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By J. E. Dutrizac, R. J. C. MacDonald, T. R. lngraham

When sintered disks of synthetic chalcopyrite (CuFeS2) were leached in acidified aqueous solutions of ferric sulfate, the following reaction stoichiometry was obtained: CuFeS2 + 2Fe2(SO4)3 = CuSO4 + 5FeSO4 + 2S Over the temperature range from 50º to 94ºC, the reaction displayed parabolic kinetics. The parabolic rate constant for the dissolution of copper is given by the equation: log.k(mg2/cm4-hr)= 11.850 - 3780/T The activation energy for the dissolution process is 17 ± 3 kcal per mole. The parabolic kinetics have been attributed to the progressive thickening of a sulfur film on the surface of the chalcopyrite. When the leaching solutions contain less than 0.01 molar Fe+3 , the Fe concentration influences the rate of leaching, probably through a mechanism involving the diffusion of ferric sulfate through the sulfur layer. At higher Fe+3 concentrations, the rate control in the leaching. reaction has been attributed to the diffusion of ferrous sulfate through the sulfur. The rate of reaction is insensitive to changes in acid concentration and in disk rotation speed. ThE reaction of acidic ferric sulfate solutions with various sulfide minerals is of practical interest for both bacterial and heap leaching. This leaching medium is generally used with low-grade ores that cannot be treated profitably by conventional means. In both bacterial leaching1-3 and heap leaching, the active agent for sulfide dissolution is ferric sulfate. Although the reactions of ferric sulfate with chalcocite, covellite, and bornite have been investigated,4*7 the kinetics of leaching chalcopyrite with ferric sulfate have not been thoroughly studied. This paper reports a study of that reaction. EXPERIMENTAL Reagent-grade sulfur was purified by the method of Bacon and FanelliB and then it was vacuum-distilled to remove any soluble magnesium salts that had been introduced during the purification procedure.9 From stoichiometric quantities of the purified sulfur and hydrogen-reduced electrolytic copper sheet (99.90 pct Cu), CuS was synthesized at 450°C in a vacuum-sealed, pyrex vessel. About 24 hr was required for the completion of the reaction. A similar procedure involving hydrogen-reduced iron wire (99.90 pct Fe) was used to synthesize FeS1.002. A 2-furnace arrangement was required. The iron was heated to 800°C while the sulfur was maintained at about 400°C. Although the reaction to consume the sulfur was rapid, the material required additional heating (1 week) in a sealed silica ampoule at 800°C before it was homogenized. X-ray powder diffraction analysis confirmed that the copper sulfide was covellite and that the iron sulfide was troilite. The composition of the iron mineral was confirmed by wet chemical analysis. The two sulfides were ground to minus 100 mesh, weighed in equimolar amounts, mixed thoroughly, and pressed into pellets at 80,000 psi. The pellets were vacuum-sealed in pyrex ampoules and then sintered for 3 days at 550°C after an initial heating at 450°C for a few hours. The pellets were then cooled, polished with 3/0 emery paper, rinsed in acetone, and stored. The material had the characteristic brassy color of chalcopyrite and was shown by X-ray diffraction to be CuFeS2. Microscopic examination of the polished surfaces revealed small inclusions of pyrite (approximately 0.5 vol pct) as the only impurity. The presence of small amounts of a second iron compound will not alter the amount of dissolved copper but might increase the amount of ferrous ion slightly. It was calculated that dissolution of all of the pyrite and 100 mg of Cu (a typical value) would change the expected ferrous concentration by only 4 pct. Microscopic examination of a pellet after leaching revealed that the pyrite was not preferentially solubilized; only those pyrite grains at the surface were attacked. Hence, the pyrite is unlikely to alter the rate of copper dissolution. The chalcopyrite disks were about 1.7 mm thick and 27 mm in diam. They were about 80 pct of theoretical density, and for this reason their true reaction area was somewhat larger than the 5.8 sq cm area presented by the polished face. The disks were cemented to lucite cylinders in such a way that only the polished face was exposed. The disks were then leached by methods previously described.6,7 RESULTS AND DISCUSSION Stoichiometry and Kinetics. The initial experiments were directed to the problem of resolving the stoichiometry of the leaching reaction. Disks of CuFeS2 were leached at 80°C for various periods of time in acidified ferric sulfate solutions that were protected from oxidation by a cover of flowing nitrogen. When the disks had been partly leached, they were removed, their soluble salts were washed out, and then they were treated with CS2 in a Soxhlet extraction apparatus. The ratio of elemental sulfur to dissolved copper thus obtained was approximately 2 to 1. After the extraction of elemental sulfur from the pellet, the residue consisted of unreacted chalcopyrite only. For runs in which an appreciable amount of copper was dissolved, the ratio of ferrous ion to cupric ion in the solution was

Jan 1, 1970

By P. M. Robinson, M. B. Bever

The heats oj formation at 273°K of the compounds CdTe, I)z2Te, InTe, In2Te3. In2Te5, SrzTe, and PbTe have been rleasrred in a liquid metal solutiotz caloritrete? 1.t1itlz bismuth as solvent. The?, are iterpretecl in yelation to tlze stability and bonding of the cott/pozltzds. Tile heats of fusion atzd the melting- points of tlze cotlzpounds InTe and Itzz,Te3 1lcti.e been measured in a cotrslant-temperature gradient calorimeter. The entropies of fusion are disc,ztssecl in YIIIS 01. the degree of order in the solid at the melting point. THE heats of formation of the tellurides of cadmium, indium, tin, and lead have been measured as a continuation of research on the thermodynamic properties of compounds of tellurim.' The tellurides of these metals were selected with a view to examining the relation between the heat of formation and the position of the metal in the periodic system. The elements cadmium, indium, and tin are in the same period and tin and lead are in the same group of the periodic system. The tellurides of indium are of special interest because four compounds, In2Te, InTe, In2Te3, and InzTe5, occur in this system. The available information on the heats of formation of the compounds investigated consists of values for CdTe, SnTe, and PbTe derived from electromotive-force measurements,J a value for CdTe obtained by tin solution alorimetr, and values for InTe and In2Te3 determined by combustion calorimetry.5 These values, however, refer to various temperatures ranging from 273' to 673°K and some of the reported error limits are large. Liquid metal solution calorime-try may be expected to yield more accurate values for the heats of formation than electromotive-force measurements or combustion calorimetry. The heats of fusion and the melting points of the compounds InTe and In,Te3 were determined in a constant-temperature gradient calorimeter. No published information appears to be available on the heat of fusion of these compounds. The results reported here give an indication of the degree of order in the solid compounds at the melting point. 1) MATERIALS AND EXPERIMENTAL PROCEDURE Materials. Samples of the compounds SnTe and PbTe were obtained from the Westinghouse Research Laboratories and samples of the compound InTe from Lincoln Laboratory, Massachusetts Institute of Tech- nology. Additional samples of the compounds InTe, SnTe, and PbTe and samples of CdTe, In2Te, In2Te3, and In,Tes were prepared from 99.995 pct Cd (Baker Chemical CO.), 99.999+ pct In (American Smelting and Refining Co.), 99.99 pct Sn (Baker Chemical Co.), 99.999+ pct Pb (Fisher Scientific Co.), and 99.999+ pct Te (American Smelting and Refining Co.). Stoichiometric amounts of the component elements were melted in sealed, evacuated Vycor tubes. The melts were held at approximately 100°C above the liquidus for about 16 hr and shaken repeatedly. The melts of the compounds In2Te and InzTe5, which form by peritectic reactions, were quenched into iced water. The melts of the other compounds, which have congruent melting points, were slowly cooled to room temperature. The samples were then annealed for 5 days at approximately 50°C below their respective solidus temperatures. Metallographic examination did not reveal any evidence of second phases or segregation. At least two batches of each compound were prepared. Samples from each batch were used in determining the heats of formation and, in the cases of InTe and In,Te3, the heats of fusion. The Heats of Formation. The heats of formation at 273°K of the compounds were measured by metal solution calorimetry with liquid bismuth at 623" as solvent. In this technique, the heat of formation is determined from the measured heat effects on dissolution of the compound and of a mechanical mixture of the component elements. The difference between these heat effects adjusted for changes in the composition of the bath gives the heat of formation at the temperature from which the samples are added to the bath (273°K). The experimental technique and method of calculation have been described in detail elsewhere.= It should be emphasized that the reported heats of formation depend on the thermodynamic data used in calculating the heat effects for the calibration additions. In the present investigation, the calorimeter was calibrated by adding pure bismuth at 273°K to the bismuth bath at 623°K. The reported heats of formation are based on a value of 4.96 kcal per g-atom for the difference in the heat contents of bismuth at 623" and 273". If a new value for this quantity becomes available, the reported results may be adjusted in direct proportion. The concentration of solute in the bath at the end of a calorimetric run did not exceed 1.7 at. pct and was usually less. In this range, the heat effect on dissolution of the solute was a linear function of the concentration of solute. In determining the heats of formation of the compounds in the system In-Te, a few runs were carried out in which two neighboring compounds such as InTe and In,Te3 and the corresponding mechanical mixtures of the components were added to the calorimeter. The

Jan 1, 1967

By R. J. Brison, O. F. Tangel

The development of a new method of mineral separation was sponsored by the International Salt Company, which requested Battelle Institute to investigate means for improving the quality and appearance of rock salt from the Company's Detroit mine. Although developed specifically for removing impurities from rock salt, the general method may be applicable to other separation problems. The principal impurities in rock salt from the Detroit mine are dolomite and anhydrite which represent 2 to 5 pct of the weight of the mined salt. In the size range from 1/4 to M in. (the range of primary interest in this project) the impurities are only partially liberated from the halite in normal production. Further size reduction to improve the liberation of impurities is not practicable in view of the market requirements for the coarse grades of rock salt. Laboratory separations in heavy liquids showed that, to improve the quality and appearance of the rock salt substantially, it would be necessary to remove not only free gangue particles but also a large proportion of the locked-in particles. Because rock salt is an inexpensive commodity, a low-cost process was required. Gravity methods were, of course, considered. The heavy-liquid separations indicated that a split at an effective specific gravity of 2.2 to 2.3 would be required. (The specific gravity of pure halite is 2.16.) Heavy-media separation was investigated but had the disadvantages that it was necessary both to operate with saturated brine and to dry the cleaned salt, and that the cleaned salt was darkened by the magnetite medium. Air tabling was tried but did not give the desired separation. It soon became apparent that established methods would not provide a satisfactory solution and work was undertaken on the development of a new process to solve the problem. PROCESS DEVELOPMENT Preliminary Experiments: At the start of the investigation, an analysis of the problem indicated that the diathermacy of rock salt—that is, its ability to transmit radiant heat—might form the basis for an efficient separation process. Under this theory, the impurities might be selectively heated by radiant heat. The particles could then be fed over a belt coated with a heat-sensitive substance so that the warm impure particles would adhere preferentially to the coating. After the initial experiments, made by heating the rock salt with an infrared lamp and separating the product on small sheets of resin-coated rubber, proved encouraging, a small continuous separation unit was set up. This comprised 1) a simple heating unit consisting of a vibrating feeder covered with aluminum foil and an infrared lamp mounted above the feeder and 2) a separation belt 6 in. wide and 36 in. long. A sketch of the device is shown in Fig. 1. Results with this apparatus confirmed the fact that a good separation was possible. It was apparent, however, that a considerable amount of experimental work would be needed to develop the scheme to a practical and economical process. The Process: Basically, the process consists of two main steps: 1) selective heating by radiation and 2) separation of the heated particles on a heat-sensitive surface. Because neither of these steps had previously been utilized commercially in mineral processing, it was necessary to do basic research on both aspects. Factors studied in the investigation included type of heat source, design of heating unit, design of separation belt, selection of heat-sensitive coating, removal of heated particles from the belt, contact between particles and coating, and maintenance of the heat-sensitive surface. Part of the experimental work was carried out on a small-scale unit consisting of the 36x6 in. belt and auxiliary apparatus, and part on a larger unit. For simplicity, discussion of work on both of these units is grouped together. SELECTIVE HEATING Radiant-Heat Source: The essential requirements for a radiant-heat source were 1) that the radiant heat be in a wave length range which is effectively absorbed by the impurities but not absorbed appreciably by the rock salt and 2) that it be dependable, practical, and economical. Selection of a heat source of suitable wave length range was one of the first considerations. It is well known that pure halite is highly transparent to radiant energy in wave lengths from 0.3 to 13 microns. However, the available data on infrared transmission by dolomite and anhydrite, particularly in the range below two microns, were not complete enough to serve as a reliable basis for selection of a heat source. Although it may have been possible to obtain sufficient data on infrared transmission and absorption to enable one to select the best heat source, a more direct procedure was used. This consisted simply of exposing the crude rock salt to each of several types of radiant-heat source on the small continuous separation device. The heat sources investigated, approximate source temperature used, and calculated wave length of maximum radiation are tabulated in Table I. Of the two types of tungsten-filament lamps investigated, both the short wave length photoflood lamps and the longer wave length infrared lamps were satisfactory from the standpoint of selectivity

Jan 1, 1961

By P. W. Gilles, B. D. Pollock

THE pioneering work of Steinitz1 and Steinitz, Binder, and Moskowitz2 has shown conclusively the existence at high temperature of two additional phases in the molybdenum-boron system and thus brings to a total of six the number of structures appearing in this system. To the structures Mo2B, MOB, and Mo2B5 they have added MO3B2, a new -MOB form, and have shown that MOB,, which has the same range of composition as Mo2B5, is only a high temperature structure of the latter. This solid solution, interestingly enough, includes neither of the compositions corresponding to the stoichiomet-ric compounds, MOB, or Mo2B5, but rather at all temperatures has intermediate values of composition. These workers have also, in the course of their work, measured melting points, transition temperatures, eutectic and peritectic points in the system and have shown that Mo3B2, because of its dispro-portionation at low temperature to Mo2B and MOB, is stable only in a limited high temperature range. During the course of the present work on the vaporization properties of the molybdenum-boron compounds, a few transition temperatures were observed. When the report of the other workers appeared, it was decided to repeat, in part, their study of the system. As a result, considerable evidence has been obtained that substantiates the specific kinds of melting processes they report as well as the general features of their diagram. However, a marked difference was found between the temperatures they report and the ones observed in this study, with the latter being higher. The purposes of this paper are to present the evidence obtained in this laboratory that verifies their diagram of the system, to give some important temperatures in the system, to compare them with those previously published, and to seek an explanation of the difference. Samples The metal starting material was 400 mesh molybdenum powder with a purity stated by the manufacturer to be 99.9 pct. The initial treatment, designed to remove volatile contamination, consisted of heating in a vacuum for 10 min to a temperature of from 800" to 1000°C during which a loss of 0.3 to 0.4 pct occurred. An assay following this treatment showed it to be 99.4 pct pure, with the principal impurity probably being oxygen. The boron starting material was obtained from the Cooper Metallurgical Laboratories and the Fair-mount Chemical Co. as 325 mesh powder with manufacturers' analyses of 99 pct or better. Initial treatment consisted of heating in molybdenum in a vacuum at about 1700°C for 10 min. During this time a loss of 3.5 pct occurred. An assay following this treatment showed the different samples to have purities ranging from 95.5 to 99.0 pct with iron and carbon as the principal impurities. Following the initial treatment, the elements were combined to form stocks of Mo2B and MOB by heating pressed mixtures in a vacuum to 1100" to 1200°C to accomplish reaction and to 1500" to 1900°C for a few minutes to evaporate the more volatile impurities. Analysis of the two compounds for boron by a modification of the method of Blumenthal3 and for molybdenum by the lead-molybdate method indicated them to have purities greater than 99 pct. The individual samples to be studied had compositions in the Mo2B-MOB range and consisted of mixtures of the stock compounds. Procedure As is usually the case in high temperature work the selection of containers for the samples posed some problems. For vapor pressure studies tantalum crucibles, allowing little contact with the pressed samples, were used and some of the observations made during these experiments are pertinent to the study of the phase diagram. Most of the experiments, however, were performed in graphite containers, as were those of the previous authors. Two kinds of spectroscopic grade graphite crucibles were used. One was a % in. cylinder, 3/4 in. high, containing seven 3/16 in. holes drilled 1/2 in. deep into which were packed samples of the different mixtures weighing 250 to 500 milligrams. The other, consisting of separate crucibles, was prepared by drilling 3/16 in. holes, 1/2 in. deep into 1/4 in. graphite rods % in. long. The 7/8 in. cylinder was heated directly by induction while the small crucibles were packed in a tantalum heating element for induction heating. All heating was done in a high vacuum system in which the pressure was generally less than 1x10-5mm and never rose above 2x10-5mm when the samples were hot. The general pattern of the heating in graphite was to heat rapidly to a temperature somewhat below the desired one, then to raise the temperature slowly. The samples were held for 2 to 5 min at the maximum temperature, which in all cases was far higher than that needed to produce reaction. The short time was employed to reduce possible contamination by the crucible material and to reduce composition changes that would occur because of vaporization. After examination following the heating, the samples were reheated to a higher temperature. Temperatures were measured with a Leeds and Northrup disappearing filament optical pyrometer, certified by the National Bureau of Standards, by sighting through a window at the top of the vacuum

Jan 1, 1954

By J. E. Campbell, G. D. Calkins, N. M. Ewbank, M. Pobereskin, A. Wesner

GRINDING for size reduction affects the economics of many processes and products. It is essential as the first step in many industrial processes and is also a finishing step for materials with properties depending on particle size, such as talc, cement, and silica sand. Intermediate and fine grinding are vital operations in the U. S. cement industry, which is producing more than 250 million bbl of cement per year.' Wear of the grinding media is a large part of the grinding operation cost. Problems encountered in grinding cement are so complex that evaluation of efficiency and economy of grinding media is difficult.2 It has been especially difficult to evaluate the relative effectiveness of different types of balls because there are no good testing techniques. Many other industrial operations can be evaluated on a laboratory scale with reasonable accuracy. This does not hold true for evaluation of grinding balls. The consistent results obtained in a laboratory test under a given set of conditions are not always borne out in field application. Rough evaluations of the effectiveness of various compositions and types of grinding balls have been made in the field by using a full charge of one type in a mill and comparing the production record with another run using another type of ball. This method is time-consuming and not very precise, as the second run may not have been carried out under identical conditions. Laboratory-scale tests, on the other hand, have yielded inconclusive results, and many investigators have turned their attention to the development of a field testing technique. Field testing small sample lots of grinding balls has been impractical because it is difficult to identify and recover the test specimens from the grinding mill, and individual groups of balls that have undergone different heat treatments can not be separated.".4 To overcome these difficulties, previous investigators have identified the balls by distinctive marks, notches, and drilled holes, but this procedure has three serious drawbacks: 1) Grinding characteristics and quality of the steel balls may be affected. 2) Physical markings may be worn away in the grinding process, especially during a prolonged run. 3) Recovery from the bulk of the charge will be extremely difficult because the markings are hard to see and may be masked by a coating of the product. To circumvent these difficulties, a radioactive-tracer technique was proposed for recovery and separation of steel grinding balls and subsequent evaluation of the various compositions of the balls. The proposed technique involved five basic operations: 1) Thermal-neutron irradiation activation5 of each group of test grinding balls to a different level of specific radioactivity. 2) Addition of groups of radioactive steel-ball specimens into a ball tube mill. 3) Recovery of radioactive steel-ball specimens from the bulk of the mill charge. 4) Separation of the various groups by their specific radioactivity. 5) Evaluation of actual grinding ball wear. Before any physical tests were performed, required neutron irradiation intensity and time were calculated. Probable composition of the steels to be used was ascertained. An examination was made of the radioactive nuclides8 to be formed which would contribute measurably to the radiation level immediately after irradiation and during the test operation. The radioisotopes formed, their types of radiation, and their half lives are listed in Table I. Of these radioisotopes only iron-59 and chromium-51 were significant for the actual wear test. The intensity of radiation that could be detected by a Geiger counter when the test was completed was the basis for the minimum activation level established. The intensity of radiaton that could be safely handled at the beginning of the test was the basis for the maximum activation level, although this was not considered a major problem. Ten groups of grinding balls of various composition and/or surface or heat treatment were to be tested. One group was designated for the minimum irradiation time. The remaining groups were designated for irradiation periods that increased by increments of 33 pct from that of each preceding group. This difference was considered enough for separation and identification of the groups by comparison of specific activity. Potential Hazards: Possible radiation hazards that might be encountered during this experiment were evaluated for the three important phases: 1) the radiation hazard of placing balls and removing them from the mill, 2) contamination of the product cement by radioactive material worn from the balls, and 3) contamination of the steel by the radioactive balls left in the mill. The radiation intensity expected from the whole group of radioactive balls was calculated to be 250 milliroentgen per hr at 1 ft. This meant the balls would require special shielded packaging and warning labels on the shipping containers. In a radiation field of 250 mr per hr a man can work for 1 hr without exceeding maximum permissible weekly exposure. Since the balls could be dumped into the mill in a matter of seconds, relatively little radiation exposure was anticipated at this stage of the operation. If the weight loss in the balls was 7.7 pct per month and the cement feed through the mill was

Jan 1, 1958

By A. Raman, P. P. Singh

The constitution of the La-Rh system was studied by powder X-ray diffraction, metallopaphic, and differential thermal analysis techniques and an equilibrium diagram is presented. Eleven intermediate phases occur in the system and the crystal structural data for nine of them were determined. La3Rh crystallizes in an orthorhombic structure of undetermined type, whose unit cell is obtained by doubling the 'a; and 'c,,' edges of an FesC type unit cell. The other intermediate phases of the system are LarRh-3( undetermined structures also occur in the system. LaRh, undergoes a polymorphic phase transformation at 1240°C. LaRh3 and La2Rh7 also exhibit polymorphisnz. The phases Laah and LazRh7 melt congruently. The latter undergoes a eutectoid transformation into LaRh, and Rh at 1205°C. Laah3 is formed by a peritectoid reaction between Laah and La,Rh,,. The other Phases result from peritectic reactions between the liquid and the adjacent rhodium-rich phases. The intermediate Phases of the La-Rh system are compared with those of the La-Co and La-Ni systems. DURING the course of a detailed investigation to study the occurrence of CrB, FeB, A1B2, and related structures in the rare earth alloys it was found that much information is lacking for the rare earth noble metal systems. Although the structures of several rare earth alloys containing the noble metals at the AB and AB2 stoichiometries have been reported, the occurrence of related structures at other stoichiometries has not been studied. We have initiated a project to study the crystal structural features of selected rare earth-rhodium alloys and to map the equilibrium diagrams of representative systems with conventional methods. The results of our investigation in the La-Rh system are presented in this paper. Two phases were known in the La-Rh system. LaRh has the CrB-type structure.' LaRhz is a MgCu2-type Laves phase.z EXPERIMENTAL PROCEDURE Alloys weighing less than 1 g were prepared from commercially pure lanthanum (99.9 pct +), supplied by Lunex Company, Pleasant Valley, Iowa, and rhodium (99.92 pct +), supplied by Engelhardt Industries, Newark, N.J., in a conventional arc melting furnace under argon atmosphere. The buttons were turned upside down and remelted three times to insure homogeneity in the samples. Since negligible loss of material was encountered during melting, a chemical analysis of the alloy buttons was not undertaken. Powder specimens for X-ray diffraction studies in the as cast state were then prepared. The buttons were wrapped in thin molybdenum foils and homogenized by heating in vacuum at suitable high temperatures for more than 1 week. They were then broken into three or four pieces for annealing experiments. The pieces were wrapped in molybdenum foils and annealed at various temperatures in evacuated quartz capsules. The annealing was carried out for 2 hr at or above 1200°C, 1 day at temperatures close to llOO°C, 2 days at 1000°C, and for 1 week at temperatures below 1000°C. After annealing the alloy pieces were again broken and powder specimens for X-ray diffraction were prepared. The powders of the lanthanum rich alloys with more than 80 at. pct La were prepared by filing. The filings were sealed in molybdenum tubings and stress-relieved at 600°C in vacuum. It was not deemed necessary to stress-relieve the powders of the other alloys, since the alloys were very brittle and were ground easily. POWDER X-RAY DIFFRACTION X-ray diffraction photographs of powders (-325 mesh size) of the alloys in the as cast and annealed states were prepared in a Guinier-de Wolff focussing camera with copper K, X radiations. These patterns were studied to identify the stoichiometries and the crystal structures of the intermediate phases. The lattice parameters of the phases were calculated after minimizing the differences between the observed sin2 6 values, calculated from the diffraction angles 8, and the sin2 8 values, calculated using approximate lattice constants obtained from a few lines. These differences were minimized manually to less than 0.0005. The latLice constants are judged to be accurate to *0.005A for values less thp about 10A and to k0.01~ for values greater than 10A. The relative intensities of the lines were calculated using a computer program written by Jeitschko and Parthk.~ No attempt was made to refine the atomic positional parameters in the phases. METALLOGRAPHY The phase equilibria in the investigated alloys in the as cast and annealed states were also studied by metallographic examination. The polished specimen surfaces were etched with 10 pct picric acid in alcohol (alloys up to 25 pct Rh), concentrated picric acid (from 25 to 37.5 pct Rh), 2 pct nital (40 to 50 pct Rh), 10 pct nital (from 50 to 66.7 pct Rh) and with concentrated 48 pct HF for the other rhodium-rich alloys. Selected microstruture~ were then photographed using a Po-laroid Land camera. THERMAL ANALYSIS Differential thermal analysis of the alloys was carried out in DTA-668 Stone differential thermal ana-

Jan 1, 1970

By B. W. Christ, P. M. Giles

Mossbauer effect measurewents have been made on I-mil-thick foils of commercial 1 wt pct C steel and Fe-2 wt pct C alloy. The experimental method required about 3 to 5 vol pct of a phase in the nzultiphase steel sample for detection. Room-temperature Md'ssbauer patterns obtained on austenitized atid quenched samples exhibit fifteen, and possibly twenty-one, lines. A sharp parama&tetic singlet and a quadrupole doublet, poorly resolued from the singlet, are attributed to austenite. Remaining lines are due to tnartensite. Accurate evaluation of austenite line paranzeters is not feasible if significant amounts of other phases such as carbides or martensite occur simultaneously with austenite. This is demonstrated by comparison of hyperfine interactions determined for austenite in multiphase high-carbon samples with those reported for Fe-C austenite in a nearly 100 pct austenitic sanple. Lines from carbides are incompletely resolced from austenite lines, as demonstrated by comparison of austenite line positions with carbide line positions calculated frow published values of hyperfine interactions. One martensite line overlaps an austenite line in the pattern for commercial 1 wt pct C steel. Results of this study suggest that the usefulness of e M6ssbauer pectroscopy for quantitatizle analysis of austenite in bulk samples of quenched and tempered high-carbon steels is restricted by poor resolution. Use of Mossbauer spectroscopy for phase identification and for evaluation of atomic and electronic structures appears quite feasible, however, The Mijssbauer effect has been widely discssed,'-and e Mossbauer effect measurements have been reported on materials of metallurgical interest.7"20 In particular, it has been proposed that e Mossbauer patterns of commercial steels and laboratory-made Fe-C alloys, in the quenched condition, are composed of lines originating in two phases, Fe-C austenite and Fe-C martenite.-' Evidence accumulated in this study demonstrates that three absorption lines found in the central region of the e Mossbauer pattern obtained on quenched steels are attributable to retained austenite. This interpretation is supported by parallel decreases in the intensity of these three lines caused by subambient cooling of commercial 1 wt pct C steel samples after water quenching to room temperature. A second result of this study is to clarify effects of line resolution and sensitivity in the Mossbauer patterns of multiphase steels on the accu- rate determination of austenite line parameters. Experimental line widths (full width at half height) are generally 1.5 to 3 times larger than the natural line width of 0.19 mm per sec. At least two lines, and sometimes more, from a single phase such as cementite (Fe3C), other carbides, martensite, and austenite fall in the energy band, i0.85 mm per sec. hhis band width is employed simply for convenient reference. It represents approximately the energy interval between the + 112 to 112 transitions in ferrite and is expressed as the velocity needed to Doppler shift a 14.4kev 7 ray to the aforementioned ferrite energy levels. This energy band is referred to as "the central region of the Mossbauer atttern:: in this paper. Hence, due to the large number of lines from different phases in a multiphase steel falling in a relatively narrow energy band, absorption lines from the different phases may overlap. Analysis of available data, presented below, indicates that this occurs to a significant extent for phases which commonly occur in quenched and quenched and tempered high-carbon steels. One consequence of limited resolution in the Mdssbauer patterns from multiphase steels is difficulty in accurate determination of such line parameters as position, width, and intensity. In fact, it appears that quantitative analysis for retained austenite in quenched and tempered high-carbon steels is not practical with the present experimental method. Line resolution is influenced to some extent by sensitivity. We point out below that atom or volume fractions of less than about 3 to 5 pct are not detected by the present experimental method. Thus, the presence of a multiplicity of phases does not always lead to impaired resolution. Finally, we report in this paper room-temperature MGssbauer parameters determined for austenite in a freshly quenched, commercial 1 wt pct C steel and in a freshly quenched laboratory heat of an Fe-2 wt pct C alloy. These parameters are compared with others reported in the literature. Three types of hyperfine interactions are detectable in a Mossbauer effect measurement: isomer shift, quadrupole interaction, and magnetic dipole interaction. These interactions are evidenced by one, two, and six line patterns, respectively.'-4 More than one type of interaction has been reported in certain metallurgical phases thus far studied by this method. Isomer shift is the experimentally measured displacement of line position from some arbitrarily defined reference position. In the case of a multiline pattern, isomer shift is given by the displacement of the centroid (center of gravity) of that pattern from the reference position. All isomer shifts measured at finite temperatures contain a second-order Doppler effect characteristic of that temperature. The isomer shift is related to the total s electron density at the nucleus, becoming more negative with increasing s electron density. The first-order quadrupole effect arises from the interaction between the nuclear quadrupole moment and any axially symmetric electric field gradient in

Jan 1, 1969

By Arthur Notman

DESPITE the tremendous drop in the volume of domestic production of metals, their prices, and profits, the world as a whole has managed to produce and consume nearly as much as in 1937. Measured by production, 1937 was the record year for copper, lead, and zinc. The Copper Institute figures for 1938 (estimating December as equal to November) show that although apparent domestic consumption declined 309,422 tons, foreign consumption increased 133.035 tons. The total for 1938 was 1,971,790 tons compared with 2,148,177 tons for 1937. The domestic decline was 38.5 per cent, the foreign increase 9.9 per cent, and the total decline 8.2 per cent.

Jan 1, 1939

By R. W. Fountain, J. Chipman

THE solubility of nitrogen in iron and steel has been of considerable interest due to the role of nitrogen in strain-aging and in quench-aging. It is generally considered that quench-aging is the result of precipitation of carbide and nitride particles from supersaturated solid solution, while strain-aging results from the segregation of carbon and nitrogen atoms to dislocations.1-9 The rate of strain-aging is controlled primarily by the amount of carbon and nitrogen in solution and the temperature. In experiments on strain-aging of pure iron with only carbon or nitrogen as impurities, Fast" has shown that even after 40 hr at 50°C carbon did not give any strain-aging while

Jan 1, 1959

By T. D. Thomas

CONTENTS PAGE T. D. Thomas-Misfires in Anthracite Coal Mines 3 W. H. Forbes-Misfires in Bituminous Coal Mines 12 A. W. Worthington-Misfires in Non-metallic Mining (Limestone) 18 Misfires in Anthracite Coal Mines BY T. D. THOMAS,* LANSFORD, PA. (New York Meeting, February, 1929) IN THIS paper, major attention is given to misfires in mines where electric multiple shot-firing is the system used. Misfires are sometimes caused by one action or condition and at other times by a combination of two or more. They may be divided into two classes: (1) those caused by workers in the mines, (2) mechanical or manufacturer's causes. The second cause will be discussed first.

Jan 1, 1929

By H. Yoshida, B. G. Liebmann, R. E. Green

In recent years considerable work has been undertaken in order to gain an understanding of the mechanisms responsible for the generation of recrystal- lization textures in face-centered-cubic metals. Two theories have been proposed, that of oriented growth1 and that of oriented nucleation,' and several attempts have been made to check these theories directly by recrystallizing deformed single crystals.3-5 Two groups, Graham-Cahn and Liebmann-Liicke-Masing, studied the orientation of recrystallized grains and their rate of growth, both using strained aluminum single crystals of commercial purity (Graham et al., 99.6 pct, Liebmann et al., 99.8 pct). Surprisingly, the results obtained by the two groups were completely

Jan 1, 1960

By Zay Jeffries

IN this paper, it is proposed to outline a method for the determination of melting points of those metals and alloys having high fusion temperatures. The application of the method as used to determine the melting points of alloys of tungsten and molybdenum will be given. It will be seen from these results that tungsten and molybdenum form a completely FIG. 1.-PARTIAL SECTION OF APPARATUS USED TO DETERMINE MELTING POINTS OF TUNGSTEN AND MOLYBDENUM ALLOYS. isomorphous series. This is also verified by the accompanying photomicrographs. Tungsten and molybdenum have been found to crystallize in the salve system, namely, isometric, and the crystal units are cubes. These determinations were made by examining etching pits in the pure metals.

Jan 7, 1916

By N. A. Gokcen, R. A. Dodd

Solubility of nitrogen in liquid iron-manganese system at 1550°C and one atmosphere pressure has been determined by a simple method. Results show that the solubility increases from 0.040 pct for pure iron to 1.41 pct for pure manganese. DETERMINATION of the solubility of gases in volatile metals. and alloys by the well-known Sievertsl method is unreliable. This is particularly true for the Fe-Mn system since Mn vaporizes readily from the alloys containing as little as 2 pct Mn, and, upon condensing on the cooler parts of the apparatus, it absorbs large amounts of nitrogen. Further, the condensing Mn vapor interferes with the usual method of temperature measurements with an optical pyrometer.

Jan 1, 1962

By Oscar Johnson

WITH capacities of milling plants expanding from a few hundred tons per day to many thousand, replenishment of grinding media is an important phase of mill operation. Information on this aspect of milling procedure, solicited from several mining companies, is summarized here. At International Nickel's Copper Cliff concentrator the normally strenuous job of changing rods is considerably simplified by the use of the Garrow rod charging machine, Fig. 1. The overhead crane, Fig. 2, brings a bundle of rods, weighing four to a ton, to the loading platform of the machine, positioned in front of the mill. The rods roll one by one down the slight incline of the platform onto a conveyor which sends them into the mill.

Jan 6, 1954

By Carl Swartz

IN the course of a recent investigation1 to develop a more satisfactory white-metal. bearing alloy, a number of alloy systems were studied. The cadmium-nickel system showed characteristics desirable in a bearing alloy, and the system was therefore studied in some detail. EXPERIMENTAL METHOD Alloying cadmium with nickel offered no serious difficulty. After melting the cadmium, clean sheet nickel was added while the temperature was maintained at 500° to 600° C: A few crystals of ammonium chloride2 served to clean the nickel when the latter did not "wet" readily. In preparing the individual alloys for thermal and microscopic investigation, a "hardener" containing about 10 per cent nickel was used.

Jan 1, 1933

By John J. Sense

The Mission unit of the American Smelting and Refining Co., located 20 miles south of Tucson, Ariz., is a high-volume, 15,000 tpd operation which utilizes a relatively light equipment fleet. As such, management is very conscious of the mechanical and operational availability of the equipment in use. One of the key items in attaining this efficiency is a complete and reliable record of mechanical and operational machine availability which is an invaluable guide for: 1) Estimating future equipment and personnel requirements of an operating property. 2) Planning an expansion program of an operating property. 3) Estimating equipment and personnel requirements of a new property. 4) Selection of replacement equipment. 5) Comparison of separate operating properties.

Jan 3, 1964

By E. R. Borcherdt

IT is notable that the first large-scale mine operation equipped entirely with detachable bits was the Badger State mine of the Anaconda Copper Mining Co. in Butte, Montana, just 30 years ago. This mine in 1922 was producing approximately 1200 tons of ore per day. Much of the data presented in C. L. Berrien's article1 describing the development and installation of the Hawkesworth detachable drill bit were obtained from these operations. As in any pioneering effort, no precedent existed and many difficult problems required solution, so that the changeover to detachable bits at all Butte hill mines was not completed for 6 years. There was widespread disbelief as to the probable efficiency of the new installation.

Jan 2, 1953

By D. M. Given

HOW much can the mine operator afford to spend on his coal burning boiler plant? The usual answer is as little as possible and still get the job done. Thus, attention must be focused on the spot where excessive costs are most likely to arise - the materials handling end of the job. Boiler plants consuming less than 30,000 tons of coal annually can be controlled to the point where costs for handling coal and ashes are under $1.00 per ton. There is a wide selection of coal and ash-handling systems that can be used in smaller boiler plants to provide labor savings and convenience required if management is to accept coal as fuel.

Jan 7, 1953

By Reed S. C. Rogers, Robin P. Gardner, Kuruvilla Verghese

The development and use of short-lived radioactive tracer methods for the onstream determination of residence time distributions in large-scale ball mills is described. Tests are reported on a pilot-plant ball mill with 0.43 m diameter and 0.86 m length and on an industrial mill with 1.83 m diameter and 2.74 m length. Tests with different tracer feed sizes indicate that the residence time distributions on both mills are independent of charge particle size. Similar tests are planned for a large ball mill of 4.57 m diameter and 9.30 m length. No safety problems were encountered in these tests and none are anticipated in tests of the larger mill.

Jan 1, 1981

By Charles Fulton

The study of the condensation of zinc from its vapor was undertaken to shed light on certain problems encountered in large-scale electric zinc-furnace work recently conducted. It is a matter of common knowledge that one of the disadvantages of the arc type, electric zinc furnace, is the production of a large amount of blue powder and proportionately little liquid spelter, for, as stated by Stansfield,1 "A notable defect in the electric smelting of zinc ores is the difficulty experienced in obtaining the distilled zinc in the liquid state; when zinc ores are smelted electrically, very little liquid metal is commonly obtained, nearly all of the zinc being in the state of powder."

Jan 8, 1918