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By R. C. Buehl, J. P. Riott, E. P. Shoub

PILOT-PLANT tests have demonstrated that it is possible to produce low-sulphur sponge iron (0.03 to 0.05 per cent sulphur) as a continuous process in an internally fired rotary kiln from iron ore or mill scale; a solid carbonaceous reducing agent; and dolomite to control the sulphur content. The proportion of dolomite employed is small, so that it does not add materially to the cost of the sponge iron. The entire operation is carried out at temperatures well below the melting point of iron, so that the product is discharged in granular form. Compared with other methods for the production of sponge iron, the rotary-kiln method has the advantage of simplicity and low cost of equipment and; in addition, requires little labor for the operation of the process. The pilot-plant equipment used for this work was sufficiently large to demonstrate that the production of low-sulphur sponge iron in rotary kilns is feasible and that the costs are not excessive for applications in which sponge iron has distinct advantages over competing materials. This report constitutes a part of a program by the Bureau of Mines under a special Congressional appropriation for studying gaseous and solid fuel reduction of iron ores. Numerous articles on various phases of these investigations have appeared in Bureau of Mines publications or technical journals. Other articles are being prepared and will be published in the near future. The present program, which is under the supervision of Dr. R. S. Dean, Assistant Director of the Bureau of Mines, was initiated in .1942. However, a considerable portion of the work was a continuation of previous research performed by the Bureau. Previous investigators1-4 utilizing the rotary kiln for the production of sponge iron did not develop a suitable method for controlling the sulphur content. A review of the literature shows that the sulphur content in the product usually exceeded 0.2 -per cent unless reducing agents with very low sulphur contents were employed. This high sulphur value made the product generally undesirable for use as melting stock in electric or open-hearth furnaces. The production of sponge iron in an internally fired rotary kiln has been described in detail in Bureau of Mines Bulletin 2702; consequently, this article will be confined mostly to new features of the process-that is, means for controlling the sulphur content of the sponge iron. Suitable raw materials include iron ores or mill scale; coal or coke for reducing them, and sized dolomite (-20+100-mesh) as the sulphur-controlling agent. A mixture of the raw materials in granular form is fed into the elevated end of the kiln, which is fired axially from the lower or discharge end. In the reducing zone, which is approximately one third the length of the kiln measured from the dis-

Jan 1, 1946

By J. R. Thoenen, M. C. Malamphy, G. K. Dale

The beginning of the war and the events leading up to it precipitated a near crisis in the aluminum industry. Demands for the metal reached proportions far beyond the prewar production capacities and, in addition, the submarine menace seriously curtailed the importation of bauxite from South America, hitherto a chief source of high-grade ore. The situation required an intensive search for domestic ore to augment the reserves and in October 1941 Congress directed the Department of the Interior to investigate the extent, mode of occurrence, and quality of bauxite in the United States. In December of that year the Bureau of Mines and the Geological Survey began the search for bauxite in Arkansas, where more than go per cent of the domestic ore had been produced and where the greatest amount of bauxite was known to occur. The program involves the geophysical and geological investigation of the Arkansas bauxite region and the core drilling of areas considered favorable for the occurrence of bauxite deposits. Cores taken from the bauxite-kaolin zone are sampled and analyzed in the Bureau of Mines laboratory in Little Rock. The information from each of the deposits discovered is then assembled, the bauxite is graded with respect to its possible utility, tonnage estimates are made, and the whole is presented in the form of a war minerals report. Thirty-eight new bauxite deposits had been discovered and investigated at the end of the calendar year 1944, and the presence of several others had been indicated by the drilling. More than 5000 holes had been drilled throughout the bauxite region, and more than 60,000 chemical analyses had been made of samples taken from the bauxite-kaolin zone. A study of the chemical analyses led to certain general conclusions not only with regard to the chemical composition of Arkansas bauxite, but also with regard to its component minerals. Charts and diagrams based on these conclusions have been developed for practical use by the Bureau of Mines: (I) to serve as a check against laboratory analyses, (2) to present tonnage estimates of ore bodies based on mineral composition, (3) to illustrate the relationship of tonnages of bauxite to the alumina, silica, and iron content, and (4) to serve as a control for mining operations by providing a means for quick estimates of the value of the ore from a partial analysis of its chemical constituents. The use of charts and diagrams similar to those discussed in this paper-- is not new. The use of the trilinear diagram for studying the ultimate analyses of coals as of proposed by Ralston in Bureau of Mines Technical Paper 93 (1915) showed that the various ranks of coal fell in different areas on the diagram and that volatile matter, calorific value and other properties could also be plotted by the use of contours. A considerable subsequent literature, largely on classification of coals, has accurnulated since then, showing the utility

Jan 1, 1948

By J. R. Thoenen, M. C. Malamphy, G. K. Dale

The beginning of the war and the events leading up to it precipitated a near crisis in the aluminum industry. Demands for the metal reached proportions far beyond the prewar production capacities and, in addition, the submarine menace seriously curtailed the importation of bauxite from South America, hitherto a chief source of high-grade ore. The situation required an intensive search for domestic ore to augment the reserves and in October 1941 Congress directed the Department of the Interior to investigate the extent, mode of occurrence, and quality of bauxite in the United States. In December of that year the Bureau of Mines and the Geological Survey began the search for bauxite in Arkansas, where more than go per cent of the domestic ore had been produced and where the greatest amount of bauxite was known to occur. The program involves the geophysical and geological investigation of the Arkansas bauxite region and the core drilling of areas considered favorable for the occurrence of bauxite deposits. Cores taken from the bauxite-kaolin zone are sampled and analyzed in the Bureau of Mines laboratory in Little Rock. The information from each of the deposits discovered is then assembled, the bauxite is graded with respect to its possible utility, tonnage estimates are made, and the whole is presented in the form of a war minerals report. Thirty-eight new bauxite deposits had been discovered and investigated at the end of the calendar year 1944, and the presence of several others had been indicated by the drilling. More than 5000 holes had been drilled throughout the bauxite region, and more than 60,000 chemical analyses had been made of samples taken from the bauxite-kaolin zone. A study of the chemical analyses led to certain general conclusions not only with regard to the chemical composition of Arkansas bauxite, but also with regard to its component minerals. Charts and diagrams based on these conclusions have been developed for practical use by the Bureau of Mines: (I) to serve as a check against laboratory analyses, (2) to present tonnage estimates of ore bodies based on mineral composition, (3) to illustrate the relationship of tonnages of bauxite to the alumina, silica, and iron content, and (4) to serve as a control for mining operations by providing a means for quick estimates of the value of the ore from a partial analysis of its chemical constituents. The use of charts and diagrams similar to those discussed in this paper-- is not new. The use of the trilinear diagram for studying the ultimate analyses of coals as of proposed by Ralston in Bureau of Mines Technical Paper 93 (1915) showed that the various ranks of coal fell in different areas on the diagram and that volatile matter, calorific value and other properties could also be plotted by the use of contours. A considerable subsequent literature, largely on classification of coals, has accurnulated since then, showing the utility

Jan 1, 1948

By W. F. Carew, F. A. Crossley

Tensile, creep-rupture, and stability tests were employed to evaluate the effect of a-strengthening and ß-complexing additions on the base composition Ti-6Al-3Mo. The ultimate objective was to produce an alloy of greater strength than the Ti-7A1-3Mo alloy. Strengthening of a was accomplished by additions of 2 and 4 pct Ge, 4 pct Sn, 4 pct Zr, and 2 pct Sn-2 pct Zr. Making the ß more complex while keeping the total of ß-stabilizing additions constant at 3 pct resulted in higher tensile strengths but lower creep and rwpture strengths, especially at 1000°F. None of the more complex versions of the base alloy offers greater promise than the Ti-7A1-3Mo alloy. However, some improvement in the strength of the latter may follow from additions of zirconium perhaps up to 4 pct. PREVIOUS work directed at the development of titanium-base alloys with: 1) minimum room-temperature tensile elongation of 10 pct in 1 in., 2) high creep resistance at elevated temperature, and 3) the ability to retain original room temperature tensile ductility following exposure to creep conditions at elevated temperatures, demonstrated Ti-Al-Mo ternary compositions in the range 5 to 7 pct Al-3 to 6 pct Mo to be the most promising. Of this group the Ti-7Al-3Mo alloy was the strongest.'-= The objective of the present work was to determine if alloys of this type could be further strengthened by making additions which dissolve preferentially in the a-phase and by making the ß-phase more complex. For this study the base composition Ti-6Al-3Mo was selected rather than Ti-7Al-3Mo in order to minimize the possibility that in a more complex alloy with a-strengthening additions, low ductility might obscure the strength contribution. The metals

Jan 1, 1959

By L. Himmel, R. F. Mehl, C. E. Birchenall

The rates of self-diffusion of iron in artifically prepared wustites of various compositions have been determined using the decrease in surface activity technique. Similar measurements are reported for artificial magnetites of nearly stoichiometric composition and for natural hematite single crystals. These data, together with appropriate thermodynamic data derived from the present study or from the literature, are used to calculate the rates of oxidation of iron and its oxides, taking as a basis the theoretical rate equations developed by Wagner. The calculations are compared with experimental rate constant data for these same reactions and are shown to provide essential confirmation for the Wagner theory. For the most part, the results are also consistent with the previously proposed transport mechanisms in the oxides of iron. WHEN a metal is exposed to an oxidizing atmosphere at elevated temperatures, a superficial oxide layer is formed which then thickens according to some characteristic rate law. Provided that the oxide layer is dense and continuous and does not present any paths for gaseous diffusion, continued growth must inevitably involve the migration of the reactants—either the metal or oxygen or both—through the lattice of the solid oxide. This is true whether the reaction rate is controlled by the diffusion process itself or by a slow step in a reaction at one of the interfaces. If the overall rate is limited by diffusion, and if the concentrations or thermodynamic activities of the reactants at the boundaries of the oxide layer are independent of time, the familiar parabolic rate law is observed. Under these conditions, Wagner1 has shown that the rate constant may be expressed in terms of the mobilities of the reacting components and the appropriate concentration or activity gradients which are established across the growing oxide layer. In presenting the phenomenological basis for the theory, Wagner has emphasized the role played by lattice defects in diffusion processes in oxides. The essential validity of this theory has been confirmed by experiment for a number of simple systems including the growth of Cu2O on copper.'-' One of the objectives of the present study has been to extend the Wagner approach to the more complex process of the oxidation of iron and its oxides, and particularly to wustite, which is normally the major constituent of the oxide scales formed on iron at temperatures above approximately 570°C. For this purpose the rates of self-diffusion of iron in w?stite, magnetite, and hematite have been measured by tracer techniques and the necessary thermodynamic data have been obtained from equilibrium studies involving the oxides and their atmospheres. These data have subsequently been used to test the underlying assumptions of the Wagner theory as well as the detailed mechanism of the scaling of iron previously proposed by Davies, Simnad, and Birchenall.5 Lengthy treatments of diffusion and conduction phenomena in ionic crystals have been published." * The latest, by Jost,8 also summarizes much of the existing experimental data. In general, however, the oxides of iron have not been considered specifically and hence a brief review of the available

Jan 1, 1954

By W. A. Anderson, F. N. Rhines, W. A. Johnson

The rate of the high-temperature oxidation of pure copper has been measured repeatedly by numerous investigators. It appears to be generally agreed: (I) that at constant temperature, after the initial stages of oxidation have been passed and the scale has attained a substantial depth, the film thickness increases in proportion to the square root of the time of oxidation; and (2) that for any given period of oxidation the logarithm of the square of the film thickness is proportional to the reciprocal of the absolute temperature of oxidation.' These relationships are explained upon the basis that the rate of diffusion of copper to the external surface of the film is the controlling factor in establishing the rate of growth. Extensive studies have been devoted also to the mechanism and rates of the early stages of oxidation. There is thus available a reasonably well established theory of the oxidation of pure copper upon which to construct an explanation of the more complex oxidation of copper alloys. Few general principles have as yet emerged from the chaos of observations that have been reported in the field of the oxidation of alloys.2 It is evident, however, that the copper alloys may be divided into two main groups, whose oxidation characteristics are distinguish- able. The first group, composed of the alloys with the noble metals, forms substantially pure copper oxide scales; the alloying element is concentrated within the residual metal, and sometimes particles of almost pure noble metal are found in the scales completely surrounded by copper oxide. In the second group, composed of the alloys of copper with the baser metals, the alloying element appears as an oxide in the scale, often in greater concentration than in the alloy itself and sometimes to the exclusion of copper oxide. The oxide scales of the latter class have been found to be made up of one, two, and sometimes more distinguishable layers of which the innermost is often metallic in character, composed of particles of the oxide of the alloying element embedded in essentially pure copper and known as the subscale or zone of internal oxidation. The need for a thorough quantitative study of these modes of oxidation is evident. Since it is apparent that several mechanisms must be cooperating to produce the complex oxide scales found on copper alloys, the analysis of the process into its several simple operations should prove instructive. Fortunately, it is possible experimentally to produce internal oxidation in the absence of an external scale; this permits the isolation and intensive study of one of the steps in the oxidation process. In the present research the rates of internal oxidation of an extensive series of dilute solid solution alloys of copper have been measured and a theory has been developed to predict the observed

Jan 1, 1942

By G. L. F. Powell

Bulk samples of silver have beat undercooled lo a large degree in contact with crystalline siliceous and ceramic oxide materials, indicating lhat stable oxides and oxide compounds are not the heterogeneous nucleants which normally catalyze cryslallization within a feu degrees of the equilibrium freezing point. Since 400-g samples were undercooled 250°C in contact with cristobalite, it is concluded that the undercooling required for homogeneous nucleation of sil11er is greater than 250°C. Undercooling was Jacilitated by precleaning the crucibles with a high-fires -sure blast of gas. IN numerous experiments on the undercooling of metal melts it has been assumed that a solid glassy surface, being non crystal line, will have no effect in catalyzing crystal nucleation from the melt. Conversely, it is usually accepted that any crystalline surface, in contact with a metal melt, will catalyze nucleation of metal crystals from the melt at degrees of undercooling less than that at which homogeneous nucleation will occur. Both these assumptions were implicit in the claim that homogeneous nucleation was observed in experiments1'2 on the undercooling of small metal droplets (10 to 100 mp diam). The droplets were thought to be freed of suspended crystalline particles which would otherwise catalyze heterogeneous nucleation. They were supported on flakes of silica glass which were assumed to be amorphous, and therefore incapable of acting as substrates for heterogeneous nucleation. In later experiments, large samples of molten metal were undercooled to temperatures similar to those achieved by the droplet technique by melting in a fused-silica crucible3 or a boro-silicate glass slag.4 Since these samples were usually fully enclosed in glass at the moment of freezing, it seemed possible that nucleation was homogeneous when maximum degrees of undercooling were achieved, despite the large size of the samples (up to 500 g). In experiments on the undercooling of silver5 the metal was contained in vitreous silica crucibles, the

Jan 1, 1968

By Wallace Thorneycroft

This paper by Mr. Thorneycroft, Past President of the Institution of Mining Engineers (Great Britain), and chairman of its Subsidence Committee, is a valuable contribution to the assemblage of data on ground movement and subsidence from coal mining. It deals with the effects of advancing longwall, a method almost universal in Europe but as yet little used in the United States outside of Northern Illinois and in a few scattered places elsewhere in thin coal beds, as in the Lexington field, Missouri. Canon City field, Colorado, and the Birmingham field, Alabama. Although by advancing lougwall, a maximum recovery of coal is obtained and it has to be employed where there are weak shale roofs, especially in deep mines, it is a more expensive method of operation unless the mining conditions are suitable, which is unusual in the United States. On the other hand, there is a growing use in this country of what is essentially retreating longwall, with an approximately straight break-line as described by Rayburn.1 With this method, in which the pillars are substantial, it was shown that the ground movement effect is practically identical with that of advancing longwall, hence the value to mining engineers of the precise data given by Mr. Thorneycroft. His study is unusual in several respects; it deals with conditions connected with the mining of a coal bed 20 in. thick, about 490 ft. below the surface, over a mined-out area in a 5-ft. bed about 90 ft. below, which had been mined about 12 years earlier. Both mines passed under Plean House, a building of massive cut stone construction built over a century ago, in which Mr. Thorneycroft resided throughout the under-mining period. Slight cracks opened in the walls as the longwall face approached the house in mining the upper seam, and closed after the face passed and subsidence took place. In the northwest wall, the last wall the face passed under, some stone blocks were broken, which was attributed to a strike period when the advance of face came nearly to a standstill. Other than this there was no perceptible permanent damage, as indicated by the photographs taken by the undersigned in 1923 (Figs. 1 and 2). Mr. Thorneycroft used a novel means of studying the successive positions of the corners of the building: he hung plumb bobs from the eaves and traced the paths of the respective plumb bob points on level surfaces. The angles made by the house walls with the plumb bob lines gave measures of the slope of the subsidence wave at the respective points. A slight upward wave was indicated by the surveys ahead of the subsidence, which would appear to be due to a tilting over of the massive sandstone stratum in the roof measures near the surface, the edge of the coal face acting as the fulcrum.

Jan 1, 1931

By Russell Paul

THE Wisconsin zinc district, also known as the Upper Mississippi lead and zinc district, is an area of about 2500 sq. mi. in the southwestern portion of Wisconsin and adjacent parts of Illinois and Iowa. It includes Iowa, Grant and Lafayette counties in Wisconsin, Jo Davies County in Illinois, and an irregular strip of Clayton and Dubuque counties in Iowa, parallel to the Mississippi River. During periods of high metal prices mining has been quite active in this district, but recently the lower metal prices have caused many companies to suspend, so that at the present time there are only a small number of mines operating. The short life of these mines and the low mineral content of the zinc deposits limit the investment in development and equipment, and necessitates the operation of this equipment at maximum running time and maximum capacity. The tonnage of rock handled (locally termed dirt) is large in comparison with the tonnage of concentrate produced. Moreover, the zinc content of the concentrate is low, varying from 25 to 40 per cent zinc, and the value per ton is correspondingly low. The life of the mines varies greatly. An exception-ally good deposit may produce 2,000,000 tons of rock during a period of ten years, market value permitting, from which will be obtained 100,000 to 150,000 tons of concentrate. One property which might be con-sidered as fulfilling the requirements of a profitable operation was developed and equipped in 1925, oper-ated continuously for a period of two and a half years, produced 484,292 tons of rock, from which was obtained 37,659 tons of zinc concentrate, 34.4 per cent Zn, and 1155 tons of lead concentrate, 67 per cent Pb. During the war period prices of ore permitted the mining of lower grade ores than has been possible in the past few years. The maintaining of a higher grade mill-feed has resulted in reducing the size of stopes formerly carried in the old mines and confining the workings within narrower limits.

Jan 7, 1928

By P. E. Baker

An improved method of logging formation density has been developed in which the formation is bombarded with a collimuted beam of gamma rays. By means of a scintillation detector and pulse height discriminator, the gamma-ray energy band is accepted and recorded which corresponds to deepest penetration into the formation. Laboratory tests on a field tool revealed no borehole diameter effect for smooth holes and no effect of formation chemistry, except insofar as chemistry affects density. In extensive field tests, the density log has exhibited satisfactory agree-ment with core measurements and has correlated accurately with other logs. INTRODUCTION This paper describes an improved method of logging formation density by means of back-scattered gamma rays to penetrate the formation together with energy discrimination to select only that energy (or frequency) range corresponding to deepest penetration into the forma- tion. This method of density logging was developed at the La Habra laboratory of California Research Corp.* Field instruments have been built and tested by McCullough Tool Co. and commercial service has begun in some areas. All of the data discussed here were obtained for the original field tool. The density log can be a valuable adjunct to existing logs because of its use in determining porosity quantitatively. It is useful also in connection with seismic and gravity surveys where formation density information is of interest. PHYSICAL PRINCIPLES The intensity, I, of a beam of gamma rays after traversing a distance, x, in an absorbing medium is given by I = loe -ax where I, is the intensity of the beam entering the medium and a the attenuation constant or macroscopic cross section of the medium for gamma-ray absorption. The macroscopic cross section depends on the number and types of atoms per unit volume and the gamma-ray energy. In brief, it is the sum of the atomic cross sections of all atoms per cubic centimeter. The density of the material is the sum of the masses of all atoms per cubic centimeter. Thus, the density and the macroscopic cross section for gam-ma-ray absorption vary in propor- tion to the number of atoms per cubic centimeter. The density of the material increases, of course, if the atomic masses increase without a change in the number of atoms per cubic centimeter. When the density increases in this latter way, the macroscopic cross section increases also, but disproportionately. This results from the fact that part of the gamma-ray absorption arises from the photoelectric effect and the pair-production effect**, which are proportional to the sixth and to the second power, respectively, of the atomic number of the absorber. The remainder of the absorption results from the Compton effect, and is directly proportional to the atomic number. The gamma rays that undergo Compton scattering are not immediately absorbed. Since these rays are scattered in all directions, a fraction will emerge from the face of the medium at which they entered. If a gamma-ray shield is placed between the source and detector, most gamma rays reaching the detector will be those scattered out of the medium. The intensity will depend on absorption and scattering in the medium, and so indicates the density of the medium. For gamma rays for which Compton scattering prevails, the intensity

Jan 1, 1958

By T. A. Read, M. W. Burkart

The crystal geometry of the cubic-tetragonal interface after partial transformation of an indium-thallium alloy single crystal is described and a general theory is presented. The effects of applied stresses on this transformation are interpreted and the latent heat of transformation is obtained from observations of transformation under stress. A DIFFUSIONLESS phase transformation between face-centered cubic and face-centered tetragonal structures has been reported for the indium-thallium system by Bowles, Barrett, and Guttman1, 2 The transformation takes place at approximately 105 "C at 18 atomic pct Tl and 25°C at 23 pct Tl. In their study, Bowles, Barrett, and Guttman used poly-crystalline samples whereas in the present study single crystals were used to eliminate the transformation constraints imposed by adjoining grains. The use of single crystals made possible a comprehensive study of the effect of stress on the transformation. In the course of the work, it was possible to formulate a new method of analyzing dif-fusionless transformations (presented in this paper) which permits calculation of the geometry of the interphase interface from a knowledge of the crystal structures of the initial and final phases. The specimens were prepared from chemically pure thallium and 99.97 pct In which were weighed out to produce 3 to 4 grams of alloy of the desired concentration. The metal was placed in clean fused silica tubing, then melted, degassed and sealed under vacuum. (To obtain single crystals, it was found that both degassing and extreme cleanliness were essential.) Single-crystal specimens were grown by a modified Bridgman technique.8 pecimens were removed from the tube by dissolving the quartz in concentrated hydrofluoric acid which attacks the specimen very slowly. The specimen then was polished mechanically to produce four flat surfaces, electropolished, and annealed at 140°C for 48 hr. The electropolishing solution used was that described by Bowles, Barrett, and Guttman and the polishing was carried out on both the high and low temperature phases of the alloy. The high temperature polishing was done at 110°C with a stainless steel cathode. Visual Observation of the Transformation in Single Crystals A visual study of the transformation was made on specimens which had been electropolished in the high temperature phase. The specimens were supported on the stage of a metallograph by an electrically heated holder which contained an opening for observing the specimen. Visual evidence of transformation was found in the presence of an interface which separated the two phases. The interface plane defines the boundary of the phase undergoing transformation and manifests itself by the sharp change in angle between the surface of the specimen and the incident light at the juncture of the two phases. On slow cooling, well-annealed specimens transformed from the face-centered cubic structure to the face-centered tetragonal structure by the motion of a single plane interface which traversed the specimen from one end to the other. Upon heating, the interface moved back in the reverse direction. The interface could be started, stopped, or reversed at will. A temperature hysteresis of about 31/2oC was observed in the reversal of the interface. Holding an interface stationary caused it to disappear completely in most cases, whereas in other instances the interface became less distinct depending upon its orientation. The interface could be made to reappear by changing the temperature of the specimen. The low temperature tetragonal structure exhibits only the fine markings or subbands reported by Bowles, Barrett, and Guttman and is illustrated in Fig. 1. These subbands are twin-related. Back-reflection Laue patterns show the breakup of the cubic spots into pairs of spots corresponding to the twin orientations of the tetragonal phase.

Jan 1, 1954

By Howard A. Meyerhoff

In western Argentina, in the Province of Mendoza and the Territory of Neuquen, there is a series of solid bitumen deposits which are claimed to be the most extensive in the world. In a linear belt 500 km (311 miles) long, roughly paralleling the axis of the Andes but occupying a variety of positions with respect to the orogenic structures, more than 100 outcrops have been reported. Approximately 70 of these have been prospected, and some mining has been planned or attempted for about half this number. Limited tonnage, high sulphur content, inaccessibility, labor shortages, and disastrous fires have taken a heavy toll among these operations, and in 1947, only 4 deposits were being actively mined, but 8 more were being explored and developed with a view to placing them in production. Inasmuch as these deposits are currently yielding a substantial fraction of Argentina's limited domestic supply of solid fuels, a brief account of the deposits and of the small industry based upon them will provide a commentary on Argentina's fuel problem. Character of Solid Bitumens The solid bitumens of Mendoza and Neuquen are petroleum derivatives, as is indicated by the following ultimate analysis : Constituents Per Cent Hydrogen.................... 6.8 Carbon...................... 82.4 Nitrogen..................... 1.6 Oxygen...................... 2.7 Sulphur...................... 2.2 Ash.......................... 4.3 100. 0 In physical appearance they bear a close resemblance to coal and are commonly called carbon. Their specific gravity has an extreme range of 1.10 to 1.777 in 36 samples weighed, but the average is between 1.14 and 1.24. The material is black, lustrous to dull, with blocky to sub-con-choidal fracture. Though brittle, the purest material is softer than anthracite and exhibits slightly more cohesion. This bituminous material is generally known as asfaltita or asphaltite, but definitive chemical studies indicate that the term asphaltite or grahamite can be applied correctly only to the exceptionally pure material of the Auca Mahuida district in Neuquen. Some other name should be used for the chemically variable bitumens found in all other districts, and the designation "asphaltitic pyrobitumen" has been proposed by Carlos A. S. Piscione.1 At the present time these bitumens are finding favor as solid fuel and as a gas-producing medium. They yield heat values of 8650 to 9750 cal,2 or 14,500 to 16,750 Btu per pound, and in consequence of their excellent heating qualities and the scarcity of imported coal, they are marketed as far away as Buenos Aires at a price of go to 95 pesos, or approximately $22 to 23, per metric ton. In burning, the material swells and decomposes into solid, fluid, and gaseous fractions which burn violently though nonexplosively. Its combustibility has been responsible for disasters and virtually complete destruction at Mina La Es-peranza and Mina Santa Marta, and for minor mishaps elsewhere, as at Mina Escondida in August 1947.

Jan 1, 1949

By D. N. Seidman

In the course of a study of the electronic and thermodynamic properties of Pb-Se alloys it was found necessary to have an accurate knowledge of the phase diagram. However, the literature is in disagreement as to whether or not a monotectic reaction occurs in the lead rich portion of the phase diagram. Pelabonl reported only a two-phase region consisting of lead-rich liquid and solid PbSe extending from almost pure lead to the compound PbSe, and gave the melting point of PbSe as 1065°C. The data of Friedrich and Leroux2 are in general agreement with this type of diagram, with the melting point of the compound being 1088°C. However, Nozato and Igaki by inverse rate thermal analysis observed a monotectic reaction isotherm exlacing at 860°C with a monotectic composition of 20.5 at. pct Se. The miscibility gap in the liquid state extends from 7.5 to 20.5 at. pct Se. Hansen and Anderko4 accepted Nozato and Igaki's phase diagram in the region of the lead-rich monotectic. To reinvestigate this portion of the phase diagram, both thermal analysis and metallographic examination of various compositions were performed. The thermal analysis apparatus was constructed according to the specifications of the National Bureau of Standards. A t/t-l pct Rh thermocouple was calibrated against the melting point of copper (NBS), zinc (NBS), and antimony (A. D. Mackay), the emf being measured with a Rubicon Type B potentiometer sensitive to lpv. The absolute accuracy of the thermal analysis obtainable with this system is ± 0.5oC. Starting materials were semiconductor grade lead and selenium purchased from the American Smelting and Refining Co. Both elements were 99.999 pct pure with only trace impurities detected upon spectroscopic examination. One hundred galloys were sealed in quartz crucibles with a central thermocouple well under a vacuum of less than 1 p. This procedure prevented any composition change due to vaporization during the run. Cooling curves were obtained on the alloys listed in Table I. Data was taken by the direct method at cooling rates ranging between 1/2 to 2°C per min. The alloys were heated well above the liquidus and shaken vigorously to insure homogeneity. No evidence of an arrest indicative of the monotectic reaction was observed, and the two-phase region reported by Pelabonl and Friedrich and Leroux? was confirmed in general, although our data give higher liquidus temperatures than Friedrich and Leroux. The melting point of stoichiomet-ric PbSe determined for two different samples was 1080.7 0.5oC. The results of this investigation are compared with Nozato and Igaki's data in Fig. 1. To Complement the thermal analysis data, an 86 at. pct Pb specimen was examined microscopically. This composition was in the center of the miscibility gap reported by Nozato and Igaki.3 The alloy was heated to 1000°C, held for 1/2 hr, and water quenched. The specimen was polished using standard metallographic techniques for lead. The alloy was etched with an acetic-nitric acid etchant for 10 min at 45°C. Microscopic examination did not indicate the existence of two separate layers or solidified droplets imbedded in a matrix, as would be expected if a miscibility gap were present. The mi-crostructure shown in Fig. 2 consists of uniformly dispersed, dendritic PbSe in a lead-rich matrix.

Jan 1, 1962

By E. H. Edwards, J. Washburn, E. R. Parker

The mechanism of strain hardening was discussed in connection with some recent observations on the stress-induced motion of dislocation boundaries and on the simple shear deformation of zinc, cadmium, and copper crystals. THE nature of work hardening accompanying plastic deformation of metals has long been the subject of speculation. As early as 1925, Becker' suggested a thermodynamic process to explain slip based on the statistical probability for the occurrence of local glide steps. The theory that plastic glide was due to the presence of lattice defects known as dislocations was first introduced in 1934 by Taylor: and Orowan, and Polanyi.4 Taylor presented a rather complete analysis of the behavior and interaction of dislocations. He assumed a certain type of stress field to be associated with a single dislocation, and postulated that work hardening would result from plastic flow in two ways. First, dislocations following one another across a slip plane might encounter a barrier which would impede their movement, thereby gradually diminishing and eventually stopping plastic flow on that plane. The second mechanism involved the concept of dislocations traveling in opposite directions on nearby planes attracting one another to form a meta-stable lattice. The interaction of dislocations in such an array was shown to be large enough to require an increase in stress before plastic flow would continue. Kochendorfer5,6 extended the concept of work hardening involving a back stress due to an accumulation of like dislocations on a slip plane. He suggested that the formation of a new dislocation is hindered by those dislocations already present. The hardening resulting from the interaction of newly forming dislocations with bound dislocations was designated as "formative hardening," and indicated to be the only type of hardening necessarily connected with the slip process. In another detailed picture of work hardening, Mott and Nabarro7 assumed that sufficient dislocations are primarily present in the crystal as a consequence of growth irregularities (mosaic structure) to initiate slip. Work hardening resulted from the interaction of migrating dislocations with localized internal stresses produced during deformation. More recently, however, Mott8 as modified his treatment to include the generation of dislocations at Frank-Read sources and he accounts for the hardening by the formation of sessile dislocations. It has been widely accepted that metals of hexagonal structure, usually possessing only one set of glide planes, exhibit mechanical behavior markedly different from those having cubic structures. However, the differences in behavior of the two classes may be less fundamental than suggested. Rohm and Kochendorfer9 have shown that a single crystal of aluminum subjected to approximately simple shear gives the type of stress-strain curve associated with the hexagonal metals. Similar behavior has been demonstrated for gold and silver crystals by Andrade and Henderson.'" Thus when glide in cubic metals is restricted to one plane, the strain hardening characteristics closely resemble those of the hexagonal metals. It would appear, therefore, that an investigation of some of the strain hardening properties of single crystals sheared in simple glide might provide a more complete understanding of the phenomenon of work hardening. This report relates a number of recent observations made on single crystals of copper, zinc, and cadmium tested in simple shear. In addition, pertinent observations of effects accompanying stress-induced movement of dislocation boundaries are reported. Experimental Procedure and Results Details of the production and advantages of the type of single-crystal shear specimen employed for the following tests have been presented in a previous publication.n The method of testing makes

Jan 1, 1954

By AIME AIME

WILLIAM ("BILL") EMBRY WRATHER, recently elected to a second term as Director of the Institute, is widely known as petroleum geologist, gentleman, and scholar. Born in Brandenburg, Ky., he was early endowed with a Southern accent which has remained with him strongly flavored by his later life in the oil-fields of Texas and the Mid-Continent region, and only thinly concealed by a Middle Western burr acquired during his student days at the University of Chicago. After graduating there with the Ph. B. in 1908, young Wrather (the adjective still fits!) joined the Gulf Production Co. Soon afterwards he married a charming Chicago girl, Alice Dolling, who, with their two daughters, has been his companion on many of his more distant trios.

Jan 1, 1945

By Henry Faul

Measurement of radioactivity of rocks and ores has developed into a complete method of geophysical exploration. The problem falls into three natural categories: (1) surface radiation measurement in the field and underground; (2) radioactivity logging of drillholes; and (3) laboratory analysis of samples. Portable counters are used in the field for tracing radioactive formations and for quanti tative estimates of radioactive content of surface rock. Wartime advances in battery design make it possible to construct small precision counters that can be carried easily. Even the smallest conventional diamond drillholes can be logged, and actual content of the radioactive element can be measured. The exact grade of very thin active layers or veins can be estimated only approximately. Samples may be analyzed for their alpha, beta or gamma activity, and beta assaying is the best suited to rapid routine operation. Simple calibration with standard samples is sufficient for rough work, but a density correction is necessary when greater precision is required. Samples with high emanating power should be fixed and stored for three weeks to reestablish the radium-radon equilibrium prior to precision assaying. Carno-tite can be fixed by sintering or molding with plastics. Among the important new developments, a low-voltage Geiger tube has been 'designed recently, and crystal scintillation counters hold great promise for high-efficiency gamma-ray measurement. Introduction During the last few years we have witnessed an unprecedented rise in the demand for radioactive minerals, coming as a direct consequence of the discovery of nuclear fission and subsequent developments, the full impact of which is by no means in sight even now. It remains certain, however, that radioactive minerals, and especially those which can be used as ores of uranium and thorium, will continue to be of great interest not only to the prospector and mine operator but also to the various inspection parties envisioned by most of the schemes advanced for the control of nuclear energy on a world-wide basis. It is clear, therefore, that the measurement of radioactivity in rocks in the field as well as in samples in the laboratory has become a method of geophysical exploration of some importance. If we consider the recent technological advances in the general fields of nuclear physics and electronics it seems proper to review the present status of the methods and procedures of radiological exploration. General Considerations Equilibrium If we take a fixed amount of uranium that has just been purified, some of it will immediately start decaying into its first daughter element which in turn decays into its own daughter and so on down the line until the last daughter is reached—a stable isotope of lead. The rate at which a radioactive element decays is frequently expressed as the half-life, which is the length of time required for the decay of half the atoms in a given amount. The half-life is inversely proportional to the decay constanl X which is defined as the number of atoms which decay in one unit of time divided by

Jan 1, 1949

By Henry Faul

Measurement of radioactivity of rocks and ores has developed into a complete method of geophysical exploration. The problem falls into three natural categories: (1) surface radiation measurement in the field and underground; (2) radioactivity logging of drillholes; and (3) laboratory analysis of samples. Portable counters are used in the field for tracing radioactive formations and for quanti tative estimates of radioactive content of surface rock. Wartime advances in battery design make it possible to construct small precision counters that can be carried easily. Even the smallest conventional diamond drillholes can be logged, and actual content of the radioactive element can be measured. The exact grade of very thin active layers or veins can be estimated only approximately. Samples may be analyzed for their alpha, beta or gamma activity, and beta assaying is the best suited to rapid routine operation. Simple calibration with standard samples is sufficient for rough work, but a density correction is necessary when greater precision is required. Samples with high emanating power should be fixed and stored for three weeks to reestablish the radium-radon equilibrium prior to precision assaying. Carno-tite can be fixed by sintering or molding with plastics. Among the important new developments, a low-voltage Geiger tube has been 'designed recently, and crystal scintillation counters hold great promise for high-efficiency gamma-ray measurement. Introduction During the last few years we have witnessed an unprecedented rise in the demand for radioactive minerals, coming as a direct consequence of the discovery of nuclear fission and subsequent developments, the full impact of which is by no means in sight even now. It remains certain, however, that radioactive minerals, and especially those which can be used as ores of uranium and thorium, will continue to be of great interest not only to the prospector and mine operator but also to the various inspection parties envisioned by most of the schemes advanced for the control of nuclear energy on a world-wide basis. It is clear, therefore, that the measurement of radioactivity in rocks in the field as well as in samples in the laboratory has become a method of geophysical exploration of some importance. If we consider the recent technological advances in the general fields of nuclear physics and electronics it seems proper to review the present status of the methods and procedures of radiological exploration. General Considerations Equilibrium If we take a fixed amount of uranium that has just been purified, some of it will immediately start decaying into its first daughter element which in turn decays into its own daughter and so on down the line until the last daughter is reached—a stable isotope of lead. The rate at which a radioactive element decays is frequently expressed as the half-life, which is the length of time required for the decay of half the atoms in a given amount. The half-life is inversely proportional to the decay constanl X which is defined as the number of atoms which decay in one unit of time divided by

Jan 1, 1949

By Robert Goodrich

THERE is a small area about Murray where bedded gold quartz veins occur in Prichard slate. The ore taken from the upper levels, during the early days, was free milling and was treated by stamp milling and amalgamation. There was likewise a considerable placer working. The report is current that tungsten (scheelite) was encountered, which interfered with the amalgamation in the stamp mills and which, in placering, collected in the riffles in the sluice boxes and. clogged them. Consequently, in the quartz mines, the scheelite, when encountered, was rejected, being thrown into the waste, sometimes inside the mine and at other times outside on the clump. The free surface ores became worked out and as the ore in depth became pyritic and rebellious to amalgamation the mines closed down. Last spring tungsten ore brought a high price, near $80 per unit, 60 per cent. W03 and up. This so stimulated the output of tungsten ore that old clumps were explored and waste stored in the mines was gone over. Tungsten was likewise mined from virgin ground. So the district produced quite heavily for a time. The condition now is different. The price is not so high, about $20 per unit W03, which makes profits questionable when mining in new ground. The accumulations from early clay mining have been exhausted and the output has greatly declined. The Golden Chest mine was the heaviest producer of tungsten. The months of June and July were spent at this mine studying the problem. Since the mine had produced both gold and tungsten, we looked forward to the problem of recovering both from what might be called a gold-tungsten ore. A study of the Golden Chest vein showed this not to be so there. While gold ore and tungsten ore come from the same vein, the tungsten ore is confined to a more or less disturbed or distorted portion

Jan 8, 1917

By John L. Lamont, Walter Crafts

STUDIES of the effect of composition of steel on hardenability by Grossmann,1 and as-quenched hardness by Field2 and by the authors,3 have made it possible to predict the results of quenching when the composition and cooling rate are known. In order to extend the application of the hardenability calculation to the quenched and tempered condition in which steel is finally used, a survey has been made of the hardness changes caused by tempering. From this study a method has been developed for the prediction of hardness and tensile strength of steel in the tempered condition. The method of calculation was developed from Rockwell C hardness tests on quenched and tempered Jominy specimens and is expressed in Rockwell C hardness units. It is of an additive type in which the degree of softening from as-quenched hardness is estimated. Tempered properties may be calculated within about plus or minus 5 Rockwell C hardness or plus or minus 15,000 lb. per sq. in. tensile strength. This degree of accuracy is less than that necessary for the control of heat-treatment, but is adequate for the comparative evaluation and selection of alloy steels. The formula indicates that tempered hardness is primarily dependent on as- quenched hardness and, as in the hardening reaction, the progress of tempering is controlled mainly by the carbon content- Alloys tend to retard softening by a secondary hardening mechanism in which the alloy appears to migrate from ferrite to the carbide phase. The factors for the effects of alloys in tempering vary so much from the effects of alloys in hardening that different steels of equivalent hardenability may, after lie heat-treatment, differ considerably in tensile strength. PROCEDURE In developing the method for calculating tempered Rockwell C hardness, simple and complex steels were tested over a range from 0.08-to 0.65 per cent carbon and up to 2.68 per cent manganese, 2.18 silicon, 3.50 chromium, 4.94 nickel, and 1.06 molybdenum. The steels were made as small induction-furnace heats at the Union Carbide and Carbon Research Laboratories, Inc. The accuracy of the method was finally checked on a variety of carbon, low-alloy and high- alloy types of heat-treating steels produced under commercial conditions. The method was based on a study of tempered Jominy bars, and its validity was tested by correlation with the center hardness and tensile strength of oil-quenched and tempered bars from ¼ to 4 in. in diameter. The method of calculation was derived from the differences in Rockwell C hardness between as-quenched and quenched and tempered Jominy specimens. Prenormalized Jominy hardenability specimens quenched from a normal temperature for austenitization were used to obtain a range of as-quenched Rockwell C

Jan 1, 1946

By R. M. Asimow

Both smith1 and wells2 have shown that the dif-fusivity of carbon in austenite increases rapidly with increasing carbon concentration. Smith has shown, in addition, that part but not all of this increase can be attributed to the concentration dependence of the activity coefficient of carbon in austenite. From the work of Eshelby', it is known that, because of the image displacements, there is a uniform dilatation of the material in a body containing random centers of dilatation. It is thus tempting to explain the enhanced diffusivity as resulting from this apparent negative pressure caused by the interstitial carbon atoms.* That is, the activation free energy for diffusion is not directly a function of concentration if we consider that the alloy is subjected to a concentration-dependent pressure. To proceed with a quantitative solution, it is necessary to determine the activation volume AV for the diffusion process. An exact calculation of AV is quite a difficult problem and does not appear to have been solved as yet. A simpler procedure is to use the semiempirical, macroscopic theory of seyes' which relates the activation free energy AG to AV. Keyes has shown that for many types of diffusion processes the following relationship is valid Where p is the Gruneisen constant and x the compressibility. This relationship is based on the assumption that AG can be identified with strain-energy terms. In general there will also be contributions to AG due to a change in the energy of the valence electrons of the metal; thus the relation must be considered largely empirical. Surprisingly, for self-diffusion where it is well-known that the electronic contribution is quite important,' the Keyes relation works quite well for many systems. For interstitial diffusion where it might be expected that the relationship is on a firmer theoretical basis, the limited experimental data available is not in particularly good agreement as can be seen from Table I. However, it must be remembered that besides the uncertain basis of the Keyes formula there is considerable uncertainty in some of the experimental values of AV. The only real justification for using the Keyes formula in the present analysis is that it gives a result which satisfactorily solves the problem at hand and, further, there are no more reliable procedures for calculating AV available. The coefficient 3 in Eq. [I] is determined such that the room-temperature value for x is to be used. The activation entropy AS is estimated as 8.95 x 10"3 kcal per OK mole using the values in Table I1 and the Zener" relation AS = PAHIT, where p is a dimensionless thermal coefficient of Young's modulus which is to be evaluated at low values of T/T,, aH is the activation enthalpy, and T, is the melting temperature of the alloy. The resulting value of AG at 1000°C is 25.6 kcal per mole. The Gruneisen constant (p = 3cup/XC,), where p is the density, is evaluated from the room-temperature data in Table I1 after calculating C, from the relation. A value of p = 8.32 g per cu cm based on the value of a. in Table I is used. The result is C, = 5.0 x lo6 erg per g, H = 2.32, and AV = 3.41 cu cm per mole at 1000°C and infinite carbon dilution. It is assumed that the activation volume is not a function of carbon concentration. The theory could be refined to consider AV a function of concentration, but due to the uncertainties in the parameters there seems little justification for this. Carbon dissolved in austenite forms a nonideal solid solution, so that in writing an equation for. the diffusivity of carbon it is necessary to take into account the change in activity coefficient with concentration. The resulting equation is16

Jan 1, 1964