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By Carle R. Hayward

This work was first undertaken in the metallurgical laboratory of the Massachusetts Institute of Technology in 1907 by L. A. Dickinson, E. Phelps, and V. S. Rood, under the author's direction. They attempted to determine the diagram for the system Cu2S-MiS, but several inexplicable results were obtained. The following year, P. H. Mayer with Mr. Dickinson carried on some experiments with nickel sulphide and found that the molten material slowly lost sulphur until it reached a composition corresponding to the compound Ni3S2, established by Bornemann.l At this point the composition remained stable. The freezing points of the mixtures gradually fell off with the loss of sulphur. Since the above facts seemed to explain the erratic results obtained in the first experiments, Mr. Mayer with F. Jaeger attempted in 1910 to establish a correct equilibrium diagram for the Cu2S-Ni3S2 series. They prepared pure Cu2S and Ni3S2 and determined the cooling curves for various mixtures. The fusions were made in a platinum resistance furnace and the temperatures were measured with a platinum-iridium thermocouple connected with a Sullivan galvanometer. The curve was established for mixtures containing more than 40 per cent. Cu2S, but they were unable to determine certainly the direction of the curve beyond that point. Nothing further was attempted with this series until the present year, when the work was carried to a successful conclusion with the assistance of A. Butts, Jr., and E. H. Weil. The results of this work are given in the following pages. Preparation of Cu2S.—A piece of cathode' copper from the Buffalo plant of the Calumet & Hecla Co. was cut into shavings by a shaper and converted into sulphide by heating in boiling sulphur. A porcelain casserole was used for the purpose, the heat being furnished by a Bunsen burner. It was found that after boiling in the sulphur for an hour the copper shavings were completely converted into sulphide. The liquid sulphur was then poured off, leaving the solid sulphide in the casserole in

Jan 1, 1915

By B. M. Loring, W. H. Baer, G. M. Carlton

It is a well known fact that age-hardening alloys remain in a supersaturated, or partially supersaturated, condition only for limited periods of time at temperatures below the solvus. In order to develop optimum properties by subjecting the quenched alloy to precipitation or age-hardening treatment at a specified temperature, it is necessary that the cooling rate be sufficiently high to maintain the required degree of supersaturation of the solid solution. In practical applications the size and shape of the specimens obviously have considerable influence on the rate of cooling and there is need for more information on the effects of various rates of cooling. Cooling rates of quenched aluminum alloys generally have been established by the type of quenching medium, the temperature of the medium and the dimensions of the specimen. Except for the work of Roth3 little quantitative information is available on the measurement of cooling rates of aluminum alloys and the significance of the influence of various cooling rates upon the mechanical properties. The purpose of the present investigation was to study the use of the Jominy test for aluminum alloys (Table I). The material for this investigation consisted of extruded rods 1 1/4 to 136 in. in diam. The chemical compositions were as follows: The modified L-type Jominy specimen with dimensions shown in Fig I was selected as the most convenient means for obtaining a wide range of cooling rates. The standard Jominy specimen was not satisfactory because its cooling rate was not sufficiently high. The four flat surfaces machined at right angles along the length of the L-type specimen to a depth of 0.015 in. facilitated the hardness measurements. The specimens were machined from the extruded stock with no intermediate forging. New specimens were used for each aging experiment. The specimens were given solution treatments of 2 hr duration at recommended temperatures in a Hoskins furnace (Table 2). The temperature of the furnace was maintained constant to 3°C. No protective atmosphere was necessary because the thin film of oxide that formed on the surface of the specimens had no effect on the hardness measurements. AT

Jan 1, 1949

By Frank Foote, E. R. Jette

In recent years the constitution of the high-silver aluminum-silver alloys has been extensively investigated. Hansenl has reviewed the literature to 1935. More recently, Obinata and Hagiya,2 Hofmann and Volk,3 Taziri4 and Tishchenko5 have confirmed the general features of the phase diagram in the region around 25 atomic per cent aluminum. In this paper we present the results of high-precision measurements of lattice constants of the silver-rich alpha solid solution in the homogeneous range and the neighboring two-phase regions. These results are used to establish the nature of the solid solution, the identity of directly measured densities with those calculated from lattice constants and the homogeneity limits of the alpha solid solution with respect to three different neighboring phases. A study of the earlier investigations indicated that the last two subjects in particular required new and accurate data. Experimental Procedure Preparation of the Alloys.—The alloys were made from high-purity silver and aluminum. The silver was "Proof Silver," 99.999 per cent pure, supplied by the U. S. Metals Refining Co. The aluminum was 99.97 per cent pure (contained Si, 0.009 per cent; Fe, 0.0016 per cent; Cu, 0.004 per cent) and was supplied by the Aluminum Company of America. The lattice constants of these two materials have been reported by Jette and Foote.6 Weighed amounts of the two metals were placed in alundum crucibles and melted in vacuo in a high-frequency induction furnace. The melts were allowed to cool in the crucible, the ingots thus obtained weighed about 10 grams. These ingots were then filed clean, hamered, again cleaned and given a homogenizing anneal in vacuo of from 6 to 15 days at temperatures ranging from 500" to 695°C. The ingots were air-cooled from the annealing temperature. Lattice-constant Measurements.—Carefully prepared filings for X-ray analysis were sealed into evacuated quartz or Pyrex tubes and annealed for various periods of time at suitable temperatures. The furnaces used were vertical, rapid-quenching furnaces, the samples being quenched by crushing the sample tube under water by means of a heavy plunger. The general X-ray technique has been previously described6 The cameras were of the symmetrical, back-reflection, focussing type. Ka, radiation from a cobait-nickel alloy target was used. The wave-length values were taken from the second edition of Siegbaum's book.7 A correction for the index of refraction was applied and the lattice constants were calculated by the method of Cohen.8, 6 The lattice constants were calculated to a common temperature of 25°C., using the value of the linear expansion coefficient of pure silver as 18.9 X 10-6. Presumably the expansion coefficient for

Jan 1, 1941

By Frank Foote, E. R. Jette

In recent years the constitution of the high-silver aluminum-silver alloys has been extensively investigated. Hansenl has reviewed the literature to 1935. More recently, Obinata and Hagiya,2 Hofmann and Volk,3 Taziri4 and Tishchenko5 have confirmed the general features of the phase diagram in the region around 25 atomic per cent aluminum. In this paper we present the results of high-precision measurements of lattice constants of the silver-rich alpha solid solution in the homogeneous range and the neighboring two-phase regions. These results are used to establish the nature of the solid solution, the identity of directly measured densities with those calculated from lattice constants and the homogeneity limits of the alpha solid solution with respect to three different neighboring phases. A study of the earlier investigations indicated that the last two subjects in particular required new and accurate data. Experimental Procedure Preparation of the Alloys.—The alloys were made from high-purity silver and aluminum. The silver was "Proof Silver," 99.999 per cent pure, supplied by the U. S. Metals Refining Co. The aluminum was 99.97 per cent pure (contained Si, 0.009 per cent; Fe, 0.0016 per cent; Cu, 0.004 per cent) and was supplied by the Aluminum Company of America. The lattice constants of these two materials have been reported by Jette and Foote.6 Weighed amounts of the two metals were placed in alundum crucibles and melted in vacuo in a high-frequency induction furnace. The melts were allowed to cool in the crucible, the ingots thus obtained weighed about 10 grams. These ingots were then filed clean, hamered, again cleaned and given a homogenizing anneal in vacuo of from 6 to 15 days at temperatures ranging from 500" to 695°C. The ingots were air-cooled from the annealing temperature. Lattice-constant Measurements.—Carefully prepared filings for X-ray analysis were sealed into evacuated quartz or Pyrex tubes and annealed for various periods of time at suitable temperatures. The furnaces used were vertical, rapid-quenching furnaces, the samples being quenched by crushing the sample tube under water by means of a heavy plunger. The general X-ray technique has been previously described6 The cameras were of the symmetrical, back-reflection, focussing type. Ka, radiation from a cobait-nickel alloy target was used. The wave-length values were taken from the second edition of Siegbaum's book.7 A correction for the index of refraction was applied and the lattice constants were calculated by the method of Cohen.8, 6 The lattice constants were calculated to a common temperature of 25°C., using the value of the linear expansion coefficient of pure silver as 18.9 X 10-6. Presumably the expansion coefficient for

Jan 1, 1941

By William H. Baer, George M. Carlton, Blake M. Loring

IT is a well known fact that age-hardening alloys remain in a supersaturated, or partially supersaturated, condition only for limited periods of time at temperatures below the solvus. In order to develop optimum properties by subjecting the quenched alloy to precipitation or age-hardening treatment at a specified temperature, it is necessary that the cooling rate be sufficiently high to maintain the required degree of supersaturation of the solid solution. In practical applications the size and shape of the specimens obviously have considerable influence on the rate of cooling and there is need for more information on the effects of various rates of cooling. Cooling rates of quenched aluminum alloys generally have been established by the type of quenching medium, the temperature of the medium and the dimensions of the specimen.1,2,3 Except for the work of Roth3 little quantitative information is available on the measurement of cooling rates of aluminum alloys and the significance of the influence of various cooling rates upon the mechanical properties. The purpose of the present investigation was to study the use of the Jominy test for aluminum alloys (Table I). EXPERIMENTAL PROCEDURE The material for this investigation consisted of extruded rods 1 ¼ to 1 ½ in. in diam. The chemical compositions were as follows: [ ] The modified L-type Jominy specimen with dimensions shown in Fig I was selected as the most convenient means for obtaining a wide range of cooling rates. The standard Jominy specimen was not satisfactory because its cooling rate was not sufficiently high. The four flat surfaces machined at right angles along the length of the L-type specimen to a depth of 0-015 in. facilitated the hardness measurements. The specimens were machined from the extruded stock with no intermediate forging. New specimens were used for each aging experiment. The specimens were given solution treatments of 2 hr duration at recommended temperatures in a Hoskins furnace (Table 2). The temperature of the furnace was maintained constant to ±3°C. No protective atmosphere was necessary because the thin film of oxide that formed on the surface of the specimens had no effect on the hardness measurements.

Jan 1, 1948

By Warren B. Weeks

Continued development in the deeper fields discovered during 1937 and 1938 was largely responsible for the 16 per cent (2,913,400-bbl.) increase in production, bringing the 1939 output to 21,376,230 bbl., the largest for South Arkansas since 1929. The older settled fields continued to decline and Rodessa was added to this classification. Magnolia field accounted for much of the increase, with Schuler field showing only a slight increase. There were 248 wells drilled during 1939, five more than during the previous year. Of 198 wells drilled in proven fields, 21 were dry; 46 of the 50 wildcats drilled were dry. The old depth record of 8332 ft. was increased to the present record of 9028. Trend of Prospecting Production from the porous " Reynolds " oolite zone of the Smackover limestone continued to be the objective of prospecting. During the year 20 seismograph, 3 gravity meter, 1 magnetometer, 1 soil analysis and 1 electromagnetic crews were reported in the state. The geophysical work was largely concentrated in three southern counties: Columbia, Lafayette and Union. As indicated in Table 2, the same three counties received most of the important drilling tests. At the end of the year only three seismograph crews remained in the areas. The area for prospecting Smackover limestone was greatly narrowed during the year by the failure of two "fault zone" wells to find satisfactory permeability in the oolite zone, and by the relatively thin sections of porosity found in wells drilled in townships 18 and 19 South. Geology Most of the wells listed in Table 2 afforded additional control on structure of the lower beds, but gave little new information on stratigraphy. Of the 248 wells drilled, 3 ended in Tertiary, 34 in Gulf, 1 in Paluxy, 29 in Glen Rose, 15 in Travis Peak, 15 in Cotton Valley, 139 in Smackover, 2 in Eagle Mills and 10 in Carboniferous. The age of the beds between the Travis Peak formation and Carboniferous is still questionable. Most

Jan 1, 1940

By Warren B. Weeks

Continued development in the deeper fields discovered during 1937 and 1938 was largely responsible for the 16 per cent (2,913,400-bbl.) increase in production, bringing the 1939 output to 21,376,230 bbl., the largest for South Arkansas since 1929. The older settled fields continued to decline and Rodessa was added to this classification. Magnolia field accounted for much of the increase, with Schuler field showing only a slight increase. There were 248 wells drilled during 1939, five more than during the previous year. Of 198 wells drilled in proven fields, 21 were dry; 46 of the 50 wildcats drilled were dry. The old depth record of 8332 ft. was increased to the present record of 9028. Trend of Prospecting Production from the porous " Reynolds " oolite zone of the Smackover limestone continued to be the objective of prospecting. During the year 20 seismograph, 3 gravity meter, 1 magnetometer, 1 soil analysis and 1 electromagnetic crews were reported in the state. The geophysical work was largely concentrated in three southern counties: Columbia, Lafayette and Union. As indicated in Table 2, the same three counties received most of the important drilling tests. At the end of the year only three seismograph crews remained in the areas. The area for prospecting Smackover limestone was greatly narrowed during the year by the failure of two "fault zone" wells to find satisfactory permeability in the oolite zone, and by the relatively thin sections of porosity found in wells drilled in townships 18 and 19 South. Geology Most of the wells listed in Table 2 afforded additional control on structure of the lower beds, but gave little new information on stratigraphy. Of the 248 wells drilled, 3 ended in Tertiary, 34 in Gulf, 1 in Paluxy, 29 in Glen Rose, 15 in Travis Peak, 15 in Cotton Valley, 139 in Smackover, 2 in Eagle Mills and 10 in Carboniferous. The age of the beds between the Travis Peak formation and Carboniferous is still questionable. Most

Jan 1, 1940

By W. V. Green

Creep of tantalum was measured at temperatures from 0.6 to 0.89 of the absolute melting temperature. The creep curves include first, second, and third stages. Steady-state creep rate depends on the fourth power of stress. The activation energy for creep throughout this temperature range is approximately 114 kcal per mole, measured by the aT technique. Subgrain formation occurs as a result of creep strain, and pile-up dislocation arrays are observed in etch-pit patterns. BECAUSE of its high melting point-which is exceeded only by those of rhenium and tungsten—and its high room-temperature ductility compared to most of the other high-melting-point metals, tantalum will undoubtedly be utilized in an increasing number of high-temperature applications. Alloying studies directed toward increased high-temperature strength must use data on tantalum itself as a base line in order to evaluate the effectiveness of the alloying additions. However, to date, no systematic study of creep of tantalum at temperatures above one-half of its melting point has been reported in the literature. Conway, Salyards, McCullough, and Flagella1 have measured linear creep rate of tantalum sheet as a function of stress, but at only one temperature, 2600°C. This paper describes a relatively thorough study of the high-temperature creep of tantalum. METHOD Material Tested. The commercially supplied, l/2-innch-diameter tantalum rod used for this work was electron-beam-melted, cold-forged, rolled, swaged, cleaned chemically, and vacuum-annealed for 1 hr at 1000°C, all by its manufacturer. The vendor's analysis included 60 to 170 ppm C, 3.4 to 4.2 ppm H, 60 to 80 ppm 0, 15 ppm N, and a hardness ranging from 66 to 81 Bhn and averaging 76 Bhn. Creep eimens Used. Two creep-tested specimens are shown in Fig. 1. The 1/4 in.-diameter gage section was 3/4 to 1 in. long, and terminated either at shoulders 5 mils high or at 20-mil-diameter tantalum wires spot-welded to the circumference of the gage section. Both kinds of shoulders served equally well as fiducial marks for optical strain measurements. The spot welding did not alter the creep behavior in any detectable way; the 5-mil- high sharp shoulders did not result in any detectable localized effect on the strain. Before testing, each tensile bar was first mechanically polished -id then electrochemically polished according to the method referred to by Forgeng2 as the "Thompson Ramo Woolridge" method, which was suitable for tantalum after small adjustments of technique were made. Two tensile bars tested at low stresses had 1/8-in.-diameter gage sections and utilized only the weight of the bottom grip for the applied load. Although these diameters were smaller than were desired for other reasons, applied loads were known with high precision in the tests in which they were used. Testing Procedure. Two different constant-load creep-testing machines were employed, one of which has been described by Smith, Olson, and Brown.3 In both, the tensile bar is held vertically on the axis of a cylindrical tungsten tube or screen heater by threaded tungsten grips. The tensile bars and associated grips are heated by radiation from the incandescent heaters, which are heated by their own electrical resistance. Both testing machines use pins to hold the bottom grips in place. The load is applied to a tensile bar through hanging weights, a constant force-multiplication lever, a pull rod sealed to the chamber lid, and a top grip threaded to the pull rod at one end and to the tensile bar at the other. In one machine, the vacuum seal is a bellows with a low spring constant; in the other, the seal involves a rotating "0 ring". With the latter, rotation is converted to translation with a crank shaft, so that elongation of the tensile bar is accommodated with no change of tensile load. The incandescent tensile bar is viewed by an external optical system through slots in the radiation shields and heater, and an enlarged image is projected on a ground-glass screen. Gage-length measurements are made on this image with cathetometers on traveling microscopes. With regard to creep-test results, the two machines were identical. Thorium oxide coatings were applied to the threaded ends of the tensile bars, to prevent diffusion welding of the tensile bars to the grips during testing. Specimen temperatures were measured with an L. & N. optical pyrometer which had been calibrated against a standard carbon arc, and were corrected fir window absorption by calculation from the measured spectral transmittance of the quartz observation windows. Longitudinal temperature gradients in the tensile-bar gage length and temperature drifts during testing were detectable but small, and were estimated to be 10°C or less. Accuracy of temperature measurement was confirmed by comparing the temperature measured on the surface of a special

Jan 1, 1965

By M. J. Pool

The partial molar heats of solution in liquid tin of cadmium, silver, tellurium, and zinc have been measured at 655°. 700°, and 750°K by liquid-metal solution calorimetry. Silver, cadmium, and zinc are endothermic at these temperatures while tellurium is exothermic. Only the heat of solution of silver depends on composition while all four elements show a temperature-de pendent heat of solution. The heat of solution of tellurium is constant up to 0.6 g-at. pct, becomes increasingly more exothermic, and reaches a limiting value at 1 g-at. pct Te. The limiting value has been used to calculate the heat of formation of SnTe at 750°K. The heat effects associated with the dissolution of the compounds Ag2 Te, CdTe, and ZnTe in liquid tin were measured at 750°K. These values are cotnOined with the measured hat effects at 750°Kfor silver, cadmium, tellurium, and zinc to detertrline the heats of formation of the telluride compounds. Cadmium lelluride exhibits a heat of dissolution which has a compositional dependence. THERE is a considerable amount of interest in the compounds of tellurium because of their electronic properties. Both cadmium and zinc tellurides are thermoelectric materials and considerable work has been done on their electronic properties but a limited amount of data is available on their ther-modynamic properties. This work was undertaken to elucidate the heat of formation data on cadmium and zinc telluride. Since both cadmium and zinc are in Group II it seemed to be of interest to compare the values obtained for them with the heat of formation of a Group I telluride. Silver telluride was selected for this comparison. In the course of the work it was also possible to determine the heat of formation of tin telluride and therefore to make a comparison of some of the Group I, 11, and lV tellurides with the metallic elements silver, cadmium, and tin being in the same period. There is also a great deal of interest in the energetic changes which occur upon addition of solute elements to a common solvent. This investigation provided an opportunity to study the partial molar heats of solution of silver, cadmium, tellurium, and zinc in liquid tin. The partial molar heats of solution are of theoretical interest because solute-solute interactions are a minimum in dilute solutions and application of solution models is simpli- fied. In order to complete the analysis of solute-solute and solute-solvent interactions the temperature dependence of the partial molar heats of solution was also measured. MATERIALS AND EXPERIMENTAL PROCEDURE All materials were of the highest purity available. The silver, zinc, cadmium, and tellurium were obtained from American Smelting and Refining Co. and were reported to be 99.999 pct pure. The silver telluride, zinc telluride, and cadmium telluride were obtained from Atomergic Chemetals Co., a division of Gallard-Schlesinger Chemical Manufacturing Corp., and were electronic-grade material of 99.999 pct purity. Tin used for the solvent bath and for calibration was obtained from the Vulcan Manufacturing Co. and was reported as being 99.99 pct pure. The liquid-tin solution calorimeter used in this work is similar in principle to the differential twin-type calorimeter described by K1eppa.l Two of three identical calorimeter wells are used together during any set of experiments, one well being active and the other being passive. The wells are positioned 120 deg apart in an aluminum calorimeter block. Each well contains a multijunction thermopile and a Pyrex test tube to hold the liquid metal bath. Forty-eight of the thermopile junctions are distributed over the surface of each calorimeter well adjacent to the test tube and serve to integrate the heat effects occurring. The other forty-eight are next to the aluminum calorimeter block. The thermopiles for the three wells are connected differentially so that any change in temperature at the outer junctions (which will be the same for both wells because of the high conductivity of the aluminum block) will oppose for the two wells and result in no shift of the zero. The electrical output represents the true temperature difference between the two reaction vessels. A reaction occurring in the active well gives a comparison with another body of very similar thermal properties. In this way, any spurious heat effects due to slight temperature drifts within the entire calorimeter block are eliminated. The output of the differential thermopile goes to a dc amplifier with multiple ranges of from * 10 pv to 1 30 mv. The output of the amplifier is then fed into a Leeds and Northrup strip-chart recorder. The adiabatic temperature change is then calculated using the technique of Howlett, Leach, Ticknor, and ever.' The aluminum calorimeter block is contained in a cylindrical furnace with main and control heaters

Jan 1, 1965

By Vard H. Johnson

IN 1943 the U. S. Bureau of Mines undertook drilling in an effort to develop new reserves of coking coal in an area near Paonia, Colo., as a part of an attempt to alleviate the shortage of known coking coal of good quality in the western United States. Geologic mapping of the area was undertaken by the U. S. Geological Survey with the purpose of first furnishing guidance in location of drillholes and later aiding in interpreting the results of the drilling. The drilling program was under the general supervision of A. L. Toenges of the U. S. Bureau of Mines. J. J. Dowd and R. G. Travis were in charge of the work in the field. Geologic mapping was started by D. A. Andrews of the Geological Survey in the summer of 1943 and was continued from the spring of 1944 to 1949 by the writer. The first few holes drilled failed to locate coking coal, but in the summer of 1944 coking coal was discovered by drilling 6 miles east of Somerset, Colo., the site of present mining. In the succeeding years, 1945 to 1948, 100 to 150 million tons of coal suitable for coking were blocked out by drilling. The ensuing discussion of the geologic controls on the distribution of coking coal in the area is based on the geologic mapping as well as the drilling done in the Paonia area, more complete descriptions of which have appeared or are in process of publication."' In order that the possible geologic controls affecting the present distribution of coking coal may be considered, it is necessary to discuss briefly the indicators of coking quality coals. Coking Coal Coal that cokes has the property of softening to form a pastelike mass at high temperatures under reducing conditions in the coke oven. This softening is accompanied by the release of the volatile constituents as bubbles of gas. After release of the contained gases and upon cooling, a hard gray coherent but spongelike mass remains that is referred to as coke. This substance varies greatly in physical properties and, to be suitable for industrial use, must be sufficiently dense and strong to withstand the crushing pressure of heavy furnace loads. Western coals have a generally high volatile content and therefore form a satisfactory coke only when they attain a rather high fluidity during the process of heating arid distillation in the coke oven. When this high degree of fluidity is developed, the volatile constituents escape and leave a finely porous coke. On the other hand, when the degree of fluidity is low the product is an excessively porous and therefore physically weak mass that is called char." Small quantities of oxygen present in coal are believed to decrease the fluidity of the material during the coking process and to favor the development of char rather than coke. In consequence, coal chemists have for some time considered the possibility of developing an index to coking qualities by inspection of chemical analyses of coals.' A formula has now been developed that does permit a rough preliminary estimate of the cokability of coal on the basis of the analysis on an ash and moisture-free basis. Coals may be eliminated as possible coking fuels if the oxygen content is greater than 11 pct. Similarly the ratio of hydrogen to oxygen must be greater than 0.5 and the ratio of fixed carbon to volatile constituents must be greater than 1.3. If the coal, on the basis of these limiting factors, appears to have possible coking qualities, the following formula permits determination of the coking index: a+b+c+d Coking index = -------- 5 a equals 22/oxygen content on ash and moisture-free basis, b equals two times the hydrogen content divided by oxygen content on moisture and ash-free basis, c equals fixed carbon/l.3 x volatile matter, and d equals the heating value on moist, ash-free basis/13,600. Coking indices higher than 1.0 suggest that the coal will coke, and indices above' 1.1 indicate good coking tendencies. Although generally usable, this formula 'is not completely satisfactory because the percentage of oxygen shown in ultimate analyses is derived only by difference; i.e., by subtracting the sum of the percentages of the constituents determined analytically from 100 pct. Although the coking index indicates the coking tendencies of coal, it is necessary to make physical tests of coke before its industrial value can be determined. The U. S. Bureau of Mines has developed a standard procedure for determining the approximate strength of coke that would be formed from a given coal. In this test one part of ground coal, mixed with 15 parts of carborundum, is baked to form a standard briquette. The weight, in kilograms, necessary to crush the briquette is termed the agglutinating index. This test determines the relative fluidity attained in the coking process by measuring the cementing strength of the coal in the briquette. A

Jan 1, 1953

By Vard H. Johnson

IN 1943 the U. S. Bureau of Mines undertook drilling in an effort to develop new reserves of coking coal in an area near Paonia, Colo., as a part of an attempt to alleviate the shortage of known coking coal of good quality in the western United States. Geologic mapping of the area was undertaken by the U. S. Geological Survey with the purpose of first furnishing guidance in location of drillholes and later aiding in interpreting the results of the drilling. The drilling program was under the general supervision of A. L. Toenges of the U. S. Bureau of Mines. J. J. Dowd and R. G. Travis were in charge of the work in the field. Geologic mapping was started by D. A. Andrews of the Geological Survey in the summer of 1943 and was continued from the spring of 1944 to 1949 by the writer. The first few holes drilled failed to locate coking coal, but in the summer of 1944 coking coal was discovered by drilling 6 miles east of Somerset, Colo., the site of present mining. In the succeeding years, 1945 to 1948, 100 to 150 million tons of coal suitable for coking were blocked out by drilling. The ensuing discussion of the geologic controls on the distribution of coking coal in the area is based on the geologic mapping as well as the drilling done in the Paonia area, more complete descriptions of which have appeared or are in process of publication."' In order that the possible geologic controls affecting the present distribution of coking coal may be considered, it is necessary to discuss briefly the indicators of coking quality coals. Coking Coal Coal that cokes has the property of softening to form a pastelike mass at high temperatures under reducing conditions in the coke oven. This softening is accompanied by the release of the volatile constituents as bubbles of gas. After release of the contained gases and upon cooling, a hard gray coherent but spongelike mass remains that is referred to as coke. This substance varies greatly in physical properties and, to be suitable for industrial use, must be sufficiently dense and strong to withstand the crushing pressure of heavy furnace loads. Western coals have a generally high volatile content and therefore form a satisfactory coke only when they attain a rather high fluidity during the process of heating arid distillation in the coke oven. When this high degree of fluidity is developed, the volatile constituents escape and leave a finely porous coke. On the other hand, when the degree of fluidity is low the product is an excessively porous and therefore physically weak mass that is called char." Small quantities of oxygen present in coal are believed to decrease the fluidity of the material during the coking process and to favor the development of char rather than coke. In consequence, coal chemists have for some time considered the possibility of developing an index to coking qualities by inspection of chemical analyses of coals.' A formula has now been developed that does permit a rough preliminary estimate of the cokability of coal on the basis of the analysis on an ash and moisture-free basis. Coals may be eliminated as possible coking fuels if the oxygen content is greater than 11 pct. Similarly the ratio of hydrogen to oxygen must be greater than 0.5 and the ratio of fixed carbon to volatile constituents must be greater than 1.3. If the coal, on the basis of these limiting factors, appears to have possible coking qualities, the following formula permits determination of the coking index: a+b+c+d Coking index = -------- 5 a equals 22/oxygen content on ash and moisture-free basis, b equals two times the hydrogen content divided by oxygen content on moisture and ash-free basis, c equals fixed carbon/l.3 x volatile matter, and d equals the heating value on moist, ash-free basis/13,600. Coking indices higher than 1.0 suggest that the coal will coke, and indices above' 1.1 indicate good coking tendencies. Although generally usable, this formula 'is not completely satisfactory because the percentage of oxygen shown in ultimate analyses is derived only by difference; i.e., by subtracting the sum of the percentages of the constituents determined analytically from 100 pct. Although the coking index indicates the coking tendencies of coal, it is necessary to make physical tests of coke before its industrial value can be determined. The U. S. Bureau of Mines has developed a standard procedure for determining the approximate strength of coke that would be formed from a given coal. In this test one part of ground coal, mixed with 15 parts of carborundum, is baked to form a standard briquette. The weight, in kilograms, necessary to crush the briquette is termed the agglutinating index. This test determines the relative fluidity attained in the coking process by measuring the cementing strength of the coal in the briquette. A

Jan 1, 1953

By C. E. Sims, H. M. Banta, S. L. Hoyt

OVER the past few years, metallic arc welding has been extended to steels of the hardenable type. As compared with other methods of fabrication, production has been facilitated, service performance frequently has been improved, and the overall results have been so favorable that engineers and production men have placed great emphasis on this application of welding. The metallurgist and welding engineer, however, have been confronted with new problems, since, for one reason, the harder steels are more apt to crack and special precautions must be taken if sound joints are to be procured. Some of the factors that are pertinent to this problem are metallurgical, and it is an object of this contribution to discuss steel manufacture and processing methods and to show how their control assists in reducing the hazard of cracking. By this time, the problem of cracking specifically underbead cracking, or "hard cracks," or parent-metal cracks-is well known, and a large amount of work has been published, both here and abroad, dealing with this subject.1 The tests described are made under restraint to facilitate cracking and, are so designed that a semiquantitative, or at least a relative, value of the cracking tendency is obtained. As one would expect, it has been reported that the incidence of cracking increases with the carbon and alloy content of the steel. More specifically, the cracking tendency is said to increase with the hardenability of the steel, though it is now recognized that the situation is not so simple. The phenomenon itself, on the other hand, has been but loosely described, and it is in only broad generalizations that this cracking has been related to steel metallurgy. Thus, while it has been abundantly demonstrated that the hardenable aircraft steel, S.A.E. 4130, must tend to crack when arc-welded, the problem still remains of why two lots of the same composition and the same hardenability can vary so greatly in cracking tendency, or what it is about the prior metallurgical history that so strongly affects the results. Further, while the efficacy of preheating and postheating in preventing cracking is recognized and utilized in production, the mechanism by which they function seems not to have been described. These points are thought to be significant in the production of steel for fabrication by metallic arc welding and, hence, of interest to mill and process metallurgists and welding engineers. Consequently, it is another object of this paper to discuss the mechanism of parent-metal cracking, including the influence of the condition of the steel and the control of cracking by manipulation of the time-temperature conditions during and after welding. A new method of rating the cracking. tendency is also discussed, and the results of the test are related to steel composition and structure or prior history. The work to be described was the outgrowth of work in 1940-41 at Battelle Memorial Institute 0n two projects, one

Jan 1, 1945

By Ward C. Smith

The industry of producing and processing boron compounds is called the borax industry because the chief product is borax, the decahydrate of disodium tetraborate. For the same reason, it is common to speak of borax mining. Reference to borate mining also is common, and while appropriate where it emphasizes the diversity of borate minerals that are mined in various countries, it is rather unsatisfactory where used in a general sense, because it seems to exclude the important production of borax from brine at Searles Lake, California, and of boric acid from steam vents in Tuscany, Italy. The terms "boron industry" and "boron mining" might seem more comprehensive, but are little used, and this is fortunate because they would be misleading-the element boron is manufactured only in small amounts for special uses, and it is not found free in nature. In most occurrences, boron is combined with oxygen and is in a borate or borosilicate material. The history of the modem borax industry starts with the introduction into Europe of borax from Tibet in the 13th century, about the time of Marco Polo, if not actually by him. The discovery that borax has unique value as a flux in metal soldering and ceramic glazing must have been made at some unknown time much earlier. As a rule, any mineral that has been used so long that its early history is lost must occur in deposits that are easily recognized and worked, and this is undoubtedly true of borax in Tibet. According to meager accounts,9 the borax occurs there in arid mountain basins as surficial crusts that coat the ground about thermal springs and seeps of mineralized water, and as coarser crystals in the bottom muds of shallow pools and lakes. Much the same essential features of surface exposures and minerals easy to recognize and recover characterize most of the deposits later found and worked elsewhere. The borax industry at the present time is faced with rising demands for its products, and consequently is increasing its productive capacity and appraising its borate resources.18 The areas that contain the known borate deposits are most likely to yield additional production, hence their distribution in the world is of interest, and is summarized later in this chapter. Mineralogy The mineral raw materials used by the borax industry include various borates mined in several countries, borax extracted from brines at Searles Lake in California, and boric acid extracted from the steam of vents in Tuscany in Italy. The hydrated borates[$] of chief commercial importance are listed in Table 1, which also shows their chemical composition. The properties of only the four most important borates are summarized here, but detailed descriptions of the borates and the minerals commonly found with them can be found in mineralogy textbooks.41 Ulexite generally forms clusters of silky fibers rather than large individual crystals. A

Jan 1, 1960

By Raymond D. Sloan

Development and exploration in Oklahoma showed a definite increase in 1941 over 1940 in production, wildcat activity and total well completions. Geological and geophysical work continued and possibly increased slightly in amount. Oklahoma retained third place in the ranking of oil-producing states of the nation, topped only by Texas and California, and followed by Illinois in fourth position. Production averaged 416,800 bbl. daily, a 1.7 per cent increase, as compared with 409,900 bbl. daily for the year 1940. Maintenance of the state's relatively stable producing rate resulted from the discovery of numerous small pools, the recombing of old areas, the establishment of new producing horizons, and the drilling of an increased number of marginal wells. The market for the Mid-Continent crude was strengthened materially to meet the increased demand. Coincident with a deeline in production in Illinois, shipment of Oklahoma-Kansas crude to the eastern points averaged 453,000 bbl. per day, an increase of 49.4 per cent as compared with 1940. The movement south amounted to an average of 42,000 bbl. per day, a loss of 41.7 per cent. Secondary-recovery programs in Oklahoma were given more consideration, operators realizing that in the future many pools would necessarily have to resort to this type of operation. Five permits for water-flooding were issued by the Corporation Commission during the year. These projects were in Rogers, Wagoner and Nowata Counties, in the shallow northeastern area, which has relatively extensive development of this type in the Bartles-ville sand at from 600 to 1000 ft. in depth. Gas repressuring of an individual lease in the 35-year old Glenn pool, Creek County, proved relatively successful, and after a year's operation was extended to cover a much larger area, with several operators participating. More of this type of work is expected in the future; however, it was given an initial setback when the legislative proposal authorizing secondary recovery in the Wilcox zone of Oklahoma's largest pool, the Oklahoma City pool, was pigeonholed by the committee. A continuation of the low discovery rates within the state would possibly lead to a revival of interest in the project. Many pools formerly classified as prorated areas were removed from this classification and transferred into the group of settled production. At the close of the year the issuance of the Federal Conservation Order M-68 and the interrelated Preference Rating Order P-98 caused a sharp decline in drilling operations, which is expected to continue until such operations are stabilized at a lower rate. The ultimate effect of these two orders on discoveries, production and reserves is a matter of speculation and conjecture. During the year, 2110 new wells were drilled, an increase of approximately 18 per cent as compared with the previous year. Of the total, 1235 were oil wells with a combined initial potential of 342,754 bbl. daily, 178 were gas wells with a total

Jan 1, 1942

By Raymond D. Sloan

Development and exploration in Oklahoma showed a definite increase in 1941 over 1940 in production, wildcat activity and total well completions. Geological and geophysical work continued and possibly increased slightly in amount. Oklahoma retained third place in the ranking of oil-producing states of the nation, topped only by Texas and California, and followed by Illinois in fourth position. Production averaged 416,800 bbl. daily, a 1.7 per cent increase, as compared with 409,900 bbl. daily for the year 1940. Maintenance of the state's relatively stable producing rate resulted from the discovery of numerous small pools, the recombing of old areas, the establishment of new producing horizons, and the drilling of an increased number of marginal wells. The market for the Mid-Continent crude was strengthened materially to meet the increased demand. Coincident with a deeline in production in Illinois, shipment of Oklahoma-Kansas crude to the eastern points averaged 453,000 bbl. per day, an increase of 49.4 per cent as compared with 1940. The movement south amounted to an average of 42,000 bbl. per day, a loss of 41.7 per cent. Secondary-recovery programs in Oklahoma were given more consideration, operators realizing that in the future many pools would necessarily have to resort to this type of operation. Five permits for water-flooding were issued by the Corporation Commission during the year. These projects were in Rogers, Wagoner and Nowata Counties, in the shallow northeastern area, which has relatively extensive development of this type in the Bartles-ville sand at from 600 to 1000 ft. in depth. Gas repressuring of an individual lease in the 35-year old Glenn pool, Creek County, proved relatively successful, and after a year's operation was extended to cover a much larger area, with several operators participating. More of this type of work is expected in the future; however, it was given an initial setback when the legislative proposal authorizing secondary recovery in the Wilcox zone of Oklahoma's largest pool, the Oklahoma City pool, was pigeonholed by the committee. A continuation of the low discovery rates within the state would possibly lead to a revival of interest in the project. Many pools formerly classified as prorated areas were removed from this classification and transferred into the group of settled production. At the close of the year the issuance of the Federal Conservation Order M-68 and the interrelated Preference Rating Order P-98 caused a sharp decline in drilling operations, which is expected to continue until such operations are stabilized at a lower rate. The ultimate effect of these two orders on discoveries, production and reserves is a matter of speculation and conjecture. During the year, 2110 new wells were drilled, an increase of approximately 18 per cent as compared with the previous year. Of the total, 1235 were oil wells with a combined initial potential of 342,754 bbl. daily, 178 were gas wells with a total

Jan 1, 1942

By J. Parker

As a practicing mining engineer, I face many rock mechanics' problems daily and would like to mention one or two examples to illustrate the current gap between laboratory investigations and actual field problems. I would like to endorse Dr. Obert's suggestion that more field measurements and observations should be undertaken. There is an ever-increasing body of data beginning with Hast's results in Sweden,l then measurements at Elliot Lake, Canada, and so on, including our own measurements at White Pine, which clearly indicate that the horizontal stresses underground. are often at least as large as the vertical stresses. Visual observation of the deformation of roof and pillars (including failure due to horizontal compres- sion) also demonstrates that the horizontal stresses are often most important: Yet almost every laboratory investigation begins with the assumption that the only stresses acting are vertical. Roof spans in layered formations. for example, are calculated on the assumption that the rock behaves as a gravity loaded beam. This is all too often unrealistic.

Jan 1, 1967

By James F. McConnell, Charles W. Statler

Pennsylvania's existing large coal-fired units are limited to 2.0, 1.8, or 0.6 lb of sulfur per million Btu fired, depending on site location. Multi-stream coal preparation can be employed on system basis to extract the highest quality fraction of coal for use in units requiring the lowest sulfur. The middling fraction can be directed to units permitted higher sulfur. General Public Utilities Corp. has concluded that it is feasible to advance the state-of-the-art of heavy media coal preparation to produce an intensively cleaned primary product of 1.3 sp gr of less than 0.6 lb of sulfur per million Btu for the new unit and a middling product of 2.0 lb of sulfur per million Btu for existing units.

Jan 1, 1977

By R. Kossowsky

USING etch-pit techniques, Johnston and Gilman' have shown that the stress dependence of dislocation velocity can be represented by the expression where r, is the dislocation velocity, a is the applied stress, and oa, is the stress to produce a unit velocity. Noble and Hul12 showed that the exponent m is strain-dependent and increases rapidly in the work-hardening region. This was explained by arguing that in the work-hardened material the applied stress required for any given velocity will be greater than in the annealed material by an amount equal to a back stress due to work hardening. schadler3 has stressed the importance of substructure as a possible source of error in dislocation velocity measurements, and took care to make velocity measurements in which dislocations moved such short distances that interactions with boundaries were avoided. schadler3 also pointed out that, if standard testing equipment is used, measurements of m from flow stress data could be seriously in error in materials with a high initial work-hardening rate. Noble and Hu112 have further argued that, due to the strain dependence of m , the extrapolation to zero strain4 to obtain the true value of m can be justified only in the preyield region. Microstrain experiments in high-purity iron5,6 have led to the conclusion that aiA (Ref. 5) (defined as the stress to first produce a permanent set of 10-6 in. per in.) and oflow are not controlled by the same deformation mechanism. It has been proposed5,6 that aA is governed by the lattice resistance to the motion of screw dislocations in a given slip plane and that oflow is controlled by the lattice resistance to a full-scale cross slip. The purpose of this note is to extend Noble and Hull's argument further and to show that measurements of m from flow stress data can be in error due to the rapid increase in stress in the microstrain region6 when stress is increased beyond aA. Double z-one-refined single crystals of molybdenum (with the (101)[ 111] slip system operating and a Schmidt factor of 0.475) were used in an experimen-

Jan 1, 1968

By Dilip K. Das, Douglas T. Pitman

ONE of the major uses of barium in metallic form is as a getter material in vacuum tubes. Because of the high chemical reactivity of the metal, Ba-Al alloys are extensively used. Numerous methods for the preparation of Ba-Al alloys have been published, a few of which1-4 are cited here. Most of these methods were found to be quite elaborate, involving the reduction of BaO, and not too well adapted for the close control of the final composition of small amounts of alloys prepared for laboratory use. A simple laboratory method for the preparation of Ba-A1 alloys in small batches starting from pure metals was devised, so that it was possible to control the desired compositions to within 1 pct. The pertinent features of the alloy system Ba-Al5 are 1) an intermediate compound BaAl, with the melting point of 1050°C, and 2) a eutectic between aluminum and BaAl4 at 98 pct Al. The accompanying sketch shows the experimental arrangement for the preparation of the alloys. Weighed amounts of aluminum and barium were placed in an alumina and a stainless steel crucible, respectively. According to the supplier's specification, the purity of the metals used in the alloys is as follows: a) aluminum rods—99.9 pct Al, and b) barium rods—99.5 pct Ba. The stainless steel crucible, tapered at the bottom and having a 1/16 in. diam hole, rested on top of the alumina crucible. The assembly was placed inside a graphite sleeve which rested on a refractory platform. The platform moved the assembly up and down through the field of a radio frequency coil. A glass bell jar was placed between the crucible assembly and the radio frequency coil to maintain a steady flow of helium around the melt. A small window was cut out on the wall of the alumina crucible to observe the progress of the re- action and to record the temperature with an optical pyrometer. The platform was first raised high enough to move the barium out of the radio frequency coil field in order to allow only the aluminum to melt. The assembly was then lowered so that the barium began to melt and flow out through the small orifice into the molten aluminum. In order to keep the violence of the exothermic reaction under control, the rate of flow of barium was carefully regulated by raising or lowering the crucible assembly. All the samples prepared by this technique were examined by a Norelco X-ray diffractometer using CuKa radiation, The diffraction specimens were prepared by placing the finely powdered samples in flat specimen holders. The Ba-Al alloys prepared with a high barium content were found to consist mainly of BaAl4. The structure of BaAl4 has previously been reported by Alberti and Andress.8 They found that BaAl4 was body-centered-tetragonal with an a0 = b0 = 4.530Å and c0 = 11.14Å. An alloy whose composition was found by chemical analysis to be almost 100 pct BaA1, was used to determine the relative intensities. The d-spacings were obtained from the same alloy to which a small amount of tungsten had been added as a calibrating material. Accurate values for a, and c, were calculated according to the method proposed by Taylor and Floyd.' The calculated values are: a, = b, = 4.566Å and c0 = 11.250Å. The measured d-values for BaAl4 are shown in Table I along with relative peak intensities above background and hkl indices. Acknowledgment The authors are grateful to L. J. Cronin, the head of the Techniques Dept., for suggesting the problem and for his constant interest. References 1Froges and Camargue: German Patent No. 809107, 1951. French Patent No. 935324, 1949. 2E. Bonnier: Annales de physique, 1953, vol. 8, pp. 259-312. 3M. Orman and E. Zemhela: Prac Institute of Metals; 1952, vol. 4, pp. 437-445. 4E. Fujita and H. Yokomizo: Reports Gov. Chemical Industrial Research Institute, Tokyo, 1952, vol. 47, pp. 291-297. 5E. Alberti: Ztsch. fur Metallkunde, 1934, vol. 26, p. 6. 6E Alberti and K. R. Andress: Ztsch. fur Metallkunde, 1935, vol. 27, p. 126. 7 A. Tnslor and R. W. Floyd: Acta Crystallographica, 1950, vol. 3, p. 285.

Jan 1, 1958

By H. L. Talbot, A. J. Hall, R. S. Young

A method for the chemical differentiation of oxidized cobalt from sulphide cobalt in complex mine and concentrator products is of considerable interest to a number of mining companies throughout the world. At Rhokana Corporation, in Northern Rhodesia, for instance, cobalt is found chiefly in the sulphide form, as carrollite, but a cobalt oxide mineral also occurs irregularly underground, and relatively small quantities in the mill feed from time to time are difficult to detect visually at the concentrator. The oxide cobalt is not amenable to the sulphide flotation process used at Rhokana and nearly all of it passes into the tailing. The occasional period when high tailing losses occur with no appreciable change in the cobalt content of the mill feed has naturally been disturbing to the concentrator staff, who had no means of determining whether an influx of cobalt oxide ore or laxity on the part of the mill flotation operators as responsible for these results. A procedure for determining oxidized copper minerals, based on their solubility in dilute sulphuric acid saturated with SO2, has been used for many years in the copper industry. In the presence of cuprite the procedure fails, but otherwise it gives results quite satisfactory for control pur- poses. Empirical methods for determining oxidized forms of zinc and lead have been proposed, but they are generally unsatisfactory except in isolated cases of a very simple ore. No published procedure for determining oxidized forms of cobalt or siinilar elements has come to the authors'notice. Experimental Procedure There are obviously two alternatives in attacking a problem of this nature. One is to employ a solvent for oxide cobalt that will not dissolve cobalt sulphide. The other is to find a substance capable of oxidizing the cobalt sulphide to sulphate, which of course is water-soluble and can then be leached from the water-insoluble oxide cobalt. A representative sample of Rhokana cobalt oxide ore was secured, ground to minus 200-mesh, and carefully rolled to furnish a standard sample for this work. The analysis of this material gave the following percentages: Co, 0.55; Cu, 1.64; Fe, 2.98; S, 0.08; SiO2, 41.42; Al2o3, 11.20; CaO, 13.82; MgO, 3.80. As a source of cobalt sulphide a similar large sample of carrollite was prepared, analyzing Co, 23.36 per cent; Cu, 27.32; and S, 31.13. This sample of course was not pure carrollite, but was the best obtainable in quantities sufficient for a standard intended for considerable work. It was a pure sulphide sample, microscopic examination showing only carrollite, a little bornite, and gangue, with no visible sign of oxidized ore present. A wide variety of reagents as used in an effort to selectively dissolve oxide cobalt or to oxidize sulphide cobalt to

Jan 1, 1949