diffusion of a nickel isotope (NP3) into copper in the temperature range of 650° to 925°C, with particular emphasis on grain boundary diffusion, has been made. The extent of grain boundary diffusion is a function of the grain boundary angle and the diffusion temperature. The ratios of the grain boundary diffusion coefficient to the lattice diffusion coefficient ranges from 104 to 105. The activation energy for grain boundary diffusion decreases with increasing grain boundary angle. STUDIES and reviews&apos;-8 of metallic diffusion have indicated that grain boundary diffusion is a common phenomenon but quantitative studies of the many variables involved are not numerous. The present work was concerned with determining the influence of the crystallographic orientation of the grain boundaries and the temperature on the extent of boundary diffusion of nickel into copper. The study involved essentially three steps: 1—the production of grain boundaries of known crystallographic orientation, 2—the determination of the extent of diffusion into the boundaries, and 3—the analysis of the resulting data in terms of the usual diffusion concepts. The grain boundaries investigated approximated the simple tilt variety having l° of freedom. They were produced by controlling the solidification from a melt of Cuprovac (a high purity vacuum-melted copper obtained from Vacuum Metals Corp.) of a pair of seed crystals so that the bicrystals of copper produced had a common <100> axis. By rotating one seed crystal relative to the other, a simple tilt boundary was produced. The angle of rotation between the two crystals is the grain boundary angle 8, or what is sometimes termed the misfit angle. In all, some 16 boundaries ranging from 2" to 72" in 5" to 10" steps were investigated. The crystallographic orientations were measured with the use of both X-ray and optical goniometric techniques. The <100> axes in the crystals were found to be parallel within 2" to 3" with the exception of one crystal (8 = 12") in which the axes were 6" from being parallel. All bicrystals showed evidences of sub-grain structures. Laue analyses showed that these subgrains differed in orientation up to a maximum of 2". Because of these variations, and some curvature in the boundaries, the grain boundary angles listed are actually average values and deviate from the 1 o of freedom boundaries. The stripping film technique of high resolution autoradiography was used to detect the diffusion of the nickel isotope into the grain boundaries of the bicrystals of copper. Kodak experimental permeable stripping film with an emulsion layer 5 u thick

Jan 1, 1956

By M. E. Wadsworth, D. R. Wadia

The rate of reaction of cuprite was measured in a series of sulphuric acid solutions, from which oxygen had been excluded, at various concentrations and temperatures. The overall reaction CuzO + H2S04 + Cu " + CuO + H20 + So4&apos; may be explained quantitatively by two simultaneous rate reactions involving not only H+ but also the hydrolytic adsorption of H2SO4. The results indicate the importance of considering surface mass balance relationships associated with heterogeneous surface reactions. T EACHING has long been an important method for the recovery of metals from certain minerals. Many processes have assumed minor importance in modern practice but such operations as the recovery of uranium and present interest in high pressure-high temperature solution of sulphides&apos; &apos; well illustrate the importance of leaching as a unit operation. Little quantitative information is available in a form sufficient to determine the mechanism of solution at the solid-aqueous solution interface for given systems. For this reason, it is important that fundamental studies of leaching processes be conducted so that parameters associated with such surface reactions may be understood and correlated. Cuprite was chosen for this study as a result of a recent investigation carried out at the University of Utah on ores of the Ray and Chino Mines Divs. of the Kennecott Copper Corp. These sulphide deposits contain sufficient oxidized minerals, such as cuprite, malachite, and azurite, so that recovery of metal values contained in the oxidized fraction is of primary interest. Of these oxides, cuprite (Cu,O) is the most interesting, since it dissolves in sulphuric acid by an oxidation reduction couple resulting in the formation of 50 pct metallic Cu and 50 pct cup-

Jan 1, 1956

By H. Kenworthy

[Experimental studies were made to develop a laboratory technique for direct removal of cadmium and germanium from sphalerite concentrates. Cadmium- and germanium-bearing concentrates from the Illinois-Kentucky fluorspar field were sound to be, amenable to an inert atmosphere fuming process for removing these two moats in the form of gaseous sulfides. Treating the condensed fume by pyrometallurgical methods upgraded the material end provided a means of partly separating the constituents. Cadmium was concentrated about 35:1 arid germanium about 300:1. The extractive investigations were supplemented by vapor-pressure studies on the sulfides of germanium to obtain fundamental data for larger scale laboratory conditioning and control when treating the zinc concentrates. Vapor-pressure curves were developed for synthesized monosulfide and disulfide The results of these- investigations indicate the possibility of significantly increasing the recovery of cadmium from zinc concentrates. Comparison with present recovery of germanium cannot be made, since commercial recovery data arc not available.]

Jan 1, 1956

By R. Bakish, W. D. Robertson

IN the course of a study of stress corrosion cracking of AuCu,, it was necessary to develop new electropolishing and metallographic etching methods. The techniques are generally useful for Cu-Au alloys, including the AuCu composition in which transformation markings are well delineated. For electropolishing, the only satisfactory electrolyte and procedure that has been found1 has the composition given in Table I. The solution must be vigorously stirred while polishing and the temperature maintained in the range of 55" to 62°C. The electrolyte is very unstable and can be used only for 10 to 15 min after which its color changes and a dark-brown precipitate forms. The polishing time is between 1 and 4 min depending on the initial surface preparation. The use of a hood is recommended to avoid the danger of cyanide gas which may form at one of the electrodes even though the solution is alkaline. The optimum current and voltage conditions for vertical anode and platinum cathode are on the plateau shown in Fig. 1, in which voltage is measured across the cell terminals. At voltages below the plateau, etching of grain boundaries occurs and under some conditions, which have not been clearly defined, octahedral etch figures are observed. For general purpose grain-size determination in polycrystalline alloys, a 3 pct solution of iodine in methyl alcohol is used with excellent results. However, when it is necessary to reveal small orientation differences or concentration gradients in an alloy, the iodine etch is not satisfactory. For this purpose, a highly satisfactory etching procedure was developed during this investigation. It involves the use of the vapor given off by freshly prepared aqua regia. The solution employed is 3HC1 to lHNO, which decomposes in accordance with the reaction HNO, + 3HC1 = NOCl + 2H,O + Cl,. The polished specimen surface is held about 1 to 2 cm above an aqua regia solution for 2 to 10 sec depending on the intensity of the contrast required and the surface is not subsequently washed. The results obtained with a coarse grained cast structure are shown in Fig. 2. Subgrain boundaries in a single crystal and concentration gradients within the boundaries are developed by the same treatment with the results shown in Fig. 3. Obviously, any conclusions regarding structure-dependent properties will be modified by the pronounced heterogeneity, which is not clearly evident when more conventional methods are used. Interesting structural details are also revealed by treatment for 4 hr at 850°C in unpurified tank argon. Fig. 4 shows a pattern characteristic of orientation-dependent oxidation.

Jan 1, 1956

Jan 1, 1956

By D. S. Bloom

RECENTLY a report has been published on an investigation of the MO-RU system by E. Raub.&apos; In this report it is stated that below approximately 1200°C the system consists of two terminal solid-solution phases and the intervening two-phase field; at 1200°C and above, an intermetallic compound labeled Mo,Ru, makes an appearance. Along with some other little known systems in which it was considered possible for a u phase to form, the Mo-Ru system had been under investigation in this laboratory. Since molybdenum and ruthenium have very high melting points and also since ruthenium is expensive, the investigation was confined to X-ray diffraction by sintered powder compacts. The compositions which were studied were (in atomic percentages): 75 Mo-25 Ru, 67 Mo-33 Ru, 50 Mo-50 Ru, and 25 Mo-75 Ru. All compacts were made from the pure powders, and no chemical analyses were attempted. Each compact weighed about 5 g. All annealing was done in evacuated Vycor capsules, and even though the capsules completely collapsed at 1250°C, they still admitted no air. The results of this investigation in general corroborate the work of Raub. Up to 1150°C the two terminal solutions and the intervening two-phase field were found, and at 1200°C and above an intermetallic compound was found. However, the composition limits of the compound were estimated to lie close to 70 atomic pct Mo rather than 62.5 atomic pct Mo as Raub had reported. At least the X-ray diffraction results indicated that the 75 atomic pct Mo specimen consisted of the molybdenum solid solution plus the compound, while the 67 atomic pct Mo specimen consisted of the ruthenium solid solution plus the compound and the equiatomic composition contained only very little of the compound. The most interesting observation, however, was that the diffraction pattern of the compound was similar to that of the well known u phases, except that unusually large lattice constants were indicated. The d-values, or interplanar spacings, of the diffraction lines (as produced by filtered copper KCX radiation) of the compound are given in Table I, as determined from specimens annealed at 1250°C for 9 hr and then quenched in water. Also shown are the lines of the Mn-Mo u phase as given by Decker, Waterstrat, and Kasper,&apos; the lines of the Fe-Mo a as given by Goldschmidt," and the lines of the Mo-Ru phase multiplied by constants in order to make comparison with the Mn-Mo and Fe-Mo patterns easier. These results indicate that the compound in the Mo-Ru system is apparently isomorphous with the other o- compounds. The rather large lattice constants of the Mo-Ru a phase are acceptable in view of the comparatively large size of the constituent atoms. The data in Table I for the Mo-Ru compound check quite well with those given by Raub, not shown here, though there are some discrepancies between the two sets of data in the estimated intensities of a few lines. Although very little is known at present about this u phase, there are some things which may be pointed out, mainly in comparison with other better known u phases. Even though molybdenum and ruthenium are in the same columns in the Table of Elements as chromium and iron, respectively, the Mo-Ru u phase contains much more molybdenum than ruthenium, while the Cr-Fe u phase centers around or very nearly around the equiatomic composition; furthermore, the Mo-Ru u is stable only above approximately 1200°C, but the Cr-Fe u is stable only below about 825 °C. With respect to its being unstable below 1200°C, the Mo-Ru u is similar to the other binary molybdenum u phases in the Co-Mo and Fe-Mo systems. Similar to the latter two systems, the Mo-Ru u apparently exists over a rather narrow composition range, whereas the Cr-Fe u at lower temperatures is stable over a much wider composition range. The Mo-Ru u thus is closer to the other molybdenum u phases than to the Cr-Fe cr phase. The most striking feature of the Mo-Ru u phase, however, is the absence of any of the transition elements of the First Long Period.

Jan 1, 1956