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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 R. M. Waterstrat, E. C. van Reuth

BINARY- alloy phases having the A15-type crystal structure have been described as occurring at a simple and more or less invariant stoichiometric composition (A3B) which corresponds to the relative number of atoms occupying each of the two crystallographi lattice sites in this structure.1,2 It is frequently assumed, therefore, that each crystallographic site is occupied exclusively by one kind of atom. In most cases, however, there have been insufficient experimental data to establish whether atomic ordering is, in fact, complete. Recent studies have shown that binary A15-type phases are sometimes stable over an appreciable composition range3''* and, occasionally, the composition range of stability does not even include the "ideal" A3B stoichiometric composition.5-7 We have observed the existence of nonstoichiometric A15-type phases in the binary systems Cr-Pt and Cr-Os. This has not been reported in previous work on these alloy systems.1,8-11 A series of alloys, each weighing approximately 30 g, was prepared by are-melting in an Ar-He atmosphere using 99.999 pct Cr, 99.999 pct Os, and 99.99 pct Pt as starting materials. Each alloy was melted four times with a total weight loss of less than 1 pct. The stoichiometric (A3B) alloys were sealed in evacuated quartz tubes and annealed at 1200°C for periods of time ranging from 3 days to 2 months. Examination of the alloy microstructures revealed that little change had occurred over this time interval and it was therefore assumed that the microstructures were fairly representative of equilibrium conditions. No evidence of contamination was observed although there was apparently some loss of chromium which was confined to a thin layer at the surface of the specimens. The quartz tubes were quenched from the annealing temperature into cold water. X-ray diffraction and metallographic examination of the stoichiometric alloys revealed an estimated 10 to 30 pct of second phases which were tentatively identified as phases previously reported in these binary-alloy systems.8-11 A second series of alloys was prepared by mixing -325 mesh metal powders having a nominal purity of 99.9 pct and compressing these mixed powders in a cylindrical die at a pressure of 43,000 psi. These alloys, each weighing 15 g, and some of the arc-melted alloys were annealed in a high-temperature vacuum furnace heated by tantalum strips at a pressure of 10-8 Torr and were rapidly cooled by turning off the furnace power. X-ray and metallographic examination of both series of alloys served to establish the composition ranges of the A15-type phases. Although some chromium losses occurred during the vacuum annealing, they were largely confined to a thin layer on the outer surfaces of the samples. It was established that the A15 phases occur in the Cr-Pt system at 21 ± 1 at. pct Pt after 1 week at 1200°C and in the Cr-Os system at 28 ± 1 at. pctOs after 1 day at 1400°C (see Table I). We also observed that an arc-melted stoichiometric (A3B) alloy in the Cr-Ir system was single-phase (A15-type) in the "as-cast" condition in agreement with previous work.8,13 In addition we obtained a sample of the Cr-Os A15-type phase from Argonne National Laboratory. This alloy contained less than 1 pct second phase12 and was submitted to a density measurement. The density measurement yielded a value of 11.14 g per cu cm in comparison to a theoretical value of 11.25 g per cu cm calculated using the observed lattice constant (4.6806Å) of this alloy. The uncertainty in measurement was 0.1 pct but the sample may have contained some cracks or minor imperfections which could account for the low experimental value. We have also studied the atomic ordering in these phases by means of integrated line intensity measurements using thick, flat, rotating powder samples and CuK a radiation in an X-ray diffractometer. We have obtained order parameters of 0.90 for the Cr-Pt phase, 0.89 for the Cr-Ir phase, and 0.64 for the Cr-Os phase using the formula: where s is the usual Bragg and Williams order parameter, ra is the fraction of chromium atoms in A sites, and FA is the fraction of chromium atoms in the alloy. The values obtained are estimated to be accurate within ±4 pct. If the unusually small value for the order parameter of the Cr-Os A15 phase were due to the existence of lattice vacancies on the "B-atom" sites, then a density of 10.04 g per cu cm would be expected in contrast to the observed value of 11.14 g per cu cm. We, therefore. conclude that the fraction of lattice vacan-

Jan 1, 1967

By Richard J. Fruehan

ThE thermodynamic activities of nickel and chromium in liquid Ni-Cr alloys have not been previously reported. There have been several investigations on the solid alloys.1-3 In the present investigation the activity of chromium in liquid Ni-Cr alloys at 1600° C was determined by the use of the following galvanic cell, The use of galvanic cells employing solid oxide electrolytes for determining the activity of metals in solid alloys was first demonstrated by Rapp and Maak4 on Cu-Ni alloys between 700° and 1000°C. Recently Schwerdtfeger5 tested the performance of the ZrO2(CaO) electrolyte at 1600°C and found it satisfactory for oxygen pressures as low as 10"12 atm. He also demonstrated the use of solid oxide electrolytes for determining the activities in liquid metal systems in measuring the activity of manganese in Fe-Mn alloys at 1500°C. Extensive investigations have been carried out in this laboratory, exploring the oxygen partial pressure lower limit at which ZrO2(CaO) electrolyte can be used satisfactorily in oxygen galvanic cells at 1600°C. In a paper to be published at a later date,9 it is demonstrated conclusively that ZrO2(CaO) exhibits insignificant electronic conductivity at oxygen pressures down to about 3 x 10"13 atm which is lower than the oxygen partial pressure in equilibrium with Cr-Cr2O3 at 1600°C. Therefore, the activity of chromium can be related to the measured reversible electromotive force of the cell in the present investigation since no electronic short circulating will occur. Fig. 1 is a schematic diagram of the cell used. The Cr-Cr2O3 electrode was made of equal weights of chromium and Cr2O3 powders which were mixed and packed into a recrystallized alumina crucible. A Pt-wire lead was embedded into the Cr-Cr2O3 compact to insure good contact. A ZrO2(CaO) crucible, supplied by the Zirconium Corp. of America, contained the Ni-Cr melt equilibrated with solid Cr2O3. The ZrO2(CaO) crucible was placed on the Cr-Cr2O3 electrode and additional Cr-Cr2O3 mixture was packed around it. Contact with the Ni-Cr alloy was made with a Cr2O3 tube, which is a weak electronic conductor. A platinum wire lead was attached to the Cr2O3 tube. The galvanic cell was lowered slowly into the hot zone of the furnace tube in order to avoid too large a thermal shock which could break the ZrO2 (CaO) crucible. The furnace was con- tinuously flushed with purified argon during the experiment. The temperature was measured with a Pt-Pt/10 pet Rh thermocouple and maintained at 1600° ± 5°C. The electromotive force was measured with a recording potentiometer. The furnace was turned off when measurements were being made in order to avoid induction effects and the reversibility of the cell was demonstrated in the usual manner. The electromotive force was measured several times over a period of approximately 1 hr. During that period the electromotive force remained constant within ± 3 pet and did not continuously drift in any one direction. After the experiment the alloys were analyzed for chromium in the usual manner. The measured electromotive forces of the cell at 1600°C, (2912°F), are listed in Table I. The activity of chromium, with solid pure chromium as the reference state, (a), was calculated using Eq. [l], , n F E I, n lna RT- U] where E is the measured electromotive force, F is the Faraday constant, and n is equal to 3, the number of equivalents per mole, (nF/RT = 18.59 volts'1 at 1600°C). The resulting activities are listed in Table I. The activity of chromium relative to pure liquid chromium was also calculated. The free energy of fusion of chromium at 1600° C was calculated using

Jan 1, 1969

By Axel Sahlin

Jan 1, 1898

By J. M. McKenzie

p-n junctions to detect and measure the energy of single quanta of electromagnetic radiation are described. Useful energy range is from 1 kev to several Meu. Achieved energy resolution varies from 30 pct at 6 keu to 0.12 pct at 2 Mev. Parameters affecting the perfornzance of the present detectors and desired of a new material are discussed. DURING the last 6 years semiconductor detectors have been used extensively to detect and to measure the energy of charged particles. These detectors are made from reverse-biased p-n junctions. Electron-hole pairs are created in the depletion region of the junction, Fig. 1. The carriers are separated by the electric field and give rise to a pulse of current in the external circuit. This current pulse is proportional to the number of carriers and hence to the energy deposited in the depletion region by the ionizing event. More recently the discovery of the lithium drift process, first in silicon' and then in germanium,2 has extended the use of semiconductor detectors to the detection and the energy measurement of single quanta of electromagnetic radiation. These detectors now have a useful measurement range extending from the soft X-ray region, about 6 kev, to the hard y ray region of several Mev. Surface-contoured avalanche diodes can be used to extend this range down to 1 kev. There is however a desire for other materials suited to higher operating temperatures, and particularly for those materials with high y ray stopping power. The most important advantage of the semiconductor detector over gaseous and scintillation detectors is the average energy, E, required to form an electron-hole pair. Fig. 2 shows the quantum efficiency for germanium as a function of photon energy.3 At the band-gap energy, 0.7 ev, an electron-hole pair is generated by the absorption of the photon and the quantum efficiency is unity. The quantum efficiency remains constant at unity between 0.7 and 3 ev. It then increases as additional electron-hole pairs are formed by secondary ionization of the initial photoelectron. The rate of increase is about 1 electron-hole pair per 3 ev (actually 2.9 ev for germanium and 3.6 ev for silicon). This figure is constant irrespective of the particle type (electron, proton, a particle, heavy ion) and energy. In an ionizing event an incident particle of energy E will create N = E/e ion pairs. The statistical fluctuation in this number is proportional to &. The fractional energy resolution is therefore proportional

Jan 1, 1968

By M. O. Abo-el Fotoh, J. B. Mitchell, J. E. Dorn

The effect of strain rate and temperature on the tensile flow stress of a polycrystalline bcc alloy of magnesium containing 14 wt pct Li and 1.5 wt pct Al was investigated for strain rates of 3.13 x lom5 to 3.13 x 10-3 per sec over the range from 20° to 300°K. From about 180° to 300°K the alloy exhibited an ather-ma1 deformation behavior where the flow stress was independent of strain rate and increased only slightly with decreasing temperature. At lower temperatures the flow stress was strongly strain-rate- and temperature-dependent, characteristic of deformations controlled by thermally activated mechmzisms. The activation volume for thermally activated plastic defornzation was between 5 and 30 cu Burgers vectors, independent of plastic strain. This low-temperature thermally activated deformation behavior was found lo be in satisfactory agreement with the theoretical dictates of the Dorn-Rajnak1 formulation of the Peierls mechanism where deformation is controlled by the rate of nucleation of pairs of dislocation kinks over the Peierls energy barriers. SEVERAL studies of the low-temperature thermally activated deformation of bcc metals and alloys (molybdenum,1 tantalum,1 Fe-2 pct Mn,2 Fe-11 pct MO,3 and AgMg4) have revealed that the strain rate is controlled by the activation of dislocations over the Peierls-Nabarro energy hills. Although there is some uncertainty as to the nature and effect of solute atom-dislocation interactions during low-temperature deformation of bcc metals, it has been concluded by Dorn and Rajnak,1 Conrad,1 and Christian and Masters6 among others that overcoming the Peierls-Nabarro stress which arises from the variations in bond energies of atoms in the dislocation core as it is displaced is the probable mechanism controlling low-temperature deformation. The purpose of this research was to investigate the low-temperature plastic deformation of the bcc alloy Mg-14 wt pct Li-1.5 wt pct A1 to determine if the behavior of this alkali metal alloy might be analogous to that for other bcc metals. This alloy was selected because of its availability and its current industrial importance as a lightweight material for aircraft and aerospace applications. I) EXPERIMENTAL PROCEDURE Polycrystalline tensile specimens having cylindrical gage sections 2 in. long by 0.2 in. in diam were machined from as-received alloy sheet stock of Mg-14 wt pct Li-1.5 wt pct Al. Specimens were annealed in an argon atmosphere at 423°K for 4 hr and maintained in a kerosene bath together with the sheet stock to prevent corrosion. The resulting specimen microstructure consisted of a coarse uniform dispersion of incoherent precipitate MgLi2Al particles7 in a bcc 0 phase matrix having an average grain size of 150 p. Prior to testing the specimens were chemically polished in dilute hydrochloric acid. Comparison of tensile properties and microstructures of specimens cut from center and edge sections of the sheet stock revealed no effects of inhomogeneities in the sheet material. Tensile tests were performed on an Instron machine at crosshead speeds corresponding to tensile strain rates of 1.56 x 10-5 and 1.56 x 10"3 per sec. Stresses were determined to ±2 x 106 dynes per sq cm and strains to within ±0.0001. Average values of shear stress t and shear strain y reported were taken as one half the tensile stress and three halves the tensile strain, respectively. Flow stresses were taken at 0.05 pct strain offset. Test temperatures down to 77°K were obtained by immersing the specimens in constant-temperature baths. Lower-temperature tests were performed in a liquid helium cryostat to within ±2°K of the reported values. Prior to testing at the various temperatures and strain rates all specimens were prestrained at 2 35°K at a shear strain rate of 3.13 x 10-5 per sec to a stress level of 0.606 x 10' dynes per sq cm to obtain a uniform initial state. Additional tests were made to determine the effect of changes in strain rate and strain on the flow stress by rapidly changing the crosshead motion during testing. Shear moduli of elasticity, needed for analyses of the data, were obtained at several temperatures by a common technique of determining the resonant frequencies of vibrations of rectangular test specimens. 11) EXPERIMENTAL RESULTS Fig. 1 shows the experimentally determined flow stress vs temperature for two strain rates. Two distinct regions of behavior are evident. Below about 180°K the strong increase in flow stress with increased strain rate and decreasing temperature indicates that deformation is controlled by a thermally activated dislocation mechanism. At higher temperatures an athermal region is evident where the flow stress is independent of strain rate and only slightly dependent on temperature. The applied stress t to cause plastic flow was separated into two components:

Jan 1, 1969

By H. L. Marcus, P. W. Palmberg

As can be seen from the phase diagram A1-W1 the equilibrium solubility of tungsten in aluminum is practically nil at room temperature. By quenching from the liquid state (50,000°C per sec), Varic, Burov, and Kolesnicenko2 obtained A1-W solid solutions up to 0.15 at. pct W. The quenched alloys were in the form of foils, 0.2 to 0.3 mm thick. Considering the results of Duwez and Willens,3 it is obvious that this thickness, which makes impossible a sufficiently rapid quenching, was the main reason for the relatively low content of tungsten dissolved in aluminum found by Varic.2 he present note shows that the metastable solubility of tungsten in aluminum can be appreciably extended in aluminum-rich A1-W alloys. The quenching technique and the procedure employed for the preparation of the alloys have been described previously.475 The resulting quenched flakes varied in thickness from 1 to 20 µm from experiment to experiment. However, the measurements of the lattice parameters were carried out only with flakes thinner than 5 µm. The areas of quenched flakes were between 0.1 and 15 mm2. The quenched flakes were placed into a 0.3-mm glass capillary tube which was then mounted in a 114.6-mm-diam Debye-Scherrer camera. Straumanis asymmetric film position and nickel-filtered CuKa radiation were used. The lattice spacings were computed taking X(CuKa1) = 1.54050A for resolved and ?(CuKa) = 1.54178A for unresolved doublets. All specimens were rotated at room temperature, 26" +2°C. The lattice parameters were estimated from extrapolation against the Nelson-Riley function. It was estimated that the error in the lattice parameter of the measurements on a single film lies within +0.0004A for lower and about +0.001A for higher concentrations of tungsten. The lattice parameters of the metastable solid solutions A1-W are plotted vs the concentration of tungsten in Fig. 1 together with the parameters measured by previous investigators.' Each point of the present measurements represents a determination of the lattice spacing on different quenched flakes, for a given concentration of tungsten. With experimental accuracy, the lattice parameters of the metastable solid solutions fall on the straight line passing through the already known data.' As estimated from the uncertainties in the lattice spacings of the solid solutions, the alloys were homogeneous within 0.1 at. pct W. The solubility of tungsten in aluminum-rich A1-W solid solutions obtained by a very rapid quenching technique is increased to about 0.95 at. pct W. This value is 6 times greater than the amount known up to now. -he lattice parameters of the resultant aluminum solid solutions with higher concentrations of tungsten than 0.95 at. pct W did not remain constant AUGER electron spectroscopy has been used to clarify the role of impurities in the embrittlement of AISI 3340 steel. Analysis of fracture surfaces has shown that the embrittled condition is correlated with appreciable antimony segregation at grain boundaries. The low temperature (400" to 600°C) temper embrittlement of low alloy steels containing various combinations of Cr, Ni, Sb, Mn, P, Sn, and As has been examined extensively for many years. General reviews of the area have been made by McMahon1 in 1968, LOW' in 1959, woodfine3 in 1953, and Holloman4 in 1946. Recent work by Low, Stein, Turkalo, and LaForce5 has done much in separating the alloy and

Jan 1, 1970

By Louis B. Slichter

Prospecting is certainly the world's biggest and best gambling business. It is a game where the chips cost many thousands and where many millions, even billions, can be won. An attractive feature of this gamble is the fact that the players are free to rig the odds as favorably as possible. Only the limited bounty of nature, the restrictions of the laws of the land, the competition from other players, the limited sagacity of the player himself- only these, and other factors, restrict the possibilities for large winnings. Today probably about half the land surface of the earth remains to be searched for signs of ore visible at the surface. It is fortunate that so much land still remains for exploration by relatively economical methods. Looking to the future, it is a good guess that the costs of finding ore will increase in response to increasing technical difficulties. To continue to achieve profits from prospecting, it will become necessary to analyze the business more skillfully, in a more and more sophisticated manner. Whenever feasible, qualitative concepts must be replaced by their quantitative equivalents, improvements, and extensions.

Jan 6, 1960

By A. Tonejc, A. Bonefacic

As can be seen from the phase diagram A1-W1 the equilibrium solubility of tungsten in aluminum is practically nil at room temperature. By quenching from the liquid state (50,000°C per sec), Varic, Burov, and Kolesnicenko2 obtained A1-W solid solutions up to 0.15 at. pct W. The quenched alloys were in the form of foils, 0.2 to 0.3 mm thick. Considering the results of Duwez and Willens,3 it is obvious that this thickness, which makes impossible a sufficiently rapid quenching, was the main reason for the relatively low content of tungsten dissolved in aluminum found by varic.2 he present note shows that the metastable solubility of tungsten in aluminum can be appreciably extended in aluminum-rich A1-W alloys. The quenching technique and the procedure employed for the preparation of the alloys have been described previously.475 The resulting quenched flakes varied in thickness from 1 to 20 µm from experiment to experiment. However, the measurements of the lattice parameters were carried out only with flakes thinner than 5 µm. The areas of quenched flakes were between 0.1 and 15 mm2. The quenched flakes were placed into a 0.3-mm glass capillary tube which was then mounted in a 114.6-mm-diam Debye-Scherrer camera. Straumanis asymmetric film position and nickel-filtered CuKa radiation were used. The lattice spacings were computed taking X(CuKa1) = 1.54050A for resolved and ?(CuKa) = 1.54178A for unresolved doublets. All specimens were rotated at room temperature, 26o +2°C. The lattice parameters were estimated from extrapolation against the Nelson-Riley function. It was estimated that the error in the lattice parameter of the measurements on a single film lies within +0.0004A for lower and about +0.001A for higher concentrations of tungsten. The lattice parameters of the metastable solid solutions A1-W are plotted vs the concentration of tungsten in Fig. 1 together with the parameters measured by previous investigators.' Each point of the present measurements represents a determination of the lattice spacing on different quenched flakes, for a given concentration of tungsten. With experimental accuracy, the lattice parameters of the metastable solid solutions fall on the straight line passing through the already known data.' As estimated from the uncertainties in the lattice spacings of the solid solutions, the alloys were homogeneous within 0.1 at. pct W. The solubility of tungsten in aluminum-rich A1-W solid solutions obtained by a very rapid quenching technique is increased to about 0.95 at. pct W. This value is 6 times greater than the amount known up to now. -he lattice parameters of the resultant aluminum solid solutions with higher concentrations of tungsten than 0.95 at. pct W did not remain constant AUGER electron spectroscopy has been used to clarify the role of impurities in the embrittlement of AISI 3340 steel. Analysis of fracture surfaces has shown that the embrittled condition is correlated with appreciable antimony segregation at grain boundaries. The low temperature (400" to 600°C) temper embrittlement of low alloy steels containing various combinations of Cr , Ni , Sb , Mn , P , Sn , and As has been examined extensively for many years. General reviews of the area have been made by McMahon1 in 1968, LOW' in 1959, woodfine3 in 1953, and Holloman4 in 1946. Recent work by Low, Stein, Turkalo, and LaForce5 has done much in separating the alloy and

Jan 1, 1970

By C. E. Birchenall, H. M. Schadel, G. Derge

EXISTING distribution data' for silicon between liquid iron and silver at steelmaking temperatures, 1500" to 1600°C, has made activity relationships in liquid silver-silicon alloys desirable as a method of determining the silicon activity in molten iron. To this end, through the use of radioactive Ag110 and the molecular beam technique described in a previous paper,' the vapor pressure of silver as a function of temperature has been measured over three silver-silicon alloys containing 3.9, 9.3, and 15.4 atomic pct (eutectic composition) silicon. The technique was that described for pure silver with the exception that a porcelain liner was used inside

Jan 1, 1951

By F. Habashi

Conclusive evidence is given showing that the dissolution of gold in cyanide solution follows mainly the over-all equation A similar equation can also be written for the dissolution of silver. Theoretical derivation of the velocity equation for this reaction has been obtained, which describes quantitatively the experimental facts. The equation is as follows: where [CN-] and [O2] = the concentrations (in moles/ml) of cyanide and dissolved oxygen, respectively. DcN- and Do2 = the diffusion coefficients of cyanide and dissolved oxygen; 1.83 x 10-5 and 2.76 x 10-5 cm2 sec-1, respectively. A = the surface area of the metal in contact with the aqueous phase, in cm S = the thickness of the boundary layer; varies between 2 and 9 x 10-3 cm, depending on the speed and method of agitation. Rate being expressed in g. equiv. sec-1. INTRODUCTION During recent years a number of papers have been published on the kinetics of dissolution of gold and silver in cyanide solution.1,6 The authors agree that the rate of dissolution is diffusion-controlled, but disagree regarding the mechanism of the reaction. Some authors'-3 support the Bodlander equations: The apparently conflicting results, when critically reviewed, are concordant and lead to the conclusion that the proper equation for the dissolution reaction should be only Eq. 1. This conclusion is based on the following facts: 1) For every 2.2 equivalents of metal dissolved one mole O2 was consumed. 2) For every 1 equivalent of metal dissolved, 2 moles of cyanide were consumed.' 3) Hydrogen peroxide is formed during the dissolution of gold or silver, and for every 2.2 equivalents of metal dissolved, one mole H2O2 was produced.1,2 The fact that Kudryk and Kellogg4 did not detect H2O2 during the dissolution of gold should not throw doubt on the many affirmative reports of other investigators. Lund2 has shown that depending on the crystalline nature of the silver surface, (e.g. method of etching the sample) H2O2 may undergo catalytic decomposition heterogeneously according to: Further Kudryk and Kellogg4 carried out their experiments in the presence of 0.5% KC1 to achieve a greater electrolytic conductivity, and Matsudaira7 has shown that H2O2 is catalytically decomposed (homogeneously) in the presence of C1- ion in alkaline solution. 4) Experiments carried out by Boonstra8 and Lund2 showed that the dissolution of gold and silver respectively in KCN + H2O2 in the absence of oxygen was a slow process. Thus the reaction takes place to a minor extent only. Further kinetic studies showed that: 1) The rate of dissolution depends on the surface area of the metal in contact with the liquid phase, thus indicating that the process of dissolution is a heterogeneous process. 2) The rate of dissolution depends on the speed of stirring,5,6 thus indicating that the process is controlled by a physical phenomenon.

Jan 1, 1967

By W. Mostowitsh

I. Introductory LEAD sulphate occurs as anglesite, and is formed in every roasting of lead sulphides or sulpho-salts containing lead. In smelting in the blast furnace an ore containing natural or artificial lead sulphate, a large part of the sulphur present goes to the formation of the intermediary product matte which requires further treatment for the recovery of the values it contains. It is therefore of importance to study the behavior of lead sulphate at elevated temperatures, both without and with reducing agents, especially as the information available gives data which are more or less conflicting. II. Decomposition of Lead Sulphate by Heat The dissociation of PbSO4 into PbO and S03 or S02 and 0 has been discussed by many metallurgists. The following data are considered to be representative. Doeltz and Graumann1 found that PbSO4 was not affected by heat at 800° C.; that dissociation began at 900° C., and was rapid at 1,000° when the salt lost in 1 ½ hr. 14.3 per cent. of its weight, the dry salt containing 26.43 per cent. SO3. Hofman and Wanjukow2 summarize their work upon the dissociation of metallic sulphates with the statement that the decomposition of PbSO4 begins at 195° C., but progresses very slowly, with the formation of the basic salt 6PbO.5S03 at 705°; that this salt undergoes a transformation at 847°, begins to be decomposed at 888°, to sinter at 896°, and to fuse at 910°; rapid dissociation begins at 952°, and is accompanied by volatilization of PbO; retardations at 958° and 962° indicate an acceleration of decomposition which, however, is not complete. Proske3 found that PbSO4 gave off at 900° C. in 30 min. only 0.63 per cent. of its SO3, and that the loss increased with

Jan 5, 1916

By Frederick O?Neil

SCOPE OF THIS REPORT THE object of this paper is to describe the present status and possibilities of liquid oxygen as an explosive based upon the investigations, research and practical work of the Ingersoll-Rand Co., and of the Air Reduction Co., from early in 1922 to date. The following work was done. 1. A study of the history and physical theory of L. 0. X. as an explosive. (No attempt will be made in this paper to give the history or theory, as this has already been covered by the literature on the subject.) 2. An investigation of the use and the practice with L. 0. X. in the iron mines of Lorraine where L. 0. X. has its largest application in Europe. Although L. 0. X. is extensively employed in the; iron mines of Lorraine, many of the mines using it exclusively, and blasting with it a total of approximately three million tons of iron ore per year, the fact that the mining practice in Lorraine1 is to drill comparatively shallow holes and blast only a few holes at a time, renders the data obtained there of very little value in estimating the possibility of replacing dynamite with L. 0. X. in American mining methods. In fact, in the iron mines in Lorraine, L. 0. X. replaced black powder, or its equivalent. 3. Laboratory research work on properties of absorbent materials. 4. Work in the Bureau of Mines explosive laboratory at Pittsburgh, Pa., on the properties of L. 0. X. cartridges. 5. Practical work underground with L. 0. X. cartridges in the Witherbee-Sherman iron mines at Mineville, N. Y. 6. Practical work in the quarries of the Calcite Quarry Co., Myers-town, Pa. 7. Practical blasting in several quarries and open-pit mines.

Jan 2, 1926

By Henry Rawdon

THE following note describing the behavior of copper under rather unusual conditions is offered here for its suggestiveness rather than as a complete study of the question. The examinations described were made because of a request for information concerning the embrittlement of copper when heated in a molten salt bath (sodium chloride) for the purpose of cleaning it, as well as for softening it. It is well known that metals may be rendered very brittle by electrolytic action, in aqueous solutions, in all probability by the action of nascent hydrogen, and it was suspected that perhaps the embrittlement of the copper by means of the molten salt was produced in a somewhat similar manner. It was found that the copper was in contact with iron (or steel) while immersed in the molten salt, through the occasional use of an iron stirring rod, iron forceps for handling the pieces, and an iron pot for containing the fused salt. In the electrochemical potential series iron and copper stand some distance apart, copper being electronegative to the iron. Assuming that the two metals bear a similar relation to each other, when immersed in a bath of molten salt, as they do in an aqueous solution, they would be expected to form a galvanic couple, the copper being the cathode. By this means the copper might be embrittled, as often happens in aqueous solutions, by the action of the liberated hydrogen. In this case, however, the embrittlement must be attributed to some other agent than hydrogen. To demonstrate how copper may be embrittled under these conditions, two small rods, one of copper and the other of mild steel, approximately 3/8 in. (9.5 mm.) in diameter, were immersed in a bath of sodium chloride that had been heated somewhat above its fusion point (melting point of sodium chloride is 819° C.) and an electromotive force of approximately 6 volts from a storage battery was impressed upon the system. The copper was made the cathode and the action was continued for

Jan 2, 1920

By David R. Mitchell, Ernest M. Spokes

There is evidence that study of minerals now considered to have susceptibilities too low for magnetic separation should be continued. Present concepts may be false. INFORMATION on magnetic properties of minerals other than magnetite is scanty and sometimes erroneous. Often there is no information at all. W. R. Crane's table of tractive forces published in 1901 is still the best guide in the field, but Crane's data can be used as a guide only, since he ignored such important factors as impurities in the minerals, size, and packing effect. During the 1930's work by the U. S. Bureau of Mines added greatly to knowledge of the behavior of certain minerals in a magnetic field. The USBM bulletin gave for the first time complete magnetic characteristics for magnetite and fragmentary data for a few other minerals. The work reported here covers a study of the magnetic-susceptibility relationships of the wolframite series of minerals and sphalerites as related to their chemical compositions. Theories are proposed to explain divergences found from commonly accepted beliefs. Gouy Method for Determining Magnetic Susceptibility: The Gouy principle has been adequately described in the literature1-3 and applied in various ways.'- It may be summarized by stating that a body of material (gas, liquid, solid, or powder mixed with gas or liquid) of cylindrical shape changes in apparent weight if suspended with one end in a zone of higher magnetic field strength than is found in that portion of the field surrounding the other end of the cylinder. This may be expressed as K2 - K1 A (H2 - H2) - mg. [1] In determining the susceptibility of mineral specimens by the Gouy method, the mineral is reduced to a fine powder and packed in a glass weighing tube. Precise measurement of the bore and depth of the tube is made unnecessary by a calibration procedure. Using the basic expression of Eq. 1, Hoare"

Jan 1, 1959

By D. B. Williams

For the first time in the history of the Venezuelan petroleum industry production exceeded 200 million barrels. The total production for all fields amounted to 205,430,869 bbl., which is more than 9 per cent of the world's 1939 total. This is an increase of over 15 million barrels or 8.0 per cent above the 1938 figure, which, compared with the slightly less than 2 per cent increase of the 1938 figure over 1937, shows the marked activity in Venezuela during the past year. The Maracaibo Lake fields are still the predominating factor in Venezuelan production, showing an increase of approximately 9½ million barrels over last year's figure and accounting for 71.8 per cent of Venezuela's total. Lagunillas continues to hold precedence as a single field, having yielded 47.1 per cent of the accumulative total and 39.4 per cent of 1939's total. This field showed an increase of slightly more than 3½ million barrels over 1938. Tia Juana, the second largest field, attained a record production, increasing its percentage of the Venezuelan total from 23.4 in 1938 to 23.7 in 1939. The La Rosa field, which includes Punta Benitez and Ambrosio, declined from 13.7 to 12.0 per cent; Bachaquero, the southernmost Lake field, which came into regular production at the end of 1938, contributed over 31/3 million barrels. Quiriquire, in eastern Venezuela, ousted La Rosa as the third largest producing field, and, although production increased by 11/3 milliorl barrels, percentage of the total declined from 13.2 to 12.9. Mene Grande, the oldest field, declined from 6.6 per cent in 1938 to 5.9 in 1939. Tem-blador produced for a whole year for the first time and yielded 3,647,867 bbl. The Colon district, in the Maracaibo Lake area, comprising the Tarra-Los Manueles fields, showed slight increases, as also did Cumarebo and Pedernales. Construction of the 16-in. pipe line from Oficina to Puerto La Cruz (Guanta), the longest line of this size in the world, was completed toward the end of the year and this new field in eastern Venezuela started shipping oil in December. This field is operated by the Mene Grande Oil Co. and was credited with a production of 2,347,625 bbl. in 1939. Jusepin field, some 25 miles southwest of Quiriquire in eastern Venezuela,

Jan 1, 1940

By D. B. Williams

For the first time in the history of the Venezuelan petroleum industry production exceeded 200 million barrels. The total production for all fields amounted to 205,430,869 bbl., which is more than 9 per cent of the world's 1939 total. This is an increase of over 15 million barrels or 8.0 per cent above the 1938 figure, which, compared with the slightly less than 2 per cent increase of the 1938 figure over 1937, shows the marked activity in Venezuela during the past year. The Maracaibo Lake fields are still the predominating factor in Venezuelan production, showing an increase of approximately 9½ million barrels over last year's figure and accounting for 71.8 per cent of Venezuela's total. Lagunillas continues to hold precedence as a single field, having yielded 47.1 per cent of the accumulative total and 39.4 per cent of 1939's total. This field showed an increase of slightly more than 3½ million barrels over 1938. Tia Juana, the second largest field, attained a record production, increasing its percentage of the Venezuelan total from 23.4 in 1938 to 23.7 in 1939. The La Rosa field, which includes Punta Benitez and Ambrosio, declined from 13.7 to 12.0 per cent; Bachaquero, the southernmost Lake field, which came into regular production at the end of 1938, contributed over 31/3 million barrels. Quiriquire, in eastern Venezuela, ousted La Rosa as the third largest producing field, and, although production increased by 11/3 milliorl barrels, percentage of the total declined from 13.2 to 12.9. Mene Grande, the oldest field, declined from 6.6 per cent in 1938 to 5.9 in 1939. Tem-blador produced for a whole year for the first time and yielded 3,647,867 bbl. The Colon district, in the Maracaibo Lake area, comprising the Tarra-Los Manueles fields, showed slight increases, as also did Cumarebo and Pedernales. Construction of the 16-in. pipe line from Oficina to Puerto La Cruz (Guanta), the longest line of this size in the world, was completed toward the end of the year and this new field in eastern Venezuela started shipping oil in December. This field is operated by the Mene Grande Oil Co. and was credited with a production of 2,347,625 bbl. in 1939. Jusepin field, some 25 miles southwest of Quiriquire in eastern Venezuela,

Jan 1, 1940

By H. W. Schull

The Alligator Ridge gold deposits are located in northwest White Pine County at the southwest end of Alligator Ridge. Alligator Ridge is on the west side of Long Valley in the range of hills that separates Long and Newark valleys. The nearest population center is Ely, about 113 km (70 miles) to the southeast. Access to the Alligator Ridge gold mine from Ely is via US Highway 50 and the Long Valley Ruby Marsh Road. The latitude and longitude is approximately 39° 45' north and 116° 30' west. The Alligator Ridge gold deposits occur in the lower 61 m (200 ft) of the Mississippian-Devonian Pilot Shale formation, a laminated calcareous carbonaceous siltstone. The gold deposits contain carbonaceous, oxide, and jasperoid type gold ore. For more details on the geologic features of the deposits, see Schull, Sutherland, and Ilchik (in press). The discovery story of Alligator Ridge began in the spring of 1976 when the areas mapped as jasperoid on the 1:250,000 scale geologic map of White Pine County (Hose and Blake, 1976) were examined and sampled. Seventeen samples, about 23 kg (50 lb), were collected from an area about 0.65 km2 (0.25 sq mile). Of these 17 samples 10 reported atomic absorption values of less than 0. 1 ppm Au and 7 reported values in the 0.1 to 1.0 ppm Au range. In June of 1976 20 lode claims were staked to claim the area of the rock chip sampling. The claims' end and side center lines were used as a grid for soil sampling. Sample stations were 91 m (300 ft) apart and sample lines were 229 m (750 ft) apart. The samples were sieved to - 180 µm (- 80 mesh). Out of 99 soil samples, seven samples reported Au values in the 0.1 to 1.0 ppm range. Of the seven auriferous samples, five were located over the jasperoid outcrops previously sampled; one over unmineralized Pilot Shale a few hundred m (ft) downslope from some Au-bearing jasperoid; and one from a 15 x 15 m (50 x 50 ft) talus outcrop area of hitherto unnoticed mineralized Pilot Shale. Subsequent sampling, mapping and drilling would show that this 15 X 15 m (50 x 50 ft) outcrop area was the top of the Vantage 1 ore body, about 1.27 Mt (1,400,000 st) of over 3 g/0.9 t (0.11 oz/st) Au. Late in the summer of 1976 about 30 more 1.4 to 2.2 kg (3 to 5 lb) rock chip samples were collected in the course of preliminary geologic mapping. This mapping and sampling showed that the gold-bearing jasperoids occurred at the contact between the Pilot Shale and the underlying Devils Gate Limestone. Rock chip samples of 0.1 ppm Au or greater were restricted to the jasperoids and the mineralized outcrop area of Pilot Shale located by the soil sample survey. Rock chip samples from the area of mineralized Pilot Shale were in the 3 to 5 ppm Au range. Activity resumed in the summer of 1977 with a more detailed soil geochemical survey. The jasperoid areas were defined as large geochemical gold anomalies of values greater than 0.1 ppm and locally greater than 0.2 ppm Au. Soil samples from the area of mineralized Pilot Shale outlined a greater than 0.1 ppm gold anomaly 61 x 152 m (200 x 500 ft) in size. Further geologic mapping showed that elsewhere, even where bleached and silicified, the Pilot Shale areas were geochemically very low in gold (less than 0.1 ppm Au). In November, 1977 twelve rotary percussion drill holes were drilled to test the gold-bearing jasperoid areas and the mineralized Pilot Shale area. Drilling of the jasperoid areas showed that the jasperoids gave way at shallow depths [less than 24 m (80 ft)] to unmineralized unaltered Devils Gate Limestone. A five hole cross pattern was drilled to test the area of mineralized Pilot Shale. Four of the five holes re-

Jan 1, 1985

By T. B. Counselman

"C" VERYONE who has to calculate cyanide circuits, -¦-' using either thickeners, filters or both, realizes the headaches involved in solving a set of simultaneous equations. When you calculate a large number of these, based on experimental data, trying to arrive at the best flowsheet, you can spend days at the task. T. B. COUNSELMAN, Member AIME, is Manager, FluoSolids Division, The Dorr CO., Stamford, Conn. AIME New York Meeting, Feb. 1950. TP 2783 B. Discussion (2 copies) may be sent to Transactions AIME before March 31, 1950. Manuscript received Aug. 23, 1949. Herewith is presented a short method, equally accurate with the standard simultaneous equation method, and much quicker. Here for instance is the standard simultaneous equation method, for 100 tons per day of $10 ore, with the conditions assumed as below (fig. 1). Conditions Assumed a. 100 tons of ore per day crushed in cyanide solution. b. Discharge from all thickeners with 50 pct moisture. c. $10 value dissolved per ton of ore. d. 50 pct in mill and 50 pct in agitators. e. 400 tons of solution from thickener V precipitated to $0.02. f. Agitation with a dilution of 2 of solution to 1 of solids. g. Let V, W, X, Y and Z represent value in dollars per ton of solution discharged from the resvective thickeners. Equating Out of and Into Each Thickener 1. lOOVplus 400V = 500W plus (0.50 X $10 X 100) 2. 1OOWplus 600W= 500X plus lOOW plus (0.50 X $10 X 100) plus lOOV 3. lOOXplus 500X = 1OOWplus 500Y 4. 1OOY plus 500Y = 1002 plus 1OOX plus (400 X 0.02) 5. 100 Zplus l00Z = l00Y plus 100 tons of water (value $0.00) Simplifying: 1. v = W plus 1.00 2. W = X plus 1.20 3. X = Y plus 0.24 4. Y = 0.2Zvlus 0.064 5. 2Z= Y

Jan 1, 1951

By T. B. Counselman

"C" VERYONE who has to calculate cyanide circuits, -¦-' using either thickeners, filters or both, realizes the headaches involved in solving a set of simultaneous equations. When you calculate a large number of these, based on experimental data, trying to arrive at the best flowsheet, you can spend days at the task. T. B. COUNSELMAN, Member AIME, is Manager, FluoSolids Division, The Dorr CO., Stamford, Conn. AIME New York Meeting, Feb. 1950. TP 2783 B. Discussion (2 copies) may be sent to Transactions AIME before March 31, 1950. Manuscript received Aug. 23, 1949. Herewith is presented a short method, equally accurate with the standard simultaneous equation method, and much quicker. Here for instance is the standard simultaneous equation method, for 100 tons per day of $10 ore, with the conditions assumed as below (fig. 1). Conditions Assumed a. 100 tons of ore per day crushed in cyanide solution. b. Discharge from all thickeners with 50 pct moisture. c. $10 value dissolved per ton of ore. d. 50 pct in mill and 50 pct in agitators. e. 400 tons of solution from thickener V precipitated to $0.02. f. Agitation with a dilution of 2 of solution to 1 of solids. g. Let V, W, X, Y and Z represent value in dollars per ton of solution discharged from the resvective thickeners. Equating Out of and Into Each Thickener 1. lOOVplus 400V = 500W plus (0.50 X $10 X 100) 2. 1OOWplus 600W= 500X plus lOOW plus (0.50 X $10 X 100) plus lOOV 3. lOOXplus 500X = 1OOWplus 500Y 4. 1OOY plus 500Y = 1002 plus 1OOX plus (400 X 0.02) 5. 100 Zplus l00Z = l00Y plus 100 tons of water (value $0.00) Simplifying: 1. v = W plus 1.00 2. W = X plus 1.20 3. X = Y plus 0.24 4. Y = 0.2Zvlus 0.064 5. 2Z= Y

Jan 1, 1951