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By Ralph Hultgren, David W. Mitchell

MAGNESIUM alloys usually are superheated before casting in order to ensure fineness of grain. Superheat temperatures in common use range from 1600° to 1700°F while the casting temperature, which depends upon the mold shape, is usually 200° to 300°F lower. The process of superheating requires considerable time and seriously shortens the life of the iron pots used. Recently it has been reported' that if acetylene, carbon dioxide or natural gas is bubbled through molten electrolytic A.S.T.M. No. 4 alloy at 1400°F. for 5 min., grain refinement equivalent to that of superheating will take place. Addition of certain solids such as graphite or aluminum carbide accomplishes the same results.2 As will be shown in this paper, it is possible to achieve grain refinement in magnesium casting alloys at low temperatures by mechanical stirring of the molten metal for a short time. This process was developed in the course of research work, supervised by the War Metallurgy Committee under the "Restricted" Project NRC-550, for the Office of Production Research and Development of the War Production Board. This paper, based on that work, has been released for publication by the O.P.R.D. MATERIALS AND METHODS The alloys studied were the most common American sand-casting alloys designated as No. 4 and No. 17 by the American Society for Testing Materials. The magnesium used in these alloys was of both carbothermic3 and electrolytic4 origin. Chemical analyses supplied by the producers are shown in Table I. Each heat consisted of approximately 5 lb. of alloy melted in a Tercod crucible. It was refined by fluxing with Permanente No. 7* refining flux at 1300° to 1350°F. After cooling to 1200' to 1250°F., portions of approximately one pound each were ladled into iron crucibles contained in an electric furnace at about 1250°F. The molten metal was covered with Permanente No. 21† covering flux and then heated to the temperature to be investigated. Normally each of the four portions was given a different treatment. In a typical case one portion was stirred vigorously for 5 min., acetylene gas was passed through a second portion for 5 min., a third portion was superheated to 1600°F for 15 min., then cooled to casting temperature, and the fourth was held for 5 min. at the temperature of stirring or gassing without other treatment. Each portion was then cast into one-inch diameter cylinders in three "nonturbulent" molds of identical shape. One mold was made of cast iron and the other two of baked sand. The cast-iron mold and one of the baked sand molds were heated to 360°F., the other baked sand mold was at room temperature. The freezing times in these molds were

Jan 1, 1945

By E. B. Brauer, B. F. Pennington, E. W. Hough, G. L. Stegemeier

Interfacial tension divided by the difference in density between the liquid and the vapor phases was determined experimentally by the pendant drop method on several isotherms in the two phase region below the critical point for the methane-normal decane system. The density difference data of Sage and Lacey was used in the calculation of interfacial tension. Both interfacial tension and and interfacial tension divided by density difference were found to vanish at the critical point. Interfacial tensions of less than one dyne/centimeter were observed as far as 1,000 pounds per square inch below the critical pressure. EXPERIMENTAL PROCEDURE The interfacial tension divided by the density difference for the methane-normal decane system was determined at the 100°, 130°, 160' and 190°F isotherms, from pressures of about 1,000 psi to the critical pressure, which is more than 5,000 psi for these isotherms. Particular emphasis was placed upon the investigation at pressures slightly below the critical pressure where the interfacial tension is less than 0.5 dyne/cm. Volumetric properties in the two-phase region, including the critical pressures and temperatures, were taken from the work of Sage and Lacey.1 The experimental pendant-drop technique used for the determination of interfacial tensions at high pressures incorporated the ideas of Michaels and Hauser,2 Hough, et a1,3 Walker4 and Heuer.5 In addition, the technique for determination of extremely small interfacial tension by Jennings6 was utilized in the region near the critical points. A detailed description of the apparatus is given in a dissertation by one of the authors.7 Cleaning operations on the stainless-steel sample system included successive washings with chromic acid, tap water and, finally, distilled water. Subsequent cleanings were performed with re-distilled normal pentane, which had an extremely low residue upon evaporation. Specific composition requirements necessitated a fairly precise sample introduction — although, fora two-phase, two-component system, the composition of each phase is completely determined if pressure and temperature are controlled. The normal decane was delivered into the evacuated sample system as a liquid from a burette. The methane was then introduced into the system from a calibrated isothermal container, so that pressure differentials could be used to determine the amount introduced. High pressures were obtained by compressing the sample with a mercury injection pump until the critical pressure was reached for the particular isotherm being studied. Experimental data were then obtained for specific pressures by first decreasing the pressure slightly so that two phases would appear, and then photographing a drop at that pressure. Subsequent photographs were made at increments throughout the pressure range. Calculation of interfacial tension divided by density difference was made from measurements

By R. E. Reed, C. J. McHargue

Poly crystalline aluminum specimens having random and diffuse (001) initial orientations were reduced 90 pct in area at room temperature by drawing, extruding, and swaging. Although each procedure produced the duplex (001)- (111) texture, there were marked dqferences in the relative amounts of each component. This also produced variations in the tensile properties of the aluminum rods. It is generally agreed that the fiber texture found in aluminum rods consists of a strong (111) and a weak (001) component after reductions in area of 90 pct or more. An examination of data summarized in recent reviews'-3 shows much spread in the values for the relative amounts of the two components reported by different investigators. That the initial orientation has a marked influence on the final texture even after reductions in area greater than 90 pct is well-documented.4-7 Another factor which may influence the relative amounts of the two components is the method of fabricating the wires or rods. Barrett and ~assalski' state that the center of wires formed by rolling, swaging, and drawing have the same textures. The data cited in support of this conclusion came from qualitative X-ray techniques. In recent years there has been renewed interest in correlating the type of preferred orientation with such parameters as stacking fault energy and onset of mechanical twinning.'' Since these analyses have often used many sources of data, it is essential that the data be evaluated for the effect of fabrication variables. In this study we have produced aluminum rods by drawing, swaging, and extruding and have quantitatively determined their textures. All specimens had the same purity and fabrication temperature, and the amount of deformation and the starting textures were determined. We have compared our results with published studies on similar materials and fabricating parameters. We have also compared results from the same three fabricating procedures for single-crystal specimens in three instances. EXPERIMENTAL PROCEDURE The aluminum was 99.99+ pct with the only detected impurities being (by weight) 0.002 pct Cu, 0.001 pct Si, and 0.001 pct Mg. Cylinders a in. in diam by 1 in. long with a fine-grain random texture were made by the following method. Cubes 1+ in. on a side were machined from 2-in.-diam ingots. These cubes were slowly pressed about 30 pct in each of the cube directions. The material was recrystallized by annealing 1 hr at 350°C. Three deformation-anneal cycles produced the desired material. Polycrystalline specimens with a diffuse (001) texture were made by casting into a graphite tube 1 in. ID, li in. OD, by 8 in. long which had been preheated to 900°C. One end of the tube was placed on a water-

Jan 1, 1969

By D. B. Carson, D. L. Katz

Natural gases under pressure form crystalline hydrates with water. Experimental data are reported on four-phase equilibrium for the methane-propane-water, methanc-pentane-water, and methane-hexane-water systems. Temperatures and pressures for equilibrium between gas, water-rich liquid, hydrocarbon-rich liquid, and hydrate were measured, as well as the percentages of methane and propane in the hydrate. The data indicate that natural gas hydrate behaves as a solid solution and that pentanes and heavier hydrocarbons do not enter into the solid phase. Vapor-solid equilibrium constants are presented that permit the approximation of the conditions for hydrate formation, from the composition of a gas. Introduction Natural gas hydrates have been the object of considerable research in recent years, because of the trouble they have caused in the natural-gas and natural-gasoline industries. Natural gas hydrates are white crystalline compounds of water and gas, which, under pressure, exist at temperatures considerably above the freezing point of water. Because of the relatively high temperatures at which the hydrates exist, they become a nuisance in high-pressure gas operations where water is present, since their formation causes partial or complete plugging of valves and pipes. From a practical standpoint, the trouble incident to hydrate formation has been solved by dehydration of the gas before it enters the plant or pipe line, or by other remedial measures. Extensive work on gas hydrates in the latter part of the nineteenth century, by Villardl and others, gave data on methane hydrate and on ethane hydrate. Schroeder summarized these theoretical studies2 Hammerschmidt3 introduced the information on gas hydrates to the gas industry and Dcaton and Frost4-6 gathered a considerable number of data on the behavior of natural gas hydrates. Recent papers7,8 have extended both the data and the theory of these hydrates. At present, data are available on tem-peraturcs and pressures of hydrate forma. tion for pure methane, ethane, propane, n-butane, methane-ethane mixtures, meth-ane-propane mixtures, methane-butane mixtures, and some Is natural gases, all- in the Presence of excess water. However, up to the Present time no method has been available for predicting the temperature at given pressures or the pressure at given at at which natural gases will form hydrates if hydrates with water. 'This Paper Presents data on the methane-propane-water, methane-pentane-water and methane-hex-""e water systems in four phases, one of which is the hydrate. he application of the phase rule to the methane-~ro~ane-water data Proves that hydrates behave as solid solutions. The data of this paper and those in the literature were used to develop vapor-solid. equilibrium constants,8 which permit prediction of conditions of hydrate formation from the analysis of a natural gas.

Jan 1, 1942

By D. M. Davidson

The drill sampling and evaluation of the Piney River ilmenite property was carried out during the early part of 1944 by E. J. Longyear Co., using the company's standard core-drill outfits to complete 44 holes to an average depth of IIO ft., from which were collected 1100 samples. The Piney River ilmenite-apatite lode is 25 miles north of Lynchburg, in Nelson and Amherst Counties, Virginia (Fig. I). Its elevation is about 900 ft. above sea level and it lies in the old pre-Cambrian complex of crystalline rocks that make up the Piedmont physiographic province lying east of the Blue Ridge Mountains. The terrain is gently rolling and well watered and is drained by the Piney and Tye Rivers, which are tributary to the James. Geology The Piney River ore body comprises the upper, weathered part of a tabular basic rock, which occurs in a large area of granite-gneiss. The section containing profitable ore is about 3000 ft. long. It is separated naturally by thinning, into northeastern and southwestern segments with widths of 300 and 100 ft. respectively. The dip averages 4.5° southeast but steepens locally (Figs. 2 and 3). The unaltered rock is an even, granular mixture of feldspar, ilmenite, and apatite, to which Watson1 gave the name Nelson-ite. The decomposed ore body, which is now being exploited by open cut, is a yellowish clay material in which black ilmenite and glassy apatite are the only conspicuous minerals. An economically important structural feature of the deposit is a banding of minerals coinciding with the dip and strike of the dike. This is more pronounced in the footwall of the northeastern part of the intrusive, where there is also a higher than average concentration of ilmenite. According to Watson,' the TiO2 content of the Nelsonites of this region ranges from 10 to 42 per cent, while P205 varies from 4 to 15 per cent. It is inexpedient at present to disclose exact metal content of the Piney River ore body; suffice it to say that the average tenor lies well within the extremes noted by Watson. Sampling Methods and Procedure During a preliminary inspection of the ore body, Longyear engineers surmised that because of its soft, clayey character, drill sampling would yield little core, therefore they made all possible preparations to procure accurate samples of the drill cuttings, or sludge. The first requisite in obtaining representative drill cuttings is to secure their full recovery. Only under certain conditions, and by employing a most careful and rigid sampling technique, is this pos sible. There must be no loss of the water circulating in the hole, and the velocity

Jan 1, 1949

By H. N. Mills

The glass industry is a major user of many industrial minerals in the manufacture of its product. It is the intent of this chapter to: (1) acquaint the reader with the glass industry by including a few production statistics, and (2) cover the various aspects of the major raw materials used to make glass. The matter of glass compositions, properties, and batches is considered beyond the scope of this chapter which deals only with raw materials. For more details on the particular minerals and rocks used in glassmaking, the reader is referred to chapters in the commodity section of this book. Glass Industry Statistics Glass manufacture in the United States can be divided into three major product classifications as follows: 1) Glass containers 2) Pressed and blown glass 3) Flat glass Glass containers include bottles and jars for the packaging of food and beverages, as well as drugs, chemicals, and cosmetics. Pressed and blown glass includes table, kitchen, art and novelty ware, lighting and electronic glassware, and fiber glass. Flat glass covers sheet or window glass, plate, laminated, and safety glass. The US Department of Commerce statistics, as recorded in the 1977 Census of Manufacturers, compares the dollar value of glass shipments for each product category. These statistics are shown in Table 1 (Anon., 1980) and are self-explanatory. A comparison of the tonnage output in each product classification is difficult, as production data is reported in "gross" for glass containers, "pounds" for fiber glass, "pieces" for glassware, [ ] and "square feet" for flat glass. In the case of glass containers, an average "pounds per gross" factor can be applied to the total production figures reported in thousands of gross in Bureau of Census industrial reports. Table 2 presents the calculated annual production tonnage for glass containers for the years 1974-1979. Except for 1979, there was a yearly increase in production. The tonnage figures of Table 2 are further influenced by decreasing weight per gross which has occurred in the glass container industry since 1975. This reflects the gradual shift to lighter weight containers for beverages. Other segments of the glass industry have experienced growth, but the figures in tons are not published information. Fiber glass growth has been influenced by the heavy demand for insulation as part of energy conservation efforts on a national basis. The production of flat glass by the float process has continued to grow with several new plants entering production. All portions of the glass industry experienced the effects of the general economic decline of 1979-1980, but the outlook for the future is bright. Batch Materials For Glass Use Materials and Function Soda-lime-silica glass represents the largest proportion of glass manufactured for commercial use. It is produced by the fluxing and

Jan 1, 1983

By J. S. Aronofsky, R. Jenkins

A simple means of predicting the flowing well pressure history in a natural gas reservoir has been developed. The differential equation for unsteady radial flow of gases through porous media was solved by numerical methods using electronic punch card machines. The results obtained from these calculations are presented in a generalized form which is believed to be most convenient for engineering use. These results are compared with those presented in a paper by Bruce, et al4. An effective radius of drainage has been defined which permits the equation of steady state gas flow to be used easily to predict well pressures in gas reservoir depletion. An equivalent effective radius of drainage is defined for liquid flow systems and a comparison is made of the gas solution to the liquid solutions. INTRODUCTION This paper presents a numerical method for describing the transient flow of gases radially through a porous medium from which the production rate is specified. The results obtained from these calculations are presented in a generalized form which is believed to be the most convenient for engineering use. The principal application of these calculations should be to flow in natural gas reservoirs, in the interpretation of pressure drawdown tests, in the estimation of reserves, and in calculation of injection pressures required in gas injection and cycling operations. The evaluation of natural gas wells is based upon back-pressure tests in which measurements of production rate and flowing well pressure are made for periods of one, two, or more days. The flow is assumed to have stabilized at this time, and the observed values of pressure and production rate are used with standardized formulae to determine the well's allowable production rate. Furthermore, the results obtained from such a test of short time duration are extrapolated in such a manner to allow a prediction of what the well pressure will be at some future time for a specified (but possibly untested) flow rate. The manner of conducting such back-pressure tests suggests several questions as follows: 1. 'What is the definition of stabilized flow and what factors determine the length of time required for the flow to become stabilized? 2. How may the recorded values of pressure and rate be utilized? 3. As the well is produced and the reservoir pressure falls, how will the flowing well pressure change? Can this flowing well pressure be predicted from the back-pressure test? 4. Are the results obtainable from the test influenced by a particular procedure used in obtaining the results? 5. Is it possible to estimate the gross reservoir permeability from back-pressure data? It is not within the scope of this paper to provide solutions Or even to discuss adequately all the above questions. However. in considering such matters, the

Jan 1, 1955

By George D. Roberts

INTRODUCTION CIVIL engineers are primarily interested in maximum core recovery. This is even more important in foundation work than in mining investigations where sludge samples are of some value. The soft materials, such as clay, gouge, or partially decomposed seams that are most readily ground up or washed away, are the materials that usually have the greatest influence on foundation and leakage conditions. Undisturbed samples of such materials should be obtained for detailed geological examination and laboratory tests. Therefore the attainable goal of sampling in connection with foundation investigations is the recovery of 99.9 pct of undisturbed core. FACTORS CAUSING CORE LOSSES The principal factors contributing to core losses are: (I) coring badly fractured or very soft material; (2) use of improperly designed coring equipment, including the use of bits of too small a diameter; (3) lack of the proper training and attitude on the part of the drillers and pertinent technical information on the part of the supervising personnel. Little can be done about the character of the material being cored but the other two factors contributing to unsatisfactory performance can be corrected. Although the title of this paper is the improvement and standardization of core barrels, it is believed that the drillers' shortcomings and the lack of pertinent technical literature are more detrimental to good core recovery than either of the other factors. USES FOR LARGE DIAMETER CORE BARRELS It is well known that the use of larger diameter bits and core barrels generally produce better cores, particularly when sampling soft or broken material. The use of larger and larger bit diameters and the insistence on better core recovery is well demonstrated by the change in practices of the various districts of the Corps of Engineers. Today NX core is the smallest diameter commonly permitted for investigational work and the more active districts are using coring bits up to 6 in. in diameter, as well as 36 and 40-in. calyx rigs. The latter size has proved to be just as economical because it provides more room for core removal and cleanup operations. The use of large diameter cores to replace the driving and jacking methods of obtaining soil samples is also increasing. The 5 7/8-in. Denison sampler, developed by H. L. Johnson to obtain samples from soft formations, is one example. The principal uses for bits larger than NX are: sampling soils and semi-consolidated rock; sampling decomposed rock or rock with soft seams; sampling concrete; obtaining samples for laboratory tests; drilling drainage holes, and other miscellaneous work. CORE DRILLING PRACTICES OF SEVERAL ENGINEER DISTRICTS Little Rock District The writer was employed in the Little Rock District from 1938 until 1942. Prior

Jan 1, 1947

By D. M. Davidson

The drill sampling and evaluation of the Piney River ilmenite property was carried out during the early part of 1944 by E. J. Longyear Co., using the company's standard core-drill outfits to complete 44 holes to an average depth of IIO ft., from which were collected 1100 samples. The Piney River ilmenite-apatite lode is 25 miles north of Lynchburg, in Nelson and Amherst Counties, Virginia (Fig. I). Its elevation is about 900 ft. above sea level and it lies in the old pre-Cambrian complex of crystalline rocks that make up the Piedmont physiographic province lying east of the Blue Ridge Mountains. The terrain is gently rolling and well watered and is drained by the Piney and Tye Rivers, which are tributary to the James. Geology The Piney River ore body comprises the upper, weathered part of a tabular basic rock, which occurs in a large area of granite-gneiss. The section containing profitable ore is about 3000 ft. long. It is separated naturally by thinning, into northeastern and southwestern segments with widths of 300 and 100 ft. respectively. The dip averages 4.5° southeast but steepens locally (Figs. 2 and 3). The unaltered rock is an even, granular mixture of feldspar, ilmenite, and apatite, to which Watson1 gave the name Nelson-ite. The decomposed ore body, which is now being exploited by open cut, is a yellowish clay material in which black ilmenite and glassy apatite are the only conspicuous minerals. An economically important structural feature of the deposit is a banding of minerals coinciding with the dip and strike of the dike. This is more pronounced in the footwall of the northeastern part of the intrusive, where there is also a higher than average concentration of ilmenite. According to Watson,' the TiO2 content of the Nelsonites of this region ranges from 10 to 42 per cent, while P205 varies from 4 to 15 per cent. It is inexpedient at present to disclose exact metal content of the Piney River ore body; suffice it to say that the average tenor lies well within the extremes noted by Watson. Sampling Methods and Procedure During a preliminary inspection of the ore body, Longyear engineers surmised that because of its soft, clayey character, drill sampling would yield little core, therefore they made all possible preparations to procure accurate samples of the drill cuttings, or sludge. The first requisite in obtaining representative drill cuttings is to secure their full recovery. Only under certain conditions, and by employing a most careful and rigid sampling technique, is this pos sible. There must be no loss of the water circulating in the hole, and the velocity

Jan 1, 1949

By L. C. De Jong, J. F. Shirley, M. L. Campbell

At the Southern Peru Copper operation in Toque-pala, Peru, a new process flowsheet for the recovery of byproduct molybdenite has proved successful in dealing with complex and highly variable ores. This paper describes the process and the functions of each of the chemicals used. The Toquepala concentrator of the Southern Peru Copper Corp., located approximately 720 miles southeast of Lima near the Chilean border, processes a daily 36,500 tons of ore containing between 0.50 and 3.00% copper. The molybdenite content in the ore also varies greatly ranging from essentially nothing to as high as 0.15%. The 1966 yearly averages were approximately 1.20% copper and 0.03% molybdenite. The Toquepala porphyry deposit is a mushroom-shaped ore body consisting of a flat-lying enriched zone of predominant chalcocite with a stem-like extension of hypogene chalcopyrite ore in depth within and around a large breccia pipe.1 The underlying chalcopyrite ore has not been reached; however, due to the presence of a major post orebody fault, predominantly chalcopyrite ore is present in the north side of the pit. Most of the molybdenite occurs either as small, fine granular, pulverulent masses in vugs or empty voids of breccia, or as thin foliated masses and narrow thread-like filling in rock joints and fractures. The normal occurrence of quartz gangue with the molybdenite gives some basis for correlating the molybdenite mineralization to some later periods of silicification. On April 18, 1962, the molybdenite recovery plant at Toquepala went on stream, approximately 27 months after the copper concentrator had been in production. The plant was designed and built by Southern Peru Copper Corp.'s engineering and mechanical departments. The basic method chosen for separating the molybdenite from the copper concentrate was the sodium hypochlorite-sodium ferrocyan-ide process. The selection of this process was based on the results of an extensive testing program performed by the Colorado School of Mines Research Foundation, Inc. and the economic conditions of the area. The originally designed process could never be fully implemented due to a lack of sodium hypo-chlorite and has had to be continually modified to satisfy the requirements of the kaleidoscope of ores from the mine. The three basic problems that plague the operation of any molybdenite recovery plant are all present at Toquepala in large measure. Both the quantity of plant feed and the quantity of molybdenite contained in the plant feed are continuously changing. Even more detrimental to an efficient operation is the fact that the copper mineralization in the feed frequently changes once in every 24 hours and occasionally once a shift. From the point of view of the molyb-

Jan 1, 1968

By D. B. Carson, D. L. Katz

Natural gases under pressure form crystalline hydrates with water. Experimental data are reported on four-phase equilibrium for the methane-propane-water, methanc-pentane-water, and methane-hexane-water systems. Temperatures and pressures for equilibrium between gas, water-rich liquid, hydrocarbon-rich liquid, and hydrate were measured, as well as the percentages of methane and propane in the hydrate. The data indicate that natural gas hydrate behaves as a solid solution and that pentanes and heavier hydrocarbons do not enter into the solid phase. Vapor-solid equilibrium constants are presented that permit the approximation of the conditions for hydrate formation, from the composition of a gas. Introduction Natural gas hydrates have been the object of considerable research in recent years, because of the trouble they have caused in the natural-gas and natural-gasoline industries. Natural gas hydrates are white crystalline compounds of water and gas, which, under pressure, exist at temperatures considerably above the freezing point of water. Because of the relatively high temperatures at which the hydrates exist, they become a nuisance in high-pressure gas operations where water is present, since their formation causes partial or complete plugging of valves and pipes. From a practical standpoint, the trouble incident to hydrate formation has been solved by dehydration of the gas before it enters the plant or pipe line, or by other remedial measures. Extensive work on gas hydrates in the latter part of the nineteenth century, by Villardl and others, gave data on methane hydrate and on ethane hydrate. Schroeder summarized these theoretical studies2 Hammerschmidt3 introduced the information on gas hydrates to the gas industry and Dcaton and Frost4-6 gathered a considerable number of data on the behavior of natural gas hydrates. Recent papers7,8 have extended both the data and the theory of these hydrates. At present, data are available on tem-peraturcs and pressures of hydrate forma. tion for pure methane, ethane, propane, n-butane, methane-ethane mixtures, meth-ane-propane mixtures, methane-butane mixtures, and some Is natural gases, all- in the Presence of excess water. However, up to the Present time no method has been available for predicting the temperature at given pressures or the pressure at given at at which natural gases will form hydrates if hydrates with water. 'This Paper Presents data on the methane-propane-water, methane-pentane-water and methane-hex-""e water systems in four phases, one of which is the hydrate. he application of the phase rule to the methane-~ro~ane-water data Proves that hydrates behave as solid solutions. The data of this paper and those in the literature were used to develop vapor-solid. equilibrium constants,8 which permit prediction of conditions of hydrate formation from the analysis of a natural gas.

Jan 1, 1942

By H. Becke, D. Stolnitz, D. Flatley, W. Kern

Zinc difhsions in gallium arsenide having surface concentrations as low as 5 x 10'' atoms per cu cm have been attained. A multiple-difhsion sequence is employed during which zinc enters the gallium arsenide from a silicon dioxide film in a solid-to-solid diffusion step. The technique is illustrated for the case of a zinc surface concentration of -1 x 1017 atoms per cu cm and a junction depth of 1.2 p. Radiotracer measurements of -0.1-p layers of gallium arsenide are used to delineate the resulting profile. A diffusion coefficient for zinc in pyrolytically deposited silicon dioxide is reported. ZINC is frequently used as an acceptor impurity in gallium arsenide. As examples, p-n junctions are formed using zinc-diffused layers in solar cells, lasers, and varactor diodes. For these purposes surface concentrations of 10'' to over loz0 zinc atoms per cu cm are desired and readily obtained from a vapor source. Diffusion of zinc into gallium arsenide to yield surface concentrations of about 1017 atoms per cu cm, however, is more difficult. For instance, oldstein' reports that large changes in the vapor density of zinc produce only small changes in surface concentration. Such low surface concentrations are necessary in forming the diffused base of a gallium arsenide double-diffused n-p-n transistor in order to obtain an adequate emitter efficiency. An alternative approach to zinc diffusion which can provide reduction in surface concentration of several orders of magnitude is the introduction of the diffusant from a solid source. This can be conveniently accomplished by using oxide films of the type generally employed for selective diffusion masking. Such oxides also serve to prevent the dissociation of the gallium arsenide surface at the high temperatures of diffusion. DIFFUSION PROCEDURE Fig. 1 illustrates the diffusion sequence which is employed for obtaining zinc surface concentrations in the range from 5 x lom to 1 X 10" atoms per cu cm. The description of technique will be given for the instance of -1 x 1017, which is typically utilized in double-diffused gallium arsenide transistor investigations at this laboratory. Tin- or germanium-doped gallium arsenide wafers drawn from crystals grown by horizontal Bridgman or Czochralski techniques are used, with bulk concentrations ranging from 1 to 3 X 10" carrier atoms per cu cm. Each wafer is chemically polished on the (iii) arsenic face using a mixture of five parts concentrated sul-furic acid, one part water, and one part 30 pct hydrogen peroxide at room temperature, followed by rinsing in deionized and quartz-distilled water. Pyrolytic silicon dioxide was chosen as the oxide coating because of the high quality of the films obtainable, the ease of their preparation, and the excellent control over film thickness and uniformity.

Jan 1, 1964

By G. E. McElroy

Though air jets occupy only a minor role in the ventilation of mines and other enclosures, their importance in this respect is greater than is commonly recognized and may be considerably increased as our conception of their modes of operation becomes clearer. The object of this paper is to discuss some of the ways in which air jets are involved in mine ventilation and some possible applications to the ventilation of mines and other enclosed spaces. The mention of air jets ordinarily suggests the use of some form of an air injector, such as the Venturi blower occasionally used for auxiliary ventilation in mines, or the Saccardo (injector) system used to a limited extent for ventilating railroad tunnels. Actually, the term covers such common phenomena as the discharge of air from fan pipes and coal-mine line brattices, and even from smoke stacks and fans. A knowledge of the general mode of air entrainment by jets also helps to explain certain phenomena—some mine-gas explosions, for instance—that otherwise would remain obscure. Jet action has been involved in three recent series of Bureau of Mines experi-ments in which the author has participated: experiments on fan-pipe discharge, On the dilution of gases discharged from a stack and On the ventilation of a ship's hold. Available data on the discharge of jets into large openings and on the design and performance of air injectors have been analyzed in considerable detail and supplementary experiments are planned for after the war. The results of the fan-pipe experiments have been combined with the analyses of data on jet discharge into large spaces, and have been published.' The results of the stack-gas dilution tests, which refer to a jet discharged into a crosswind, have also been published2 and a paper on the design and performance of injectors has been prepared for publication.3 These technical experiments and analyses form the background and the documented evidence for the following nontechnical discussion of the use of air jets in mine ventilation. Jet Characteristics The jets commonly encountered are those in which the air is in turbulent— as opposed to laminar, or streamline-— motion. The characteristics under discussion apply only to such turbulent jets and have their basis in theories of the mixing of turbulent air currents. Such jets have basic characteristics that are present, though variable in form, regardless of whether the jet expands freely in space, whether the expansion is limited by adjacent walls, or whether the jet propels air through a flow circuit. They expand at definite angles and entrain the surrounding air, even though the entrained air must be obtained by recirculation of their own air streams. As the quantity of air in motion in the mixed stream increases, the average velocity of the stream decreases.

Jan 1, 1946

By W. C. Ellis, M. E. Fine

In the iron-cobalt system there are several property-composition relationships of theoretical importance. The alloys are ferromagnetic exhibiting a maximum saturation at approximately 33 at. pct cobalt;' the interatomic distances at room temperature show large positive deviations from Vegard's rule;2 and in the region of 50 at. pct cobalt there is an order-disorder transition2 which has a large effect on other properties. The thermal expansion data for the system have been reported only from room temperature to 100 C and for this temperature range a minimum in coefticient in the rcgion of 50 at. pct cobalt is well established.3,4,6 This paper reports the expansion properties in the iron-cobalt system for temperatures from 30 to 850°C, shows the correlation with other physical properties, and proposes an explanation for the tcrrelation. Experimental Procedure The thermal expansivities of iron-cobalt alloys in 10 pct steps in composition were determined from 30 to about 850°C. The major series of alloys was prepared by induction melting from Armco iron and cobalt rondelles with the addition of about 0.6 wt pct manganese. This series was supplemented by three compositions: high purity electrolytic iron, high purity electrolytic cobalt, and an alloy of 52.1 wt pct cobalt prepared from the high purity electrolytic iron and electrolytic cobalt by vacuum-melting. The compositions of both series of alloys are given in Table I. The specimens for measurement were prepared from the cast ingots by first hot-swaging followed in most instances by cold-swaging to 0.180-in. diam rod. Some alloys in the region of 5c pct cobalt, because of inherent cold-brittleness, were swaged hot to the final diameter. The expansion specimens were approximately 2 1/2 in. long with flat-ground and polished ends. Before measurement they were annealed in hydrogen for I hr at 900°C. In the apparatus used for the thermal expansivity measurements (Fig I), a modification of that designed by Hidnert and Sweeney,? the differential expausion between the specimen and vitreous silica was measured by a dial micrometer reading to 0.001 mm. An invar fixture supported the dial gauge, and this fixture, in turn, was connected to a split invar collar which supported the outer silica tube. A pyrex "T" was placed over the outcr silica tube and was sealed to the invar collar by Apiezon Q sealing compound. A movable hollow vitreous silica rod which rested on top of the test specimen slid through a flexible rubber diaphragm cemented to the top of the pyrex "T." The specimen rested On a vitreous silica pedestal fused into the outer tube and was kept centered by a silica sleeve. A nonoxidizing atmosphere was obtained by admitting hydrogen into the

Jan 1, 1949

By J. B. Cheatham

An analysis of indexing is given for an idealized plastic rock. Indexing refers to chipping from a bit tooth to a previously formed crater. A method is indicated for computing the dependence of chip size and shape as well as force on the tooth for various tooth shapes as a function of crater configuration and distance to the previous crater. Pressure on the tooth is found to vary with depth of penetration after a critical depth has been reached. Damp sand model experiments indicate that simple solutions using linear and logarithmic spiral slip-line fields for Coulomb plastic materials give reasonable approximations to the failure patterns. Both idealized roller cone bits and fixed blade or drag bits are considered, and methods are presented for approximating the force on the bit and the chip volume when the rock is subjected to sufficiently high pressure to behave plastically. One of the primary objectives of drilling research investigations is to develop theoretical equations which can be used to predict the behavior of rock under drilling loading conditions. Since rocks usually fail in a brittle manner at atmospheric conditions, much current research is directed to studies of the brittle failure of rock under the action of drilling too1s. 1,2 The results of triaxial test on rocks indicate that both rock strength and ductility increase at high confining pressures.3 Recent results from single bit-tooth indentation experiments on dry rocks indicate that the transition from brittle to ductile failure under a bit tooth can occur at pressures sufficiently low to be of interest in oil well drilling.4 Single bit tooth experiments and analyses are not directly applicable to the drilling process since one of the important facets in drilling is the interaction between a bit-tooth and the previously formed crater. This interaction is referred to as indexing.' The purpose of the present paper is to indicate how plasticity theory can be applied to the analysis of indexing for plastic rock. Drag bit or fixed-blade drilling is considered and a discussion is given of the drilling action of an idealized roller cone bit. Results of simple experimental studies using a damp sand model are given as a method of visualizing the failure patterns in rocks under high confining pressures. These results are compared with plasticity theory using simple solutions based on linear and logarithmic spiral slip-lines. Discontinuous stress fields are proposed for drag bit drilling based upon the soil mechanics analysis of Shields. SINGLE BIT TOOTH RESULTS Single bit tooth indentation experiments using dry rocks under pressures from 0 to 5000 psi have indicated a correlation between the shape of a force-displacement curve and the nature of the rock failure beneath the tool.4 Continuous linear curves are in-

Jan 1, 1965

By James K. Stanley

PREFERRED orientation, particularly in irons and low-carbon steel, is a phenomenon that is both of considerable importance and theoretical interest. At times it is a liability and at other times an asset. In deep-drawing operations, preferred orientation is extremely undesirable because it necessitates trimming operations and increases scrap loss. Furthermore, oriented metals are likely to crack more easily than randomly oriented material because the forming of symmetrical and unsymmetrical shapes out of preferentially oriented metals and alloys increases the probability of rupture in regions of high stress, owing to differential ductility.1 In the electrical industry, on the other hand, preferentially oriented silicon irons are in demand for transformer application because of the improved magnetic permeabilities in the rolling direction.2 This phenomenon of preferred orientation in soft magnetic materials has been responsible for the tremendous improvement in transformer design and construction in recent years. Directional properties in metals have received a great deal of attention in the metallurgical literature,3-9 in which much of the information reported about orientation has been obtained by conventional methods, mechanical properties and X-rays. A wealth of data has been obtained and often at a great expenditure of time. The recent introduction of the magnetic torque measurements on ferromagnetic materials provides a very simple and rapid method of evaluating orientation. The judicious use of the method can supply important in- formation, but it should be borne in mind that such studies must be supplemented by X-rays, optical methods,10 and etch and pressure figures" to get a rational under- standing of the orientation phenomena. No claims are made that the magnetic torque of evaluating orientation will reveal the behavior of the metal in deep drawing. For this purpose the accepted tests for deep-drawing quality must be used. For a good drawing 'stock, which must have low impurities, desirable grain size, ductility, strength, hardness, good surface, random orientation, and good recrystallization behavior, it cannot be expected that any simple test will be satisfactory for appraising all the factors. The only factor on which the magnetic method can be used is orientation, which is, of course, of considerable importance. When directionality can cause a 10 to 15 per cent change in tensile strength and a IOO to 300 per cent change in tear length,12 it goes without saying that a reliable as well as rapid method for detecting these changes would be desirable. There are certain inherent advantages in testing orientation by the torque method: The method is rapid with the proper type of equipment; no elaborate preparation of specimens is required-it is only necessary punch or machine a disk of the sheet material and insert it into the testing device.

Jan 1, 1943

By J. J. Arps, T. G. Roberts

Since the introduction of the relative permeability concept in the middle thirties1,2 various investigators have shown3,10,11,12,15 how the basic equations for the flow of oil and gas through porous media can he utilized to compute the recovery from depletion type or solution gas drive type reservoirs under certain conditions, when the necessary physical data pertaining to the reservoir rock and its reservoir fluids are known. In the study by Muskat and Taylor" in 1945, the effects of viscosity, gas solubility, shrinkage, and the permeability-saturation characteristics of the producing formation on the production histories and the recovery of gas drive reservoirs were analyzed. Each parameter was varied a limited number of times, while keeping the others constant. The work was not carried to the point where the data could be used directly to estimate the primary recovery in those cases where certain rock and fluid characteristics were known or could be assumed. Since the publication of this classic study, the work by Beal in 194616 and Standing in 1952'" has established general correlations of oil viscosity and shrinkage with gas solubility and oil gravity. In addition. a considerable number of relative permeability relationships for different types of reservoir rocks has been published2,5,13,17,19,20. Also, the burden of the numerical work required in the solutions of the differential equation has. during the last few years, been greatly reduced with the availability of modern electronic computing facilities. The purpose of this paper is therefore to present the results of a large number of such recovery computations covering the normal range of variation of the main parameters such as the type of rock, the API gravity of the oil, and the amount of gas in solution. As is to be expected, the ultimate recovery is found to increase with the oil gravity. except for the higher solution gas-oil ratios. Within the normal range of solubilities, the ultimate recovery generally appears to decrease with the amount of gas in solution for the higher oil gravities, and to show a slight increase for the lower oil gravities. Intermediate oil gravities seem to fall between the two trends. The type of reservoir rock, as identified by its relative permeability relationship, appears to have a very pronounced effect on the ultimate recovery. In general, sands and sandstones show higher recoveries than limestones and dolomites, although certain intergranular limestones seem to show a higher theoretical recovery than unconsolidated sand. The recovery from sands and sandstones generally decreases with increasing cementation and consolidation, while the recoveries from limestones and dolomites are highest for the intergranular type and lowest for the fracture type porosity.

Jan 1, 1956

By Grafton M. Thrasher

Discussion of the paper of GRAFTON M. THRASHER, presented at the New York meeting, February, 1916, and printed in Bulletin No. 106, October, 1915, pp. 2129 to 2138. RICHARD MOLDENKE, Watchung, N. J.-Mr. Thrasher is to be commended for developing a very interesting comparison between high- and low-carbon and silicon malleable cast irons for an equal degree of chill. His deductions are unquestionably correct, though the application to daily practice is open to serious criticism, from the standpoint of the man who receives the castings, as will be shown later on. Running over some of the points which affect the tests in question: Mr. Thrasher admits that the temperature of pouring has a serious influence on the degree of chill shown in the test plugs he made. This is a well-known fact, and I would like to add that another serious trouble comes from oxidized iron when the heats have been unduly prolonged. Such metal always shows more chilling action for a given silicon and carbon content than normally melted iron. Indeed, the test piece quoted giving the extreme of the chill line (1.07 per cent. Si and 2.47 per cent. total carbon) was such a poor heat, a ferro-silicon addition never "doctoring" up the metal sufficiently to show normal good strength. In spite of these irregularities, which would simply change the curve slightly, I take it that Mr. Thrasher's results can be accepted as reliable enough to establish the relationship of silicon and total carbon as shown. When, however, the claim is made that silicon and carbon can be substituted for each other in mixture-making (a claim which may be perfectly correct metallurgically), a very important factor is forgotten, causing the purchaser of the castings much annoyance. This is the contraction (erroneously called shrinkage) of the castings. They will no longer be true to pattern. The lower the total carbon is allowed to drop, the greater the contraction, and increasing the silicon correspondingly will not correct this trouble. No wonder that recently, in revising the Standard Specifications for Malleable Castings it was necessary to increase the variation of castings from requirements considerably over what was formerly found sufficient. The habit of running up the proportion of silicon and escaping danger from grayness of the metal by copious steel additions was evidently too tempting to manufacturers, as their molding losses were thus kept down and a very soft malleable iron resulted. The customer, however, got serious variations in his work, which was not the case when the total carbon was kept between 3.25 and 2.75, and the silicon held as low as possible without undue cracking of the hard castings.

Jan 5, 1916

By E. A. Peretti

BEFORE embarking on a detailed investigation of the system indium-antimony-bismuth, experiments were carried out to determine the existence of quasi-binary sections. The bordering binary systems are known1 and show the occurrence of three intermetallic binary species corresponding closely to InSb, InBi and In2Bi. Attention was focused on the low-indium end of the ternary diagram where the possible quasi-binary sections, excluding ternary compound formation, would involve the pairs: InSb-Bi, InBi-Sb and InSb-InBi. The latter pair revealed itself as a true quasi-binary, so it was investigated fully by thermal analysis, x-ray and microscopic examinations. All compositions were made by proper combination of three elements involved. The indium had a guaranteed purity of 99.97 pet; the antimony contained 99.99 pet Sb, and the bismuth had a purity of 99.99 pet. Alloys were made by melting together antimony, bismuth and indium in evacuated, sealed pyrex-glass tubes at a temperature of 600°C with vigorous agitation. The melts, weighing about 80 grams, were allowed to freeze in the sealed tubes and finally were transferred to glass tubes for the taking of cooling and heating curves. A protective atmosphere of helium was used, and the melts were stirred mechanically while cooling at rates of from 0.5 to 3°C per min. Temperatures were measured with a calibrated chromel-alumel thermocouple and were recorded graphically on a Minneapolis-Honeywell extended-range recorder working in conjunction with a Leeds and Northrup type K-2 potentiometer. Conventional polishing techniques gave satisfactory results in preparing specimens for microscopic examination. Etching was carried out with Vilella's reagent or aqueous mixtures of chromic oxide with either nitric acid or sulfuric acid plus dichromate. Conclusions deduced from the thermal analysis and microscopic examinations were confirmed by X-ray photograms using Co-K alpha radiation. The phase diagram is shown in Fig. 1. The liqui-dus consists of an uninterrupted line running from the freezing point of InSb (525°C) to a eutectic point experimentally indistinguishable from the freezing point of InBi (110°C). X-ray patterns of the InSb show a slight expansion of the lattice with the addition of InBi, and microscopic work indicated the solid solubility of InBi in InSb to be less than 0.5 pet at room temperature. Acknowledgment We wish to thank the Indium Corporation of America for the loan of the indium used in this investigation. References 1 E. A. Peretti and S. C. Carapella, Jr.: Trans. ASM., 1949, vol. 41, P. 947. T. S. Liu and E. A. Peretti: Trans. ASM, 1952, vol. 44, p. 539. Metals Reference Book, vol. 1, 2nd ed., AIME, p. 345.

Jan 1, 1959

By H. R. Stahl

The disseminated lead district of Southeast Missouri lies 70 miles south of St. Louis. The only metal of economic importance in the ore is lead, but minor amounts occur of iron, zinc, copper, cobalt, nickel, silver and cadmium. These minor metals, as might be expected, tend to concentrate in both the flotation and table middlings. In the past, some zinc has been recovered by differential flotation. The silver and cadmium tend to associate with the zinc, and some recovery is made of these two metals at the smelter. The lead occurs as galena, or lead sulphide. The minor metals are also present as sulphides. The presence of oxidized lead is suspected, but has not been definitely proved. The gangue is chiefly dolomitic limestone, with small amounts of sandstone and shaly glauconitic and chloritic minerals. The ore contains about 3.25 per cent lead, occurring as galena disseminated through the gangue. Some of the galena is very finely disseminated, and the mineral in the gravity tailings, or chat; is seldom or never in the free state. The method of treatment of the ore has been evolved over a period of 75 years; hence probably is not far from correct. The milling processes have tended toward simplification during the past 15 years, but recoveries have never been sacrificed for the sake of simplicity. In many cases, simplification of flowsheets has led to better recoveries and operating economies. A simplified flowsheet is shown in Fig. I. The St. Joseph Lead Co. operates four mills in the Flat River district, with a normal total capacity of about 21,000 tons per day, divided as follows: Federal mill, 11,000 tons; Leadwood mill, 4500 tons; Desloge mill, 3400 tons and Bonne Terre mill 2400 tons. The methods of concentration used at these plants are similar in principle; they differ mainly in details and in the type and size of the equipment used. The process of concentration may be divided into five main steps; i.e., dry crushing, wet grinding, classification with its attendant desliming, tabling and flotation. A brief description of these processes will be given, noting important differences in the various plants, and also noting the more important changes or developments of the past few years. Dry Crushing The run-of-mine ore is hoisted in skips, the capacity of these skips ranging from 23/4 tons to 81/4 tons. At the Desloge plant, the ore is hoisted in 2-ton mine cars on self-dumping cages. All ore is hoisted at shafts adjacent to the various crushing plants, no ore being transported on the surface. Primary breaking at all the mills is accomplished with 9E Telsmith breakers. Preliminary screening is provided ahead of most of these crushers, either by station-

Jan 1, 1943