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By J. F. Smith, J. E. Davison

The heat capacity of CaMg2 was measured over the temperature interval, 4.8° to 287°K, by the technique of low-temperature adiabatic calorimetry. Heat content measurements were performed with a drop calorimeter over the temperature interval, 273" to 673°K. From these data the thermodynamic functions, (FT - H0)/T, ST - So, and & - Ho, were evaluated. A third-Law calculation of the standard entropy of formation of CaMg2 yields a value of -0.25 * 0.06 cal per (°K g-atom) , and the free-energy function derived from this study when combined with existing equilibria data yields a value for the standard enthalpy of formation which is in agreement with direct calorimetric enthalpy measurements. The accompanying paper' shows that the enthalpy of formation of CaMg2 has been determined with good precision by three different calorimetric techniques.'-= TWO independent determinations of the Gibbs free energy of formation of CaMg2 have also been made; both determinations were based on vapor pressure measurements, being in one case hydrogen vapor pressures over ternary Ca-Mg-H alloys4 and in the other case magnesium vapor pressures over binary Ca-Mg alloys.5 The present determination of heat capacity of CaMg2 below room temperature and of the heat content of CaMg2 above room temperature was undertaken to provide supplementary data. These data are useful in their own right but can in addition be used to evaluate an entropy of formation for CaMg2 which, because of the interrelation of free energy, enthalpy, and entropy, can be used as a check of the self-consistency of the composite of the presently available information. LOW-TEMPERATURE HEAT CAPACITY The heat capacity of CaMg2 was measured over the temperature interval 4.87° to 286.64°K in an adiabatic calorimeter. The physical details of the calorimeter and the experimental procedure for measuring the heat capacity of a specimen have been adequately described by Gerstein et a1.6 The source and purity of the calcium and magnesium are described together with the methods of sample preparation and chemical analyses in the accompanying paper.' Results of chemical analyses of the material which was used in the present investigation are shown in Table I. These analyses show that, on the basis of the published phase diagram,7 the heat capacity sample contained a slight excess of a calcium while the heat content sample contained a slight excess of magnesium. However, in both cases the excess was small, and X-ray diffraction patterns showed reflections which were without exception attributable to CaMg2. The sample which was used for heat capacity measurements weighed 69 g while the sample container and addenda weighed 132 g. The sample was in the form of annealed powder, 50 to 60 mesh, and was sealed into the sample container under 0.1 atm of helium. Copper fins inside the sample container facilitated thermal equilibrium of the powdered Sample. Time intervals of the order of 10 min were required for thermal equilibration, and such times are normal for this calorimeter regardless of the form of the sample. The observed heat capacities were corrected for the small excess of a calcium through use of the heat capacity values tabulated by Hultgren et a1.8 The corrected heat capacities are tabulated as a function of temperature in Table II. The free-energy function and the absolute entropy of CaMg2, which were calculated from the experimental heat capacity data, are listed in Table 111. A smooth curve was fitted to a plot of the experimental values of the heat capacity and in only two instances above 30°K did the plotted points deviate from the curve by more than 0.2 pct. Below 10°K the deviation of several of the points was as much as 50 pct. These large percentage deviations were attributed to the small value of the heat capacity and to the low sensitivity of the platinum resistance thermometer in this temperature range. The deviations in the region of 10°to 30°K were less than 5 pct. Although the percentage deviations of some of the low-temperature measurements are large, the actual value of these deviations is small since the magnitude of the heat capacity in that temperature range is small. The error in the value of the third-law entropy at 298.15°K was estimated to be less than 0.01 cal per (°K g-atom). A value of -0.25 ±0.06 cal per (°K g-atom) was obtained for the standard entropy of formation at 298.15°K from the relation:

Jan 1, 1969

By Irving Cadoff, Kurt Komarek, Edward Miller

THE lead-telluride phase diagram as compiled by ansen' has one intermetallic compound, PbTe, with solid-solubility limits extending from 22 to 45 wt pct Te (31.4 to 57.1 at. pct). Pelzel2 redetermined the solubility limits on the lead-rich side of the compound by measuring the relative areas of the two phases in samples annealed in the liquid + compound region, and obtained data that agreed with that of Hansen. Recent studies of the semiconducting properties of PbTe3 however, have indicated that addition of either lead or tellurium to PbTe does not produce samples having carrier concentrations greater than about 10 19 cm-3. Assuming that each impurity atom results in one ionized charge carrier, this carrier concentration corresponds to a solubility range of less than 0.04 at. pct. Fritts and Karrar4 have also observed two phases in samples containing from 0.15 to 3.0 pct excess Pb. To resolve the discrepancy between these data, the solid solubility limits of the compound PbTe were reinvestigated, using several other techniques. Ten 25-g samples with compositions of 1/2, 1, 3, 5, and 10 wt pct excess Pb and Te and two 100-g samples of 15 and 65 wt pct Te were prepared, sealed in evacuated quartz capsules, and melted at 950oC. The 1 pct excess Pb and Te and the 15 and 65 wt pct Te alloys were homogenized for 96 hr at 450°C; the remaining specimens were annealed 50°C below the solidus temperature reported in Hansen. The specimens were polished and etched with dilute HNO,. All the samples were two phase, the second phase appearing at grain boundaries or as spheroidized inclusions in the grains. In the case of the tellurium rich specimens, the second phase could be identified as a eutectic. Debye-Scherrer powder diffraction patterns of the i, 1, 3, 5, and 10 pct excess samples were obtained using CuKa filtered radiation. The films were indexed as the B1 or NaCl structure. The calculated lattice parameter of PbTe was the same for all the specimens, with an average of a0 = 6.460 ± 0.0005A. Lines due to excess lead or tellurium were very faint but could be clearly seen in all the films. The relative areas of the two phases in the 15 and 65 wt pct Te samples were corrected for the differences in density of Pb, Te, and PbTe, and taken as proportional to the relative volumes of the two phases. The corrected relative volumes agreed with a phase diagram having negligible solubility of both lead and tellurium in lead tellurium. The density of the two specimens was obtained to give a third independent determination of the phase limits. The specimens were broken into small pieces to eliminate any internal porosity, and adherent air bubbles were removed by vigorous shaking under water for several hours. The density of lead (11.34 g per cm3) and of tellurium (6.25 g per cm3) was taken from the International Critical Tables and that of stoichiometric PbTe (8.25 g per cm3) calculated from the lattice parameter. For the 15 wt pct Te samples, the density assuming no solubility was calculated to be 9.89 g per cm3; the observed density was 9.86 g per cm8. For the 65 wt pct Te alloy, the density calculated for the case of no solubility was 7.24 g per cm3; the measured density wag 7.22 g per cm3. These results are consistent with those of planimetry and X-ray. SUMMARY Data have been presented which show that the solid solubility of both lead and tellurium in PbTe is

Jan 1, 1961

KNOWING the endpoint, or the equilibrium state, in steelmaking reactions is only part of the story. The rate at which the reactions proceed can be equally important. But the power of thermodynamics, which enables us to estimate the endpoint, is that a knowledge of the mechanism is not required. The methods of kinetics, however, are step-by-step analysis in which a knowledge of the detailed reaction mechanism is essential. As is evident from Chapter 16, a great deal of thermo- dynamic data for steelmaking are available and the underlying theory rests on a completely sound basis. This is far from the case with kinetic data and even kinetic theory. Nevertheless, it is worthwhile to examine the present state of knowledge, to see how far it may be applied to electric furnace reactions. KINETIC THEORY Heterogeneous Reactions. Classical kinetic theory and experimentation have been mainly concerned with homogeneous reactions taking place between different chemical species in a gas or liquid phase. The species are mixed together and the progress of the reaction can then be observed. This is possible because most experiments have been done at relatively low temperatures where the characteristic time for the mixing process is much shorter than the time for the chemical reaction to be completed. For example, in the homogeneous gas reaction, H2 (g) + I2 (g) 2HI (g) hydrogen and iodine may be added to opposite ends of a tube containing a diaphragm. When this is withdrawn, gaseous diffusion (and convection) mixes the two types of molecule almost completely before any hydrogen iodide molecules begin to appear. Such an experiment is inconceivable at more elevated temperatures, since the rate of the chemical process is so sensitive to temperature that reaction would be completed almost instantaneously wherever hydrogen and iodine came into contact; the rate of the mixing process would then determine the rate at which hydrogen iodide was formed. We should not, therefore, expect to observe many homogeneous reac-

Jan 1, 1964

By Colin M. Sargent

ALTHOUGH annealing twins are frequently observed in many fcc metals, their occurrence in aluminum is relatively rare. ~ahn' in his review of twinning has listed only a few references to observations of twins in aluminum, e.g., Refs. 2 and 3. They have also been shown to occur in evaporated aluminum layers.4 During the present work, several annealing twins were studied in aluminum. The specimens of 1099-grade aluminum had the following thermomechanical treatment: deformed 90 pct by rolling, partially re-crystallized, further deformed 60 pct to a final thickness of 100 p, then annealed for 24 hr at 120°C. This treatment produced several annealing twins—-about ten per electron microscope specimen. The specimens were produced by the window technique and examined in a Phillips E.M. 200 operating at 100 kv. A typical twin boundary is shown in Fig. 1. For several of the twins studied the twin plane could be tilted so that it was parallel to the electron beam, e.g., Fig. 2. The associated diffraction pattern, Fig. 3, shows the twinned relationship between the grains. The twinning plane in each case was (111). Use of a reflection common to both the twin and the matrix,* i.e., using reflecting planes parallel in the twin and the matrix, the coherent twin boundary becomes invisible and only the noncoherent segments of the stepped boundary are seen, e.g., Fig. 4. Trace analysis of the boundaries showed that the long straight portions were invariably the twin plane; i.e., these portions are coherent. The planes of the shorter segments are shown by Fig. 5 to be (551 1, (7111, and {211).

Jan 1, 1969

By L. S. Darken

A quadratic formalism is developed lor the representation of the excess free energy, and of the activity coefficients of each component of a ternary system in the vicinity of a single component selected as solvent. This formalism, in contrast to the e formalism, is thermodynamically consistent at .finite concentrations. Numerous specific systems are used as illustrations, with cross checks where possible; these systems are Fe-C-X systems in the vicinity of 1600°C and include practically all those for which reliable data are available. It is shown that this formalism is usually quite adequate to rebresent available data up to a solute concentration of 20 to 30 at. pet. It is hoped that the formalism here presented may prove useful for the treatment and tabulation of data on ternary and multi-component solutions. SINCE, as discussed in a prior paper,' we do not as yet have an adequate basic understanding of the nature of binary metallic solutions, we cannot hope to be in better position for ternary and multicomponent systems. However, the accumulation of thermodynamic data on ternary and multicomponent metallic solutions has led to an urgent need for a rational formalism for the presentation and use of such data. Notable attempts to represent the isothermal isobaric thermodynamics of ternary solutions were made by Benedict et 01.' and by Wohl.3 These attempts were directed toward developing an analytic expression adequate to encompass the entire ternary triangle, primarily for organic systems; they generally involve the power-series approach, which has been shown' to be inappropriate, in general, even for binary metallic systems. On the other hand, interest in the thermodynamics of ternary and multicomponent metallic solutions has tended to focus either on general thermodynamic relations4-10 over wide compositional ranges, or on cases where one or more components have been at rather low concentration. This latter approach has been followed by Wagner,= by chipman,11 and by Alcock and Richardson,12 and more recently in many publications by the same and other authors. It has already been shown' that the thermodynamic behavior of binary metallic systems is, in general, relatively simple only in the terminal regions. Hence, it would appear that any approach, at this time, to a simple formalism for ternary and multicomponent systems must, a fortiori, be limited to the vicinity of the major component or solvent. The present treatment is aimed to be useful for a given solvent with moderate solute concentrations ranging up to 20 or 25 at. pet and in exceptional cases to considerably higher concentrations. In order to achieve even this modest objective, it is necessary that any appropriate formalism have built into it 1) a thermodynamic consistency (at least within the desired degree of approximation), and 2) an approach at infinite dilution to Raoult's law for the solvent and to Henry's law for each solute. Let us first formulate the condition of thermodynamic consistency for a ternary system. Under isothermal isobaric conditions, we may write for the molal value G of any extensive function dG - C1 dN1 + G2 dN2 + G3 dN3 [l] where the G's are the corresponding partial molal quantities and the N's are the atom fractions. Taking component 1 as the solvent, this relation may be rewritten in terms of the independent variables N2 and N3

Jan 1, 1968

By John F. Elliott, John P. Hager

The standard free energies of formation of the lowest stable sulfides of chromium, molybdenum, and tungsten in equilibrium with the corresponding metal hazle been determined by reacting the sulfide and metal with H2(g)/H2S(g) mixtures. The reaction is A method for estimating the standard ~nolav entropies and standard entropies of formation at 298°K of the sul-fides of refractory metals is presented. The standard free energies of formation of the lowest sulfides of the metals in group VIa of the periodic table are probably best determined with the reaction* is known with greater accuracy than is that property for any other sulfur-bearing compound or solution which might serve as a reference phase to establish the chemical potential of sulfur for the essential re- However, there still remain significant problems to the use of Reaction [I] in studying these sulfides. First, the equilibrium gas ratios (Ph2S/PH2) are very small, and with the most stable sulfides in the series the ratios tend to be at the limit of the range for precise chemical analysis (10-4); and second, the reaction rate for the formation or reduction of these sulfides appears to be relatively slow. A primary reason for the latter problem is that the gas phase near the equilibrium concentration has very little capacity for transport of sulfur. It is to be noted that the thermo-dynamic properties obtained from the experimental results by Eq. [I] apply for 1 g-atom of sulfur in the metal-saturated compound even though the exact composition of the compound has not been determined. The work reported here is a study of the standard free energies of formation of the lowest sulfides of chromium, molybdenum, and tungsten, and of copper, by Reaction [I]. In planning the experimental program, it was decided that the technique that has been used previously3"' could be used with modification and that an improved analytical method was needed for determining H2S in the gas phase. THE EXPERIMENT The once-through flow of gas was selected in preference to recirculating the gas, a) because of the low sulfur capacity of the gas, b) because of the relatively slow rate of reaction and the danger of the

Jan 1, 1968

1. What Is a Rock Burst? . . . . 569 Jack Spalding . . 569 A. F. Robertson . 569 W. R. Crane . 569 G. S. Rice......569 P. J. Shenon........... 569 L. C. Graton........... 569 2. What Are the Causes of Rock Bursts? 573 Jack Spalding..........573 A. B. Yates and P. J. Shenon 574, 578, 592, 596 A. F. Robertson . . . . . 575, 595 W. R. Crane. ... 579 G. S. Rice.........582 Oscar Weiss .........582 P. B. Bucky..........582 P. H. Bird.....588, 592, 593, 595 M. K. Hubbert.........593 G. Wheeler.......... .593 B. F. Tillson........593, 595 T. T. Read............594 3. How Can Rock Bursts Be Prevented?. 597 Jack Spalding..........597 A. B. Yates and P. J. Shenon ... 598 A. F. Robertson.......599 W. R. Crane....... .602 G. S. Rice............602 Page 4. How Can Rock Bursts Be Predicted?. 602 Jack Spalding.........602 A. F. Robertson.......602, 603 A. B. Yates and P. J. Shenon ... 602 W. R. Crane......602 G. S. Rice......602 B. F. Tillson...........603 5. How Can Rock Bursts Be Controlled? 603 Jack Spalding..........603 A. F. Robertson.......603 W. R. Crane...........604 A. B. Yates and P. J. Shenon 604 Oscar Weiss........605 G. S. Rice......- 604, 609 R.D.Hoffman..609, 610 R. D. Hall..........609 R. H. Cromwell . . 609 P. J. Shenon...........609 P. B. Bucky......609, 611 B. F. Tillson.........609, 611 A. B. Yates...610, 611 P. H. Bird.......610 6. General Discussion........ 611 Jack Spalding.......... 611 R. D. Parker....... . 616 C. Baring Horwood........ 618 P. B. Bucky........... 619 Foreword This symposium brings together points of view, experiences and ideas on rock bursts from a goodly portion of the globe. Some conceptions, particularly those regarding the necessity of depth, have been fairly well shattered, as we find that they are present in the water tunnels of New York, on the surface at marble quarries in Vermont, and in the coal mines of the United States, as well as in the deep mines of the South African and Kolar gold fields, and in the nickel, copper and gold mines of Canada. Their occurrence under such a variety of conditions is, therefore, a challenge, which, if successfully met and overcome,

Jan 1, 1946

By Luther Wagoner

Having given in a former paper1 the results of assays of sea-water, bay-mud, dredgings from San Francisco bay, etc., and believing it might be interesting to extend the work to include some deep-sea dredgings, I procured from the Smithsonian Institution six samples taken by the U. S. steamer Albatross, and marked as follows: Depth in No. station. Locality. Latitude. Longitude. Fathoms. 1. 2103. Off Delaware bay. 38' 47' 20" N., 72o 37' W., 1,091. 2. 2265 to Between Chesapeake 35° 37' N., 74O to 75O W., 49 to 70. 2297. bay and Hatteras. 3. 2420. Off Chesapeake bay. 37' 03' 20" N., 74O 31' 40" W., 104. 4. 2528. East of Georges 41° 47' N., 65o 37' 30" W., 677. bank. 5. 2572. SE. of Georges bank. 40° 29' N., 66O 041 W., 1,769. 6. 2681 South of Nantucket. 39' 43' N., 70' 29' W., 990. The above samples were assayed by the cyanide-method, described in my former paper (p. 807), about 30 g. of sample being used, and the following results were obtained: Value in Milligrams Per Metric Ton. No. Station. Gold. Silver. 1. 2103. 145 1,014 2. 2265 to 2297. 44 304 3. 2420. 15 353 4. 2628. 267 1,963 5. 2572. 125 377 6. 2681. 66 414 No. 4, Station 2528, consisting of red clay and volcanic ash, mas re-assayed ; 35 g. was roasted at a low heat for one hour and weighed 34.05 g. after roasting; the color was changed to a deep brick-red; and when assayed by the cyanide-method

Jan 1, 1908

By Gordon H. Geiger, J. Bruce Wagner

Electrical conductavity and therrnoelectvic nzeasuretnents on synthetic hematite slabs with 0.01 to 0.90 at. pet Ti and with 0.30 at. pet Ca were made. Additions of titanium and of calcium both increased the electronic conductivity with titanium yielding greater n-type behavior and calciurn p-type behavior. Reduction studies of hematite to magnetite in CO-CO2 atmospheres between 600° and 900°C initially exhibited linear kinetics. These linear rates were increased by additions of titanium and decreased by calcium. IN recent years many studies have been reported in the literature on the kinetics of the reduction of hematite and magnetite to iron. In addition, Hansen and Josephl and Schenck and Schultz2 have reported studies on the reduction of hematite to magnetite, the first step in total reduction to iron. In order to evaluate the results of the studies of over-all reduction in terms of the actual mechanism of the reaction and to define further the important factors in the rate- controlling mechanism of the magnetic roasting reaction, the following experiments were undertaken. Specimens of undoped hematite and hematite containing titanium or calcium in solution as doping agents were reduced to magnetite in CO-CO2 mixtures. In addition, electrical-conductivity measurements were correlated with the reduction kinetics using concepts of defect solid-state chemistry. EXPERIMENTAL Fisher certified Fe2O3 powder was used to make specimens for both the electrical and kinetic studies (see Table I for analysis). Doping with titanium and calcium was accomplished by adding TiO2 and CaO powders to the Fe2O3 powder. The powders were mixed in a Waring blender for minimum times of 1/2 hr. Satisfactory blending was achieved based on comparison of analyses of individual specimens af- ter reduction. The specimens were formed in a steel die using opposed punches with a rectangular opening 10.0 by 40.0 mm. The Fe2O3-TiO, platelets were pressed cold at 16,000 psi. They were sintered for approximately 16 hr at 1075°C in air, in accordance with information in the literature3, 4 on the time and temperature needed to obtain solution of the titanium in the hematite. The Fe2O3-CaO mixtures were first cold-pressed at 20,000 psi and sintered for 3 hr at 1225°C to insure solution of CaO. This material was then ground to -325 mesh in a 6-in. ball mill and the resulting powder was used to make platelets in the same manner as above. The sintered platelets were usually between 1/16 and 1/8 in. thick. They were ground on a carborundum wheel and polished on 2/0 paper. Typical dimensions of the kinetic-study specimens were 1.6 by 0.8 by 0.05 cm, and a typical weight was 0.3 g. Conductivity and thermoelectric specimens were approximately the same size, but were subjected to further sintering in order to ensure maximum densification. Finally, all specimens were measured to the nearest 0.0005 in. and weighed on a Mettler H-15 balance to the nearest 0.0001 g and the density calculated. The average density of the specimens used for the reduction studies was 4.87 g per cc, or 7.1 pet total porosity. The standard deviation ranged from 0.14 to 0.063 g per cc within a composition group. In the present study, the apparent surface area as measured with a micrometer was taken as the true surface area. The chemical analyses for calcium and for titanium within a group showed maximum variations of 50.04 pet from the average values used in Figs. 9 and 11. In order to suspend the specimen from the balance for the kinetic studies, a hole, 0.03 in. in

Jan 1, 1965

By J. B. Hiskey, W. J. Schlitt, W. G. Pitt

Aqueous SO2 (sulfurous acid) is an interesting chemical compound. It functions as a reagent in various hydrometallurgical systems, but also represents an undesirable constituent in gyro- and hydrometallurgical effluent solutions. When present in such streams, SO2 can be oxidized to the more stable sulfate form to avoid exsolution of SO2 as a source of fugitive emissions and to simplify standard water treatment plant operation. This study provides information on the stoichiometry, kinetics, and mechanism of SO2 oxidation using oxygen and an iron salt catalyst with solutions containing 0.05-20 g/L (0.002-0.7 oz per gal) SO2. The effects of iron salt concentration, oxygen pressure, temperature, degree of agitation, and pH on SO2 oxidation are also described.

Jan 1, 1984

By John D. Roach

DURING an investigation of the yttrium-hydrogen system aimed at producing solid yttrium hydride specimens containing various amounts of hydrogen, it was observed that yttrium containing approximately 2 wt pct H exhibited a tendency to crack and crumble to a powder on standing in air at room temperature. It was also observed that longer hydriding times, at a given temperature, increased this susceptibility to powdering without an increase in hydrogen content, also that moisture in the air is necessary for the observed effects to occur. Even if cracking did not occur, there was a continual formation of a light gray powder on the as-treated surface of the hydrided yttrium and this reaction continues until the entire hydrided piece has been reduced to a powder. Storing the hydrided specimens in the absence of air or removing the surface either by machining or grinding were effective means of preventing this disintegration of hydrided yttrium. In an attempt to determine the reason for this powdering phenomenon, the surfaces of a number of as-hydrided yttrium specimens were examined by X-ray techniques. In all cases the X-ray pattern obtained showed the major phase to be yttrium hydride (YH2) as would be expected since the specimens contained 2 to 2.2 wt pct H. In some cases a trace of yttrium oxide was observed. There was also a third phase present on the surface of these hydrided specimens which could not immediately be identified. This unknown phase was a face-centered cubic material, NaC1-type structure, with a lattice parameter of 4.855 and a calculated density of 5.914 g per cc. Very slight hand polishing of the surface of the hydrided yttrium specimens completely removed both the unknown phase and the traces of oxide so that only the yttrium hydride pattern remained. Based on the X-ray patterns the quantity of the unknown phase on the surface of the hydrided yttrium appeared to be directly related to the susceptibility of the material to powdering. Work at the Denver Research Institute on the yttrium-nitrogen binary system showed that yttrium nitride (YN) is a face-centered cubic material with a lattice parameter of 4.878A and a density of 5.890 g per cc. They also noted that this compound rapidly disintegrated to a powder on standing in air. The unknown pattern observed in the above specimens corresponds very closely to that of the nitride—fcc structure, 4.885 parameter, and density of 5.914 g per cc. The presence of this thin film of nitride on the surface of the hydrided specimens probably accounts for the observed powder formation and crumbling. The nitride reacts with the water vapor in the air (verified by private communication from Dr. C. Huffine, General Electric Co.) to yield yttrium oxide and ammonia. Ammonia is readily detected when hydrided yttrium specimens were allowed to stand in bottled moist air. The powder formed on the surface of the hydrided specimens was shown by X-ray analysis to be yttrium oxide. This reaction appears to occur primarily at the grain boundaries since discrete particles of yttrium hydride separate from the specimens during this powdering process. The reaction of yttrium nitride with water vapor is believed to be as follows: 2YN + 3H2O - Y203 + 2NH3. Despite the fact that this nitride is present only as an extremely thin surface film, if the above reaction is not prevented by removing this film from the surface either by machining or grinding, the reaction continues until the entire hydrided piece has been reduced to a powder. To account for this continuation of the reaction, it is believed that the following reactionalsooccurs: 2YH2 + 2NH3 -2YN + 5H2. The nitride produced by the latter reaction reacts in turn with water vapor. The reaction therefore becomes autocatalytic and continues until the hydride has been consumed and the entire piece reduced to oxide powder. The amount of nitride required to initiate this reaction is quite small and this nitrogen contamination can occur from a number of sources—hydrogen gas employed, minute leak in the hydriding apparatus or even from degassing of the reaction vessel itself. Longer hydriding times increase the possibility of nitrogen contamination and this is especially true when a dynamic gas system is employed in the hydriding process. The production of stable, solid hydrided yttrium is dependent on the complete absence of nitrogen contamination during processing. If such contamination does occur, powdering of the hydrided product can be prevented by removing the nitride from the surface e.g. grinding or by preventing access of air to the pieces e.g. sealing in wax or plastic. The author wishes to express his appreciation to General Electric Co. for sponsoring this research and for permission to publish the results of work under Subcontract AT-93.

Jan 1, 1962

By AIME

The following corrections (in italics and bold face) were received too late for the September issue of Transactions: Page 270, Abstract, line 1, spelling should be goethite. Page 270, column 1, authors' box, authors' affiliations should read: L. A. BAKER, formerly Principal Research Scientist, is Pellet Plant Superintendent, Cliffs Western Australian Mining, Cape Lambert, W. A., Australia. C. G. THOMAS is Experimental Officer, Minerals Research Laboratories, C.S.I.R.O., North Ryde, N.S.W., Australia. R. J. CORNELIUS and K. S. LYNCH are General Superintendent, Product and Process Development, and Superintendent, Pellet Plant, respectively, Hamersley Iron Pty. Ltd., Dampier, W. A., Australia. G. J. ARMSTRONG, formerly Chief Metallurgist, Hamersley Iron Pty. Ltd., is Mill Superintendent, Samin Ltd., Burra, S. A., Australia. Page 271, column 2, line 41, should read "highest possible spalling temperature and to adjust the. . :' Page 275, column 1, line 1, should read "(LOI) figures are shown in Table 1 and vary from 2.61..." Page 275, column 1, line 16, spelling should be goethite. Page 276, column 2, line 6, should read "Predicting Grate Speed and Production Rate: The cor-..." Page 276, column 2, line 8, should read "basis of Blends A, B, C, D, and Plant Ore 1, shown in Table..." Page 276, Table 3, heading under "Prediction Method" should read Blend E. Page 277, column 1, line 38, should read "=293 tph of specification pellets (see Table 1 for loss-..." Page 277, column 2, replace caption for Fig. 14 with the following: Fig. 14-Example of calculation of hood temperature profile during downdraft free-water drying, given plant free-water drying time. Page 277, column 2, replace caption for Fig. 15 with the following: Fig. 15-Example of calculation of hood temperature profile during drying, given plant goethite drying time.

Jan 1, 1974

By Andrew Corry

GEOPHYSICAL investigations based on radioactivity have been applied to the earth's crust for the purpose of discovering bodies rich in radioactive substances, or for the location of solutions with high emanation or radioactive-salt content, or for the detection of oil, which, in virtue of colloidal properties, has strong powers of radioactive absorption. RADIOACTIVE SUBSTANCES Radioactive substances are distributed in all rocks, waters, and gases in the earth's crust in small quantities. Granites and similar acidic rocks are richest in uranium and thorium, two chief radioactive substances; yet the quantities present in such rocks are of the order 10-12g., this concentration being expressed in grams per gram of the whole substance per cubic centimeter. In granites the uranium yields, according to Haddock, 3 X 10-12 g. of radium per gram of rock. In basalts the uranium yields 1.19 X 10-12 g. per gram per cubic centimeter. Of thorium the granites yield -2 X 10-5 g. per gram of rock; the basalts, 0.77 X 10-5 g. per gram. Certain series of alkalis of low atomic weight, like potassium and rubidium, show weak radioactivity; this property has no significance so far for geological research. The uranium is esti-mated indirectly from the electrical properties of one of its derivatives as a -gas (emanation) into which it is transformed. The thorium is expressed directly, though it is measured as a derivative, thorium emana-tion. There is a measure for the gaseous radium emanation, the curie, which is that quantity of radium emanation, or radon, which stands in equilibrium with 1 g. of radium. The concentration of the emanation is the Mache unit corresponding to 3.64 X 10-10 curie per liter. When gases become permeated by alpha, beta, and gamma rays, plus and minus ions are produced in them by the decomposition of neutral gas molecules, and under the influence of an electrical field these ions are given opposite motions. The measurement of the alpha rays and the bisection thicknesses of the beta and gamma rays is a means of analyzing unknown radioactive substances. These rays accompany the disintegration of radioactive substances and arise from "spontaneous internal changes

Jan 1, 1929

By Yves Dardel

INTRODUCTION SINCE the first determination of Dumas1 in 1880, many authors have tried to measure the solubility of hydrogen in solid aluminum, or at least the amount of dissolved gas in it. However, the interpretation of the results which have been obtained is still difficult. Sieverts,2 then Baukloh and Oesterlen,3 during their gassing experiments could not determine any solubility of hydrogen in solid aluminum. On the other hand, Portevin, Chaudron and Moreau,4 leaving the determination of the hydrogen solubility beyond the scope of their experiments, measured only the amount of gas that they could extract by high voltage positive ion bombardment and found up to 151 cm3 of gas per 100 g of metal. Winterhager,5 by repeated vacuum extraction during severe cold rolling, extracted up to 161 cm3 per 100 g. In both series of experiments, the extracted gas contained chiefly hydrogen with a small amount of nitrogen, carbon monoxide, carbon dioxide and methan. Later, Schmidt and von Schweinitz6 as well as Chaudron and Moreau7 showed the importance of the adsorbed layer of hydrogen, the extracted quantities being proportional to the surface and not to the weight of the sample, when its cleaning was not perfect. In earlier experiments, Steinhauser8 extracted from more massive samples nothing but a little amount (< 0. 5 cm3 per 100 g) of hydrogen, carbon monoxide and methane. Thus, according to these experiments the quantity of dissolved gas is probably very small and the effect of the surface could falsify the results of the extraction. However, owing to the care taken by Chaudron and his coworkers, it was clear that all the hydrogen extracted could not come from the superficial layer, or that the links which bound hydrogen to the surface were so strong that the usual method of cleaning could not destroy them. After the main parts of the experiments reported here had already been carried out, Eborall and Ransley9 published the results which they obtained with an analysor having an accuracy of 0.03 cm3 per 100 g, while that of the usual apparatus was only about 0.2 cm3 per 100 g. During all their experiments the adsorbed layer would have been a difficulty, for the value of the adsorbed hydrogen was approximately equal to that of the dissolved amount. [ ] Since always keeping the same adsorbed layer is very difficult, an error in the correction for the adsorption can be made when using the apparatus of Eborall and Ransley, as well as the earlier apparatus,

Jan 1, 1948

By Louis A. Panek

The purpose of this paper is to present a method of designing safe and economical arch structures that are to be constructed of concrete or directly of original earth materials. The experimental data used to illustrate the design method are taken from Bucky and Fen tress,1,2 and the application of the ideas presented by them is extended by obtaining an additional set of curves from which arch structures may be designed. This design method is based upon the following principles of similitude: A scalar model made of the same material as that of the full sized structure will behave similarly to its prototype if the density of the model is increased in the same proportion as its linear scale is decreased. Let R represent the scale or model ratio, namely, the ratio of a prototype linear dimension to the corresponding model linear dimension. The effect of increased density may be obtained by rotating the model in a centrifuge at a speed such that the centrifugal held exerts on the model an accelerative force R times the accelerative force of gravity. Under these conditions; (I) model unit stresses are equal to corresponding prototype unit stresses, (2) the ratio of the prototype deformation at a given point to the model deformation at a similar point is equal to the scale ratio, R, and (3) the model and the prototype will behave similarly within and beyond the elastic limits of strain. According to the above relations, such models can be used to solve the following problems: I. The dimensions of the most economical safe arch structure for a given load. 2. The miaximum safe roof span underground for given geologic conditions. The procedure is described briefly as follows. Tests are made by rotating in a centrifuge a number of models that repiesent a variety of prototype loads and dimensions. From the experimental data, curves are plotted to show the relations between these loads and dimensions. The curves are used to solve directly the problems stated above. Structural design is based upon the working (safe) stress of the material of construction, which is established by applying a factor of safety to the experimentally determined ultimate strength of the material. In conformity with this principle, each model is gradually loaded until failure occurs. A safety factor is then applied to the results. If a safety factor of 4 is used, a given model at failure represents a safe prototype, the linear dimensions of which are equal to one-fourth the model ratio at failure times the corresponding model dimensions. The safe model ratio is computed from the following formula: Safe R =(1/4)4p2n2r/g=p2n2r/g [I] in which: n = centrifuge revolutions per second at model failure; r = radius of rotation of the model in feet; g = 32.2 ft/sec2.

Jan 1, 1949

[A AALSETH, Earl P (M 51) Consult Geol Engr 2019 Eldorado Dr, Billings, Monl ABADIE, Henry G (M 43) Asst to Supt of Oper Long Beach Oil Dev Co 925 Harbor Plaza, Long Beach 2, Calif ABBE, T Waldo (A 56) Asst Dist Oper Supt Sun Oil Co PO Box 66, Stowell, Tax ABBOTT, Fred E Jr (M 59) Abqaiq Dist Mgr Arabian American Oil Co Dhahran, Saudi, Arabia ABBOTT, Clifton T (A 60) Apartado 677, Maracaibo, Venezuela ABBOTT, J L (M 56) Partner Pritchard & Abbott 1010 Ft Worth Natl Bk Bldg, Fort Worth 2, Tex ABBOTT, Richard H (J 51) Partner Abbott & Howard 422 W Hermosa San Antonio 12, Tex .ABBOTT, William G (M 50) Div Mgr Rice Engrg & Operating Inc Box 1142, Hobbs, N. M. ABDERHALDEN, Ronald R (J 59) Prod Engr Continental Oil Co Box 100, Carmi, III ABEL, Malcolm D (J 50) Gen Partner Abel & Bancroft PO Box 865, Midland, Tex ABEL, Ramond L (M 28) Prof of Chem Eng Univ of Pittsburgh, Pittsburgh 13, Pa ABEL, Wayne K (M 57) 1513 Patton Drive, Odessa, Tex ABELL, Joseph M (J 55) Petr Engr Tennessee Gas & Oil Co Box 1772, Casper, Wyo ABELS, Thomas A (J 60) Exploit Engr Shell Oil Co Box 193, New Orleans 3, La ABENDROTH, G F (M 46) Dring Prod Supt Lyons & Logan 1500 Beck Bldg, Shreveport, La ABERCROMBIE, Bolling A (M 60) Mgr Product Planning Axelson-Garrett PO Box 2427, Longview, Tex ABERCROMBIE, C T (160) Prod Engr Cities Ser Petr Co Box 472, Brownfield, Tex ABERCROMBIE, H L Jr (J 55) Prod Engr Mobil Oil Co Room 1800 Gr PI Life Bldg, Lubbock, Tex ABERCROMBIE, Robert (J 57) Prod Engr Mobil Oil Co PO Box 1770 Shreveport, La ABERG, Richard S (M 57) Area Prod Geol Shell Oil Co of Canada, Box 100 Calgary, Alta, Canada]

Jan 1, 1961

By S. J. Im

Bupyung Silver Mines daily treats average 14 tons of concentrates containing 9,000 g Ag per ton. Bupyung Silver Refinery uses Merrill Crowe process to recover the silver from the leach solution containing 1.0 g/l Ag; Series of experiments were carried out to recover the silver from the solution by means of direct electrowinning in place of Merrill Crowe process. The recovery of the silver was 99% when the cell voltage and the retention time were 1.9 v and 3.0 hours, respectively. Power consumption was 3.2 Kwh/kg of Ag. It was found that impurity buildup was not significant during the recycling. The direct operating cost for the electrowinning was evaluated to be $ 0.35/kg of Ag.

Jan 1, 1984

By William D. Klopp

A study was conducted of the tensile and creep properties of are-melted and electron-beam-melted tungsten over the temperature range 2250° to 4140°F. The tensile and creep strengths vary with pain size, the finer -grained materials being stronger. The activation energy for transient creep at 2250° to 3500°F is 95,000 cal per (g)(mole), while that for steady creep at 3300o to 4000°F is 141,000 cal per (g)(mole). At 2875o to 3300°F the apparent activation energy for steady creep decreased with decreasing temperature. It is suggested that cross slip is rate controlling during transient creep, while dislocation climb is rate controlling during steady creep above 3300° F. ALTHOUGH considerable data have been generated on the high-temperature tensile properties of powder-metallurgy tungsten,1 relative few data have been published on the properties of are-melted2 or electron-beam melted tungsten.3 Furthermore, the available data show a fairly large amount of scatter at high temperatures. The effects of structure and purity have not yet been defined, aside from observations that high-purity electron-beam (EB)-melted tungsten3 and single-crystal-plasma-flame tungsten4 are weaker than less pure powder-metallurgy tungsten. The creep behavior of powder-metallurgy tungsten has been studied, but no data are available on the creep behavior of tungsten consolidated by melting. Green5 found that powder-metallurgy tungsten exhibited linear creep at 4082° to 5072°F with an activation energy of 160,000 cal per (g) (mole). The similarity of this activation energy to that of 153,000 cal per (g)(mole) for volume self-diffusion6 suggests that recovery of strain hardening by dislocation climb is rate controlling in this temperature range. In studies at 4800°F, Sutherland and Klopp7 concluded that grain size significantly affected the creep behavior of commercial powder-metallurgy materials. This grain-size effect was suggested by sherby,8 although the opposite relation had been reported for aluminum.&apos; The purpose of the present study was twofold: first, to provide baseline data on high-temperature tensile and creep properties of are-melted and EB-melted tungsten for concurrent tungsten alloy studies, and, second, to determine the phenomenolo-gical effects of structural and purity variables on the high - temperature mechanical properties of tungsten. EXPERIMENTAL The are-melted tungsten materials were prepared by melting sintered 1-1/4-in.-diam electrodes into 2-1/2-in.-diam by 5-in.-long ingots. The are-melting facility has been described previously.&apos; Eight ingots were melted, machined, and hot-extruded at

Jan 1, 1965

By S. A. Mersol, C. T. Lynch, F. W. Vahldiek

The room-temperature microhardness of as-grown and annealed MoaC single crystals was measured on the (0001), {2110), and1012) planes using Knoop and Vickevs indenters at loads ranging front 25 to 1000 g. The orientatimz dependence of hardness with respect to crystal axes was also studied. The average random hardness of as-grown crystals was determined to be 1520 kg per sq nm. Annealing to 2000°C decreased. the average hardness by 150 units. An increase in hardness after annealing at 2200 ;C was noted. Optical and electron microscopy revealed slip and twin traces on all planes studied, as produced by mi-cvohavdness indentations. Basal (0001)(2i10) slip was determined to be the primary slip system and was substantiated by electron transmission microscopy. A secondary {1010)(2110) slip was produced by mi-crohardness indentations. The lattev also produced twinning- of the {10i2)[0001] type, as proven by electron diffraction. Electrical resistivity and elastic-modulus anisotropy were found and correlated with hardness anisotropy and Mo2C crystal structure. Elastic-modulus values were obtained by microhard-uess and ullrasonic methods. Bonding mechanism of Mo2C is discussed. ROOM-TEMPERATURE microhardness indentations are useful for studying hardness anisotropy, slip, and twinning in brittle materials. Slip has previously been produced in this manner in and WS~~.~ Recently, the authors5 reported slip of the {10i0)(11~0) type produced by high pressure and microhardness indentations on hexagonal TiBz (c/a = 1.066) single and polycrystals. This slip system was also reported by French and ~homas&apos; and Taka-hashi and ~reise~ for hexagonal WC (c/a = 0.976) crystals. These results suggest that prismatic rather than basal slip is favored in hexagonal nonmetallic materials having a c/a ratio considerably less than the ideal (1.633). Buerger precession and cylindrical X-ray rotation patterns were previously&apos; taken on cleaved sections of the Mo2C single crystals studied in this work. Th~y were found to be hexagonal MoaC with a. = 3.0233A, co = 4.7344A, and C/O = 1.5660. The latter ratio is close to that of the beryllium metal (c/a = 1.57), which slips primarily on the (0001) plane: but also slips on the (1010) planes.&apos;0 ~irconium" (c/u = 1.59) and titanium12 (c/o = 1.59) deform mainly by slip on nonbasal planes which contain a close-packed direction. This is due to the fact that for these two metals the initial resolved shear stress for slip on the (10i0) prismatic planes is lower than that on the (0001) plane. The prominence of basal rather than prismatic slip in metals of high c/o ratios is shown by cadmium (c/a = 1.89), zinc (c/a = 1.86), and magnesium (c/a = 1.62) which deform mainly by basal slip. However, in case of the latter, by stressing magnesium crystals in tension or compression parallel to the basal plane, slip on (10i0) planes can also be produced.13 Several hardness values for polycrystalline Mo2C are reported in the literature: Biickle &apos; and Samsonov&apos;~ give a value of 1800 and 1479 kg per sq mm, respectively, at a 100-g load; and Kieffer and Benesovsk~&apos;~ report a value of 1950 kg per sq mm at a 50-g load. ~ott&apos;~ reports a Vickers hardness value of 2000 kg per sq mm, with the load unspecified. A Rockwell A hardness value of RA = 88 has also been reported.&apos;&apos; In the present work, for comparison with single-crystal Mo2C hardness values, a Khnloo value of 1600 It 150 kg per sq mm was found on 99.6 pct pure and 99 pct dense hot-pressed Mo2C. This work was undertaken partly to explain the considerable differences in hardness values reported for polycrystalline Mo2C. EXPERIMENTAL The Mo2C single crystals investigated were prepared by a Verneuil-type process using an electric arc by the Linde Co. of the Union Carbide Corp.lg The largest specimens grown were boules 7 mm in diam by 40 mm in length. The crystals had an average density of 9.04 g per cu cm, with a Mo + C content of 99.8 wt pct. The major impurities were: 100 ppm each Na, Zr, and Ca; 85 ppm 0, 55 ppm Fe, and 10 ppm each Cr and Ta. The crystals were found to be carbon-poor, the average carbon content being 5.73 wt pct (stoichiometric value is 5.89 pct). The molybdenum content was found to be 94.08 pct, which is nearly stoichiometric. Electron-microprobe traverses of selected specimens were done with a Phillips-AMR microanalyzer. Thin-film and carbon replicas were used to prepare electron micrographs. This work was done with a JEM-6A electron microscope. Prior to optical and electron-optical studies, specimens were mounted in Lucite and polished on a vibratory polisher using diamond-paste grades ranging from 9-1 p and Linde A powder for up to 48 hr. Dilute nitric acid was used for thin-section polishing and chemical etching for 1-15 min. Electrical-resistivity measurements at room temperature were taken with a Rubicon bridge, using gold contacts. For hardness measurements, a Tukon Microhardness Tester Type FB with Knoop and Vickers indenters was used. Measurements were taken at loads ranging from 25 to 1000 g; however, the 100-g load was chosen as the standard load. All measurements were taken at room temperature. Indentations of cracking classes 1 and 2 only were considered for hardness determinations.20)21 (There are six cracking classes, ranging from "class 1" for a perfect inden-

Jan 1, 1967

By U. N. Bhrany, N. Arbiter

F. C. Bond (Consulting Engineer, Processing Machin-Dept., AllisChalmers Manufacturing Co., Milwaukee) This is a very comprehensive paper. It deals with 1) size distribution functions, 2) energy-particle size relationships, and 3) criteria for grinding efficiency. The method of analysis used consists of tracing the increase and decrease of successive Tyler scale screen fractions as grinding progresses. The treatment is based upon the assumption that the work done in grinding is concentrated entirely upon the coarse size fractions in the mill. It is postulated that when a feed consisting entirely of particles of one size fraction is batch ground that finer fractions increase at a constant rate as grinding progresses, until finally each in turn begins to be ground and to decrease in amount. It is shown that under these conditions the empirical Gates-Gaudin-Schuhmann log-log size distribution plot can be logically explained. It is difficult to imagine any condition of ball mill operation, or any probability analysis, which would result in no grinding contacts on the finer particles present. However, the authors&apos; postulate must be accepted if their conclusions are to be sustained. They conclude that the equation expressing the for mation rate of each size fraction can be resolved into the G.-G.-S. size distribution equation, and that the curvilinear portion of the log-logsize distribution line represents the only particle sizes which are being ground as well as produced. The author&apos;s statement that the G.-G.-S. Eq. 4 applies only to the finer portion of the size distribution while the Rosin-Rammler Eq. 6 applies over the whole size distribution range certainly supports the view that an exponential equation of the Rosin-Rammler type corresponds more closely to actual size distribution than does the power law G.-G.-S. equation. However, the G.-G.-S. equation is used to derive Eq. 8 and Eq. 9, which state that the energy required to grind a ton through a particular mesh varies inversely as the particle size to the exponent -a , whic h is the slope of the extended G.-G.-S straight line. This is stated to apply to both batch and continuous grinding. The G.-G.-S. slope exponent thus becomes very important in all crushing and grinding analyses by this method. The authors include some data which can be used to test their conclusions, as described below: We will consider grinding a feed composed of 14 mesh (1190u) to -200 mesh (74u). The average of 17 Allis-Chalmers grindability tests on quartz gives a work index (Wi) of 12.77. The -200 mesh product should have 80 pct passing 41.6u or P = 41.6. The equivalent 80 pct passing size of the 14 mesh feed particles is considered to be the particle diameter, as is true for spherical particles. Thus F is 1190u. In the work index equation 10 wi 10 wi 127.7 127.7 P f 41.6 1190 = 16.1 kw-hrperton. In Table I the ball mill exponent for quartz is 1.0 and from Eqs. 9 and 10: w=kw-hr/ton =Constan/(do/di) = 16.1 ton so that (1190) Constant/ Constant and the Constant equals 259. The tons per horsepower-hour value is 0.0464, in agreement with Table IV. The exponents for other minerals are listed in Tabl e 11. In Table IIA, the kilowatt hours per ton required to grind these minerals between the same sizes as the quartz, both by the authors&apos; method and the work index equation, are listed. According to the authors kw-hrperton = 259/(16.1)".

Jan 1, 1961