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By H. F. Webster, C. G. Dunn

Rolling md annealing procedures are described for developing the (110) preferred orientation in tantalum for use as a thermionic-emission materinl where electrodes of a uniform high work function are needed. The development of a (110) [001] annealing texture is also reported. A preferential growth process due to low (110) gas-metal surface energy is considered in explanation of the observed growth of (110) grains. ThE growth of (110)-oriented grains in thin strips of rolled zone-refined tantalum, previously discussed briefly,' is reported together with more recent information on the formation of a (110)[001.] annealing texture, i.e., one where the [001] direction of each grain lies close to the rolling direction. The development of tantalum sheet with a (110) preferred orientation (position of [001 ] directions unspecified) is of importance as a thermionic-emission material in thermionic-energy converters. Since therm ionic-emission properties of cesium-coated crystals vary over a wide range depending on (hkl) a2-7 a single (hkl) preferred orientation is more useful than either several preferred orientations or none. Furthermore, the (110) preferred orientation yields the highest thermionic-emission density for a cesium coverage of less than a monolayer.5-7 A consideration of the stability of the grain structure needed at high operating temperatures suggests that the preferred orientation itself should be produced by annealing processes. Information on annealing textures in tantalum, however, is rather limited. Pugh and Hibbard 8 obtained (111)[112] and (lll)[112] components in a 1400°C recrystallization texture in 95 pct cold-rolled foil; these components were enhanced on annealing at 2500°C. Muller9 rolled 99.97 Ta to 90 pct reduction in thickness in the final stage and noted only a slight sharpening of the rolling texture, with some intensification of the (111)[112] component upon annealing at 1200°C. The experimental procedure followed in the present work stemmed from the idea of using possible differences in (hkl) surface energies to provide a small driving force for growth of grains having the lowest (hkl) surface energy.l0* This would mean using high-purity tantalum processed into thin sheet form and annealed at high temperatures either in a noncontaminating atmosphere or in one producing additional sample purification. EXPERIMENTAL Zone-Refined Tantalum. National Research Corp. tantalum in the form of 1/8-in.-diam rod and of 99.98 purity (53 ppm 0, 15 ppm N, and 8 ppm C) was zone-melted four times. The traversing speed was 4 mm per min. Such treatment increased the resistance ratio, R293k/R20K , where R293K is the resistance of the specimen at 20°C and R20K the re-resistance at liquid-hydrogen temperature, from a value of 25 for the initial rod to 175 for the zone-refined rod (the increase in the resistance ratio provides a measure of purification11,12). Part of a zone-refined rod was rolled unidirec-tionally to a strip 0.003 in. thick and 0.28 in. wide. Samples were given anneals in the range 1300" to 2100°C using ac conduction heating in an oil-free vacuum system. Recrystallization to small grains appeared to be complete at 1300°C. Large grains were formed at higher temperatures, but these were not entirely strain-free, some grains showing asterism in Laue X-ray patterns and some displaying a range in orientation. Part of the difficulty was caused by thermal expansion of the tantalum strip as it was held between fixed supports. However, in a different arrangement with the tantalum freely suspended in a tantalum can, high-frequency induction heating in vacuo at about l0-6 Torr produced

Jan 1, 1964

By Philip Lindstrom

Retreat mining, using yielding steel friction props, over a seven-year period has been successful at a uranium mine operated by Hecla Mining Company in southeast Utah. The support system allow good roof control, maximum profit, complete extraction, and good ventilation. Unusual subsidence observations were made in that some of the surface was raised rather than lowered, Longwall mining, commonly practiced in European coal mines, has a potential of broader application because of mechanization possibilities and better roof control and ventilation at greater depths.

Jan 1, 1964

By J K. Irwin

The authors discuss the application of drum and friction hoists under modern conditions and give four examples of friction hoists proposed for various applications. The paper concludes with a summary of the advantages and limitations of friction hoists relative to drum hoists. Introduction T H~ introduction of the multiple-rope friction hoist m the late 1940's has complicated the se-lection of the right hoist for a given job. Once such considerations as rope safety factor, drum to rope ratio, hoisting distance, tons per hour and/or service duty have been decided upon, the selection of a drum hoist is relatively simple. We now ask our-selves "which hoist -drum or friction? (See Figure 1 and Figure 2). When a friction hoist is a possibility we are immediately concerned with how many ropes to use, whether to hoist balanced or counter-balanced, whether a friction hoist will be flexible enough for the application and, of course, what the relative costs will be.

Jan 1, 1964

By Avnulf Muan, Egil Aukrust

Activity-composition curves jor cobalt oxide and manganese oxide in solid solutions with spinel-type structure have been determined by studying the equilibrium between the spinel phase and a coexisting solid-solution phase in the tewzperature range 1100" to 1400"C. Within limits of experimental error, the system displays the behavior of a regular solution. The excess integral free energy of mixing is represented by the equation . The standard free energy of formation of cobalt manganite, CoMn,O,, from the oxide components COO mzd Mn2OS at 1200°C is calculated to be -8.6 kcal. AMONG the technologically and theoretically most important oxide phases are those which crystallize with the same structure type as the mineral MgO . A120,. Although the name spinel originally was used only for this mineral, the term is generally used today to designate the whole group of oxide phases with this same structure type. It is in this wider meaning that the term is being used in the present paper. The previous literature on spinels is very extensive. There are two aspects of spinels which have attracted particular attention: the structure, including the nature and distribution of the cations present, and the physical properties (electric, magnetic). The status of knowledge in these fields has been well-summarized in recent review articles.1'2 By contrast, thermodynamic properties of spinels are virtually unknown. Delineation of the activity-composition curve over the whole composition range of a solid-solution series with spinel-type structure is the objective of the present work. The system at elevated temperatures (>1000"C) constitutes such a series. The activity-composition curves for this system can be calculated from a study of the equilibrium between the above spinel solid solution and a solid solution (Co,Mn)O with sodium chloride-type structure. Data for the latter solid solution have become available recently.3 The system, in contact with metallic CO at 1200°C, obeys Raoult's law. The determination of the activity-composition curve for the spinel phase is based on the following relations. Consider the reduction-oxidation equilibrium for cobalt ions according to the equation: Because it is impossible in practice to measure single activities of electrically charged constituents, we will treat the equilibria in terms of electrically neutral components. Eq. [I] can then formally be written as follows: where and the activities of cobalt oxide in the (Co,Mn)O and the spinel solid-solution phases, respectively, K is a constant at constant temperature, and Pa is the oxygen pressure of the gas phase. The numerical value of K can be determined from a determination of the oxygen pressure P& for the equilibrium coexistence of Cos04 and COO in the binary system Co-0. Under these circumstances be set equal to 1, and hence K = [Po Eq. [3] can therefore be written

Jan 1, 1964

By D. A. Shock

Utilizing the technology developed for oil well stimulation by hydrofracing, a disposal system which permanently fixes the waste has been proven. Large quantities of radioactive waste can be processed by a single well system making this method an attractive method for permanent radioactive waste disposal. The system depends on locating a relatively thick formation of impermeable, but easily fracturable rock such as a shale, creating a horizontal fracture, pumping the waste into the fracture in a form which will subsequently solidify and seal the fracture from the well system. The paper presents the theoretical considerations from creating and extending horizontal fractures and how these considerations were used in designing a waste disposal system which is now operating.

Jan 1, 1964

By Y. Nakada, B. Chalmers

The work-hardening behavior of surface layers of aluminum and gold single crystals was investigated by alternately deforming and then removing a thin surface layer by electropolishing or by etching. Aluminum crystals exhibited lower flow stresses after the surface removal; gold crystals did not. Abrasion of surface eliminated easy glide in both gold and aluminum crystals. By alternately deforming and removing the surface layer, it was shown that the abraded crystals work-harden preferentially under the abraded layer. It is suggested that this phenomenon is caused by the difficulty of propagating dislocations through the abraded layer. It has been demonstrated in numerous cases'-3 that the plastic behavior of metals in either single-crystal or polycrystal form is sensitive to the environment and to the condition of the surface; it has also been reported4-6 that single crystals of some metals, when deformed in tension, exhibit more work hardening near the surface than in the interior. A third type of effect that has been attributed to the special part played by the surface in plastic deformation is the influence of the dimensions of the specimen on the various parameters that define its plastic-deformation characteris- tics.?-'' Many of these experiments were made on aluminum, on which an oxide film is always present under available experimental conditions; many of the effects have been attributed to the oxide film, either in terms of its higher elastic moduli, which would cause local stress redistribution, or its higher strength, which would oppose the escape of dislocations at the surface of the metal. On the other hand, it has been suggested II,12 that the mere presence of a surface should be sufficient to produce the observed results. A rigorous examination of this question could, in principle, be carried out by comparing the behavior of aluminum with its oxide film with that of the same material without oxide. This experiment would present great difficulties. The most practical alternative is to compare aluminum with gold, which has no crystalline surface film at room temperature, and to study the effects of various surface treatments on gold. The experiments described in this paper fall into two groups, the objectives of which were to determine 1) whether single crystals of gold shared the property of aluminum that the removal of a surface layer after some plastic deformation reduced the flow stress for further deformation and, since the result of this was negative, 2) whether a surface treatment could be found that caused gold to behave in this way. I) EXPERIMENTS AND RESULTS All the tests described below were carried out on single crystals of about 6 by 6 mm cross section and of sufficient length to provide a gage length of about 10 cm.

Jan 1, 1964

By E. J. Rapperport, M. F. Smith

A presentation of the W-Ru constitution diagram is given. Techniques utilized in the determination of phase boundary values include electron micro-probe analysis of two-phased alloys and diffusion couples, as well as normal metallographic and X-ray methods. The primary features of the diagram are: 1) a terminal solid solution of ruthenium in tungsten with a maximum solubility of 23 at. pct Ru at 2300°C; 2) a terminal solid solution of tungsten in ruthenium with a maximum solubility of 48 at. pct W at 2205°C; 3) a o phase of maximum breadth about 6 at. pct based on the composition W3Ru2 which forms peritectically from the melt at 2300°C, and which decomposes eutectoidally at 1667 °C to form a twigs ten and 0 ruthenium; 4) a eutectic at 45 at. pct Ru and 2205°C with the products being o plus ß ruthenium. THE W-Ru diagram has previously been studied only in a cursory fashion. Raub and alter' obtained a 1400°C isotherm in which they observed no intermediate phases, and on which they established the limits of solubility as 36.5 at. pct W in ruthenium and about 1.5 at. pct Ru in tungsten. In addition, Obrowski2 found a o phase forming peritectically from the melt and existing only above 1650°C. Below this temperature the phase was presumed to decompose eutectoidally. The present work finds the diagram as given in Fig. 1. I) EXPERIMENTAL PROCEDURE The materials used for alloy preparation in determining the W-Ru constitution diagram were 99.9 pct pure ruthenium powder supplied by Baker Chemical Co., and 99.9 pct pure tungsten powder from General Electric Co. Typical analyses of these elements are given in Table I. Initial alloys at 10 at. pct intervals were prepared from the metal powders by the following method. Powders sufficient for 25 g of the alloys were weighed out with an accuracy of 0.1 mg and blended mechanically. After blending, the powders were compacted, in a steel die, at approximately 30,000 psi. The compacts were sintered in an electric vacuum furnace in order to remove adsorbed gases and to achieve partial densification prior to arc-melting. Vacua of 10-4 mm Hg or less were maintained in sintering as the furnace temperature was raised to approximately 2000°C. Sintering times ranged from 10 to 20 hr. The sintered compacts were arc-melted under a protective atmosphere of purified helium. Melting was conducted on a water-cooled copper hearth, utilizing a nonconsumable tungsten electrode. In the melting process, each alloy was turned over and re-melted on opposite sides from four to six times to ensure complete melting and to eliminate gross in-homogeneities. The arc-melter used had a vacuum capability of 5 X 10-6 mm Hg, and a leak rate of about 20 -liters per hr. Chemical analysis techniques for refractory metal-platinum group metal combinations are not well-established; therefore, composition control and determination depended principally upon weight-loss observations and calculations. This consisted in weighing each alloy after sintering and after arc-melting, and calculating the maximum and minimum composition values, assuming the total weight losses to be first all tungsten, and then all ruthenium. Since composition uncertainty was directly related to weight loss, care was taken to minimize losses in handling, compacting, and melting. Prior to homogenization and equilibration the as-arc-melted alloys were analyzed in several

Jan 1, 1964

By Leonard R. Weisberg

The general properties of diffusion in GaAs are reviewed. A total of .fourteen atoms have been studied to date, and activation energies for eleven reported are (in ev): Ga (5.6), As (lo), Zn (2.49), Cd (2.43), Sn (2.5). Mn (2.75). S (4.0). Se (4.2). Ag (0.33), Cu (0.52). and Li (1.0). The dijfusion of the first eight atoms, as measured by Goldstein using radiotracer techniques, established the principle of sub lattice diffusion for both host and impurity atoms, since atoms substituting for gallium have lower activation energies than those substituting for arsenic. The diffusion constant of interstitial copper has been determined for the first time by Hall and Racette using heavily doped p-type samples in which interstitial copper predominates. The anomalous behavior of zinc, which has an abrupt diffusion front and a strong dependence on zinc concentration, has recently been quantitatively explained in terms of an interstitial-substi-tutional equilibrium-diffusion mechanism. Lithium and silver diffuse mainly interstitially, while the diffusion of phosphorus is complicated by the continual formation ofGap. Junction-migration measurements indicate diiferent results than radiotracer techniques, and this is one problem that still remains, together with discrepancies in cadmium-diffusion results, and an unexplained dependence of impurity diffusion on arsenic pressure. BESIDES the usual insights into the behavior of atoms in solids, studies of diffusion in semiconductors have additional importance for device applications. In fact, the amount of diffusion studies performed on a semiconductor might serve as a simple barometer of its technological importance. Thus, the information accumulated for GaAs is not yet quite comparable to that for germanium or silicon, but considerable knowledge is available. The diffusion of at least fourteen atoms has been investigated for GaAs, and the diffusion constants have been determined for eleven of these. Interesting results were found for GaAs that elucidated problems not previously solved for germanium or silicon. For example, the interstitial-diffusion constant for the very fast diffusant, copper, was first measured in GaAs. Also, solutions for interstitial-substitu-tional equilibrium diffusion in extrinsic material were provided first for GaAs, although they are ap- plicable to germanium, silicon, and other semiconductors. Studies in GaAs firmly established the concept of sublattice diffusion, which should have application in many different compound systems. The purpose of this paper is to review briefly the general state of knowledge concerning diffusion in GaAs. First some general aspects of diffusion will be covered, and next attention will be given to the results mentioned above. Diffusion in GaAs has been measured both by radiotracer and junction-penetration techniques, and some discussion will be given of differences in the two sets of results. The comprehensive work of oldsteinl-' has served as the primary reference for the diffusion of well-behaved substitutional atoms in GaAs. Since a review has recently been presented of many of these reults, details of the diffusion data will not be repeated. Neither will any discussion be given of the experimental techniques of diffusion measurements, except to note here, in passing, the simplicity and effectiveness of the precision lapping device employed by Goldstein.' I) EXPERIMENTAL RESULTS AND DISCUSSION A) Summary of Experimental Results. Diffusion constants D = Do exp(E/kT) have been determined for eleven atoms in GaAs: a,' AS,' n,'" Cd,'" n,' n,8 s, e,' Ag,O CU," and i." These results are summarized in Table I. In addition, diffusion was investigated for phosphorus,4'12 germanium,I3 and ilicon,' but Do and E were not determined. Radiotracer techniques were used for most of the studies except for lithium, where a combination of chemical and electrical techniques was employed, and germanium and silicon, where junction-migration techniques were applied. The diffusion of zinc, manganese, sulfur, and tin was also measured using junction migration.13'14 Goldstein demon-

Jan 1, 1964

By J R. O Walli

Large production shafts can be successfully sunk through the ubiquitous Blairmore formation of southern Saskatchewan by employing the freezing process and by the installation of a cast iron tubbing lining. Although the freezing technique for shaft sinking and the use of cast iron tubbing to preserve the shaft are new to the North American continent, these procedures have been employed in Europe for the past eighty years. More than 200 shafts, covering a wide variety of ground conditions, have been sunk by the freezing process, and most of these have been lined with cast iron tubbing. The No. 1 shaft of International Minerals and Chemical Corporation, near Esterhazy, Saskatchewan, comprises the first major example in Canada of the employment of European methods to overcome extremely difficult ground conditions. The Blairmore formation was solidified by the deep freezing process, employing a lithium chloride solution as the refrigerant, with input temperatures ranging to -55°F

Jan 1, 1964

By d&apos, Kathleen J. Amico

THIS summary appears in Minerals Yearbook volumes I and III, which cover mineral production in the United States, its island possessions, the Canal Zone, and the Commonwealth of Puerto Rico, as well as the principal minerals imported into and exported from the United States. The several commodity and area chapters contain further details on production. A summary table comparing world and U.S mineral production also is included.

Jan 1, 1964

Gold was determined directly in eight different mill cyanide solutions, by atomic absorption spectroscopy in an acetylene-air flame. Some of the mill solutions were diluted with water to bring them into the most sensitive absorption region (5-50 p.p.m. Au) whereas those solutions with very low gold content «2 p.p.m.) were concentrated by evaporation.Calcium was complexed with ethylene diamine tetra-acetic acid (EDTA) to avoid the undesirable effect of a precipitate on atomization.When added to standard gold solutions, EDTA had no effect on absorption, nor did any of the impurities common in mill cyanide solutions.Known amounts of gold, ranging from 2 to 30 p.p.m., were added to mill solution'aliquots and recovered to within 100 ± 2·5 per cent. For duplicate determinations under normal worKing conditions, standard deviation was 1·32 p.p.m.Excellent agreement was found between atomic absorption gold values and accurate fire assay values.INTRODUCTIONAtomic absorption spectroscopy has been shown to offer a rapid and accurate method for the determination of trace amounts of a number of metal ions. In the field of primary metallurgy atomic adsorption has been used for routine determinations of lead, copper, silver, zinc, cadmium and iron in a variety of raw materials and intermediate products.The scope of atomic absorption spectroscopy was reviewed recently by Willis (1963).The noble metals silver, gold, platinum, rhodium and palladium were determined by atomic absorption from chloride solutions by Lockyer ·and Hames (1959). In their determination of gold down to 1 p.p.m., they found no interference from the noble metals, nor from considerable excess...

Jan 1, 1964

By S. Floreen

Measurements have been mode of the effects of tempering and austenitizing heat treatments, the work-hardening characteristics, and the effects of test temperature and strain rate on the properties of a low-carbon Fe-18 pet Ni martensitic alloy. In many respects the alloy behaved quite similarly to cold-worked iron. One notable quality was the excellent ductility at temperatures as low as 20°K. Many of the qualities of the maraging steels could he related to the properties of the Fe-Ni matrix. THE 18 pet Ni maraging steels have demonstrated that unusual combinations of strength and toughness may be obtained by age hardening a low-carbon Fe-Ni martensite matrix.' These properties must, to some extent, reflect the properties of this Fe-Ni matrix, and therefore an understanding of the properties of this matrix is a prerequisite to a complete understanding of the steels. There have been several recent studies of Fe-Ni-C martensites, but not much attention has been paid to alloys with very low carbon contents. At low carbon levels the crystal structure of these alloys is essentially bee.2 Electron transmission microscopic examination of a 20 pet Ni binary alloy showed martensite platelets separated by low angle boundaries.3 Plastic deformation of the low-carbon alloys has been shown to proceed by wavy glide.4 The hardness of these martensites is typically RC 28, and their yield strengths are 70 to 80 kg per sq mm.2, 5 Their ductility is excellent. Room-temperature tensile elongations of 18 pet and reductions of area of 70 pet have been observed in an Fe-18 pet Ni binary alloy.5 These observations have provided a qualitative understanding of the flow characteristics of these alloys. To date, however, no thorough study of their properties has been made. In particular, it is not known to what extent the deformation characteristics of low-carbon martensites are similar or dissimilar to those of pure iron or other bee metals. The present work was undertaken to provide more detailed information on the flow characteristics of a low-carbon Fe-18 pet Ni martensite. PROCEDURES, RESULTS, AND DISCUSSION Materials. A 40-lb heat of the Fe-18 pet Ni alloy used in this study was made by vacuum-induction melting. The charge materials were electrolytic iron and electrolytic nickel. A carbon boil was used to achieve deoxidation. After the boil the heat was refined by additions of 0.1 wt pet Ti and Al. These additions are commonly used in the maraging steels to keep the carbon and nitrogen contents in solid solution at a minimum. After casting, the heat was

Jan 1, 1964

By G. B. Craig, G. L. Montgomery

A simple technique has been developed which reveals glide dislocations in zone-refined aluminum as etch pits. The technique has been tested quantitatively by making dislocation counts on aluminum single crystals deformed in pure bending. The method has the advantage of being insensitive to the orientation of the surface under examination. A number of etchants which will reveal dislocations in annealed aluminum have been reported.'-' These etchants apparently depend on decoration of the dislocations by an impurity (probably iron) and cannot, therefore, be used to reveal fresh glide dislocations. In addition, it is unlikely that screw dislocations will be etched because of their small attraction for impurity atoms. Amelinckx6 has reported that glide dislocations located along slip traces can be revealed by fluo-rated aqua regia. This work indicated that dislocations themselves, irrespective of decoration by impurity atoms, are responsible for the etch pits. However, as a result of additional etching experiments, Wyon and Marchin7 concluded that dislocations alone are not sufficient to explain the localization of etch pits on slip lines in aluminum using chemical etch-pitting techniques. In addition, their results show that glide dislocations are revealed only on surfaces approximately parallel to a (100) axis and that not all slip systems are attacked. These observations have been confirmed by the present authors. The technique described in this article is insensitive to the orientation of the surface, and reveals dislocations on all glide systems. Fig. 1 shows a deformed region in the neighborhood of a scratch. Dislocations can be seen along three slip traces. In the present work, single crystals of zone-refined aluminum are polished for from 2 to 5 min in a chemical polishing reagent held at 100°C, as described by Herenguel and second:' H2Sol 60 pct H3PO4 30 pct HNO3 10 pet The samples are then coated with a thin oxide film by annealing in air at 450°C for 1 hr and cooling in the furnace. After deformation, dislocation etch pits are developed by immersing the specimen in the same polishing solution which is now held at a temperature of 50°C. The formation of small hydrogen bubbles indicates that etching has occurred. The sample is immediately removed from the solution. Prolonged etching results in enlargement of the pits and, in regions of high dislocation density, the overlapping and loss of resolution of individual pits. It is the experience of the authors that contact with iron will ruinously contaminate the reagent. With careful etching, dislocations separated by half a micron can be resolved optically and the method has been shown to be sufficiently sensitive to reveal dislocations produced during the pre-easy glide region of deformation, Fig. 2. A few examples of glide-dislocation configurations, as revealed by this technique, are shown in Figs. 1 to 4.

Jan 1, 1964

By C. R. Hubbard

The Bureau of Mines investigated the mineral resources of the Upper Missouri River Basin as a part of a comprehensive water and related land resources study by six Bureaus of the Department of the Interior, coordinated by the Department?s Missouri River Basin Field Committee. The mineral resource study covers an area of about 18,000 square miles within the Great Plains physiographic province of central Montana. Exposed formations in the plains are chiefly flat-lying Cretaceous sediments. Plutonic rocks crop out in the central parts of the mountain uplifts, with steeply tilted Paleozoic sediments exposed around the margins. Oil and gas have been produced from several fields in the study area; total value exceeds $45 million. Coal-bearing formations of Upper Jurassic and Cretaceous age cover approximately 45 percent of the study area. Total production of coal since 1880 has been between 40 and 50 million tons, exceeding $75 million in value. Total metal production has been about $52.5 million. Industrial mineral production from 1925 through 1960, is valued at $24 million.

Jan 1, 1964

By L. W. Pommier, F. B. Brien

In order to determine the ability of cyclones with heavy liquids to preconcentrate ores, a study of the variables which govern the behavior of the solids in the apparatus has been made. To assess the test results, the cyclone products have been examined by sink and float analysis at various specific gravities and the results examined by the Tromp type curves. This analysis has allowed the development of the SG50 unit — specific gravity of the particles, 50% of which goes to overflow and 50% to underflow — rather than the d50 (size) unit used in classification. The results of tests using the closed circuit laboratory cyclone assembly with dry feed samples show the validity of the equation: Results indicate that 83% of the feed may be rejected containing 0.1% Sn. Recoveries in excess of 80% are obtained at a grade of 1.7% Sn from feed samples assaying 0.4% Sn. As water-wetted particles may comprise the plant feed, separate tests were performed to examine the effect of water in the feed material. Results indicate that the entrained water divides into two fractions, one of which is defined as free water and is rejected to the cyclone overflow, the other fraction forms an adhering envelope of water on the ore particles, altering their effective size and density. The presence of the envelope of water on the particles increases the ease with which the heavy liquid can be recovered but decreases the concentration efficiency. It is proposed that the detrimental effect of water in the cyclone may be minimized by using a higher feed pressure cx by the use of surfactants. A higher feed pressure, by increasing shearing forces, would reduce the thickness of the water envelope on the particles. The surfactants, by adsorbing on the particles and producing hydrophobic surfaces, would displace the water envelope and allow the heavy liquids to wet the modified surfaces. In both cases a larger proportion of the entrained water would report to the cyclone overflow as free water, thus minimizing the detrimental effect of water on the concentration efficiency. Additional testing is required on the behavior of water in the system; to determine the optimum particle size for the preconcentration step; to determine final particle size for optimum liberation and subsequent treatment of the products in present plants and to determine the efficiency with which the heavy liquids may be recovered from the products. For many years tin mining in Bolivia has been very important to the economy of the country. In recent years the tin content of the ore reserves has been steadily declining. An improvement in concentration efficiency is highly desirable in order to increase productivity from the present low-grade mine ores and to allow retreatment of the many millions of tons of tailings from past operations, some of which equal the present ores in tin content. A number of investigators have been or at present are working on various phases or approaches to the problem. Gravity concentration is used in Boliva today as it has been in the past to recover tin minerals from the mine ores. An objective of the work reported in this paper was to examine the possibility of treating present low-grade ores and sink-float tailings products, at a relatively coarse grind, in order to produce a higher grade feed material to the present gravity concentration plants. The possibility of using heavy liquids in cyclones to treat large tonnages with a minimum of outlay presented itself and is of particular interest since heavy liquids are now available with physical properties which lend themselves to simple recovery methods. Tests were carried out using a closed circuit laboratory cyclone assembly. It was desirable to determine the value of using the SG50 concept and Tromp curves for analyzing the cyclone concentration test results. The effects of entrained water on the behavior of ore particles in the cyclone were examined. THEORY AND TECHNICAL CONSIDERATIONS Three types of heavy liquids are available: aqueous solutions of very soluble salts, salts or mixtures of

Jan 1, 1964

By J. H. Smith, H. W. Paxton

ALTHOUGH many structural and kinetic investigations have been made for alloys of iron and nickel, only meager data exist from thermodynamic investigations. The purpose of this note is to estimate the free energy of the Fe-Ni solid solutions from thermodynamic data available for ternary alloys containing iron and nickel. The lack of a description of the thermodynamic behavior for the Fe-Ni system has required the structural and kinetic analyses of the system to assume some form of solution behavior, usually regular, e.g., the mar-tensite transformation analysis of Kaufman and Cohen, 1 consistent with the limited thermodynamic data. Indications that this system could exhibit ideal solution departures might have been suggested by the large deviations from additivity rules observed in the density and lattice-parameter measurements of Jette and Foote2 who interpreted this in terms of possible solute-solvent interactions. Later Turkdogan et al. 3 and more recently Ward and wright 4 found a minimum in the graphite solubility in liquid Fe-Ni solutions near the concentration of FeNi3 with deviations from linearity persisting at all concentrations. This was interpreted by Ward and wright4 to indicate negative heats of solution and was suggestive of short-range ordering. The infinitely dilute activity coefficient of carbon (?oC) was also observed by smith5 to pass through a maximum near the FeNi3 concentration in Fe-Ni solid solutions. Recent investigations of the liquid solutions over the entire concentration range by Zellars et a1.' and Speiser et a1.," using vapor-pressure determinations, revealed both negative departures from Raoult's law and a nonregular solution behavior. The solid alloys have been studied by Oriani 8 and Kubaschew-ski and von Goldbeck6 employing gaseous H2/H2O equilibria with Fe and FeO. Both investigations were in substantial agreement, indicating very small departures from ideality. However, Oriani observed the formation of Fe3O4 (instead of FeO) at XFe= 0.441 which severed the equilibrium and precluded experimental investigation of the nickel-rich alloys. Heat-capacity and heat-content measurements have been evaluated by Montgomery10 and found generally unsatisfactory for gleaning thermodynamic information. This is due to the unknown final states of the alloys caused by the interference of the martensite transformation on cooling iron-rich concentrations and superlattice formation, magnetic transformation, and the varied heat treatments used by investigators of nickel-rich concentrations. As an alternative to the experimental difficulties, indirect estimates of the solid-solution behavior have been made by Fleischer and Elliott11 and Smith et a1.12 From their measurements of the solubility of Fe-Ni alloys in liquid lead, Fleischer and Elliott calculated the nickel activity (aNi) (and integrated for aFe) by assuming: 1) liquid lead has no solubility in solid Fe-Ni alloys, 2) Henry's law is obeyed throughout the liquid lead-rich phase (0— 12 at. pct Nil, and 3) Henry's law constant is independent of relative iron and nickel concentrations. The estimate of Smith et a1.12 was obtained

Jan 1, 1964

By Randolph H. Schnitzel

MARINGER and schwopel have investigated the internal friction of high-purity molybdenum. After light tensile deformation, they observed internal-friction peaks at about 230° to 290°C, 310" to 370°C, and 820° to 870°C, which they have attributed to the interstitials carbon and nitrogen, and to stress relaxation across grain boundaries, respectively. The electron-beam melting technique has been successfully applied to refractory metals including molybdenum. By this technique single crystals and higher-purity levels than those of commercial molybdenum are readily obtained. Since electron-beam processed molybdenum possesses such desirable qualities, it seems reasonable to determine: u) if internal-friction peaks do exist in these single crystals, and b) if so, whether or not these peaks can possibly be attributed to the motion of specific interstitials. The molybdenum crystal used in this investigation received four melting passes in the electron-beam furnace. This crystal was about 11 in. long and had an orientation 4 deg from the [loo]. The process of making wire consisted of grinding the crystal rod to a diameter of 0.040 in. and then electropolishing to a final diameter of 0.030 in. Since Maringer and schwopel have indicated that the peak at 230" to 290°C may be due to the presence of carbon, the wire was cut into two equal lengths and one length was carburized prior to the internal-friction measurements. The critical condition necessary for the controlled addition of carbon proved to be a difficult problem. Therefore, a simpler nonequilibrium method was used. This consisted of carburizing at 2000°C in graphite powder to obtain a case, annealing at higher temperatures in vacuum to partially dissolve carbon into the molybdenum, and then removing the remaining case by dissolving it elec-trolytically. After this treatment, metallographic examination of a small section of the specimen revealed carbides in the matrix. Vacuum fusion and carbon analyses for both the virgin (as melted) and carburized specimens are given in Table I. Internal-friction measurements of these specimens were conducted in an apparatus of conventional

Jan 1, 1964

By Toivo Toivanen

The paper begins with a brief history of the nickel industry in Finland, and then deals with the introduction of the flash smelting process. The main part of the paper is devoted to nickel refining, which is studied under four main headings -grinding, leaching, electrolyte precipitation, and nickel electrowinning. Flowsheets are illustrated, and the equipment used is described. Analyses of the material in the various stages, from concentrate to high-grade nickel matte, are also presented. N ICKEL made its appearance in the Finnish mining industry forty years ago, when a nickel deposit was discovered at Petsamo in Lapland. Mond Nickel Co. received the concession for this deposit from the Finnish Government, and the Petsamon Nikkeli Company constructed a mine and a nickel smelter (1), the completion of which was prevented by the 1939 Winter War. The mine and smelter were, however, completed soon afterwards in spite of World War II,

Jan 1, 1964

Although the 'exi'stence of bauxite in Australia has been known for many years it is only recently that exploitation has commenced.. of the two most' important` deposits, strangely at almost diagonally opposite tips of the continent. Recognition of the importance. of the bauxite in the South/West corner came about initially through the efforts of a well-known Australian mining company which,` with some outside financial help, tackled the early exploration with commendable foresight and courage.

Jan 1, 1964

By J. W. Spretnak, H. R. Ogden, A. G. Imgram

The effect of working reduction, stress-relief annealing, and recrystallized grain size on the tensile and notch-tensile properties of molybdenum and Mo-0.5 Ti was studied. It was found that increasing the amount of working reduction increased the strength and reduced the tendencies toward brittle behavior. Stress -relief annealing did not alter the strength but lowered the transition temperature. Increasing the recrystallized grain size lowered the strength and raised the transition temperature. The notch -unnotch strength ratio began to decrease with decreasing temperature at temperatures below those at which the notched ductility fell to zero for all of the micro structural conditions investigated. BEING bcc metals, the refractory metals in Groups Va and VIa (V, Cb, Ta, and Cr, Mo, W) undergo a ductile-to-brittle transition and exhibit brittle fractures at low temperatures. Previous research has shown that molybdenum and tungsten not only have higher transition temperatures than columbium and tantalum but show a marked sensitivity of transition temperature to structure as well.' Recrystallized materials become brittle at considerably higher temperatures than is the case with material having a worked or fibered micro-structure. Evidence of structure sensitivity has also been detected in columbium- and tantalum-base alloys containing appreciable amounts of molybdenum or tungsten such as F-48 (Cb-15W-5Mo-1Zr) and Ta-10w.2 This paper describes the results of research conducted to further evaluate the effects of metal. lurgical structure on the low-temperature tensile and notch-tensile properties of molybdenum and Mo-0.5Ti. The effects of rolling reduction, stress-relief annealing temperature, and recrystallized grain size were studied. Considerable progress has been made in explaining the fundamental mechanisms of the flow and fracture characteristics of bcc metals. Several of these concepts are helpful in interpreting the data obtained in this study. Brittle fractures occur when the highly temperature-sensitive yield strength equals, or exceeds, the temperature-insensitive brittle cleavage fracture stress.3 The rapid increase in yield strength with decreasing temperature, characteristic of all bcc metals, is therefore of primary concern. petch4 has described the yield strength, ay, (stress required to initiate plastic flow) of bcc metals by the expression where ai is the frictional resistance to slip, Ky is a constant numerically equal to the slope of a a vs curve, and 2d is the average grain diamefer. The oi term itself is thought to be composed of a temperature-insensitive component dependent on impurity content and second-phase particles and a temperature-sensitive component dependent on the Pierls-Nabarro force.5 This equation has also been demonstrated to hold for the flow stress (stress required to maintain continued plastic flow).' Brittle-crack nucleation is thought to occur by the coalescence of dislocations piled up in slip planes at sessile dislocations or twin and grain boundaries.7,8 These proposed mechanisms require that a large number of dislocations be released into the active slip planes so that sufficiently large stress concentrations are produced at the dislocation pile-ups to enable coalescence into a micro-crack. Therefore, at least a microscopic amount of slip must occur in some grains to facilitate initial crack formation. Cottrell 7 has predicted that brittle fracture, nucleated by slip, should occur when where ty is the shear yield strength, ß = 1 in un- notched xension, u is the shear modulus, and y is the effective surface energy. This equation incorporates the Griffith concept of fracture that a crack will propagate if the decrease in strain energy equals or exceeds the increase in surface energy.

Jan 1, 1964