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By H. R. Peiffer

Composite alloys of silver and alumina are shown to resist flow above the melting point of the continuous matrix. The ability to resist flow depends on the fineness of the dispersion and the oxygen content of the silver. It is believed that the oxygen influences very strongly the bond between the molten silver and the finely divided alumina. RECENT needs for materials with high strength and creep resistance at high temperatures initiated mechanical property studies on dispersed phase materials to near the melting point of the continuous matrix material. Results' of these investigations have shown that certain of these materials do have promise for high-temperature applications. Experiments performed on composite materials of silver and alumina by the author have resulted in the discovery of an interesting effect above the melting point of the silver. In these materials the silver was continuous and the alumina very finely divided (Linde B). It was observed that these materials exhibited strength and resistance to flow above the melting point of the silver matrix. The purpose of this paper will be to describe these properties. METHOD OF PREPARATION The materials were prepared by mixing the proper amount of Linde B alumina and high-purity silver oxide. The alumina content was varied from 5 to 20 wt pct alumina in silver in 5 pct steps. The materials were mixed by blending the constituents in an ordinary food blendor using ethyl alcohol as a vehicle. Enough alcohol was added to the powders to form a mixture with the consistency of a thin mud. After blending for about | hr the material was dried and the silver oxide reduced by heating to 450 OC. The material was then pressed at 25 tsi into a -in. billets 3 in. long. EXPERIMENTAL PROCEDURE The specimens were horizontally supported at either end by knife edge supports of cold-rolled steel. This holder was then placed in a "globar" furnace and a chromel-alumel thermocouple placed very close to the specimen recorded its temperature to within 10°C. Each specimen was heated rapidly to 900°C initially. The specimens were held at temperature approximately 30 min and then the temperature was raised 50 deg. The procedure was repeated until deformation was noted. Photographs were made of the specimens at various temperatures and increments of time using a Polaroid Land camera. RESULTS Fig. 1 shows the 5 pct by weight "Linde B" alumina and silver material after reaching 980 °C. Failure occurred after 15 min at this temperature. There were two points of failure and silver collected at them. No additional flow of the molten silver was noted at any other place. Fig. 2 shows a 20 pct by weight "Linde B" alumina in silver specimen. After 30 min at 1400°C, bowing of this material was observed. Other concentrations of alumina were added to

Jan 1, 1961

By T. E. SCHTVARZ

THE publication of the report by Mr. F. L. Ransome was welcomed by many engineers who had mined in the heart of the Sail Juan country, braved its long and snowy winters, climbed its lofty peaks, run the gauntlet of its snow-slides, and studied its problems of geology, while making dividends for their English or American clients. This report helps one to understand why the bonanzas occurred, and why the inevitable borrasca presents itself where least expected. The Red Mountain district of Ouray county, a very productive section from 1884 to 1893, occupies considerable space in the report mentioned.. The character of the ore-occurrence, being distinctive and presenting many features not existing elsewhere, has been deserving of special study. It is to be regretted that Mr. Ransome was .unable to observe the conditions underground, as all the principal properties, many of which I opened and developed, were closed at the time of his investigation: It has been my privilege to have contributed a few brief papers recording my observations in developing these properties ; and it is the object of the present paper to present certain sections of the Yankee Girl mine, which throw additional light on the geology of the section and make the available data more complete. The main Yankee Girl chimney or " stock" was the most productive for the first 500 ft. in depth of any chimney in the district.

Mar 1, 1905

By A. U. Seybolt

DURING the course of experiments involving oxygen equilibrations with a high-purity Pd-5 at. pct Rh alloy, the appearance of a subscale was noted. Most of the heat treatments in a pure oxygen atmosphere were performed at 900°C. The presence of the subscale was noted when the oxygen partial pressure was in excess of approximately 95 mm, up to 1 atm, the highest pressure used. According to available thermodynamic information' on the free energy of formation of Rh2O3 (the only reliably reported solid oxide of rhodium), this oxide should not be stable under these conditions, nor, of course, any oxide of palladium. Extraction of the subscale from the matrix was affected by treatment with aqua regia, and the resulting X-ray diffraction powder pattern is shown in Table I. This pattern is not that of Rh2O3, nor that of any known rhodium or palladium oxide. It can be indexed on a hexagonal lattice with a. = 5.22Å and co = 6.0Å. In addition to this unknown material, there was a weak Rh2O3 pattern. An X-ray fluorescence analysis of the powder gave 3214 palladium counts per sec and 5381 rhodium counts per sec, thus indicating the likelihood of a double oxide of palladium and rhodium. In view of the fact that the above result was obtained on a single sample, it is perhaps best not to insist upon the above ratio of about 0.6, but possibly to tentatively assume 0.5 or 1/1. The small amount of Rh2O3 in the X-ray pattern might have occurred on cooling, and it seems possible that the double oxide, below some temperature level, is not as stable as Rh2O3. To examine this point, some of the extracted double oxide was heated on a sheet of pure palladium in air at 900°C, and allowed to furnace-cool over a period of several hours. The X-ray diffraction pattern of the powder showed approximately the same intensity of Rh2O3 and the "hexagonal" oxide as before, but, in addition, a rather faint pattern of another crystalline species made its appearance. This finding again suggests partial transformation of the major (double) oxide to other oxides on cooling from 900°C. Application of the phase rule shows that only one equilibrium oxide (subscale) could have been present at temperature. Vacuum-fusion, oxygen analysis of the extracted subscale showed 7.7 ± 0.7 pct O. Combining this information with that of the X-ray fluorescence analysis suggests the formula PdRhO. This compound should have an oxygen content of 7.07 pct, which is within the range of error of the oxygen analysis. However, until a more careful stoichiometric study is made, it is suggested that the formula be written

Jan 1, 1965

By N. E. Truitt, D. G. Russell

The transient pressure behavior of a well which produces a single compressible fluid through a singte-plane wrticat fracture has been investigated mathematically. The fracture is assumed to possess infinite flow capacity, to be of limited mdial extent, and' to penetrate the producing formation completely in the vertical direction. Previous studies of vertically fractured wells have been concerned primarily with production rate performance or semisteady-state pressure behavior. This study was undertaken to ascertain the influence of vertical fractures on transient pressure tests such as pressure build-ups and flow tests. In a vertically fractured system, flow in the region nearest the fracture is practically linear, whereas farther away from the fracture essentially radial flow prevails. Thus, transient pressure analyses based on radial flow theory are somewhat inaccurate. As fracture penetration increases radially, kh values calcutated from pressure build-up and flow test curves become increasingly larger than true values. Failure to consider the effect of fracture penetration also introduces inaccuracies into the catculation of fracture length from the apparent skin factor and into the determination of average reservoir pressure. If the total length of the fracture is 20 per cent, or greater, of the drainage radius of the well, corrections must be made to pressure build-up and flow test results. Methods for correcting such results are discussed in this paper. For wells with prefracturing pressure build-up or flow test data, it is possible to estimate fracture length by comparison with postfracturing build-up or flow test results. In new wells or wells without prefracturing build-up or flow test data, fracture length must be estimated to correct the values obtained from analysis of pressure tests after fracturing. Fracturing efficiency calculations should be made whenever possible to provide an estimate of fracture length. Tables of the dimensionless pressure drop as a function of time and fracture penetration are included in this paper. Using these values should permit analysis of other types of transient pressure behavior in vertically fractured wells. INTRODUCTION Hydraulic fracturing has been used quite successfully for over a decade as a completion and stimulation technique in oil and gas wells completed in low-permeability reservoirs During this period a considerable amount of theory has evolved on the performance of hydraulically fractured reservoirs and on more efficient means of artificial fracturing. Although theory has been developed, no rigorous investigation has been made of pressure build-up and flow test behavior in such wells. Prats et al.1 first discussed the performance of vertically fractured reservoirs for the case of a compressible fluid. Their work was primarily concerned with production performance at constant flowing pressure. These authors also considered large-time (semisteady-state) constant production rate behavior for vertically fractured wells; however, transient pressure behavior at constant rate was not investigated. McGuire and Sikora10 and Dyes, Kemp, and Caudle2 employed an electrical analog to investigate the influence of artificial vertical fractures on well productivity and pressure build-up. They found that fractures which extend beyond 15 per cent of the drainage radius away from the well alter the position and slope of the straight-line portion of the build-up curve. They concluded that these effects must be considered both in the determination of the effective permeability of the formation and in any calculations of final build-up pressure. Although these authors did not undertake an exhaustive study of the influence of vertical fractures on pressure build-up performance, their limited results were quite interesting from the standpoint of the effects they demonstrated. In a more recent paper, Scott- reported the results of an investigation of the effect of vertical fractures on pressure behavior, which was conducted with a heat flow model. Scott's results appear to be consistent with those reported in Refs. 1 and 2. However, the effects of different fracture lengths on performance were not investigated. Pressure build-ups and transient flow tests are among the most diagnostic tools available to the reservoir engineer or production engineer. Since a very high percentage of present-day well completions incorporate the hydraulic fracturing technique, a definite need exists for information on the effect of fractures on transient pressure performance. For these reasons we have undertaken a rigorous study of pressure build-up and flow test behavior in vertically fractured reservoirs. The objectives of this study were (1) to obtain synthetic pressure build-up and flow test

Jan 1, 1965

By J. K. Edgar

For a number of years the production and use of super-purity aluminum (better than 99.99 pct) has been steadily increasing. High-grade lots of. such aluminum show certain outstanding characteristics not found in lower grades containing principally silicon, iron and copper as impurities. One such characteristic is the so-called "self annealing," that is, the re-crystallization of the heavily cold worked metal at room temperature.' Interest therefore is aroused as to the effects of the impurities. It is well known that the amounts of silicon and copper which occur in aluminum of better than 99.95 pct are completely soluble, at least at elevated temperatures (above 200°C). Iron, on the other hand, is known to be fairly insoluble in solid aluminum. Thus, a knowledge of the limits of this solubility would he of considerable use in studying the characteristics of the high purity metal. All investigators have agreed that iron has very low solubility in solid aluminum. Rosenhain, Archbutt and Hanson2 reported traces of an aluminum-iron phase in the "purest samples of aluminum obtainable." Gwyer and Phillips3 reported that an iron constituent was visible under the microscope in metal containing ".0088 per cent iron." Roth4 found that in the solid state the solubility of iron in high purity aluminum was 0.01, 0.01, 0.017 and 0.022 pct at 225, 320, 500 and 600°C respectively. Dix5 working with alloys containing less than 0.03 pct impurities, concluded from microscopic and chemical analyses of eutectic areas that the eutectic composition was close to 1.7 pct iron. Dix placed the eutectic temperature at 65s°C. Archer and Fink,6 using high purity aluminum-iron alloys, found that the hypoeutectic liquidus intersects the eutec-tic horizontal at 1.7 pct. This is in fair agreement with the investigation of the aluminum-iron system by Gwyer and Phillips who placed the eutectic at 1.89 pct iron with a freezing point of 653'C. Preparation and Chemical Analysis oP Alloys Electrolytically refined aluminum (99.991 pct aluminum) and a high purity alumi-num-iron alloy (11.45 Pet iron) were used in the preparation of the alloys for this investigation. To aid in controlling the iron content of the experimental alloys, an alloy of lower iron content was prepared first from these materials. The high purity aluminum was melted and heated to about 700°C in a plumbago crucible coated with alundum cement and the aluminum-iron alloy was then added. The alloy was thoroughly stirred, fluxed and skimmed and then chill-cast into notch bars. The aIlalyses of the three materials are given in Table I. The alloys for the determination of the solid solubility of iron in aluminum were prepared by melting 600 g total of the aluminum plus the required quantity of the aluminum-iron alloy (No. 92531). These

Jan 1, 1949

By J. Chipman, H. R. Larson

The data previously reported for the quantity as a function of oxygen pressure at 1550°C have been used to compute the activities of Fe, FeO, Fe2O3, and COO in slags of the ternary system. Activities of the first three have been obtained also for two quasi-ternaries involving fixed CaO:SiO2 ratios. IN a previous paper1' the authors reported the results of an investigation into the effects of oxygen pressure on the composition of various simple slags analogous to some of those which are found in steel-making practice. The ratio of ferric iron to total iron was studied at 1550°C in iron oxide melts to which lime, magnesia, lime-plus-silica, and other oxides were added. The oxygen pressures involved those of air, carbon dioxide, and carbon dioxide plus carbon monoxide in several proportions. Although very low oxygen pressures could not be used, the slag-metal equilibrium studies of Fetters and Chip-man' permitted extending the results to slags in equilibrium with iron. For the ternary system CaO-FeO-Fe,O, the oxygen pressure-composition relationship has been determined from zero percent lime to lime saturation over an oxygen pressure range from air to that represented by equilibrium with liquid iron. Lime and silica were added to iron oxide in the ratios 0.54, 1.306, and 2.235 to form three quasi-ternary systems which were also studied over the entire region of liquid melts at 1550°C. Ternary Gibbs-Duhem Equation Wagner" has developed a method by which the activities of two components of a ternary system can be calculated if' the activity of the third component is known throughout the composition range being considered. The fundamental form of the Gibbs-Duhem equation for ternary systems is N, d In a, + N2 d In a, + N3 d In a3 — 0. Wagner has developed a usable form of this equation by introducing the term y = N3/(N3 + N1) and rearranging the equation to give (? In a1/?N2)x = -y/(1-N2)2 (? In a2/?y) x2 N2/1-N2 (? In a2/?N2) y To apply this equation to the slag system CaO-FeO-Fe,O,, the activity of one of these components must be known. However, the only activity which is known from the experimental data is the activity or pressure of oxygen in the gas phase with which the slag is in equilibrium. The activity of oxygen in the slag can be defined as the square root of the oxygen pressure. In order to use oxygen as one component, the composition of the slags must be converted to the basis Fe-O-CaO. Oxygen, exclu-sive of that contained in CaO, then becomes com-ponent 2 in Eq. 1, Fe is selected as 1 and CaO as 3. Then y = Ncao/(Ncao + NFe). Eq. 1 then becomes (? In a fe/? Nx) y = -y/(1-No)2 (? In ao/?y) xp - No/ 1- No (? In ao/ O No) y. In order to evaluate Eq. 2, the boundary conditions must be known. The obvious choice of a standard state for iron is to assign slags in equilibrium with iron an activity of one. Then In a,., or log aFe, which is substituted for convenience, is determined by integrating along a line of constant y from the slag in equilibrium with iron to the composition at which log a,, is to be determined. Mathematically this can be expressed as log aFe (Nlog y) = log a'Fe + (? log a Fe/? No) dNo where the primes indicate equilibrium with liquid iron and a'Fe = 1. When Eq. 3 is integrated along a line of constant y, the following is obtained: log a Fe (No, y) = - y No ?/ No ? y ( log ao/(1- No)2) No d No - No/1-No d log ao. Lime-Iron Oxide Slags Iron Activity: The oxygen pressure of lime-iron oxide slags is shown in Fig. 1 as a function of j, de-fined as j = Fe+++/(Fe++ + Fe +++) for various constant mol percentages of lime. The j values at 0 to 60 pct lime were then determined for oxygen pressures of 1, 10-1, etc. to 10-" atm. For purposes of calculation, the line for zero percent lime was extrapolated to

Jan 1, 1955

By Ramesh Malhotra, Hubert E. (Deceased) Risser

THE WORLD Coal, as a source of energy and as a source of coke for the smelting of iron ore, has contributed significantly to the development of every major industrial nation of the world A number of other materials-oil, natural gas, wood, waste materials, water, and, in some applications, nuclear materials -can be used satisfactorily for the generation of heat and energy, but no generally acceptable and economic substitute has been found to supplant coke in iron ore smelting in conventional blast furnaces. In the development of many nations, coal provided the initial source of energy for industrialization Although coal provided more than 60% of the world's energy each year between 1902 and 1929, oil and natural gas have surpassed it as a source of energy in more recent years (Ref. 38, pp. 439, 441). Despite the rapid rise in importance of other fuels, a considerable amount of the total energy consumed is still supplied by coal. In 1972, coal supplied 32.1 % of the total world energy (Ref. 49, pp. 2-3). To produce this energy, 2.4 billion metric tons of coal were consumed-a 16.0% increase over the amount consumed in 1962. A further worldwide increase in the amount of coal used to supply energy is projected. According to Dr. Karlheinz Bund (Ref. 37, p 145), by the year 2000 world coal consumption could amount to 5 billion mt. Coal Resources and Production The world's coal resources are estimated to be about 10,872 billion mt. Of this amount, 1,297 billion mt are classified as measured reserves (Ref. 50, p. 57). In Table 13.A.1 the estimates of measured reserves and total resources, recent production, and the ratio of measured reserves to production of major coal-producing countries are shown. About 90% of the world's total coal resources are estimated to be in the USSR, the United States, and China. The United States ranks second in the world in coal resources, but in measured reserves, it ranks first. Because of the difference in rate at which available coal resources are being exploited, the ratio of measured reserves to actual production varies widely among areas and countries. France and East Germany have the lowest reserve to production ratios, 49.5 and 60.1, respectively. In Mexico, where currently less than 5 million mtpy of coal are produced, the ratio is 1257 For all countries producing more than 200 million mtpy of coal (except East Germany), the ratio ranges from 350 to 670. For the United States, the ratio is 669.7. In Table 13.A.2, distribution of the world's coal resources by area is shown. More than 97% of the total resources lie in the northern hemisphere, with Asia, including European USSR, having 63.4%. Only 1.9% of the total coal resources are estimat-

Jan 1, 1976

By Ronald C. Koo

THE effect of grain size on the mechanical properties of the bcc metals has been a subject of intensive theoretical and experimental study.'-l5 Quantitative relationships have been established experimentally between yield stress and grain size and between the ductile-brittle transition temperature and grain size in a number of metals.6"15 Much significance has therefore been attached theoretically to the grain size dependence. In all these experiments, different grain sizes were always achieved by annealing specimens at various temperatures. The implicit assumption was that any change in the dislocation substructure or in the distribution of impurities which might occur simultaneously with the production of various grain sizes had only a negligible effect on the mechanical properties. The validity of this assumption, however, is questionable. transformation in iron-nickel alloys is actually an extraneous phenomenon due to inadvertent compositional changes in the martensite if the heating rate is not sufficiently rapid. This complication can be avoided by up-quenching for the reversal treatment,5 and then the stabilization does not appear. Clearly, the lattice imperfections and strengthening produced by the reverse transformation are not responsible for the marked stabilization which has been observed by other investigators in these alloys. Data will be presented in this note to show that, at least in recrystallized tungsten of commercial purity, the difference in the ductile-brittle transition temperature of specimens annealed at various temperatures is more a result of a variation in the distribution of impurities rather than of the difference in grain size produced by the anneal. Ductile-brittle transition temperatures in tension were determined on powder-metallurgy tungsten specimens recrystallized at various temperatures. Tensile specimens having a gage length of 1.50 in. and gage diam of 0.18 in. were recrystallized at 1450°, 2000°, 2350°, 2550°, 2750°, or 2800" for 30 min in a vacuum furnace at a pressure of 1 x 10"5 mm of Hg and then tested at a constant extension rate of 8 x 10 per sec in an argon atmosphere from 100" to 800". Typical quantitative analyses of impurities are given in the Table. These results show that, within the precision of the analyses, see Table, annealing did not result in any detectable change in the impurity contents of the specimens, nor was there any detectable difference in purity between specimens having large differences in grain size annealed at the same temperatures . The results of the tensile tests yielded three distinct ductile-brittle transition curves approximately 225' apart. As shown in Fig. 1, data of specimens annealed at 1450°C and those of specimens annealed at 2000°C (O) fell on Curve A. Data of specimens annealed at 2350" and 2550°C fell on Curve B, and those of specimens annealed at 2750" and 2800°C fell on Curve C. The decrease in ductility with increase in annealing temperature became so pronounced that one third of the specimens annealed at 2750" and two thirds of the specimens

Jan 1, 1963

By D. H. Baldwin, R. E. Reed-Hill

DURING the course of experiments involving oxygen equilibrations with a high-purity Pd-5 at. pct Rh alloy, the appearance of a subscale was noted. Most of the heat treatments in a pure oxygen atmosphere were performed at 900°C. The presence of the subscale was noted when the oxygen partial pressure was in excess of approximately 95 mm, up to 1 atm, the highest pressure used. According to available thermodynamic information' on the free energy of formation of Rh2O3 (the only reliably reported solid oxide of rhodium), this oxide should not be stable under these conditions, nor, of course, any oxide of palladium. Extraction of the subscale from the matrix was affected by treatment with aqua regia, and the resulting X-ray diffraction powder pattern is shown in Table I. This pattern is not that of Rh2O3, nor that of any known rhodium or palladium oxide. It can be indexed on a hexagonal lattice with a. = 5.22Å and co = 6.0Å. In addition to this unknown material, there was a weak Rh2O3 pattern. An X-ray fluorescence analysis of the powder gave 3214 palladium counts per sec and 5381 rhodium counts per sec, thus indicating the likelihood of a double oxide of palladium and rhodium. In view of the fact that the above result was obtained on a single sample, it is perhaps best not to insist upon the above ratio of about 0.6, but possibly to tentatively assume 0.5 or 1/1. The small amount of Rh2O3 in the X-ray pattern might have occurred on cooling, and it seems possible that the double oxide, below some temperature level, is not as stable as Rh2O3. To examine this point, some of the extracted double oxide was heated on a sheet of pure palladium in air at 900°C, and allowed to furnace-cool over a period of several hours. The X-ray diffraction pattern of the powder showed approximately the same intensity of Rh2O3 and the "hexagonal" oxide as before, but, in addition, a rather faint pattern of another crystalline species made its appearance. This finding again suggests partial transformation of the major (double) oxide to other oxides on cooling from 900°C. Application of the phase rule shows that only one equilibrium oxide (subscale) could have been present at temperature. Vacuum-fusion, oxygen analysis of the extracted subscale showed 7.7 ± 0.7 pct O. Combining this information with that of the X-ray fluorescence analysis suggests the formula PdRhO. This compound should have an oxygen content of 7.07 pct, which is within the range of error of the oxygen analysis. However, until a more careful stoichiometric study is made, it is suggested that the formula be written

Jan 1, 1965

By L. S. Darken

It has long been recognized that the driving force in an isothermal diffusion process may be regarded as the negative gradient of the chemical potential (partial molal free energy) of the diffusing substance. This equivalence is exactly analogous to the fact that a mechanical force is the negative gradient of the potential energy. Nernstl in 1888 expressed these driving forces in terms of osmotic pressure, which is directly related to the chemical potential and free energy. The relationship between the diffusivity, mobility and activity coefficient of electrolytes in aqueous solution has been developed in great detail by Onsager and FuossZ with results which have recently been confirmed experimentally by Harned and Nuttall. This interpretation of the driving force in isothermal diffusion has been discussed earlier by the author,4,5 who pointed out4 that "for a system of more than two components it.is no longer necessarily true that a given element tends to diffuse toward a region of lower concentration even within a single phase region"; departure from the behavior of an ideal solution may be so great that the concentration gradient and the chemical potential gradient, or activity gradient, may be of different sign, thus giving rise to "up hill" diffusion. Since, in the discussion of that paper,4 some skepti- cism as to the validity of this conclusion was expressed, it seemed desirable to adduce experimental evidence to support it. Evidence of such diffusion in nonmetallic systems has already been reported. For example, it was observed by Hartley" in a series of experiments in which sodium chloride diffused from a saturated solution in about 5 pct acetone in water into a solution virtually free of salt but with essentially the same acetone concentration. Specifically, a wine glass containing crystalline salt and saturated solution was totally immersed in a large glass cylinder containing the acetone-water solution without salt; the difference in specific gravity was such as to prevent convection. Diffusion of salt was accompanied by a marked depletion of acetone in the wine glass; after 3 days the acetone concentration decreased from 5.37 pct at the top of the glass, where the salt concentration was low (0.93 pct), to 1.84 pct at the bottom where the salt concentration was high (21.64 pct). This "uphill" diffusion was found to be such that the partial pressure (activity) of acetone was essentially equalized throughout the system when a steady state gradient of sodium chloride was maintained. In order to demonstrate the existence of such diffusion in metals, a series of four weld-diffusion experiments was made. In these measurements pairs of steel of virtually the same carbon content, but differing markedly in alloy content, were welded at the end and held at 10500 C for about two weeks. Subsequent analysis showed that carbon had diffused so as to produce an inequality

Jan 1, 1949

By AIME AIME

CHARLIE WARNER, Chairman of the Petroleum Division, is no stranger to the problems of the oil industry or to those of the Petroleum Division, after more than 25 years of experience in locating and producing oil and more than 22 years of membership in the Institute. He was born at Jefferson, N. Y.. April 27, 1894, and educated in the public schools of New York State and at Cornell University where he studied geology and allied sciences from 1913 to 1917 and received a B.A. degree. Immediately upon completion of this training, he was employed by the Empire Gas & Fuel Co. as a field geologist in Oklahoma and Kansas. Two years later he became district geologist for the Emerald Oil Co. in Oklahoma and Kansas, and in 1920 he rejoined the Empire Gas & Fuel Co. in the capacity of district geologist in Oklahoma. In September of 1921 he began his association with the Houston Oil Co. of Texas. He was district manager for the company in the Mid-Continent area until 1932 when he was transferred to the head office at Houston, where he became superintendent of the land and lease department in 1934 and was elected a director of the company in 1941. In these capacities, and also as petroleum engineer for the company, he keeps in intimate touch with all phases of field activity and with the regulation of the industry by State and Federal agencies.

Jan 1, 1943

By M. J. Stewart, F. Weinberg

PREVIOUS investigations into convective flow in molten metals have examined systems in which the length-to-height ratio of the enclosure is large, usually using long graphite boats.''2 In normal castings this ratio is generally small and it is not possible to extrapolate the results of previous work to casting configurations. The present investigation was undertaken to examine liquid flow in systems of low length to height ratio. The apparatus used for the experiments is shown in Fig. 1. The molten zone of tin is contained in an aluminum mold of inside dimensions 6.4 by 6.4 by 0.31 cm. A heating block containing a resistance coil is attached to one end of the mold and a cooling block is attached to the other end. These are used to produce a wide range of temperature differences across the mold. The mold is contained in a stainless steel tank which is heated from the outside by resistance heaters to give the required operating temperature during the experiment. Temperature measurements in the molten tin are made with an iron-constantan thermocouple PT equal to 5 atm. The phase diagram derived by us was the same as that found by Krivsky and Schuhmann, except for a similar discrepancy in one boundary line representing the gas composition in equilibrium with SO a. The vapor pressures of the pure components can be neglected at 1700°K, 1 atm and 2500°K, 5 atm. There-fore, in these cases PT is essentially the total pres-sure in the system. This is valid for all the diagrams presented by Krivsky and Schuhmann except for the one at 2500°K and 0.01 atm, where the vapor pressure of silicon is comparable to PT.6 This work was supported in part by the American Iron and Steel Institute. 'C. E. Wicks and F. E. Block: Thermodynamic Properties of 65 Elements, U S. Bur Mines, Bull. No. 605, 1963. R. P. Elliott: Constitution of Binary Alloys, 1st supplementary, McGraw-Hill Book Co., New York, 1965. 3W. A. Krivsky and R. Schuhmann, Jr.: Trans. TMS-AIME, 1961, vol. 221, pp. 898-904. 4M. F. Ancey-Moret, M. Olette, and F. D. Richardson: Mem. Sci. Rev. Met., 1964, vol. 61, pp. 169-76. 5J . F. Elliott and M. Gleiser: Thermochemistry for Steelmaking, vol. 1. Addison-Wesley, Reading, Mass. 1960. 6 J.Drowart, G. De Maria, and M. G. Ingraham: J. Chem. Phys., 1958, vol. 29, p. 1015. probe of 0.4 mm diam inserted into the open top of the mold. Radioactive sn113, in the form of a small sphere, was gently lowered into the molten tin at point A in Fig. 1 THERMOCOUPLE> WATER ARGON END HEATER QUENCH ARGON Fig. 1—Apparatus for detecting liquid flow. Point A indicates position the tracer was introduced.

Jan 1, 1970

By G. T. Higgins

PREVIOUS workers1,2 have found evidence of exaggerated grain growth or secondary recrystallization on annealing sponge zirconium at temperatures high in the a, phase field, but no details of the orientation relationship between the secondary grains and "as-recrystallized" matrix were reported. In other hexagonal metals, namely dilute Mg-A13 and Cd-zn4 alloys, secondary recrystallization has been observed in which the secondary grains are related to the primary recrystallized structure by rotations about the c axis. These rotations are thus comparable with the rotations about the (111) axis observed in the secondary recrystallization of fcc metals. In the current work secondary recrystallization has been observed on annealing iodide zirconium at 800°C and the associated changes in crystallographic texture have been examined. The material employed was arc-melted iodide zirconium of the following composition: Impurity O H Fe Hf Pb I Ni C1 A1 ppm by wt 130 5 230 98 23 28 200 39 30 This was received as 0.25-in. plate, and, prior to the annealing studies, was cold-rolled to 0.040 in. Specimens 1 in. sq were chemically polished and annealed for various times at 800°C in a vacuum better than 5x 10-6 Torr. For metallographic examination specimens were first chemically polished and then anodized8 to enhance contrast between the grains when examined under polarized light. Changes in crystallographic orientation associated with the development of secondary grains were followed by (1011) and (0002) pole-figure determinations using a conventional Schulz goniometer in reflection. Filtered Cr Ka radiation was employed and great care was taken to avoid spurious re- sults due to the close proximity of the Bragg angles for the (1011) and (0002) reflections. Figs. 1 and 2 illustrate the change in grain structure on annealing at 800°C. After 24 hr the structure has ceased to be equiaxed due to the development of certain grains in preference to others. It is notable that the secondary grains do not grow to the extent observed in sponge zirconium.1,2 This appears to be due in part to the fact that normal grain growth is inhibited in the less pure sponge zirconium, with the result that the driving force for secondary recrystallization remains high, while at the same time the number of grains able to develop in the presence of the impurities is also smaller. As a consequence, in sponge zirconium those grains that do develop preferentially are able to grow into the fine -grained matrix without impingement, while in iodide zirconium the preferential growth of many grains leads to early impingement. The pole figures determined for specimens annealed for 5 min and 24 hr at 800°C are illustrated respectively in Figs. 3 and 4. These indicate that the dominant feature of the initial recrystallized texture consists of basal planes at an angle of 321/2 deg to the sheet surface, with a (1120) axis lying parallel to the

Jan 1, 1967

By R. A. Stauffer

THE chief ore of lithium is spodumene, a lithium-aluminum silicate containing up to 3 pct lithium. The preparation of lithium salts from spodumene is costly because of the low concentration of the metal and the difficulty of separating it from the other alkali metals present. Dr. Kroll's and Dr. Schlecten's recent paper' has reviewed various methods proposed for preparation of lithium. It will be seen from this paper that the methods proposed to date have required one or another of the lithium salts as a raw material. The high cost of these salts has been the chief item of expense in the lithium metal produced. This situation has made it interesting to investigate the possibility of producing the metal directly from spodumene. When spodumene is calcined at 1000°C in the presence of lime, lithium oxide is replaced in the ore as is evidenced by the fact that it may be leached from the reaction mixture with water.2 Free energy calculations suggested that lithium oxide might be reduced with aluminum or silicon and the lithium produced distilled from the reaction mixture by heating to about 1000°C in a vacuum. These facts taken together suggested that it might be possible to prepare lithium metal directly from spodumene by heating a mixture of the ore, lime, and a suitable reducing agent in vacuum and distilling off the lithium metal as formed. THE REPLACEMENT OF Li20 IN SPODUMENE A series of experiments were undertaken to determine the ratio of lime to spodumene necessary to free substantially all the lithium oxide present in the ore. The spodumene used in these experiments was supplied by Foote Mineral Co. in the form of powder of about 200 mesh. Analysis of the spodumene was as follows: [ ] Lime (cp -200 mesh) was added in various ratios to spodumene and thoroughly mixed in a ball mill. Two hundred gram samples of spodumene-lime mixtures were charged loosely in fireclay crucibles and held at 1000°C in a gas-fired furnace for 5 hrs. The product in each case was ground to pass 140 mesh and then placed in a thimble in a soxhlet extractor. Extraction with water was carried on for 6 hrs. After this period the extract was reduced in volume by evaporation in order to precipitate dissolved lime and was then filtered and titrated with 1/4 normal hydrochloric acid. After correcting for residual calcium oxide in solution, the alkali present was calculated as lithium oxide. The results of these experiments are shown in Table I and Fig I. At lime-spodumene ratios less than 1.5, the products were invariably fused. At the ratio of 1.5 and above, the product was loosely sintered with little evidence of fusion. When the ratio of lime to spodumene was three, replacement of alkali oxides in the

Jan 1, 1947

By M. C. Flemings, R. Mehrabian, G. E. Nereo

Analytical expressions derived previously are used to describe quantitatively effects on macrosegregation of some solidification and mold design variables. Al-4.5 pct Cu alloy is used as example. It is shown that abrupt changes in heat transfer rate result in solute-rich or solute-poor "bands". Severe solute-rich bands accowzpany "reheating" that can result, for example, from abrupt formation of an air gap at a mold-metal interface. With planar isotherms, solute-poor regions also result from reduction in cross section through which fluid flow to feed shrinkage takes place. It is suggested that the negative "cone" of segregation often found at the base of large ingots results from this reduction in cross section for feeding. Consideration is given to the positive and negative segregation to be expected in laboratory ingots in association with changes in ingot cross section. Under-riser positive segregation is considered and it is concluded this segregation results when vertical temperature gradient is low in the region of the riser; the segregation is accentuated by the temperature gradient reversal which can occur in inadequately insulated risers ("'hot tops"). Finally it is shown for Al-4.5 pct Cu alloy that the assumption of constant k and p in analytic solutions gives calculated results close to those obtained for the case of ziariable k and 0. A basic "local solute redistribution equation" was derived earlier' for calculation of macrosegregation resulting from flow of solute-rich liquid to feed solidification shrinkage, thermal contraction, and/or other contractions occurring during solidification. This expression relates fraction liquid, g~, to liquid composition, CL, at a given position x, y, z, in a solidifying Eq. [I] is for the general case of three-dimensional heat and fluid flow assuming constant solid (but not necessarily liquid) density during solidification, negligible net solute change from diffusion, and no pore formation. In this paper we first demonstrate application of this equation for calculation of macrosegregation in several examples involving one-dimensional heat and fluid flow. Specifically considered are examples in which segregation results from sudden changes in heat flow conditions. Next, Eq. [I] is used to describe segregation in examples where isotherms remain planar but where fluid flow is no longer one-dimensional. Application of this expression illustrates the type of segregation to be expected in unidirectionally solidified ingots of gradually or abruptly varying cross section. For segregation calculations, A1-4.5 pct Cu alloy is employed with constant k and p Vz = 0.172, 4 = 0.055), eutectic composition (CE = 33 pct Cu). In all examples, fraction eutectic is neglected in velocity calculations; this was previously shown to introduce little error.' A linear distribution of fraction liquid in the liquid-solid zone is assumed. In a concluding section it is shown that the assumption employed of constant k and /3 gives results close to those obtained when the actual (variable) values of k and 0 are employed.

Jan 1, 1969

By J. J. Thomas

THIS investigation was undertaken to determine, if possible, the relation between static and dynamic tensile tests as measured by the work required to break test specimens slowly, in a tensile testing machine, and rapidly, by means of a falling weight. It was hoped that the investigation would throw some light on the role played by ductility under different rates of application of load. FIG. 1.-STRESS-STRAIN DIAGRAM. In problems of design, it is usually assumed that the moduli of elasticity of all steels are equal; viz., about 30,000,000. The stress-strain diagram within the elastic limit is a straight line, as shown in Fig. 1, where OA is the curve of a hard steel and OB that of a soft steel. If the modulus of elasticity is constant, as assumed, the slope of the line OC

Jan 2, 1921

By J. E. Tobey

UNDER war conditions coal immediately assumes a position of highest importance for coal must carry the basic load for industry. The upward trend in production continued through 1941. Bituminous coal production alone about equaled the total output of bituminous and anthracite in 1940. The figures for 1941 approximated 500,000,000 tons for bituminous, and 54,000,000 tons for anthracite, and production of by-product and beehive coke exceeded that of the previous year. The coal industry, under the National Bituminous Coal Act, is going through a period of readjustment, and is beginning to stabilize itself under the statute. The Federal Mine Inspection Nill became law during the year.

Jan 1, 1942

By Nicholas J. Grant, A. W. Mullendore, Paul Predecki

The Duwez technique of splat cooling in which a molten droplet of metal is accelerated and made to impact on a cold, highly conducting substrate was investigated.- An apparatus for producing "splat" was constructed employing an explosive powder charge to accelerate the molten metal. Transport of the molten metal just prior to impact with the substrate was studied by means of high-speed photography. The molten particles are small spherical droplets from about 1 to 50 µ diameter. The average cooling rates for aluminum, silver, and a gold alloy splatted on nickel substrates at room temperature were determined experimentally and were found to vary from 18 to 5 x 10' C per sec. The heat-transfer coeficients for pure aluminum and pure silver splats cooled on nickel substrates at room temperature were found to be 2.7 to 6.8 and 13.6 to 54.2 cal per sec sq cm 'C (2 to 5 x 104 and 1 to 4 x 18 Btu per hr sq ft OF), respectively. Solidification rates in pure aluminum and silver splats were calculated. "SPLAT cooling" is a term describing a technique for extremely rapid freezing and cooling of molten metals and alloys to room temperature or below. The technique was developed by Duwez et al.' in 1960, and after refinement2 consisted in transferring a few tenths of a gram of molten metal to near sonic velocity to strike a suitably placed cold copper surface. Upon impact, the metal spread into a thin nonuniform film called a splat, about 10-4 cm thick. The splat particles produced in this manner were thin enough in some areas to be suitable for transmission electron microscopy, without further treatment, and, together with X-ray data, yielded a variety of structures which would be classified as follows: 1) supersaturated solid solutions (increase in solubility limit), 2) metastable crystalline stoichiometric and non-stoichiometric intermediate phases ( in Au-20.5 at. pct Si and in Au-14 at. pct Sb, respectively), 3) amorphous alloys, 4) retained high-temperature phases, 5) alloys having equilibrium phases present, but with unusual, markedly altered structures. The crystalline phases present in splats were usually extremely fine-grained and had low dislocation densities. Present interest in splat cooling centers around a study of the unusual structures produced by the technique, their contribution to alloy theory, and the possibility of the development of new or unusual properties. In addition, the technique is being examined for the production of bulk quantities of new high-strength alloys for low- and high-temperature use. Although a number of alloy systems have already been investigated by the technique, relatively little is known about the mechanism of splat formation and the physical conditions encountered by the metal during solidification and cooling. The purpose of this work was: 1) to determine the velocity, shape, and size of the molten metal droplets just prior to impact with the cold substrate; 2) to try to estimate or measure solidification rates, heat-transfer coefficients, and cooling rates in splats. EXPERIMENTAL TECHNIQUE Splatting Apparatus and Procedure. An apparatus similar to the type originated by Duwez et a1.,2 but employing an explosive charge to accelerate the molten metal, was used. A "Ramset" fastening tool (a gun normally used for driving studs into concrete, steel, and so forth) was mounted vertically above a resistance-heated graphite crucible as shown schematically in Fig. 1. A splat product was produced by melting a few tenths of a gram of metal at the position shown in Fig. 1, and then exploding a powder charge in the breach. The shock wave thus generated traveled down the barrel into the furnace, ejecting the molten metal through the 0.06-in.-diameter hole at the bottom of the crucible. The ejected metal was impacted on a high-conductivity metallic substrate where it formed a splat. High-Speed silhouette Photography. In order to investigate the size and shape of the ejected, molten metal just prior to impact with the cold substrate, high-speed silhouette photographs were taken, and are shown in Figs. 2 and 3. These photographs were obtained with the aid of an Edger-ton, Germeshausen, and Grier microflash unit and a submicrosecond flash drive equipped with a variable time delay. Two types of triggers were

Jan 1, 1965

By George Rice

THE subject of violent bumps in coal mines has been again brought to attention by a recent succession of such occurrences in the coal mines of the Cumberland field of eastern Kentucky and southern Virginia, which have caused fatalities and injuries to underground employees, a report on which is being issued by the United States Bureau of Mines1. The A.I.M.E. has had two valuable papers on bumps in the No. 2 Mine, Springhill, Nova Scotia, each followed by general discussion on bumps and their causes2. This paper gives a brief review of suggested causes and remedial measures given in English, Canadian and United States reports on bumps in coal mines, and then presents suggestions arising from the writer's recent investigation of the bumps in the Cumberland mines, made at the request of the mine operators, to determine the causes and remedies. These bumps, which occur under the simplest natural conditions, provide better opportunity for analysis of causes and effects than afforded under more complex conditions. The simple conditions in this field consist of relatively thin and level coal beds and uniform roof strata free' from folding and faulting.

Jan 1, 1935

By H. Kahata, I. Iwasaki, Y. Takahasi

A combined process of segregation roasting-flota-tion or magnetic separation was developed to recover nickel from lateritic iron ores and oxidized nickel ores. An ore was mixed with a halide, such as sodium or calcium chloride, and a solid reductant, and roasted, whereby the nickel content was segregated out as discrete metallic particles. Either by magnetic separation, or by flotation using a sulfhydryl collector together with a heavy metal salt as an activator, the metallic nickel could be concentrated, Effects of such variables as the types and amounts of the halide and solid reductant addition and of the roasting conditions were extensively investigated. The concentration results on several types of ores from Japan, the Philippines, and New Caledonia are presented. Laterite is a residual product of rock decay in tropical and subtropical regions, and consists mainly of hydrated oxides of iron and alumina. Those derived from serpentine sometimes become enriched in nickel, cobalt, and chromium contents. Oxidized nickel ores are of the similar origin, but their nickel as well as silica contents are higher due to gamierite-type silicates. Apparently, nickel enrichment is more pronounced in the transition region between the surface layer of iron laterite and the underlying serpentine. Iron laterites often contain over 50% iron, and their reserve is reported to exceed 22 billion tons, corresponding approximately to 20% of the world iron ore reserve.1 It is readily apparent, therefore, why the iron laterites have attracted much attention of the steel industry as a potential source of iron ores. Numerous attempts to remove nickel and chromium as byproducts, have been reported in literature.' Worldwide discoveries of high-grade iron ore deposits in recent years have inevitably lessened the interests in iron laterites. However, in view of the tremendous potential for their gross value and supplies of nickel, cobalt, chromium, and alumina along with iron, the problem remains as a challenge. Much of the chromium in laterites is present in the form of relatively coarse particles of chromite, and various classification methods have successfully been applied for its removal.2,3 The nickel, however, is intimately associated with limonite, and ordinary concentration techniques are totally ineffective. Much attention has, therefore, been given to hydro-metallurgical or pyrometallurgical means. Yet, all the known processes appear to have limitations either economically or for the use of products as iron raw materials due to a high residual content of nickel. Some attempts have been made to pre-roast laterites or oxidized nickel ores, particularly with sulfidizing agents, and to remove nickel either by magnetic separation,' or by flotation.4 It is apparent that any such concentration process would require grain growth of nickel during roasting for effective separation. Oxidized copper ores are reported to be concentrated by the segregation roasting-flotation process,5 in which the ores are roasted with a chloridizing agent and a carbonaceous reductant in order to promote the growth of metallic copper through repeated cycles of copper chloride volatilization and its reduction on the solid reductant surfaces. Examination of a vapor pressure-temperature diagram of various metal chlorides indicates that a separation of nickel from iron may be effected by a similar process. In fact, the segregation roasting of laterites was reported to increase the extraction of nickel by the ammonia leach process, as compared to the ordinary reduction roasting.6 In the present article some of the preliminary experimental results of the segregation roasting, followed by either flotation or magnetic separation, on laterites and oxidized nickel ores are reported. The effects of various parameters in the roasting as well as in the concentration steps are discussed. MATERIALS AND METHODS An oxidized nickel ore from Thio, New Caledonia, and three laterites from Homonhon, the Philippines, Wakasa and Miyagawa, Japan, were selected for the

Jan 1, 1967