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By H. S. Martin

The Phosphate Recovery Corporation operates three flotation plants, Nos. 1 and 2 concentrators about three miles northeast of Mulberry, Florida, and No. 3 plant at Wales, Tennessee. These plants represent the first commercial phosphate flotation operation and are also believed to be the largest nonmetallic flotation operation in the world at the present time. The details of this paper will be confined to plant No. 2, this being the newest and largest concentrator in Florida, and the flow sheet being practically the same as at plant No. 1. The No. 3 plant has been operated but a short time and has been shut down since December, 1932, on account of the decrease in phosphate rock production. The phosphate washers usually are located centrally on a known deposit so that about two hundred acres of ground can be mined economically to each washer location. The washers are moved to new areas when the distance becomes too great for economical pumping. The flotation plants are built either adjacent to a washer, so that current debris may be utilized, or on the site of a former washer where there is sufficient accumulated debris available for mining, and the flotation plants must also be moved from time to time. Most of the water used in the Florida flotation plants is recovered after passing through a circulating system where most of the fine suspended matter is settled out, but some make-up water is obtained from deep wells near the plant. Power is obtained from the Tampa Electric Co. through the distribution facilities of the International Agricultural Corporation. Flotation concentrate is hauled from the plant by trolley over the International Agricultural Corporation's trolley system, to the drying plant at Prairie, one mile northwest of Mulberry. Ore Treated In the pebble phosphate district of Florida, the phosphate mineral, or collophane, is usually found in horizontal beds of varying thickness

Jan 1, 1935

By S. J. Green, R. D. Perkins

Little data exists on the high strain rate behavior of geologic materials. Uniaxial stress tests by Kumar1 and by Serdengecti and Boozer2 present some results to strain rates in the range 10 to 103 per sec. The two references cited are the only ones the authors found for high strain rates. Techniques for experiments at high strain rates are not well developed and, in general, leave questions with respect to interpretation of data when the material behaves in a brittle manner. The most reliable data at very high strain rates (104 to 106 per sec) are found in some recent flat-plate work3-5 where experimenters have impacted one plate into another, thereby creating a uniaxial strain loading. The standard uniaxial stress-strain curves cannot be obtained directly from these tests; however, yield (or fracture) may be studied by measuring the "elastic" wave magnitude. These data then may be compared to uniaxial stress data by resorting to some preassumed yield/fracture criteria. Even with the most liberal interpretation of existing data, little can be said of the effects of high strain rate on stiffness, yield/fracture, and post-fracture behavior of geologic materials. It is the purpose of this work to begin to add to the understanding. The data presented here are intended to provide material information for use in calculating the response of geologic materials to high rate deformations. These data can be applied directly to determine parameters such as the elastic modulus and Poisson ratio as a function of stress. Furthermore, these data can be used to derive an understanding of yield/fracture and the effect of rate on the yield/fracture surface. The work presented is a first step, and is

Jan 1, 1972

By HAROLD VINTON COES

THE motive for merging or consolidation today is conspicuously different from that actuating business men in the late eighties and early nine- ties. Then they combined to secure added productive capacity and to monopolize their respective industries with a view to exploiting the consumer. So flagrant were some of these cases that they brought about their own correctives via retaliation on the part of the public and the subsequent restrictive legislation and legal curbs. The objective of the present-day merger, writes W. R. Hill in Printers' Ink, December, 1927, is summarized as follows : "In the golden days when an industry was being cut to pieces, the prevailing cure was to combine. The reason for such trusts was to strangle competition and by creating a monopoly, dominate the market, raise prices, regardless of economic business methods, and simply force larger profits.

Jan 1, 1930

With the inauguration of Petroleum Technology this year, and approval by the Board to add an Assistant Secretary to the New York staff to serve the Petroleum and Coal Divisions, the Petroleum Division looks forward to greater opportunities and responsibilities. An improved medium of publication offers further incentive to engineers and investigators in the oil industry to make contributions. The authorization by the Board of Directors of a new Assistant Secretary is an appreciation of the splendid contributions made to the industry by the open forum of the Petroleum Division. It is also a recognition of the possibilities of greater service to the membership along the lines established ten to fifteen years ago by DeGolyer, Fohs, Ambrose and Lovejoy, to mention a few leaders. It isexpected that the new officer will spend a substantial part of his time in the field, visiting the student sections, the respective Divisions, helping in the arrangement of papers and Section meetings and intensifying interest in the Institute. The Petroleum Division will hold three meetings this year. The Fall Meetings will be held on Oct. 6 and 7 in San Antonio and on Oct. 20 and 21 in Los Angeles. The programs for these meetings will deal chiefly with engineering research and production engineering problems. Papers on production statistics and general economics of the industry are reserved for the Annual Meeting in New York. The annual production symposium and statistics are accepted as standard for the industry. With continuously deeper penetration into the earth in search for and exploitation of petroleum, it is necessary to have a better understanding of reservoir conditions and to place more phases of the operation under engineering control. Among the subjects relating to reservoir conditions tha thave been proposed for the fall meeting programs are phase equilibria at high pressures, interfacial tension between oil and water, the flow of oil and water through sands, the chemistry of films and underground temperatures. Investigations relating to control of operations include methods of continuously logging while drilling both visually and electrically, methods of studying drilling samples, properties of drilling fluids, improved cementing practices for isolating thin sands under high-temperature conditions and gas conservation, particularly production from high-pressure reservoirs. Additional suggestions of general themes or individual subjects will be welcomed, since it is desirable to build a backlog of material for Petroleum Technology. 9

Jan 1, 1938

By Thomas T., Read

THE decades immediately before and after the end of the nineteenth century (1890-1910) were a period of increased activity in mineral industry education. One reason for ,this, undoubtedly, was the rapid increase in mineral production in the decade 1880-1890; pig iron and copper production tripled; coal, lead, and zinc output more than doubled. Most of the other mineral substances followed the same general trend. Aluminum production began in 1886; petroleum output, which in 1888 was less than it was in 1882, almost doubled in the next three years. Gold alone showed no appreciable change until its discovery at Cripple Creek in 1891, followed by the Klondike in 1896, brought to boiling a public interest in minerals that had been simmering for some years previously. The first cyanide plant in the United States was erected at Bodie in 1893, and the first chlorination plant at Cripple Creek* the next year. Silver- lead smelting had already greatly developed, and the metallurgy of copper was almost transformed. The hearth area and smelting capacity of copper reverberatory furnaces more than quadrupled between 1878 and 1894; matte converters were first erected at Butte in 1884. Copper production of the United States in 1899 was 30 times that of 1872. While it was the increased technology used in mineral production that really made the field attractive for educated young men, undoubtedly they did not realize that, and were impressed mainly by the quantitative increase in output. Another factor was the increased general interest in engineering education; three times as many men took engineering degrees in the United States in 1890 as in 1880; 1893 showed almost a 56 per cent increase over 1890. Industry had come to recognize that technical training was worth while. The mineral industry lagged somewhat at first; the total number of mining degrees

Jan 1, 1941

By C. S. Smith, Chih-Chung Wang

TURNBULL and his collaborators1,2 have developed the theory of homogeneous nucleation as applied, inter alia, to solidification of liquid metals. Vonnegut³ and Turnbull4 have shown that if a liquid metal is subdivided into small droplets a vast majority of them will undercool very considerably before solidification, generally to as low as about 0.8 of the freezing temperature on the absolute scale. The nuclei effective at small degrees of supercooling in bulk metal seem to be internal or surface heterogeneities, relatively small in number. If the metal is subdivided, those droplets that happen to contain such nuclei will solidify at a temperature not greatly below the true freezing point, but only a small part of the whole volume will be affected and the majority of the drops will under-cool to the much lower temperature at which homo- geneous nucleation occurs as a result of fluctuations. It occurred to one of the authors that an appropriate subdivision to give effective freedom from random nuclei is produced during the solidification of many alloys that contain a minor amount of a phase of low melting point, and that one might then expect marked undercooling of the distributed phase. Experimental: The alloys selected for initial study were copper with minor amounts of lead and bismuth, and aluminum with tin. In all these alloys, the major component freezes at a temperature not much below that of the pure metal, and there is little further change in constitution on cooling until the lower melting point constituent freezes in an almost pure state. Cooling curves were taken using the controlled heat flow method permitting approximate specific heats to be obtained. Chromel-alumel thermocouples were used, with the standard emf tables, since extreme precision was not needed. The crucible (3/4 in. id, 5/16 in. wall) was made of B & W K-20 insulating brick. It held about 10 cc of the alloy being investigated. The cooling rate was 2.5" to 2.9°C per min under a controlled temperature difference of 20°. Approximate specific heats were computed from the inverse rate curves together with data from a blank run and from a standard run with a copper cylinder of known heat capacity. The alloys for investigation were made from high-purity metals (99.99+pct) and cast into graphite molds. The castings were machined to fit the crucible and to provide a hole for the inner thermocouple. Cooling curves were taken after heating to a temperature about 50" above the melting point of the minor, lower melting-point, constituent. Results The lead phase in an alloy of copper with 5 pct lead did not undercool more than 3" below the melting point of lead (327°C) either as cast or after annealing to produce a new dispersion of the liquid phase. A copper-zinc-lead alloy with 23.75 pct zinc and 5 pct lead undercooled more but showed no thermal effect below 319°C. A cast alloy of copper with 5 pct bismuth undercooled to 249°C (M.P. bismuth 27l °C), but once solidification started it was completed at the same temperature. This was anticipated, since the bismuth forms a nearly continuous phase between the grains of copper, and a solid crystal nucleated anywhere would rapidly* con- sume the entire network of liquid, unless the physical continuity of the liquid were broken through volume changes, inadequate fluidity, or gas evolution. Similar arguments apply in the case of copper-lead alloys, where the lead-rich liquid forms a network along grain edges, though not grain faces. In both cases there would be a few isolated particles

Jan 1, 1951

By R. L. Grunes, F. K. Kies, C. D&apos, Antonio

THE several studies concerned with the annealing of thin nickel films have largely been restricted to films of a single thickness.1-4 It is well-known, however, that both physical and mechanical properties depend upon film thickness.5, 6 The strength-thickness relations found in vapor-deposited nickel films in the annealed and as-deposited states, as an example, are at least partially due to the density and arrangement of imperfections within the films.7, 8 For these reasons, the annealing characteristics of thin nickel films as a function of thickness were investigated. Electrical resistance was chosen to monitor annealing behavior since resistance changes are partially dependent upon defect structure. In addition, the equations predicting film resistivity as a function of thickness are already available.9, 10 Further advantages afforded by electrical-resistance measurements are its adaption to continuous readings during annealing and its relative simplicity. Nickel films were vapor-deposited, at average rates of 60Å per sec, on Vycor substrates held at room temperature in vacuums of about 10-5 torr. Afterwards, deposition-thickness measurements were made using a multiple-beam interferometric technique. A more detailed description of deposition procedures and the interferometer appear elsewhere.7, 8 The four-probe method was employed in measuring electrical resistance since this technique measures film resistance without contributions from lead wires and contacts. Resistance measurements were made before, during, and after annealing to temperatures of 700°C under vacuums of approximately 10-4 torr. Measurements were made every 25°C or more often when necessitated by unusual resistance changes. Cooling and heating rates were maintained at approximately 5°C per min. Typical resistivity vs temperature curves are shown in Figs. 1 through 4. It is apparent from these

Jan 1, 1965

By E. H. Wells, A. Andreas

New Mexico retained its position as the sixth largest oil-producing state for the year 1937 with a total production of 38,484,630 bbl. This was an increase of 11,680,184 bbl. over the 1936 production of 26,804,446 bbl., or a gain of 43 per cent. The production for Lea County during 1937 was 35,961,056 bbl.; for Eddy County, 2,136,251 bbl.; and for northwestern New Mexico (San Juan and McKinley Counties), 387,323 bbl. The average daily non-marginal well allowable for Lea County on Jan. 1, 1937, was 92 bbl.; at the close of the year it was 67 bbl. The average daily pipe-line runs were less than the allocations of the New Mexico Oil Conservation Commission, but slightly in excess of the state allowables recommended by the United States Bureau of Mines. The average daily production for the year was 105,437 barrels. The total number of completions in the state was 742, of which 638 were oil wells; 19 hydrocarbon gas wells; 5 carbon dioxide gas wells and 80 dry holes. Of the dry holes, 46 were in proven fields. Of these 46 dry holes, 13 were in the Artesia-Grayburg-Jackson-Maljamar area, Eddy County, two in the Getty Extension field, Eddy County, 11 in the Red Mountain field, McKinley County, three in the Rattlesnake field, San Juan County, and nine in the Aztec-Bloomfield area, San Juan County. There were only eight dry holes in the proven fields in Lea County. Southeastern New Mexico Lea County.—The Monument field was the largest producing field in Lea County, with 10,945,788 bbl., closely followed by the Eunice field with 10,927,929 bbl. The Hobbs field, formerly the largest producing field in Lea County, was relegated to third .place, with 7,292,522 barrels. Drjlling during the year closed the gap between the northern part of the Eunice field and the southern part of the Monument field. The wells in this area were relatively small, because of decreased porosity in the lime. The greatest activity in Lea County was in the Monument pool, with 199 completions, 197 being oil wells, one a gas well and one a dry hole.

Jan 1, 1938

By K. C. Gilbart, E. Stansfield

This test was described in a privately circulated First Progress Report on Slacking Characteristics of Coal, by A. C. Fieldner and W. A. Selvig, May 1, 1928. The test was described in detail in U. S. Bureau of Mines Report of Investigation 3055, in November, 1930,1 The test, in brief, is conducted as follows: A sample of freshly mined coal consisting of 18 to 25 pieces approximating 1 1/4 cubes, and weighing 500 to 600 grams, is taken for the test. The sample is subjected to a "blank sieving" of carefully regulated degree, on an 8-in. circular sieve with 0.263-in. square openings, and the undersize and oversize weighed. The oversize is placed on a sheet-iron pan and dried for about 24 hr. in an A.S.T.M. air-drying oven maintained at 30" to 35" C. through which a current of warm air is drawn. The sample is then cooled to room temperature and immersed for one hour in water at the same temperature. The water is then drained off, the sample dried for 24 hr. as before, cooled, sieved as before, and the oversize and undersize weighed. The percentage weight of the undersize is calculated and reported as the first cycle loss. This loss, corrected by subtracting the percentage loss in the blank sieving, is termed the slacking index. The sample may be subjected to further cycles of wetting, draining, air-drying, sieving and weighing. In a letter (August, 1932) W. A. Selvig approved making the blank sieving on a duplicate sample, rather than on the sample used for the test, where sufficient coal was available. This method is now employed in these laboratories. The accelerated weathering test has been employed in the laboratories of the Research Council of Alberta, at Edmonton, since 1928, but not found entirely satisfactory as repeat determinations with samples taken from the same or adjacent mines frequently showed serious differences. Differences must be expected as the coal may vary in the seam, and the selection of a typical set of lumps approximating 1 1/4-in. cubes

Jan 1, 1934

By E. Stansfield

THIS test was described in a privately circulated First Progress Report on Slacking Characteristics of Coal, by A. C. Fieldner and W. A. Selvig, May 1, 1928. The test was described in detail in U. S. Bureau of Mines Report of Investigation 3055, in November, 1930.1 The test, in brief, is conducted as follows: A sample of freshly mined coal consisting of 18 to 25 pieces approximating 1 ¼ cubes, and weighing 500 to 600 grams, is taken for the test. The sample is subjected to a "blank sieving" of carefully regulated degree, on an 8-in. circular sieve with 0.263-in. square openings; and the undersize and oversize weighed. The oversize is placed on a sheet-iron pan and dried for about 24 hr. in an A.S.T.M. air-drying oven maintained at 30° to 35° C. through which a current of warm air is drawn. The sample is then cooled to room temperature and immersed for one hour in water at the same temperature. The water is then drained off, the sample dried for 24 hr. as before, cooled, sieved as before, and the oversize and undersize weighed. The percentage weight of the undersize, is calculated and reported as the first cycle loss. This loss, corrected by subtracting the percentage loss in the blank sieving, is termed the slacking index. The sample may be subjected to further cycles of wetting, draining, air-drying, sieving and weighing. In a letter (August, 1932) W. A. Selvig approved making the blank sieving on a duplicate sample, rather than on the sample used for the test, where sufficient coal was available. This method is now employed in these laboratories. The accelerated weathering test has been employed in the labora-tories of the Research Council of Alberta, at Edmonton, since 1928, but not found entirely satisfactory as repeat determinations with samples taken from the same or adjacent mines frequently showed serious differ-ences. Differences must be expected as the coal may vary in the seam, and the selection of a typical set of lumps approximating 1 ¼ -in. cubes

Jan 1, 1934

Later this month (June 24-27) in San Francisco, the Society of Mining Engineers of AIME, together with the American Society of Civil Engineers, the Canadian Institute of Mining & Metallurgy and the Engineering Institute of Canada, is sponsoring the second biannual Rapid Excavation and Tunneling Conference. The dominant theme of the Conference is the practical application of techniques and research relating to underground rapid excavation and tunneling. In the following pages, ME gives highlights of many of the 24 technical sessions and some of the papers being presented. The full proceedings of the Conference will be published by SME-AIME later this year.

Jan 6, 1974

By Shiou-Chuan Sun

DISCUSSION shiou-chuan sun (author's correction) - Too late for revision, the author realized that the data on stability of froth presented in this paper were not based on the same height of froth column. It is recommended herein that the stability of froth is better calculated by dividing the time elapsed until the froth disappeared by the volume (in cu cm per sq cm) or height of the froth column, and is expressed in sec per cm. The stability data in Tables I, II, and III of this paper were recalculated, in accordance with this recommendation, and the results are shown respectively in the accompanying Tables VII, VIII, and IX. Compared with Tables I, II, and III of the paper, the stability data of Tables VII, VIII, and IX are more reliable in disclosing the persistence of froth of various frothers having different frothabilities. For example, the conclusion given in the paper that the stability of froth is generally proportional to the volume of froth becomes invalid when the stability of froth is expressed in sec per cm, as shown in Tables VII, VIII, and IX. Table VII shows that both the stability and volume of froth increase with the addition of small amounts of n-hexyl alcohol, and that further additions of n-hexyl alcohol decrease the stability but increase the volume of froth. Table VIII indicates that the stability of different types of frothers is governed by their chemical composition and is difficult to predict from their frothability. Table IX shows that the stability of different frothers with similar nonpolar groups tends to increase with a decrease of the hydro- philic property of their polar groups, and consequently with the decrease of their solubilities. This is further substantiated by the fact that the stability of frothers, as listed in Table IX, is generally lowered by the solvent effect of absolute ethyl alcohol. Table IX shows also that the stability of froth tends to increase with the decrease of the volume of froth* provided the frothers used have similar nonpolar groups and dissimilar polar groups.

Jan 1, 1953

By Shiou-Chuan Sun

DISCUSSION shiou-chuan sun (author's correction) - Too late for revision, the author realized that the data on stability of froth presented in this paper were not based on the same height of froth column. It is recommended herein that the stability of froth is better calculated by dividing the time elapsed until the froth disappeared by the volume (in cu cm per sq cm) or height of the froth column, and is expressed in sec per cm. The stability data in Tables I, II, and III of this paper were recalculated, in accordance with this recommendation, and the results are shown respectively in the accompanying Tables VII, VIII, and IX. Compared with Tables I, II, and III of the paper, the stability data of Tables VII, VIII, and IX are more reliable in disclosing the persistence of froth of various frothers having different frothabilities. For example, the conclusion given in the paper that the stability of froth is generally proportional to the volume of froth becomes invalid when the stability of froth is expressed in sec per cm, as shown in Tables VII, VIII, and IX. Table VII shows that both the stability and volume of froth increase with the addition of small amounts of n-hexyl alcohol, and that further additions of n-hexyl alcohol decrease the stability but increase the volume of froth. Table VIII indicates that the stability of different types of frothers is governed by their chemical composition and is difficult to predict from their frothability. Table IX shows that the stability of different frothers with similar nonpolar groups tends to increase with a decrease of the hydro- philic property of their polar groups, and consequently with the decrease of their solubilities. This is further substantiated by the fact that the stability of frothers, as listed in Table IX, is generally lowered by the solvent effect of absolute ethyl alcohol. Table IX shows also that the stability of froth tends to increase with the decrease of the volume of froth* provided the frothers used have similar nonpolar groups and dissimilar polar groups.

Jan 1, 1953

By T. K. Redden

Protective coatings based on the formation of a surface coating of nickel aluminide (NiAl) were applied to the nickel-base superalloys IN 100, SEL 15, and U-700. Coated specimens were exposed to an oxidizing environment at temperatures between 1600 and 2200 F for times up to 1000 hr. The oxidation resistance and stability of the coating were evaluated by weight gain measurements, metallographic examination, and X-ray diffraction study of surface oxides and coating. The composition of the coating and diffusion zone was determined by electron microprobe traverse of samples before and after high-temperature exposure. Intermediate phases formed in the coating and diffusion zone were identified by X-ray diffraction in situ and after electrolytic extraction. The outer coating was found to consist of the inter-metallic compound, NiAl, while the diffusion zone contained MC, M23C6 or M6C carbides, and a phase in a matrix of NiAl + Nidl. Oxidation resulted in formation of an A1203 n'ch scale containing some Tz02. Depletion of aluminum during oxidation resulted in degradation of the outer coating to Ni3Al and the nickel alloy matrix. Diffusion of aluminum into the base metal was found to be slight and did not influence coating life significantly. The o formed in the diffusion zone during coating decomposed during elevated-temperature exposure to form stable carbide phases characteristic of the base metal. Diffusion zone phase changes were found to have no effect on the life of the aluminide coating in the oxidizing envzron?nent. THE oxidation resistance of many high-strength nickel-base superalloys is inadequate for extended exposure at temperatures above about 1600°F. In addition, some applications for these materials require that they be exposed to environments containing sulfur compounds and sodium salts which can cause surface attalk known as sulfidation or hot corrosion. In order to provide the necessary corrosion resistance to the high-strength alloys, protective coatings based on an aluminizing process have been developed. These processes, usually based on a pack cementation technique, result in the formation of a NiAl-rich outer coating layer either during the coating process or by a subsequent diffusion treatment. The performance of the aluminide coatings is affected by interactions between the coating layer and the base metal both during the coating process and during subsequent exposure at elevated temperatures. Knowledge of these interactions is required to guide the development of coatings capable of longer life and improved reliability. Goward et al.' recently reported the metallurgical factors which influence coating per- formance on MAR-M200. The present work is concerned with correlating the interactions and performance of coating compositions on several representative materials. EXPERIMENTAL PROCEDURES Materials. Three cast nickel-base superalloys which are used for turbine buckets in air-breathing engines were studied: IN 100, U-700, and SEL 15. Their chemical compositions are given in Table I. The alloys were vacuum-induction-melted and cast to slabs approximately 0.3 in. thick from which rectangular specimens 0.25 by 0.5 by 1 in. were machined. Coating Procedures. The machined specimens were coated by CODEP processes which were developed at the author's laboratory. These are based on pack cementation in various media to deposit either aluminum or aluminum in combination with titanium. The coating process which deposits only aluminum is designated CODEP-C, while the CODEP-D process deposits titanium in combination with aluminum. The CODEP-D process was applied only to IN 100. Both CODEP processes are applied at 1950" or 2000°F for 4 hr without need for a subsequent diffusion treatment. An outer coating about 1 mil in thickness is produced by these processes. Test Procedures. Coated specimens were exposed to static oxidation for periods ranging from 24 to 1000 hr at temperatures of 1600" to 2200°F. Terminal weight gain measurements and visual examination were used to evaluate oxidation resistance. including oxide spalling and coating failure. Both as-coated and exposed specimens of each alloy were studied by metallographic examination, electron microprobe analysis (EMA), and X-ray diffraction analysis either of the exposed surfaces or of phases extracted from the coating and diffusion zone. RESULTS As-Coated Condition. The microstructures of as-coated conditions were generally similar, irrespective of base materials or the particular coating process. They are typified by IN 100 coated by CODEP-D as shown in Fig. 1. The predominately single-phase outer layer, area A, Fig. 1, was identified by X-ray diffraction as the intermetallic compound NiA1. The NiAl zone extended inward to the original base metal interface. The diffusion zone, area B, Fig. 1, included carbide phases, a lamellar phase oriented perpendicular to the base metal surface, and a matrix phase consisting of a mixture of NiAl and Ni3Al. The phases in the diffusion zone were electrolytically extracted using a 10 pct HCl in methanol solution at approximately 1.3 amp per sq cm. The extracted phases were found to be M6C, MC, or M=C6 carbides and o as shown in Table I1 for each of the alloys. The d spacings from a typical diffraction pattern are

Jan 1, 1969

By L. D. Jaffe, R. K. Pitler

IT would clearly be advantageous to produce molten titanium, suitable for alloying and casting, directly from the relatively inexpensive tetra-chloride, without using a metallic reducing agent. Accordingly, a preliminary investigation has been made of the production of titanium by hydrogen reduction of the tetrachloride in an electric arc furnace. For the reaction: TiCl4(g) + 2H2(g) ? Ti(s) + 4HCl(g), Lockhart and his colleagues' have calculated equilibrium constants at 800" to 1500°K, based on tables of Brewer.' Extrapolating these data on the assumption that the heat of reaction varies linearly with temperature, and using Brewer's value for the heat of fusion, there is obtained for the reaction: TiCl4(g) + 2H2(g) ? Ti(l) + 4HCl(g) an equilibrium constant at 2100°K (100" above the melting point) Kp = (PHCl)4/pTlcl4 (Ph2)2 = 0.167 atm. If this is correct, starting with hydrogen saturated with TiC14 at 25°C, where the vapor pressure of the latter3 is 12.6 mm, and maintaining the overall pressure at 1 atm, 99 1/4 pct of the TiC14 would be reduced to Ti at equilibrium. An arc furnace designed for the melting of titanium and lined with water-cooled copper was used for the preliminary experimental check. Its inside diameter was 2 7/16 in. and height 6 in. The water-cooled electrode was tipped with 3/4 in. diam tung-sten. In the one run carried out, the furnace was charged with a starting batch of 293.35 g of scrap titanium,' analyzing 99.24 pct Ti. After the system was twice pumped out and flushed with argon to remove air, the arc was struck in argon and kept at 400 amp dc, electrode negative, for 1 min to melt the starting batch. Commercial tank hydrogen, dried by passing over silica gel and bubbled through technical grade TiC14 at room temperature, was then admitted to the furnace. The inlet tube directed this gas downward toward the arc and melt; the gas outlet was at the top of the furnace. The quantity of gas passed through was not measured accurately but is estimated to be about 50 liters per min at a few mm of mercury above atmospheric pressure. The arc was held in the H2-TiC14 mixture at 400 amp with little difficulty. After 10 min the arc burned through the copper lining above the melt, admitting water and ending the run. (This had happened frequently in straight melting runs under argon, and is not thought due to the atmosphere used.) In the furnace were found an ingot, several small pieces, and a little metallic powder, evidently formed when water entered the hot furnace. Some titanium also clung to the electrode. The portions were weighed and separately analyzed for titanium. Their total weight was 321.76 g of 94.82 pct overall purity. Much of the impurity consisted of tungsten broken off when the titanium was removed from the electrode. No detailed impurity analysis was made because the starting materials were impure and flooding the furnace introduced further contamination. Thus, the metal recovered contained 305.08 g Ti, as compared to 291.12 g in the starting batch. Titanium could not have been carried over from previous melting runs in the furnace, as the interior was sandblasted and the electrode ground clean before the run. Evidently at least 13.96 g of Ti were produced from TiCl4. Since this would require complete reduction of 430 liters of TiCl, gas at 12.6 mm of Hg, the efficiency of the process must have been rather high. Experimental work is continuing. No reason is seen why the process could not be scaled up to the size of a 30-ton steel-melting arc furnace. In a large unit there would be a large molten pool from which liquid metal could be withdrawn for alloying and casting. The problems of electrodes and power supply are similar to those arising in arc furnaces for melting titanium. Unreacted TiC14 and the HC1 in the exhaust gases could be recovered; unreacted H2 could be dried and re-used. The melt would be saturated with hydrogen, whose solubility in liquid titanium is unknown. Small amounts of hydrogen seem to have little effect on the properties of titanium.5 If the amount introduced was so large as to impair properties or cause casting difficulties, it could be reduced by holding the melt under an inert gas or by pumping on it, prior to casting. Acknowledgment The authors would like to thank I. Preble and M. Goldman for their valuable aid in the experimental work and the thermodynamic calculations, respectively. References 1R. J. Lockhart, J. J. Ward, M. J. Hussey, and J. W. Clegg: In unpublished report, "U. S. Air Force Project Rand. Titanium and Titanium Base Alloys." Battelle Memorial Institute (1949) 37-44. 2 L. Brewer et al: Chemistry and Metallurgy of Miscellaneous Materials—Thermodynamics. Ed. by L. L. Quill. pp 13-39, 60-192. (1950). McGraw-Hill Book Co. 3 K. Arii: Scientific Reports. Tohoku Imp. Univ. (1933) 22, 182. 4 R. S. Dean, J. R. Long, F. S. Wartman, and E. L. Anderson: Transactions AIME (1946) 166, 369-381; Metals Technology (Feb. 1946) TP 1961E. * R. I. Jaffee and I. E. Campbell: Transactions AIME (1949) 185, 646-654; Journal of Metals (Sept. 1949) TP 26813.

Jan 1, 1951

By A. B. Kinzel

ALTHOUGH calcium carbide and other compounds of calcium, as well as a number of calcium alloys, are well known and are the basis of important industries in the of United States, calcium metal has been thought of as something of a rarity and has received comparatively little attention from industrial metallurgists. The metal may he made in a number of ways, but the electrolytic deposition of calcium from a molten calcium chloride bath was the first process to be used for its commercial production and is still the standard procedure. Calcium metal has elicited little interest among nonferrous metal producers, as the demand has been relatively small and its production restricted to only a few plants, exclusively in France and Germany.

Jan 1, 1941

By AIME AIME

BLANDFORD. C. BURGESS, the new Chairman of the Industrial Minerals Division, took the advice of Horace Greeley in reverse-he turned his hack on San Francisco and the Golden Gate, and after a few side excursions toward Alaska and Arizona, hit the trail eastward, not for the lonesome pine, but for Spruce Pine, N. C. Born Aug. 10, 1893, in San Francisco. Burgess found his first job, shortly after finishing high school at 19, as axeman for a surveying party of engineers working for the Southern Pacific Co. in Oregon. Later he moved on up with them into Alaska. He liked the engineering profession, and decided to equip himself further so he entered the University of California in the fall of 1913. and for the next two years devoted himself to acquiring an education in civil engineering.

Jan 1, 1945

By John B. Hastings

The origin of the watery vapors of vulcanism has always been an object of interest and speculation to the seismologist, and as theories of the genetic origin of ore-deposits have of late years been pretty well narrowed down to the expiring forces of plutonic action, the same question has attracted mining engineers and geologists, as is well shown by the discussions of the subject in our Transactions. The important part taken by volcanic emanations in the origin of pegmatites and quartz-veins, described in my paper, Origin of Pegmatite,' and their latent power to concentrate into useful deposits such scattered gold as occurs in the Hartsel granite, make a discussion of their derivation but a natural third and final step. It is coilceded that enormous amounts of vapor accompany vulcanism, though perhaps we are apt to forget that steam has 1,700 times the volume of water, besides which the column seen over Vesuvius and other volcanoes is greatly mixed with air; the immensity of such volumes compared with solids and liquids is shown by the experiment of Gautier, who, by heating dessicated granite to 100' C., evolved from it gases 20 times, and steam 90 times, its own volume. Dana appraised the average amount of water left in ordinary rocks as 2.5 per cent. T. M. Read estimated that the Mississippi river carries to the sea annually 150,000,000 tons of rock material. If these Mississippi sediments, as deposited, contained 20 per cent. of water, it would be 600,000,000 cu. ft., or 4,500,000,000 American gallons, annually. Allowing the vapor suspended over a volcanic cone to be mixed with 80 per cent. of air, this amount of water converted into steam would replenish anew, every 9 min., a column 15,000 ft. high, 2,000 ft. in diameter at the base, and • 10,000 ft. at the top. Read's estimate is only half of the amount given in a more recent and probably correct one.2

Jan 1, 1909

By Leonid V. Azároff, H. N. Murty

In the course of investigating the soft X-ray absorption spectra of Ni-A1 alloys, Das and ~zfiroff' observed an anomalous brittleness in solid solutions containing 3 to 5 at. pct Al. The brittle alloys also had anomalously larger lattice constants' and the fine structure at the nickel K edge of an alloy containing 3.96 at. pct A1 unexpectedly resembled that of NiA1 more closely than that of a solid solution containing 5.51 at. pct Al. This led them to suggest the possibility that short-range ordering was produced during the homogenization anneal to which each specimen was subjected, similar to that observed in dilute solutions of vanadium and of chromium in nickel: as the principal cause of embrittlement. It was decided to repeat the above measurements on several alloys in this composition range in order to test the above hypothesis and to establish the effect of heat treatment on the alloys' properties. Three solid solutions in this range were prepared containing, respectively, 3.16, 4.00, and 4.54 at. pct Al, in addition to alloys containing 6 and 9 pct. All samples were annealed in vacuum at 1800°F for 100 hr and then furnace-cooled to room temperature, as in the original study. The lattice constants of these alloys are shown by open circles in Fig. 1 and can be seen to fit quite closely the curve established by the previously measured values, indicated by solid circles. (The experimental errors are of the order of the size of the circles, +o.oo~R.) The three alloys containing 3 to 5 at. pct A1 were found to be quite brittle, as previously reported. In order to test the possibility of ordering, these three solid solutions were again heated to 1800°F and, following a few hours at that temperature, were quenched directly to room temperature. All three alloys lost their brittleness. In order to verify the proposed ordering hypothesis, it was decided to subject each sample to several cycles of quenching and annealing (disordering and ordering). After some experimentation, it was established that reproducible results could be obtained by anneal-

Jan 1, 1968

By T. P. Chen, F. W. Bowdish

Studies made with a captive bubble apparatus on the sulfidization and collection by amyl xanthate of true chrysocolla specimens have defined the ranges of pH value and sulfide concentration which permit contact between the bubble and the mineral surface. Titanium compounds were the most effective of the materials found to activate the sulfidization of chrysocolla. With titanium activation, the contact angles and the ranges of pH value and sulfide wncentration giving bubble contact were all increased. Chrysocolla ores were concentrated by flotation. Chrysocolla ores occur at many localities in grade and quantity sufficient to make mining and millin feasible, but no satisfactory method of concentratio has been found. Although chrysocolla may be leached with acid, only those ores without acid-consuming gangue may be leached economically. Because of its potential importance, a study of the conditions nece sary for flotation of chrysocolla has been carried ou The literature contains a few references to flotation of chrysocolla. Two methods were developed by the U. S. Bureau of Mines.1,2 The first consisted of a fatty acid soap and a high xanthate as collectors of chrysocolla from a synthetic ore, while the second involved the use of hydrogen sulfide and xanthate. Ludt and DeWitt3 demonstrated the difference in adsorptive powers of chrysocolla and quartz for bas triphenyl methane dyes and suggested the use of butyl, hexyl or octyl-substituted malachite green as collector. Jackel4 emphasized the effects of combin tions of reagents such as Aerofloat 31, pine oil, and Reagents 404 and 425 with sodium sulfide and zinc hydrosulfite as conditioning agents. Although he reported recoveries of 89% from a synthetic ore and 98% from a natural ore containing azurite, malachite, chalcopyrite and chrysocolla, careful application of Jackel's method to chrysocolla from Tyrone, N.M., failed to give a high recovery. MATERIALS AND TECHNIQUE Samples from Inspiration, Ariz., and Tyrone and Magdalena, N. M., were used for experimentation and verified as true chrysocolla by leaching tests, specific gravity tests and X-ray diffraction. Chrysocolla does not dissolve at pH 4, although malachite and azurite do. Chrysocolla is about half as dense as the copper carbonates. X-ray diffraction analyses by the powder camera method confirmed the samples as true chrysocolla. A captive bubble apparatus, which cast an enlarged image of the air bubble and the mineral surface upon a screen, was used to check on the character of the surfaces. The specimens were prepared by grinding a flat surface on a glass plate using fine abrasive; then they were washed and kept in distilled water until they were to be treated with reagents. Before each reagent treatment, the specimen was carefully checked for cleanliness in the captive bubble apparatus. It was assumed that the surface was clean if, after fine grinding and washing of the specimen, the bubble would not stick. Specimens were handled with glass forceps, and precautions were taken to avoid contamination of the mineral surfaces. Contact angle measurements were carefully made several times on each treated specimen to obtain reliable average values. EFFECT OF pH VALUE AND SODIUM SULFIDE CONCENTRATION In each experiment, a specimen with a freshly ground surface was immersed for 10 min in a solution of sodium sulfide, washed and immersed for 15 min in a solution containing 30 mg per 1 of potassium amyl xanthate. The specimen was then washed again in distilled water and tested for contact angle in the captive bubble apparatus while submerged in distilled water. In this series of experiments, the pH of the sulfidizing solution was varied from 3 to 7, and the concentration of sodium sulfide, containing 60% Na2S, was varied from 50 to 650 mg per 1. Many combinations of pH value and sulfide concentration resulted in no contact between the bubble and the surface, but over a limited range of conditions, contact angles varying from 24ºto 52ºwere obtained. The data in Fig. 1 show sulfidization conditions that lead to bubble contact and those that do not. The region of contact is surprisingly small, which may indicate why flotation of chrysocolla involving sulfidization has proven so difficult in practice. Several features of the system are illustrated in Fig. 1. In the region between pH values of 4 and 6 with sodium sulfide concentrations below about 350

Jan 1, 1963