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By T. C. M. Pillay, John Chipman

The Si-0 equilibrium in liquid iron was investigated in some detail by Gokcen and Chipman1 who reported equilibrium constants of the following reactions: In each case the thermodynamic equilibrium constant K was obtained by extrapolating K' to infinite dilution. Their results on reaction [I] were consistent with those of earlier observers, and there seems to be little doubt as to the approximate validity of the equilibrium product determined. On the other hand, the results on reactions [2] and [3] indicated unusual curvilinear relationships between the activity coefficients of silicon and of oxygen and the silicon concentration. Since a linear relation is observed in all other similar instances, it was concluded that some source of error had affected the gas-metal equilibrium relationships. Recently the authors undertook a restudy of these equilibria with the view especially to establishing the equilibrium constant of reaction [2]. Their experiments, however, were discontinued before a tbroughly satisfactory answer had been obtained and consequently have remained unpublished until the present time. Quite recently Matoba, Gunji, and Kuwana2 published the results of a very thorough study of these equilibria. It is the purpose of the present note to Compare these three sets of experimental data, a comparison which leads to Confirmation of the results of Matoba and coworkers. The experimental arrangements described by Dutilloy and Chipman were employed. A controlled mixture of Hz, H,0, and argon was led into the induction furnace over the surface of the Fe-Si melt contained in a silica crucible. On account of the slow approach to equilibrium, runs were continued for at least 8 hr and, in some cases, as much as 12 hr. Samples were taken by means of silica tubes at the start and during the final 4-hr period of each run. Out of twelve runs only seven appeared to have approached equilibrium with sufficient certainty to be reported here. The results of these experiments, all at 1600°c, are shown by the triangles in Fig. 1. Equilibrium was approached from both oxidizing and reducing conditions and the direction of approach is indicated by the shape of the triangle. Attempts to extend the study to higher silicon concentrations were unsuccessful on account of the transfer of silica from the metal bath to the upper portions of the crucible by means of a silicon-monoxide mechanism. Matoba, Gunji, and Kuwana used similar methods and approached equilibrium from both sides. Their results at three temperatures are shown by the solid lines of Fig. 1. A line corresponding to 1600 deg is interpolated from their equations and is shown by the dotted line. The results of Gokcen and Chipman at 1600 deg in the range 0.02 to 2.0 pct Si are also shown. At concentrations up to about 0.6 pct Si, these investigators approached equilibrium from both directions, and their results in this range appear to be trustworthy. Above 1 pct Si, however, all of their experiments involved oxidation only, as shown by a decrease in the silicon content of the bath. It now seems certain that they failed to reach equilibrium at these higher silicon concentrations and that the curvilinear relation shown by their results is incorrect. It is evident that their results in the lower silicon range are in good agreement with those of Matoba and coworkers. In fact, a straight line drawn through their results would parallel the dotted line and would differ from it by only 0.05 in log K. The new data also lie close to that line. It may thus be concluded that the three sets of data are in good agreement and that the equations proposed by Matoba and coworkers for reaction [2] are satisfactory . They take the limiting value of log K', at 0 pct Si as log K ,. The slope of each line gives the value

Jan 1, 1962

By Mary F. Koehler

Continuing a program of thermochemical investigation of compounds of to ferroalloy elements, this paper contains ins values of the heats of formation of two sodium molybdates (Na2Mo04 and Na2Mo207) and three sodium tungstates (NO2W4, Na2W207, and NA2W207, and Na2W4013). The experimental method was solution calorimetry. The solution medium was sodium hydroxide solution, except that hydrofluoric acid solution was used for sodium tetratungstate. The heat of formation values are given with reference both to the constit¬uent elements and to the constituent oxides. These data are of prime impor¬tance in the thermodynamic consideration of these substances, as their accumulation includes the most difficult and time-consuming steps toward evaluating the free energies of formation and thus the potential reactivities and thermal stabilities. Except for values for sodium monomolybdate and monotungstate, no previous similar data were contained in literature sources.

Jan 1, 1962

By L. F. Mondolfo, B. E. Sundquist

The undercooling associated with the nucleation of the secondary phase from the liquid by the solid primary phase was studied in sixty binary alloys by means of a hot-stage microscope. It was found that in a system of a and ß, a usually nucleates ß at low undercoolings, but ß does not nucleate a, except possibly at undercoolings approaching homogeneous nucleation. This behavior can be explained in terms of relative interfacial energies and shows that crystallographic disregistry is only a minor factor in heterogeneous nucleation from metallic liquids. PREVIOUS experimental work1-6 on nucleation of solids from liquids has shown that normally nucleation is heterogeneous, and that small solid particles present in the liquid are responsible for the nucleation. These experiments and the theory that has evolved from them have made apparent that there is a "characteristic undercooling" associated with the nucleation of the solid from a given liquid by a given impurity. Little is known, however, about the chemical and structural relationships between the nucleating agent and nucleated solid that control the effectiveness of the nucleating agent in catalyzing the nucleation, as measured by the required undercooling. A review of the literature has yielded seventeen undercoolingsL-6 for the nucleation of solid from liquid metals by "known" nucleating agents. All values come from experiments in which the metal studied was divided into a number of particles (10 to 300 pin diam.) much larger than the number of extraneous impurity particles so as to obtain a large number of particles free of foreign nucleating catalysts. Known nucleating agents are then introduced by coating the droplets with particles or a thin film of the catalyst. Six of the seventeen undercooling values referred to cases where, for various reasons, the identity of the nucleating species was not at all certain. Another six cases involved nucleating agents with a crystal structure that was not known. Four other cases involved undercoolings listed as greater than or equal to undercoolings which were very likely those for homogeneous nucleation. One investigation3 involved adding to droplets powdered oxides, carbides, and so forth that were doubtlessly covered with adsorbed oxide or nitride films. The highly variable nature of these films resulted in highly variable undercooling (as was also found in preliminary work in this investigation). It is apparent that the information on heterogeneous nucleation in liquid metals is too limited to give rise to any definite conclusions on the nature of the catalytic process. With these problems in mind a new method was

Jan 1, 1962

By N. M. Levine

This work defines and systematizes the physical factors of the problem of leaching and demonstrates for the first time the utility of macropore volume, micropore volume, specific surface, pore size distribution and permeability as parameters of leaching based on a study of the recovery of uranium from the Top Black member of Chattanooga Shale.

Jan 1, 1962

By John C. Machisak

THIS CHAPTER of the Minerals Yearbook (Volume III) contains overall injury experience for coal mines, both anthracite and bituminous, coke plants, petroleum and natural gas, peat, and asphalt and related bitumens (native); metal mines, their metallurgical plants, including ore-dressing plants and primary nonferrous reduction plants and refineries; nonmetal mines; nonmetal mills; sand and gravel operations; slag (iron blast-furnace) plaints; and stone quarries and their related pants. Volume I of the yearbook contains a chapter showing injury experience and employment data treated separately by metal mines, nonmetal mines, quarries and their related plants, metallurgical plants (ore-dressing plants and primary nonferrous reduction plants and refineries are shown separately), nonmetal mills, sand and gravel plants, and iron blast-furnace slag plants. Volume II contains injury and employment experience in the fuel industries (coal, coke, petroleum and natural gas, asphalt and related bitumens (native), and peat. Injury and employment data are submitted voluntarily for the mineral operations through an industry canvass made by the Bureau of Mines, except for the coal industry, whose reports are mandatory. Information published in this chapter is the result of this canvass. Figures presented in this chapter for 1961 are preliminary except for anthracite, peat, coke, petroleum and natural gas, asphalt and related bitumens, and slag. These preliminary data, with the exception of bituminous coal, are a summation of reports received by May 31, 1962, from the operators showing their injury and employment experience. Estimations of injury and employment experience are not included in these preliminary data.

Jan 1, 1962

By V. T. Dow

This report describes construction details and methods used in driving the 5490 tunnel at the Kennecott Copper Corp, property, Bingham, Utah. The tunnel will provide railroad access to the world-famous open-pit copper mine at the projected 5490 level. This publication is one of a series prepared by the Bureau of Mines to depict mining operations and techniques in various mining districts in the United States. Utah Construction and Mining Go. (formerly Utah Construction Co.), contractor on the tunnel project, began work during September 1956 and completed the project in February 1959. The tunnel is 18 feet wide, 24 feet high, and about 18,000 feet long, It will accommodate a railroad locomotive on standard- gage track. With the exception of the last 1,700 feet, the tunnel is supported by steel sets embedded in concrete lining. The 1,700-fact segment of the tunnel is supported by timber sets that will eventually be removed as the pit is deepened.

Jan 1, 1962

By D. Bienstock

As part of the development of the hot-carbonate scrubbing process by the Bureau of Mines, the corrosion rates of steel in boiling solutions of potassium carbonate saturated with carbon dioxide and hydrogen sulfide were determined, and the effectiveness of various inhibitors was evaluated by Bureau researchers. The highly corrosive solution of carbonate saturated with carbon dioxide can be inhibited with a 0.2-percent concentration of either potassium chromate or sodium metavanadate. Solutions of carbonate saturated with carbon dioxide and hydrogen sulfide are mildly corrosive, 0.01 inch per year. Complete absence of corrosion is obtained with 0.2 percent sodium metavanadate or 0.15 percent vanadium pentoxide. Oxidizing inhibitors such as potassium chromate are destroyed in the alkaline sulfide mixture, N-alkyl trimethylene diamines, at a concentration of 0.1 percent, lower the corrosion rate to about 0.005. Sodium metasilicate, at a concentration of 0.6 percent, completely inhibits the corrosion but may deposit free silica in the system. Commercial cladding materials such as the epoxy coatings also prevent corrosion.

Jan 1, 1962

By S. R. Borrowman

Physical beneficiation, leaching, and solvent extraction investigations were made to recover a high-grade thorium oxide product from Bald Mountain, Wyo., conglomerate. The monazite in the Bald Mountain deposit contains 8.8 percent Th02 and, therefore, is higher in thorium content than the usual domestic or foreign monazite. A sample of composited drill cuttings for the study contained 4.3 pounds of monazite per ton of are. The work showed that the monazite, although unusually fine grained and friable, could be concentrated by tabling and magnetic treatment to yield a product assaying 5.65 percent Th02 with a recovery of 61 percent of the thorium. Subsequent decomposition of the concentrate by treatment with sulfuric acid and solvent extraction of the resultant solution with a primary aliphatic amine yielded a thorium oxide product of 99-percent grade.

Jan 1, 1962

By D. L. King, B. A. Schepman

A number of unique thickener mechanism designs with the operating results achieved in various installations are discussed. These unusual designs include new types of raking arms, lifting devices, and feed-wells employed to obtain higher underflow densities and minimum operator control or improved overflow clarity. Several installations of large thickeners in which the underflow lines pass upward through the center to eliminate tunnels are reviewed. The location of the lines and pumps with the maintenance and operating records are included. Several types of automatic lifting device controls are used to provide storage in the thickener. Some of the installations employing underflow density controls are achieving excellent operating results. Thickeners or sedimentation basins are used in minerals beneficiation plants for three basic purposes. These are 1) Concentration, or to raise the density of a liquid-solids slurry. 2) Clarification, or removal of finely divided solids from a slurry. 3) Hydroseparation, or removal of a specific fraction of solids from a slurry. The concepts that control the size and configuration of basins used for these purposes are different. Likewise, different equipment is properly employed to accomplish these various objectives. The pattern of liquid and solids flow in the clarification zone of a sedimentation basin used for thickening or raising the density of a pulp normally is not critical. That is, the solids normally will drop or plunge to the bottom quite readily, and the liquid separates itself from these solids so as to overflow the basin in a relatively clear condition. When clarification or removal of finely divided particles is to be accomplished, the flow patterns in the basin are extremely important. The velocity of the incoming stream must be dissipated and the liquid flow distributed ]In the tank so that the feed is not divided into streams that flow directly to the overflow carrying the fine:ly divided solids that are to be removed. Similarly, the configuration of the arms that provide the raking and thickening of the pulp is not as important in basins primarily devoted to clarification. In thickening, the design of the arms and the manner in which the pulp is moved or worked, can contribute appreciably to the thickening process and achievement of a higher density underflow. THICKENING As the grade oi ore bodies throughout the world generally decreases, and chemical processes, hydro-metallurgy, and other more refined methods of minerals beneficiation are required, problems in thickening become more acute. Difficult operating conditions, previously encountered only occasionally in thickening metallurgical slurries, or clarifying process streams in the mill, are now the rule rather than the exception. Fig. 1 illustrates some of the different types of raking arms that are successfully achieving the desired goals in pulp thickening. The conventional raking arms consist of a relatively simple truss with the blades attached to the bottom chords. This design provides proper Concentration of many 'normal' slurries. A modificaiion of this design as shown in the center is being used with excellent results on large thickener basins where it is desirable to have a

Jan 1, 1962

By Donald J. Knight

HEAT Treatment at 1500' F of a mild steel containing 0.1 pct C, in an atmosphere which is oxidizing to both carbon and iron, results in the progressive oxidation of the metal surface with little or no change in the carbon content of the underlying metal. Further heat treatment of the scaled metal in either a neutral atmosphere or in a vacuum may or may not result in the decarburization of the metal depending upon the physical nature of the scale. It is apparent that if a continuous layer of oxide is present on the steel surface, the reaction OScale + Cmetal Cogas cannot progress since the SO formed gas would be unable to leave the oxide/metal interface. Thus, in order for the reaction to progress, the oxide must be cracked or porous. Vacuum heat treatment at 1500" F of samples with a thick continuous oxide scale showed no decarburization of the steel. However, when cracks were introduced mechanically into the scale prior to the vacuum heat treatment notable decarburization of the metal resulted and a structure as shown by Fig. 1 obtained, i.e., reduction of the crack walls to ferrite. With reference to the diagram of Fig. 2, it would appear that a mechanism of the following type takes place. Carbon atoms arriving at an oxide/metal/void interface, such as 'A', Fig. 2(a), can combine with oxygen atoms from the scale and leave the reaction site as Cogas thereby reducing the oxide to metal. On a greatly magnified scale, Fig. 2(b),this will appear as a ferrite projection along the crack wall. Carbon atoms entering this projection can react with oxygen atoms at point 'C', which is a new interface, and so on leading to a progressive growth of the ferrite along the crack wall and to the surface, Figs. 2 (c) and 1. It would appear that the only means by which thickening of the ferrite film can take place is by a diffusion of oxygen through the ferrite film to react with carbon at the newly formed ferrite/ void interface. Since the diffusion rate of carbon is reportedly much greater than that of oxygen, and since there is a low probability factor of oxygen and carbon atoms arriving simultaneously at the same site on the ferritehoid interface, there will be a tendency for more rapid lengthening than thickening of the ferrite layer, as is observed.

Jan 1, 1962

By William J. Campbell

The purpose of this investigation was to extend the analytical services which are required for Bureau of Mines programs in developing and evaluating high-purity materials. Determination of trace elements in minerals and ores as an aid in geochemical evaluation and prospecting was considered. Serious consideration should be given to the merits of using the avail- able fluorescent X-ray spectrographic instrumentation and techniques for determining trace elements. Limits of detectability for trace elements in metal, oxide, solution or mineral samples range from 0.1 to 100 p.p.m, depending on the element being determined, overall sample composition, and the complexity of the X-ray spectra; limits of detectability range from 0.01 to 1 microgram for elements that have been preconcentrated by a chemical or physical process, for example, by ion-exchange membrane.

Jan 1, 1962

By H. D. Kline

This publication describes methods and techniques of mining and crushing limestone at 3 of 11 small quarries operated by Anderson-Oxandale Rock Co. in northeast Kansas in 1959. It is one of a series of reports by the Bureau of Mines on methods and costs of mining in various mining districts in the United States. The three quarries selected for study -Bosse quarry, Pottawatomie County; Hansen quarry, Morris County; and Huston quarry, Dickinson County (fig. 1) -were in many respects similar to many others that had been developed solely to fill local and usually transitory demands for crushed limestone for use as concrete aggregate, roadstone, and soil conditioning. Factors governing the choice of quarry sites were quality of limestone, shallow overburden, and proximity to points of consumption of the crushed stone.

Jan 1, 1962

By J. G. Donaldson

Optimum conditions are given for chloridizing pyrite, marcasite, chalcopyrite, arsenopyrite, stibnite, and covellite with chlorine gas. The formation of metal chlorides is affected by the time and temperature of chloridizing, and by particle size of the sample. Chloridizing data also are given for chemically precipitated antimony (III) sulfide and copper (II) sulfide.

Jan 1, 1962

By Chand F

The silver deposits of Rockvale near Armidale, N.S.W., occur in fissure veins in epi-Permian granite. The ore is fine grained, mineralogically complex, and contains twenty-seven different minerals including eleven silver minerals. The ore is characterized by a unique multiple unmixing from a sphalerite solvent. The following minerals have exsolved from solid solution in sphalerite: pyrrhotite, chalcopyrite, cubanite I, cubanite II (chalcopyrrhotite), valleriite, "brown" stannite, "olive" stannite, argentian tetrahedrite, pyrargyrite, and an unknown grey-white mineral. Several of these minerals derive from a second-stage unmixing, the immediate solvents of which are the products of earlier exsolutions.INTRODUCTIONSmall silver-rich base metal deposits occur at several localities near Armidale in the New England district of New South Wales. Chief among these are the Tulloch Mine and the Rockvale Mine at Rockvale, 27 miles SE. of Armidale, and the Tait's Gulley deposits some 15 miles NE. of Armidale.At Rockvale (Kenny, 1928), irregular lenses of lode material, principally quartz and calcite, occur along a zone of shearing in biotite granite and altered sediments. The orebodies had a maximum width of 6 ft but averaged 2 ft 6 in. The largest lens was 150 ft long and 50 ft high. The Rockvale deposits were worked for both arsenic and silver; 2,897 tons of arsenic were produced but no figures are available forsilver.Little is known of the Tait's Gulley deposits which occur in folded arenites containing small but rich veins of pyrargyrite with base metal sulphides.The sediments in these localities are possibly Silurian.

Jan 1, 1962

By A. M. Poston

Introduction of radioactive elements into ore samples and/or pregnant liquors and radiometric tracing thereof have greatly improved control of fusion and extraction studies on beryllium ores and products. Extractive metallurgical research on beryllium, normally guided by the usual laborious analytical methods, is both costly and slow. Recognition of this problem by the Bureau of Mines led to the development and application of radioisotope tracer techniques" as a substitute for chemical analysis at the Salt Lake City Metallurgy Research Center, The result was that much faster progress at significantly lower cost was achieved. This report discusses the problems encountered and resolved in using radioactive tracers and radiometric methods, defines the conditions and techniques for their effective use, and delineates the limitations and flexibility inherent in applying such methods in laboratory-scale beryllium research.

Jan 1, 1962

By E. T. Turkdogan

Jan 1, 1962

By N. E. Hanna

The current list of permissible explosives includes 124 different brands. Fifteen of these are gelatinous, and the rest are the more commonly used granular ammonium nitrate type. Their rates of detonation range from 1,300 to 5,600 meters per second, and the weights of 1-1/4 x 8-inch cartridges range from 86 to 244 grams. The list of permissible blasting devices includes 1 Cobra, 2 Hydrox, and 9 Cardox models. All of these devices are based on discharge of high-pressure gas from a pressurized shell in a shothole. INTRODUCTION To be approved for use in underground coal mines in the United States, explosives and blasting devices must pass certain schedule tests prescribed by the Bureau of Mines. The explosives listed here were tested under Schedule 1-G,3 which has since been replaced by Schedule 1-H;4 the blasting devices were tested under Schedule 26A.5

Jan 1, 1962

By B. Wilshire, P. W. Davis

It has been shown that grain-boundary migration during high-temperature creep can reduce or even prevent the formation of intercrystalline voids, giving a considerable increase in ductility.' A similar observation has been made in a recent investigation of the creep properties of various grades of nickel and nickel alloys. The results can be illustrated by the observations made on: a) Pure vacuum-cast nickel (99.993 pct Ni) b) Impure vacuum-cast nickel (99.97 pct Ni) c) Pure nickel containing internal voids (produced by a process of intering). d) A substitutional solid solution alloy of pure nickel containing 1.16 pct Sn. All the materials were given a high-temperature anneal (>850°C) to produce a stable grain size of 7 to 10 grains per linear mm. The apparatus and techniques used to obtain the present results have been described elsewhere.' In this series, grain growth was observed only in the highest-purity, vacuum-cast metal. Thus we may consider that in the other materials grain-boundary migration was prevented by either preexisting voids or solute atoms. The effect of migration on the creep ductility of the above materials can be seen from Fig. 1, which

Jan 1, 1962

By W. W. Weller

Thermodynamic values for scandium and its compounds are very sparse. This is evident upon examination of any of the commonly used compilations of thermodynamic data. For example, National Bureau of Standards Circular 5004 lists only four heat of formation values, two free energy of formation values, and four heat-capacity values for scandium compounds. The entropy of crystalline scandium is one of the most fundamental values that has been lacking. This Bureau of Mines paper reports heat-capacity data for scandium metal in the temperature range from 50° to 298° K., together with the entropy value at 298.15° K. derived from these data through application of the third law of thermodynamics.

Jan 1, 1962

By W. A. Tiller, J. D. Harrison

HOT pressing of powder particles has gained importance recently, since it affords a method in which high densities are rapidly attained. In a recent study on hot pressing of alumina powders, Mangsen, Lam-bertson, and Best1 have shown within the limits of their experiment, the validity the rate equation for densification in hot pressing, originally proposed by Murray, Livey, and Williams.2 i.e., where D = fraction of theoretical density, t = time, P = pressure and 77 is the viscosity, all in appropriate units. This equation was derived from earlier work of Shuttleworth and Mackenzie3 which is based on the closing of spherical pores under the action of surface tension. The integrated form of this equation yields a straight-line relation between log (1 - D) and t. Such conditions were found by Felten4 to be true only after extended periods of pressing. In an endeavor to quantitatively evaluate the exactitude of this equation in the initial sintering stage, i.e., prior to sealing of the pores, spherical anti-

Jan 1, 1962