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By J. F. Haseman, J. E. Davenport

IN the brown rock phosphate fields of Tennessee there are large deposits of phosphate matrix in which quartz is a major constituent of the gangue, and which cannot be beneficiated by the conventional washing process to yield a concentrate of suitable grade for use in the electric furnace. A huge tonnage of high-grade phosphate concentrate is produced in the Florida pebble district from low-grade siliceous feed. However, the characteristics of the low-grade siliceous Tennessee ore are such that flotation under the conditions employed in treating the Florida ore1-2 results in inadequate beneficiation. INVESTIGATION OF FLOTATION METHODS Flotation has been used in Tennessee primarily to produce a concentrate of premium grade by moderate enrichment of a marketable grade of phosphate.3,4 A secondary use was to increase the recovery of phosphate from the fines (down to approximately 200 mesh) from medium-grade ores with a concomitant moderate increase in over-all grade.3,5 It was considered desirable to investigate methods of improving the grade of washed products from low-grade siliceous Tennessee ore when these products were substantially below the requirements for use in the electric furnace. The present paper describes the results of a laboratory-scale study of factors that affect the beneficiation of such siliceous phosphate ore by flotation. The primary objective of the investigation was to ascertain the conditions under which the ore could be made to yield a concentrate suitable for reduction in the electric furnace. It was assumed that a phosphate concentrate for electrothermal reduction should contain at least 26 pct P205 and should have a weight ratio of silica to lime of not more than 0.80. Since a concentrate of moderate grade can be used in the electric furnace, and since, as Grissom4 has shown in detail, the ore will not bear the cost of expensive treatment, the study of collectors was limited to the relatively inexpensive fatty acids. A secondary objective was to determine whether a portion of the phosphate could be recovered in a grade suitable for treatment with phosphoric acid to produce 45 pct superphosphate. The ore consisted of variably cemented sand interlayered with clay. The sand layers were composed of grains of quartz, phosphate, and clay embedded in a matrix of clay and phosphate. Some clay was finely disseminated in the phosphate grains. Little massive high-grade phosphate was present. The material used in the flotation tests was a washed sand that had been separated from the ore in a bowl classifier at the TVA phosphate-washing plant. The percentage composition of the sand was as follows: P205, 20; Si02, 40; CaO, 29; Fe203, 2; A1203, 3; F, 2.3. The particle-

Jan 1, 1947

By J. F Haseman, J. E. Davenport

In the brown rock phosphate fields of Tennessee there are large deposits of phosphate matrix in which quartz is a major constituent of the gangue, and which cannot be beneficiated by the conventional washing process to yield a concentrate of suitable grade for use in the electric furnace. A huge tonnage of high-grade phosphate concentrate is produced in the Florida pebble district from low-grade siliceous feed. However, the characteristics of the low-grade siliceous Tennessee ore are such that flotation under the conditions employed in treating the Florida ore1,2 results in inadequate beneficiation. Investigation of Flotation Methods Flotation has been used in 'Tennessee primarily to produce a concentrate of premium grade by moderate enrichment of a marketable grade of phosphate. 3,4 A secondary use was to increase the recovery of phosphate from the fines (down to approximately 200 mesh) from medium-grade ores with a concomitant moderate increase in over all grade.3,5 It was considered desirable to investigate methods of improving the grade of washed products from low-grade siliceous Tennessee ore when these products were substantially below the requirements for use in the electric furnace. The present paper describes the results of a laboratory-scale study of factors that affect the beneficiation of such siliceous phosphate ore by flotation. The primary objective of the investigation was to ascertain the conditions under which the ore could be made to yield a concentrate suitable for reduction in the electric furnace. It was assumed that a phosphate concentrate for electrothermal reduction should contain at least 26 pct P2O5 and should have a weight ratio of silica to lime of not more than 0.80. Since a concentrate of moderate grade can be used in the electric furnace, and since, as Grissom4 has shown in detail, the ore will not bear the cost of expensive treatment, the study of collectors was limited to the relatively inexpensive fatty acids. A secondary objective was to determine whether a portion of the phosphate could be recovered in a grade suitable for treatment with phosphoric acid to produce 45 pct superphosphate. The ore consisted of variably cemented sand interlayered with clay. The sand layers were composed of grains of quartz, phosphate, and clay embedded in a matrix of clay and phosphate. Some clay was finely disseminated in the phosphate grains. Little massive high-grade phosphate was present. The material used in the flotation tests was a washed sand that had been separated from the ore in a bowl classifier at the TVA phosphate-washing plant. The percentage composition of the sand was as follows: P2O5, 20; SiO2, 40; CaO, 29; Fe2O3, 2; Al2O3, 3; F, 2.3. The particle-

Jan 1, 1948

By J. F. Haseman, J. E. Davenport

In the brown rock phosphate fields of Tennessee there are large deposits of phosphate matrix in which quartz is a major constituent of the gangue, and which cannot be beneficiated by the conventional washing process to yield a concentrate of suitable grade for use in the electric furnace. A huge tonnage of high-grade phosphate concentrate is produced in the Florida pebble district from low-grade siliceous feed. However, the characteristics of the low-grade siliceous Tennessee ore are such that flotation under the conditions employed in treating the Florida ore1,2 results in inadequate beneficiation. Investigation of Flotation Methods Flotation has been used in 'Tennessee primarily to produce a concentrate of premium grade by moderate enrichment of a marketable grade of phosphate. 3,4 A secondary use was to increase the recovery of phosphate from the fines (down to approximately 200 mesh) from medium-grade ores with a concomitant moderate increase in over all grade.3,5 It was considered desirable to investigate methods of improving the grade of washed products from low-grade siliceous Tennessee ore when these products were substantially below the requirements for use in the electric furnace. The present paper describes the results of a laboratory-scale study of factors that affect the beneficiation of such siliceous phosphate ore by flotation. The primary objective of the investigation was to ascertain the conditions under which the ore could be made to yield a concentrate suitable for reduction in the electric furnace. It was assumed that a phosphate concentrate for electrothermal reduction should contain at least 26 pct P2O5 and should have a weight ratio of silica to lime of not more than 0.80. Since a concentrate of moderate grade can be used in the electric furnace, and since, as Grissom4 has shown in detail, the ore will not bear the cost of expensive treatment, the study of collectors was limited to the relatively inexpensive fatty acids. A secondary objective was to determine whether a portion of the phosphate could be recovered in a grade suitable for treatment with phosphoric acid to produce 45 pct superphosphate. The ore consisted of variably cemented sand interlayered with clay. The sand layers were composed of grains of quartz, phosphate, and clay embedded in a matrix of clay and phosphate. Some clay was finely disseminated in the phosphate grains. Little massive high-grade phosphate was present. The material used in the flotation tests was a washed sand that had been separated from the ore in a bowl classifier at the TVA phosphate-washing plant. The percentage composition of the sand was as follows: P2O5, 20; SiO2, 40; CaO, 29; Fe2O3, 2; Al2O3, 3; F, 2.3. The particle-

Jan 1, 1948

By E. M. Cox, A. S. Skapski, N. H. Nachtrieb, M. C. Bachelder

As a result of using copper-containing scrap in the steelmaking process, the copper content of steels has been steadily increasing for years. Consequently the possible role copper may play in the steelmaking process and in the finished product begins to attract the metallurgists' attention. Some time ago one of the present authors forwarded the idea—based on the results of the analysis of nonmetallic inclusions extracted electrolytically from steels—that sulphur in plain carbon steels is distributed mainly between copper and manganese, the amount of iron sulphide being very small; and that, consequently, the problem of copper and that of sulphur in steel cannot be treated separately.' At the time of the publication of the quoted paper little was known about the relative affinities of copper and manganese for sulphur at high temperatures except that at moderate temperatures (below 1000°C) the affinity of manganese for sulphur is much greater. To gather more experimental data on this subject, the present authors undertook the investigation of the equilibrium constants of the reactions: 2Mn(8 or 1) + S2(g) = 2MnS(s) 4Cu(s or 1) + S2(g) = 2Cu2S (S or I)* 2Fe(s) + S2(g) = 2FeS (s or 1) over a range of temperatures wide enough to establish the dependence of these equilibrium constants on temperature. From the equilibrium constants (K = l/Ps2) the free energy of formation (affinity) can be calculated from F° = -RTln 1/PSt (1) where the standard conditions chosen are: 1 atm of sulphur pressure and the activities of condensed components equal one. The decomposition pressure, Ps2, of sulphur over the respective sulphides is too small to be measured directly, but there is a way of eliminating this difficulty by measuring the equilibrium constant of the reaction between the sulphide and hydrogen. From the latter and from the equilibrium constant of the thermal dissociation of H2S we then calculate Ps2 for the respective sulphide. 2Mn + 2H2S = 2MnS + 2H, 2H2 + S2 = 2H2S_________ 2Mn + S2 = 2MnS The numerical values of the equilibrium constant of the thermal dissociation of H2S at different temperatures were taken from Kelley's paper, "The Thermodynamic Properties of Sulfur and its Inorganic Compounds."² In previous experimental work published by Jellinek and Zakowski3 and by Britzke and Kapustinsky4 the equilibrium constants of the reactions Metal sulphide + H2 = H2S + metal were determined by passing hydrogen, at different rates of flow, over the sulphide, analyzing the resulting H2S + H2 mixture and then extrapolating the H2S/H2 ratio (which is a function of the rate of flow) to the zero speed of flow, a method necessarily involving considerable uncertainty. In the present work the equilibrium ratio was actually measured instead of being extrapolated. The apparatus is shown in Fig 1. Experimental Procedure The sulphides were prepared by the following methods: FeS Powdered iron which had been reduced with hydrogen (ferrum reduc-tum) was mixed in stoichiometric ratio with sublimed sulphur and carefully ground. The mixture was put into an alundum crucible, covered with pure sulphur, and the reaction started by touching the mixture with a glowing iron rod. After the reaction was completed the product (still containing some metallic iron) was again ground with sulphur, put into a Rose crucible, covered with sulphur, and heated in a strong current of pure hydrogen. Analysis of the final product showed 62.46 pct Fe and 36.59 pct S. Theoretical for FeS: 63.53 pct Fe and 36.47 pct S. MnS Manganese sulphide (precipitated and carefully washed with distilled water containing H2S) was dried in a Rose crucible in an atmosphere of H2S and heated in a current of hydrogen for 2 hr at red heat. The product was then ground and ignited for several hours at 1000°C in a current of hydrogen sulphide. Analysis showed 64.53 pct Mn and 36.63 pct S. Theoretical: 63.15 pct Mn and 36.85 pct S. Some MnS samples were prepared from metallic manganese and sublimed sulphur by mixing and grinding them and then heating in a current of hydrogen sulphide in an alundum tube.

Jan 1, 1950

A discussion at a joint meeting of the New York Section of the American Electrochemical Society and the American Institute of Mining Engineers, Nov. 20, 1913. Chairman Lawrence Addicks:-Our program this evening represents an attempt to set before you the present situation and outlook in the metallurgy of zinc. It is a time-honored custom to throw bricks at the zinc man. The accusation is that he has borrowed a lime kiln and a gas retort and part of a sulphuric acid plant, hitched them together, and spent the last 50 years in regarding with holy veneration the reactions which take place in that retort. The copper man, who thinks of zinc as something with which copper is adulterated to make brass, and the iron man, who regards it as a sort of paint for corrugated sheets, and the lead man, whose opinion as to zinc is not fit for publication, have long felt that, when two or three of the minor details of their respective metallurgies were put in order, they would take a few clays and fix up zinc on a modern basis. But somehow there still seem to be some unsolved problems at home, and while we are waiting it seems only fair that the case for the defense should be adequately presented. There is probably no man in this country to-clay better able to do this than Mr. George C. Stone, of the New Jersey Zinc Co., on whom I have pleasure in calling to talk to us on "Progress in the Metallurgy of Zinc." George C. Stone:-It is frequently stated that there has been no change in the metallurgy of zinc since the first Belgian furnaces were built in the early part of the last century. It is true there have been no such spectacular and radical changes as were worked in the metallurgy of copper and iron by the introduction of converters; but, in the essentials, I believe the progress in zinc metallurgy has been as great as in that of the other common metals. The main reason that there have not been revolutionary changes is that the chemistry of zinc differs radically from that of the other metals and these differences control the type of apparatus that can be used. The differences are: 1. The temperature at which zinc is reduced by carbon is much above the volatilizing point of the metal and it is therefore always produced as a vapor.

Jan 1, 1914

By H. A. Schwartz

FROM time to time, one of the authors has had occasion to investigate the graphitizing reaction and has published the results mainly as discussion1 of the work of other investigators. In view, therefore, of the diversity of both observations and interpretation, it seemed well to attempt a revision of the entire subject in the Research Laboratory of the National Malleable Castings Co. The work consisted of a careful study of a single, impure, iron-carbon alloy. The material, which may be considered typical low-carbon white cast iron of the malleable industry, was an air-furnace iron of the following composition: carbon 2.30 per cent., silicon 1.20 per cent., manganese 0.29 per cent., phosphorus 0.156 per cent., sulfur 0.048 per cent. The freezing range extended from 1213° to 1132° C., the latter figure agreeing with Gontermann's data .2 We have attempted to define the equilibrium diagram of this alloy, in the stable condition as related to the metastable diagram, from a temperature somewhat below the eutectic freezing point to a temperature below Ar1 and for a graphitic-carbon content from practically nothing to the original total carbon of the specimen (see Fig. 6). More especially we desired to locate the line in the stable diagram corresponding to the Acm line of the metastable system, which is designated by analogy, the Atm line (tm from temper carbon) ; also to determine the location of Aim with respect to Acm toward their lower extremities at Ar1 in order to determine whether or not graphitization is completed by the separation of an iron-carbon eutectoid analagous to pearlite in the iron-cementite system. This would involve further a comparison of the locations of the stable and metastable A1 points.

Jan 8, 1922

By T. R. Wright

THE Corporation operates concentrators in four camps: Casapalca. Morococha, Cerro de Pa-co, and Mahr. The present concentrator at Cerro de Pasco is the newest having been completed in 1943. and that at Casapalca the oldest, having been built originally as a gravity concentrator, in 1889. Prior to 1925 the Corporation's milling operations were confined to the beneficiation of silver-bearing copper ores, and treatment of these ore: by flotation was started in 1918. Although fairly large deposits of complex, fine-grained lead-zinc ores existed, little progress had been made in the treatment of such ores--in Peru or elsewhere-until the early 'twentics. The Casapalca concentrator began the selettive concentration of complex leadzinc ores by all-flotation methods in 1925, or contemporaneously with the commercial development of selective lead-zinc flotation in the United State:.

Jan 1, 1945

By Donald D. Smythe

This paper describes briefly the topography and geology of the region where the mica-bearing pegmatites are found and discusses prospecting, the quality of the mica, its preparation, and evaluation of the deposits. Muscovite mica occurs in a number of widely separated localities in Brazil, but production has come largely from deposits in the southeastern and eastern part of the State of Minas Gerais (Fig. I). There the deposits form a discontinuous zone, which starts at a point go km. north of the city of Rio de Janeiro and extends north for some 500 km., roughly parallel to the coast. A maximum width of 180 km. is reached along the Rio Doce. To the west in Minas Gerais, and extending east into the states of Espirito Santo and Rio de Janeiro, the mica zone proper is fringed by areas in which there are scattered occurrences of mica-bearing pegmatites. A few of these outlying deposits have produced commercial mica, but most of them are unimportant. To the southwest, in the State of Sao Paulo, there are a number of mines, which at one time produced a very considerable amount of sheet mica, largely as a byproduct of kaolin mining. These deposits, and a few others lying between them and the main productive areas to the northeast, appear to be the southwestern continuation of the strong Minas Gerais mica zone. In the vicinity of Conquista, just north of the Minas Gerais boundary in the State of Bahia, and still farther north, near Jacobina, there are several known mica deposits. Their location indicates that they may be the northern continuation of the main mica zone. The major part of Brazilian mica production has come from four areas within the mica zone proper; from north to south, Governador Valadares, Raul Soares, Espera Feliz, and Muriaé.. The first is go km. from north to south and reaches a maximum width of 180 km. The Raul Soares area extends 135 km. from northeast to southwest, and in places is 80 km. wide. The Espera Feliz area is 100 km. from north to south, and reaches a width of 35 km. The Muriai. area extends 150 km. from northeast to southwest and its width reaches 40 kilometers. Between the known productive areas, and in the areas directly to the southwest and to the north of them, little mica has been produced. These gaps, as well as certain irregularities in the outline of the mica zone itself, are to be ascribed either to lack of prospecting or to conditions preventing the discovery of mica, rather than to its nonexistence. Elsewhere in Brazil mica has been reported from eastern Goiaz, Ceará, Pernambuco, Rio Grande do Sul, Matto Grosso, and Amazonas. Production from these sources is negligible at present. Because of the inferior quality of the mica from the more accessible of these localities, and the operational difficulties occasioned by the remoteness of others, it is improbable that they will become important producers for some time to come.

Jan 1, 1948

By Donald D. Smythe

This paper describes briefly the topography and geology of the region where the mica-bearing pegmatites are found and discusses prospecting, the quality of the mica, its preparation, and evaluation of the deposits. Muscovite mica occurs in a number of widely separated localities in Brazil, but production has come largely from deposits in the southeastern and eastern part of the State of Minas Gerais (Fig. I). There the deposits form a discontinuous zone, which starts at a point go km. north of the city of Rio de Janeiro and extends north for some 500 km., roughly parallel to the coast. A maximum width of 180 km. is reached along the Rio Doce. To the west in Minas Gerais, and extending east into the states of Espirito Santo and Rio de Janeiro, the mica zone proper is fringed by areas in which there are scattered occurrences of mica-bearing pegmatites. A few of these outlying deposits have produced commercial mica, but most of them are unimportant. To the southwest, in the State of Sao Paulo, there are a number of mines, which at one time produced a very considerable amount of sheet mica, largely as a byproduct of kaolin mining. These deposits, and a few others lying between them and the main productive areas to the northeast, appear to be the southwestern continuation of the strong Minas Gerais mica zone. In the vicinity of Conquista, just north of the Minas Gerais boundary in the State of Bahia, and still farther north, near Jacobina, there are several known mica deposits. Their location indicates that they may be the northern continuation of the main mica zone. The major part of Brazilian mica production has come from four areas within the mica zone proper; from north to south, Governador Valadares, Raul Soares, Espera Feliz, and Muriaé.. The first is go km. from north to south and reaches a maximum width of 180 km. The Raul Soares area extends 135 km. from northeast to southwest, and in places is 80 km. wide. The Espera Feliz area is 100 km. from north to south, and reaches a width of 35 km. The Muriai. area extends 150 km. from northeast to southwest and its width reaches 40 kilometers. Between the known productive areas, and in the areas directly to the southwest and to the north of them, little mica has been produced. These gaps, as well as certain irregularities in the outline of the mica zone itself, are to be ascribed either to lack of prospecting or to conditions preventing the discovery of mica, rather than to its nonexistence. Elsewhere in Brazil mica has been reported from eastern Goiaz, Ceará, Pernambuco, Rio Grande do Sul, Matto Grosso, and Amazonas. Production from these sources is negligible at present. Because of the inferior quality of the mica from the more accessible of these localities, and the operational difficulties occasioned by the remoteness of others, it is improbable that they will become important producers for some time to come.

Jan 1, 1948

By Y. Baskin

Solid-solubility relationships in the Pseudobinary systems UAS-UP, UAs-US. UAS-UC, aid UAs-UN were investigated. The first two systems exhibit complete mutual solubility, whereas the component compounds in the other two systenzs are immiscible. The above information, together with solid-solubility data joy six additional pseudobinary systems , were analyzed for compliance wilh the Hurrze-Rothery rules for rnetallic systems. The relative size difference of the component nonmetal atoms was found to be the dopainant jactor determining the extent of solid solubility between the NaC1-type uranium compounds. The anionic and covalent radii of the nonmetal atoms appear to be inadequate for these systems, but compuled radii based on rare earth compounds yield consistent results for the uranium compounds. THE actinide elements, like metallic elements of the transition and rare earth series, readily form binary compounds with nonmetallic elements of groups IV, V, and VI of the periodic table. Of particular importance are the NaC1-type equiatomic compounds with carbon, nitrogen, sulfur, phosphorus, and arsenic. The uranium members of this family of compounds have high melting points, are essentially stoichiometric, and exhibit various amounts of mutual solubility. Thus, they are of interest for investigating the factors governing the extent of solid solubility. Previous investigators have determined the solid-solubility limits in the pseudobinary systems between the compounds UC, UN, US, and UP. Anselin et a1 .' reported complete miscibility in the system UC-UN. Baskin and shalek 2 and Allbutt et a1.3 reported that UP and US exhibit complete mutual solubility. Shalek and white4 reported partial miscibility in the system US-UC. At 1800°C the maximum solubility of UC in US is 40 mol pct, but that of US in UC is 4 rnol pct. shalek5 found limited solubility in the system US-UN; the maximum solubility of UN in US is 11 rnol pct at 1800°C, while that of US in UN is only 0.3 mol pct. White and askin 6 found very limited miscibility in the system UP-UC at 1800°C. Approximately 7 mol pct UC is soluble in UP, but there is no solubility of UP in the monocarbide. Phase relations in the pseudo-binary system UN-UP were investigated by askin.' Approximately 0.7 mol pct UN is soluble in UP at 1800°C, while UP is immiscible in UN. The present study was carried out to explore the extent of terminal solubility in the systems UAs-UC, UAs-UN, UAs-US, and UAs-UP. This information, combined with existing data, provided a sufficient basis on which to determine the factors governing solid solubility in pseudobinary systems containing NaC1-type uranium conpounds. I) EXPERIMENTAL 1) Materials. The compounds UC and UN were obtained from the Kerr-McGee Corp. and United Nuclear Co., respectively. The US, UP, and UAs were synthesized by reacting finely divided uranium with H2 S, pH3, or AsH3 gas at low temperature (300° to 500°C), followed by homogenization in a vacuum at moderately high temperatures (1400° to 1700°c).8-10 The materials were essentially stoichiometric, with the exception of UC, which exhibited a C/U ratio of 1.05. Oxygen was the major contaminant in these compounds, ranging from 0.05 wt pct in US to 0.30 wt pct in UC, and it was generally combined with uranium to form UO2. The UO2 content in these materials was usually of the order of 1 wt pct, and did not exceed 2 wt pct. Furthermore, no evidence was found for a high-temperature reaction between uranium dioxide and any of the compounds. Chemical analyses of equilibrated compositions in the systems UAs-UP and UAs-US showed that the non-metal atom to uranium ratios averaged about 1.01, and that the oxygen contents ranged from 0.06 to 0.22 pct. However, the small deviations from stoichiome-try or the presence of minor oxygen impurities do not invalidate the conclusions to be drawn from this study. 2) Experimental Procedures. The component compounds in powdered from were blended in the desired proportions for 5 hr in the ball mill that consisted of stainless-steel balls in a plastic container. Chemical analyses indicated very little metallic pickup from the blending operation and virtually no increase in oxygen content. The pellets were pressed in a 0.270-in.-diam steel die under 40,000 psi pressure. One wt pct of stearic acid dissolved in CCl 4 served both as a binder and as a die lubricant. Chemical analyses revealed that the stearic acid left no carbon residue in the sintered samples. The pellets were sintered in vacuum in an unsealed tantalum crucible. The temperature, measured with a calibrated optical pyrometer, was maintained at 1800" + 30°C for 3 hr. This was sufficient time for attaining equilibrium as no change occurred in either the lattice parameters or the sharpness of the X-ray patterns when samples were annealed for longer periods of time. The pellets were cooled with the furnace. Debye-Scherrer powder patterns were taken at room temperature with a 114.59-mm-diam Norelco powder camera and CuKor radiation (CuGI = 1.5405A). Unit cell dimensions were determined from a Nelson-Riley extrapolation to the high-angle reflections. The values for were precise to k 0.001A. 11) RESULTS X-ray and met allographic investigation revealed that complete mutual solid solubility exists in the pseudobinary systems UAs-UP and UAs-US. The lattice parameter vs composition plots, Fig. 1, show a

Jan 1, 1968

By R. I. Jaffee, F. C. Holden, H. R. Ogden

ECENT papers dealing with the properties of unalloyed iodide titanium have been directed primarily at the determination of base-line properties for alloy investigations. Early work was limited to a few tests because of the limited availability of iodide titanium at the time. In the results of papers by Campbell et al.,1 Gonser and Litton,2 Jaffee and Campbell,3 inlay and Snyder,4 and Jaffee, Ogden, and Maykuth, data on mechanical properties are presented for unalloyed iodide titanium in the annealed and cold-worked conditions. Data are presented in this paper which show the effects of heat treatment on the structure and mechanical properties of commercially produced iodide titanium. Correlation is made between microstruc-tural variables and the mechanical properties. Experimental Procedures Melting Stock: The melting stock used was as-deposited iodide titanium, produced by New Jersey Zinc Co. The furnished analysis showed the following range of impurities: N, 0.004 to 0.008 pct; Mn, 0.005 to 0.013; Fe, 0.0035 to 0.025; Al, 0.013 to 0.015; Mo, 0.0015; Pb, 0.0045 to 0.0065; Cu, 0.0015 to 0.002; Sn, 0.001 to 0.01; Mg, 0.0015 to 0.002; and Ni, 0.003. Hydrogen content as determined by vacuum-fusion analysis was 0.0091 wt pct (0.44 atomic pct) after arc melting and fabrication. Nitrogen analysis on the arc-melted and fabricated titanium showed a content of less than 0.002 pct N. The average hardness of the furnished stock was Rf 70, or approximately 85 VHN. Melting Procedure: The as-deposited rods were rolled, sheared, and degreased in preparation for arc melting. The charge was arc-melted with a tungsten electrode in a water-cooled copper crucible under a positive pressure of high purity (99.96 pct) argon. The final ingot was approximately 2 in. in diameter and showed no increase in hardness over that of the initial stock. Fabrication: Heating for fabrication was done in air. It was begun by forging the ingot into a 3/4 in. diam rod, at an initial temperature of 1600°F. Scale was removed by sandblasting. The rod was then swaged to 1/4 in. diam at room temperature through a series of 20 dies, with approximately 10 pct reduction in area between each die. An anneal of 1 hr at 850 °C in air was given after the 1/2 in. die, such that the final cold reduction was 75 pct. Sections cut from this rod were used for test and microstructure specimens. Heat Treatment: Heat treatments were carried out in resistance tube furnaces with stainless-steel linings, under an atmosphere of gettered argon. As further protection against contamination, the specimens were packed in titanium turnings in a titanium sleeve. Control experiments have shown negligible hardness increases with this method, indicating that contamination from oxygen and nitrogen is slight. Three cooling rates were employed in this work; these have been designated as water quenching, argon cooling (to simulate air cooling under a controlled atmosphere), and furnace cooling. The cooling rate for an argon cool is 100°C per min for the first minute, with an average cooling rate of 35°C per min over a 15-min period. A furnace cool requires about 10 hr, with an average cooling rate of 3.6oC per min during the first hour, and an average cooling rate of 1.2°C per min over the 10-hr period. Microimpact Test: The specimen adopted was based on the cylindrical Izod Type Y specimen (ASTM, E23-41T). All dimensions were reduced to half scale, including the notch radius. Specifications are shown in Fig. 1. The specimen is held vertically in an adapter and broken as a cantilever beam. Impact tests were run on a constant-velocity (11.34 ft per sec) Tinius Olsen impact testing machine with a total available energy of 100 in.-lb. Tests were made to determine the correlation between this microimpact and the standard V-notch Charpy impact test. Curves showing impact energy as a function of temperature for both impact tests are plotted in Fig. 2. Transition temperatures, when they occur, are about the same for both impact tests. All three titanium-rich materials have the same conversion factor, 10. Tensile Testing: Tensile tests were conducted on Baldwin-Southwark testing machines using the 600, 2400, or 3000 1b range. Specifications for the test specimen were taken from the 1948 edition of the ASM Metals Handbook, and are shown in Fig. 1. Strain measurements were made using an SR-4 resistance gage (Type A-7) cemented to the reduced section in conjunction with a lever-type extenso-meter. Readings on the SR-4 strain indicator were

Jan 1, 1954

By K. Mukherjee

A quasi-thermodynamic calculation is presented for estirt~ating vacancy Parameters in fcc metals. For fcc metals the equilibrium vacancy concentration at the melting point can be approximated by a constant mole fraction. The Gibbs free energy of formation of the vacancies can then be expressed as a simple function of the absolute melting temperature alone. From this description the formation energy Ef, the vibrational entropy Sv, and the formation volume of a vacancy can be calculated in terms of known thermodynamic parameters. The calculated values are in good agree-rnent with available experimental results. IT appears that many of the physical parameters associated with lattice defects can be empirically related to thermodynamic melting parameters.'-7 Besides the implicit correlations between melting phenomenon and point defects, the melting temperature itself at atmospheric pressure can be used as a reference temperature for the purpose of comparison of vacancy concentrations in a given crystal class. The concentration at the melting point then corresponds to the maximum vacancy super saturation in the crystalline state at a fixed pressure. For pure fcc metals such as Au, Cu, Al, Ag, Pb, and Pt the mole fraction of vacancies at the melting point8 is of the order of 10*"3 to 10"1. The equation expressing the equilibrium vacancy concentration at the melting point contains three parameters: the formation energy, the vibrational entropy, and the absolute melting temperature, see Eq. [2]. Since these three parameters cover a wide range of values8 in the above-mentioned metals, it can be assumed that in other fcc metals, for which no reliable data are available, the mole fraction of vacancies at the melting point most likely lies in the range 10~3 to lO"4. This is then the basis of the calculations described in this article. Within this range the mixing entropy can be linearized and the vibrational entropy, the formation energy, and the vacancy formation volume can be calculated in terms of known thermodynamic constants. 1} LINEARIZATION OF MIXING ENTROPY The Helmholtz free energy of a crystal containing n vacancies at the melting point can be writteng as where Ef, T,, k, and S, are the formation energy of a vacancy, the absolute melting temperature, Boltz-mann's constant, and the vacancy formation entropy, respectively. After applying Stirling's approximation in Eq. [l] and minimizing with respect to n where (n/N), is the equilibrium vacancy concentration in mole fraction at the melting temperature at 1 atm pressure. If instead of setting (6~/6n) = 0 immediately after Stirling's approximation in Eq. [I], the configurational partition function is simplified, then some useful and significant results can be obtained by utilizing the experimental inforrnation After applying Stirling's approximation and rearranging is plotted as a function of (n/N) in Fig. 1. The points, not all of which are shown, are fitted by a straight line substituting from Eq. [5] into Eq. [I] and minimizing with respect to n combining Eqs. [6] and [2] It must be emphasized that Eq. [7] is only a crude approximation based on an oversimplified model of

Jan 1, 1967

By AIME AIME

IN many countries the lack of liquid petroleum supplies has centered interest upon the hydrogenation of coal and coal tars for the preparation of motor fuel. In the United States, hydrogenation has been of greater interest for grading up low-value petroleum fractions to the more valuable volatile fuels and for the preparation of a variety of premium products, including aviation gasolines, solvents, Diesel fuels, and lubricating oils. Chemically, the basic reason for this process is that, as shown in Table 1, the ratio of hydrogen to carbon (H/C ratio) in available raw materials is quite different from that characterizing the products sought.

Jan 1, 1936

By H. H. Campbell

The following paper deals almost exclusively with the results of practice at the works of the Pennsylvania Steel Company at Steelton, Pa. From the records of the furnaces at this plant, both acid and basic, large and small, are drawn the data for the various demon strations, and on a long and intimate experience with their opera tions are founded many theories and generalizations. It may seem that universal laws should not be built upon a basis so restricted ; but in reality the condition is the strongest guarantee of validity. Each table investigates some- certain variable, and by virtue of the common origin of the factors, we have good ground for assuming the corresponding agents to be equal. The examples may or may not be instances of good practice, and may be open to criticism if regarded solely as exponents of • metallurgical success. But it must be remembered that the lists are not made up of selected specimens, nor are they chosen to show su perior results; they are gathered to investigate, by strict scientific methods, the formula? of the operation. In such work no untoward results should be eliminated, save those which bear upon their face the stamp of experimental error. If the worst members be omitted, then the best must also be omitted. Only by using every available case can an honest attempt be made to deduce a true average. It is recog nized, however, that with the most careful selection it is difficult, if not impossible, to collect data representing universal conditions. In each table the records tell of a special practice, and all conclusions drawn from them are true only within the limits between which the equations have been integrated. Not assuming the prerogative of speaking for American melters in all the opinions herein expressed, nor acting as a camera in por traying an ephemeral state of national metallurgical development,

Jan 1, 1894

By J. H. McCormick

This plant, near Marysville, Mont., was planned to treat the ore from the Piegan and Gloster mines, the latter being one of the early and famous producers of the Marysville district. When the mill was closed in 1888, treatment consisted of stamp milling, followed by pans and settlers for pan amalgamation. The extraction was evidently poor, because, a few years later, thousands of tons of tailings were re-treated by the ranchers in the valley below the mill, by the then new cyanide process, and gave a handsome profit. In 1914, the present owners, after laboratory tests and an experimental mill run, decided upon the following treatment: crushing to 40 mesh in cyanide solution, concentration, amalgamation, classification, and cyani-dation of sands by leaching, and of slime by agitation and decantation in charges. The ore averaged about $7 per ton, gold and silver, the ratio of weight being 1 oz. gold to 7.56 oz. silver. The ratio of gold and silver in tailings was 1 oz. Au to 36.6 oz. Ag; the quartz was sharp and sandy, however finely ground, and rather difficult to slime. The mechanical equipment was a No. 5 Symons gyratory crusher; three 10-ft. Lane slow-speed Chilean mills; one Wilfley roughing and one finishing table; one submerged-type Akins classifier; five 26 by 10-ft. fir leaching tanks; one 24 by 7-ft. Dorr thickener; four 14 by 16-ft. Dorr agitators; four 6-compartment double-row zinc-boxes having compartments 18 in. wide, 18 in. deep, and 34 in. long; Johnson zinc lathe; acid and vacuum filter tanks for treating precipitate; roasting furnace; and Case tilting No. 275 crucible furnace for melting precipitate. The mill is driven by electric power supplied by the Montana Power Co. at the following rates, per kw.-hr.: 200 to 300 hp., 0.68 c.; 300 to 500 hp., 0.61 c.; 500 to 750 hp., 0.55 c.; plus $1 per month per installed motor horsepower. The plant as above described was operated from May, 1915, to the end of the year, when an additional Dorr thickener and a 12 by 12-ft. Portland revolving filter were added, increasing the nominal capacity of 100 tons per 24 hr., but not the percentage of extraction. The combined treatment, at a cost of $1.48 per ton, saved 90 per cent. of the gold arid

Jan 1, 1919

CONTENTS PAGE FOGLER, M. F., and QUINN, E. J.-Scratch and Brinell Hardness of Severely Cold-rolled Metals. Discussed by H. S. Rawdon, Carl Benedicks, M. F. Fogler, A. L.Davis 1 GREEN, C. H. Eutectic Patterns in Metallic Alloys. Discussed by Carl Benedicks, Carle R. Hayward, G. E. Dalbey, George F. Comstock, C. H. Green. 3 ARCHER, ROBERT S., and JEFFRIES, ZAY.-New Developments in High-strength Aluminum Alloys. - Discussed by F. B. Coyle, M. F. Fogler, Zay. Jeffries, D. J. McAdam, Jr., Horace C. Knerr, Ernest Schweizer 6 FLICK, FULTON B.-Etching Aluminum and Its Alloys for Macroscopic and Microscopic Examination. Discussed by Samuel Daniels 22. MERICA, PAUL D., and WALTENBERG, R. G.-The Malleability of Nickel. Discussed by H. W. Gillett, Ancel St. John. L. W. McKeehan, A. L. Feild, A. L. Davis 23 ANDERSON, ROBERT J., and NORTON, JOHN T.-X-ray Evidence Versus the Amorphous-metal Hypothesis. Discussed by Zay Jeffries, Chu Phay Yap, Francis B. Foley, H. H. Lester, Edgar C. Bain, Ancel St. John, L. W. McKeehan, Carle R. Hayward, R. P: Heuer, Jerome Alexander, Carl Benedicks 26 COOK, MAURICE, and EVANS, ULICK R.-Recrystallization and Grain Growth in Soft Metals. Discussed by M. F. Fogler 36 POLUSHKIN, E. P.-Determination of Structural Composition of Alloys by a . Metallographic Planimeter. Discussed by H. S. Rawdon 36 BASSETT, WILLIAM H., and DAVIS, C. H.-Corrosion of Copper Alloys in Sea Water. Discussed by W. B. Price, W.. R. Webster, George A. Orrok, A. E. White, William H. Bassett, D. K. Crampton 38, Scratch and Brinell Hardness of Severely Cold-rolled Metals Discussion of the paper of M. F. FOGLER and E. J. QUINN, presented at the New York Meeting, February, 1925, and issued as Paper No. 1395-E with MINING AND METALLURGY, January, 1925. H. S. RAWDON, * Washington, D. C.-We had the privilege of looking over the data just given before they were published and we were not able to suggest any convincing reason for the differences that were secured

Jan 6, 1925

By R. W. Gurry, L. S. Darken

The solubility of cementite in austenite is computed by thermodynamic methods from the observed solubility of graphite. It is found that the solubility of cementite is greater than that of graphite in the entire austenite temperature range. Thus the prior discrepancy between this portion of the phase diagram and the observed metastability of cementite is partially resolved. FOR several years it has been apparent that a serious discrepancy exists in certain observations pertaining to the Fe-C system. Direct experimental data indicate: 1-That the curve representing the solubility of graphite in austenite'" crosses that for cementite4 at about 945°C as shown in Fig. 1. 2— That graphite and austenite saturated therewith are stable1 relative to cementite at all temperatures between the eutectoid, about 723°C, and the eutectic, about 1153°C. These observations are mutually incompatible in view of a well-known consequence of the second law of thermodynamics, namely, that the stable phase (presumably graphite at all temperatures) has a lower solubility than the metastable phase (presumably cementite). Hence either 1 or 2 above must be in error; either the measured solubility of graphite or of cementite, or the observation as to the stability of graphite, is in error. Our present purposes are: 1—To collate the available data on cementite and prepare a table of HO — HO° and of (Fa— HO°)/T. This tabular method seems the best and most convenient way to represent the heat and free energy of formation. 2—To determine whether the measured solubilities of cementite and graphite in austenite are in accord with the above table and the measured thermodynamic properties of austenite, in order to resolve, if possible, the existing paradox of these two solubilities. Enthalpy of Cementite The enthalpy of cementite at 273 °K, H279 — HOcem, was computed by integration of the low temperature heat capacity as measured by Seltz, McDonald, and Wells" 68" to 298 °K) and as given by the Debye functions recommended by them (0" to 68°K); the result is included in Table I. At higher temperature HCem — H,,"" is given by Kelley who used the data of Naeser7 (298" to 1037°K) and of Umino8,9 (273° to 1923°K). We have recalculated Hcem — H273 cem from the data of UminoO in the following way. In the equilibrated alloy at temperature the weight fraction of cementite Pct c -Pct cr is PctC -PctCr designated f(C), and the

Jan 1, 1952

By Paul E. Rosten

Introduction This papers describes some of the latest improvements that have been incorporated or planned by the Cleveland-Cliffs Iron Co. to reduce operating costs and improve pellet quality. The Cleveland-Cliffs Iron Co. operates and manages mining, beneficiation, and pelletizing operations in Michigan, Canada, and western Australia. This paper deals with the grate-kiln pelletizing operations at Republic, Humboldt, Tilden, Empire, and Pioneer in Michigan, and the Adams and Sherman in Ontario, Canada. Table I characterizes each operation in regard to location, ore type, pellet capacity and date that pellets were first produced. All of the operations with the exception of Pioneer and Tilden, utilize downdraft-two-pass grate cycles of drying followed by preheating. Pioneer utilizes an all-downdraft, three-pass grate cycle which consists of three drying zones followed by the preheat zone. The Pioneer and Tilden cycles have been described previously (Lindroos and Koski, 1966; Villar and Dawe, 1975; Koski, 1977). Tilden utilizes a three-pass grate cycle with a stage of updraft drying, followed by two downdraft drying stages. Recuperation systems which supply hot gases to a drying zone from second stage cooling were designed and fur¬nished for Tilden I. Tilden II will be identical. Empire IV will also be furnished with a recuperation system. The Adams grate¬kiln system was retrofitted with a recuperation system. This paper will summarize some of the efforts that are in effect or planned for grate-kiln pelletizing systems to: (1) reduce operating and maintenance costs, (2) reduce energy requirements, (3) improve product quality, and (4) meet environmental standards.

Jan 1, 1981

By Arthur F. Taggart

Some years ago, A. M. Gaudin and one of the authors published a paper showing removal of tar acids from solution by sulfides preferentially as compared to gangues (specifically by galena as compared to quartz).' The underlying phenomenon was classed as adsorption, and the paper went on to develop the general thesis that so far as water-soluble frothing and collecting agents in flotation are concerned, the phenomenon of adsorption is one of controlling importance. Adsorption was defined in that paper as "a process of rearrangement of a system, which results in establishing a difference in concentration, as between the interfacial layers and the bulk of the phases, of a substance or substances initially uniformly dispersed in one or several of the phases." The paper went on to develop the relation between adsorption and surface cnergy according to Gibbs' equation (which may be thrown into the form U/c = KdT/dc, where U = excess concentration in surface layer, c = concentration, T = surface tension, and K is a constant), and pointed out that, according to this equation, degree of adsorption and change in surface tension vary directly. The present paper offers a somewhat different definition for the term adsorption; and sets up, in sweeping terms, the generalization that simple chemical reaction underlies the functioning of the flotation reagents which control mineral collection, when these reagents are soluble in and act from solution in the water of the pulp. Adsorption According to the modified definition, adsorption means concentration at an interface between different phases in a heterogeneous system (thus far the definition runs as before), by the action of some mechanism, of which nothing is properly implied in the word, and concerning which the user of the word is probably in entire ignorance. Thus defined,

Jan 1, 1930

By Peter K. Strangway

During 1973, a 20,000 net ton (18 100 metric ton) formcoke test was carried out at Inland's 26.5-foot (8.08-meter) hearth diameter on NO. 5 Blast Furnace. The formcoke briquettes were produced from Elko1 coal by FMC at their pilot plant in Kemmerer, Wyoming. The briquettes were shipped to Inland in open railroad cars and most of them were placed in an outside storage field until a sufficient amount was available for the actual blast furnace test. The test consisted of three phases: an initial four-week base period; the actual 33-day formcoke test period; and a final three-week post-test base period. During the formcoke test period, the regular coke skip loads were gradually replaced with skips of formcoke until, after a three-week period, the replacement ratio reached 80%. The furnace operated smoothly and quality hot metal was produced. The burden remained permeable and it was possible to maintain wind rates 9 of over 100,000 scfm (47 Nm3/s) without significant blast pressure increases. Dusting from the formcoke was not a problem either in the stockhouse or in the top gas. The formcoke briquettes maintained their original shape and density as they descended through the furnace. When the 80 percent replacement level had been reached, the inwall temperatures became higher than normal (about 2000 ºF (1090 ºC)) and followed an unusual steady pattern. In addition, the top gas temperature became higher than normal, and the hot metal analyses and temperatures began to fluctuate unacceptably. In general, it is felt that the high inwall temperatures were a result of channeling of the hot furnace gases along the stack walls. This channeling appears to have been promoted by a change in distribution of the burden in the top of the furnace which, undoubtedly, was caused by the increased increments of formcoke. Since it was felt to be unsafe to operate the furnace for an extended period of time with the inwall temperatures at the high level, a decision was made to remove the formcoke from the furnace. When this was done, the inwall temperatures returned to normal. Once the inwall temperatures had returned to normal, the remaining 3,800 net tons (3450 metric tons) of formcoke were used in the furnace at a nominal 40% replacement level for five continuous days. The furnace operated smoothly during this period, and the results were representative of satisfactory furnace operation with partial replacement of regular coke with formcoke. The test was successful in proving that formcoke can replace up to about 50% of the regular coke in a large furnace operating at high wind rates. However, additional work will be required to develop acceptable charging practices for using higher levels of formcoke replacement.

Jan 1, 1977