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By William P. Jones

THE consumption of sulphuric acid, one of the most important commodities in our modern industrial world, is often used as a barometer for industrial activity. The economics of acid manufacture are largely dependent upon the location of the place of consumption and the availability of raw materials in that locality. Sulphuric acid is made from SO2 oxygen from the air and water. Therefore the sulphur dioxide is the only raw material to be considered in an economic study. SO2 can be obtained from almost any material containing inorganic sulphur, such as elemental sulphur, pyrites, coal, sour gas and oil, metallurgical gases, waste gases, or gypsum and anhydrite. Many tons of acid can also be reclaimed by the recovery and concentration of spent acids. The aim of this paper is to present a guide to the economic aspects to be considered when the installation of an acid plant is contemplated. It must be remembered that 1 ton of elemental sulphur produces 3 tons of sulphuric acid and that the shipping of sulphuric acid by tank car is very costly. The size of the plant must also be given careful consideration. For instance, operation of a plant producing 5 tons of acid per day might be warranted in Brazil or Pakistan, whereas economics usually favor buying quantities up to 50 tons per day for use within the United States. Elemental sulphur, when available at the low price of 1 ½ ¢ per lb delivered at an acid plant, has always been the raw material most frequently used for sulphuric acid. All conditions favor its use at this price. The so-called sulphur shortage has been the subject of so many technical papers, magazine articles, and newspaper items during the past year that it hardly seems necessary to mention it again, but a very brief review of the matter will serve as a foundation for the discussion that follows. There is no shortage of sulphur. Only a shortage of low-cost Frasch-mined brimstone exists today. Other more expensive sulphur-bearing materials are plentiful, both in the United States and abroad. The low cost of Frasch-mined brimstone has discouraged the development of higher cost sources. However, the approaching depletion of Gulf Coast dome deposits and the greatly increased demand for sulphur here and abroad have made it necessary for industry to prepare for conversion to utilize sulphur in other forms. For future planning this situation must be considered permanent and not temporary. This conclusion is based on the fact that although sulphur demand will continue to rise, the production of Frasch-mined sulphur probably will not increase greatly beyond its present level of about 5,000,000 long tons per year. The International Materials Conference in Washington estimates 1952 requirements of the free world at nearly 7 ½ million long tons; and the Defense Production Administration has recently set a new goal for 8,400,000 long tons annual domestic production by 1955. The total sulphur equivalent produced in this country in 1950 was 6 million tons. What, then, are the alternatives for the manufacture of the vital chemical, sulphuric acid? Today about 85 pct of this country's sulphur, and nearly 50 pct of the world supply, comes from our Gulf Coast salt domes and is extracted from the earth by Frasch's hot water process. The Gulf Coast salt dome deposits have been the most important known natural deposits in the world, producing 90 million tons of sulphur during the past 50 years. However, at the present rate of extraction these deposits cannot be expected to last indefinitely. Pyrites Pyrites are, and have been for many years, the source of more than 50 pct of the world's sulphur requirements. The principal use, of course, is in the manufacture of sulphuric acid. The use of pyrites in the United States has diminished greatly because of the availability of low cost native sulphur, but pyrites have continued a major source of sulphur in many other countries. The most available pyrites for use in this country are in the form of lump pyritic ore and in mill tailings from flotation of other minerals such as lead, zinc, copper, gold, and silver. An important factor, when the use of pyrites for acid manufacture is being considered, is the disposal of calcine. A ton of sulphuric acid requires approximately ¾ ton of high-grade pyrite and results in ½ ton of calcine. If the calcine is a fairly pure oxide, free of harmful impurities, it can be used, after sintering, in an iron blast furnace burden. Its value might be as high as 15¢ per unit of Fe at the blast furnace; or possibly $10.00 per ton of sinter, if it assays 65 pct Fe. This might result in a credit of $4.00 per ton of acid if the sintering plant and blast furnace are both located adjacent to the acid plant. On the other hand, several factors must be considered before this credit can be realized, i.e., freight to blast furnace, availability of sintering facilities, methods of eliminating impurities, and the removal of valuable metal values. In some locations it would be most economical to dump the calcines.

Jan 1, 1952

By S. Luszcz, R. W. Vook, Fred Witt

In situ X-ray investigations were made on polycrys-talline silver films deposited by vacuum evaporation on (111) CaF2 and (100) NaCl single-crystal substrates at 80°K. The films were evaporated and annealed in an X-ray diffractometer attachment having a residual gas pressure of 2 x lo-' Torr. All measurements were made without exposing the films to the atmosphere. Measurements were made on the films in the as-deposited state and after various annealing treatments. The intrinsic stacking and twin fault densities, the magnitudes of the uniform and nonuniform strains, and the crystallite sizes were determined. In addition the textures in the films were measured qualitatively. The results obtained for the as-deposited films on single-crystal substrates are in substantial agreement with previously reported results for silver films deposited on glass. Intrinsic stacking and twin faults, as well as uniform and nonuniform strains, were present in these films. During the various annealing treatments (up to 350°C) the faults and nonuniform strains annealed out. Considerable grain growth and texture changes occurred also. The effects were much greater for the NaCl substrate than for the CaFz substrate. The relative magnitudes of the grain growth in the variously oriented grains could be explained qualitatively in terms of the thermal strains and strain energies introduced into the differently oriented grains during the initial, irreversible anneal. These strains were due to the different thermal expansion coefficients of the film and substrate. X-RAY diffraction measurements on evaporated films deposited on substrates at low temperature have the advantage that many of the imperfections introduced into the film during deposition are "frozen in". Thus, the influence of a very important experimental variable, substrate temperature, on the imperfection structure of evaporated metal films may be studied. Moreover, the effects of annealing such films makes possible the study of thermally activated recovery processes in these films. The present study was designed to determine the influence of single-crystal substrates on the resultant film structure relative to the previous results obtained using glass substrates.' To this end great care was taken to keep the experimental variables the same in the two cases. Different experimental conditions would, of course, result in films having different physical properties. Again the initial substrate temperature was in the neighborhood of 80°K and the films were subsequently annealed to 350°C. The pure metal silver was chosen for evaporation, primarily because of its relatively low stacking fault energy and consequent high fault density in the as-deposited state. The silver films were formed by evaporation onto air-cleaved {ill} CaF, and (100) NaCl surfaces cooled to 80°K in an X-ray diffractometer attachment2 having a base residual gas pressure of 2 X l0-' Torr. The films were not exposed to the atmosphere until all of the X-ray data had been recorded. In this way one of the most important experimental variables, environment, could be well-controlled and reproduced. X-ray measurements were made at the temperature of deposition and included determinations of the diffraction line peak positions, line shapes, and integrated intensities. The peak position measurements were used to determine the intrinsic stacking fault densities and the average uniform strain in the film. The shapes of the diffraction lines provided information on the twin fault density, true crystallite size, and average nonuniform strain. The preferred orientation in the film was determined qualitatively from the integrated intensities. I) EXPERIMENTAL PROCEDURE The evaporator attachmentZ was charged with 99.999 pct Ag pellets positioned in a tantalum filament which had been outgassed previously at l0-8 Torr. The CaFz and NaCl single crystals were cleaved in air and then placed in position in the chamber so that their cleavage surfaces were on the diffractometer axis. The chamber was prepumped using a sorption pump, sealed off, and then baked at 150°C for 24 hr. The ion pump operated during the bakeout cycle. The substrate was then heated to 500° C by means of an auxiliary heater and kept hot until the rest of the chamber was cooled slowly to room temperature. This bakeout procedure consistently resulted in an ultimate pressure in the low lo-' Torr range. The substrate was then cooled down on 80°K. Its temperature was monitored by a thermocouple wedged into the rear of the copper substrate holder. The diffracted intensity and peak position of the 111, 222, and 333 CaF, lines were measured prior to evaporation. Nickel-filtered, pulse-height-discriminated copper radiation was used. Similar measurements were made for the 200 and 400 lines from NaC1. These measurements were used as a lattice parameter check and to determine the thickness of the evaporated silver films from the attenuation of the substrate lines. The evaporation rates were approximately 3A per sec for both films while the maximum pressures during evaporation were 3 x lo- ' and 7 x 10"8 Torr for the CaF, and NaCl cases, respectively. The film thickness was measured by the attenuation of the CaF, and NaCl substrate lines and by at optical interference method. Values of 1700 and 1500A, respectively, were obtained for the silver

Jan 1, 1969

By R. H. Jacoby, V. J. Berry, R. C. Koeller

The experimental phase behavior of several field gas-condensate systems, one field volatile oil system, and a series of synthetic systems having gas-oil ratios from 2,000 to 20,000 scf/bbl stock tank oil was measured. The data were used to calculate the depletion performance of the field systems at their respective reservoir temperatures and of the synthetic systems at various temperatures. The results of the performance calculations were used to prepare correlations of total stock tank oil and separator gas in-place, and the amount of each recovered by primary depletion. Data needed to use the correlations are initial gas-oil ratio, initial tank oil gravity, reservoir temperature and reservoir pressure. The correlations presented should be useful for estiinating recovery from reservoirs producing volatile oils or rich gas condensates having gas-oil ratios from about 2,000 to 30,000 scf/bbl of stock tank oil. INTRODUCTION Prediction of depletion performance for gas-condensate reservoirs usually requires extensive laboratory work or lengthy phase-behavior calculations. For many small gas-condensate bearing zones the expense of such work is often not justified. Furthermore, where large holdings are involved, it is useful to have estimates of future oil and gas production in advance of the results of a laboratory analysis, even if such work is ultimately planned. For these reasons, it would be of value to have a method for rapidly estimating the depletion performance of gas-condensate reservoirs from the type of field data usually available. Few data on the reservoir depletion performance are available for the purpose of developing correlations. The increasing number of gas-condensate discoveries and the advent of high-speed computers have stimulated the development of methods for predicting performance. Such calculated performance data have been shown to be reliable and are becoming accepted as a basis for reserve estimates and for engineering studies. It therefore seems satisfactory to use results of performance predictions themselves for the purpose of developing the desired correlations. Such an approach is described in this paper. Several rich natural gas-condensate systems (gas-oil ratios of from about 3,600 to 60,000 scf/bbl) and one natural volatile oil system were studied (2,363 scf/bbl). In addition, to provide a more systematic basis for correlating purposes, a series of related, synthetic reservoir fluid mixtures was also studied (GOR's from about 2,000 to 25,000 scf/bbl). The purpose of this paper is to show how the recovery of oil and gas by primary depletion may be estimated from surface gas-oil ratio, reservoir temperature and pressure, and tank oil gravity. procedure Experiments Companion samples of gas and oil were collected from the high pressure separators in nine different fields at the time of their discovery. These samples were each recombined in accordance with the respective producing GOR to reproduce the reservoir fluids. Eight of these fluids, designated F-2 through F-9, were rich gas-condensate systems at the respective reser-

By Frederic L. Kadey

Perlite, as a volcanic glass, has been recognized since the Third Century, B.C. (Langford, 1978). The precise details of discovery often become lost in antiquity, and the variations among the stories pertaining to the more recent discovery of perlite as a material of commerce are no exception. Credit in the United States is given to a dentist who, while experimenting with tooth enamels about 1941, discovered that perlite-the rock-intumesced when subjected to heat. At about the same time it is reported that the chief geologist of Silver and Barytes Ores Mining Co. attempted to put out a picnic bonfire on the shores of Milos Island, Greece by throwing beach sand on it. The ensuing pyrotechnic display immediately conjured up in that man's mind the possibility of a new use for the volcanic rock that constituted most of the island. Very little was done with this discovery either here or abroad until after World War II. Today the name perlite is applied to both the hydrated volcanic glass, generally of rhyolitic composition, and to the lightweight aggregate that is produced from the expansion of the glass after it has been crushed and sized. Petrologically, it is defined as a glassy rhyolite that has a pearly luster and concentric, onionskin parting. Occurrences of perlite are restricted to several Tertiary to Quaternary age rhyolitic belts that trend in a generally north-south direction around the world. Commercially suitable deposits generally occur as domes of several hundred feet in height, although glassy zones in welded ash-flow tuffs and others associated with dikes and sills also have been reported. Mining is by ripping and blasting from open pits. Because of weight considerations, perlite usually is shipped to the local market area for subsequent expanding. In the United States, New Mexico leads in production with Arizona, California, Nevada, Idaho, and Colorado following in approximately that order. The principal use for expanded perlite is as a lightweight insulating aggregate in cryogenics, in plaster, concrete, and in loose fill insulation. Expanded perlite is also used in horticultural applications, and after subsequent milling and classification, as a filter aid. The United States is the world's largest producer and consumer of perlite. Table 1 shows the world production of perlite and Table 2 shows the perlite mined, processed, expanded, and sold or used by producers in the United States. Geology Composition and Morphology Any discussion of perlite must take into consideration its dual nomenclature, for it is known by the same name as both the naturally occurring rock and, after processing and expansion, as the lightweight aggregate of commercial significance. In its naturally occurring form, perlite is a rhyolitic glass that contains from 2 to 5% combined water. While perlite also can occur as andesitic or dacitic glass, these latter types are of negligible commercial significance. Table 3 lists the chemical composition of a few typical perlites (Anderson, et al., 1956; Langford, 1979). What sets perlite of commercial significance apart from other volcanic glasses is the fact that under the proper conditions of preparation-crushing and sizing-it will, when rapidly introduced into a flame of sufficient temperature, expand or "pop." All of the elements of composition contribute to the expansibility of the rock. The role of the combined water, however, is the most significant because it is believed not only to produce a fluxing effect in the softening of the highly siliceous glass prior to expansion, but it is also responsible for the explosive force of expansion through volatilization during heating. The current theory of the origin of the water in perlite is now less con-

Jan 1, 1983

By H. D. Kessler, F. A. Crossley, J. J. Rausch

The titanium-rich corner of the system Ti-AI-V has been studied to determine the phase relationships in the temperature interval 600° to 1200°C. Metallographic examination of long time isothermally annealed specimens was the principal method of investigation. TWENTY-SIX alloys in the region 1 to 22 pct A1 and 2 to 11 pct V, and the temperature range 600° to 1200°C, were studied as part of a program on phase relationships and transformation processes of titanium alloy systems. Experimental Procedure Preparation of Alloys—Materials used in the preparation of alloys were high purity Bureau of Mines sponge titanium (103 Bhn), 99.7 pct pure V chips obtained from the Electro Metallurgical Div., union Carbide and Carbon carp., and 99.71 pet pure A1 in the form of granulated shot from Aluminum cO. Of The alloy ingots, weighing l5 g, were melted in a nonconsumable tungsten electrode arc furnace un-

Jan 1, 1957

By George A. Moore, Donald P. Smith

In spite of many investigations of the occlusion of hydrogen in iron, the nature of the process and the reasons for the accompanying effects upon the metal are still open questions. This is in large part due to three causes: (1) the difficulty of obtaining iron of adequate purity as starting material; (2) the occurrence of allotropic transformations, which complicate the effects; and (3) the fact that the body-centered cubic modification does not lend itself readily to crystallographic investigation. The present paper attempts a critical review and correlation of the somewhat scattered and disconnected existing observations, and an experimental determination of the extent to which the conclusions that appear to follow from these are applicable to iron of really high purity, studied under well-defined conditions. Review Although only a comparatively few investigations have so far been made on the pure system iron-hydrogen, there is a much larger volume of literature which throws some light on the problem but falls short of a place in the systematic investigations, either because no attempt was made to measure equilibrium conditions or because the metal used was not iron or the gas not pure hydrogen. Such results have been variously dismissed in the past as of no importance, or as too complicated to try to explain; or they have been explained in terms of any of a dozen or more pictures, each of which is contradicted by data from other sources. The present importance of these data thus arises from their very mass and diversity, which present a picture of occlusion as a phenomenon whose variability cannot be ignored. We have attempted to organize the literature into groups comprising similar experiments or data leading to similar conclusions, thus of necessity sacrificing accuracy of historical order. Lattice Occlusion.—Throughout this discussion, the term "lattice occlusion" will be used to denote the formation of a simple solid solution of a gas in a metal lattice, usually of interstitial distribution. The word

Jan 1, 1939

By C. E. Sims

The carbon-oxygen reaction without doubt is the basic reaction in steelmaking. It is important on several counts: In the first place, carbon is the element that distinguishes steel from iron. It is the principal element controlling properties, and its control is of prime concern. Although the principal objective of the carbon-oxygen reaction is to oxidize excess carbon, the accompanying boil should not be underrated. The mechanical agitation, stirring, and mixing resulting from the boil are so useful in the distribution of heat and in promoting uniformity of composition in the bath that, were it not a natural accompaniment of the carbon-oxygen reaction, it is probable that something would have to be invented to replace it. The open-hearth operation, for example, with the bath heated from above by radiation, would be impracticable without the carbon boil. The electric-arc furnace is somewhat less dependent on it, but every melter knows how much easier it is to gain temperature with minimum damage to refractories during the boil than with a dead bath The motor action of the induced current of the induction furnace makes the carbon boil unnecessary but even there a severe oxidation has been found useful in giving greater freedom from porosity in certain steels. The quantitative aspects of the carbon-oxygen reaction have been given considerable attention by a large number of investigators, and the principles of physical chemistry have played an important part in these studies. Physical chemistry is the science of the mechanics and mathematics of chemical reactions. It is possible to study the mechanisms of reactions in a qualitative manner writhout reference to mathematics and thus obtain valuable concepts as to the manner in which the wheels go around. When it is desired to express quantitative relations in these reactions, however, resort to mathematics is not only convenient but necessary. Mathematics may also be regarded as the shorthand language of physical chemistry. A basic relation whose description requires numerous words may be expressed very simply by a mathematical formula or equation. A good example of this is the equilibrium constant for a chemical reaction. Expressed verbally, it is: When a chemical reaction has reached a condition of equilibrium, the Product of the concentration of the reacting substances on one side of the equation, divided by the product of the concentration of the reacting substances on the other side, gives a quotient that is a constant at constant temperature For the carbon-oxygen reaction C + O ^ CO this is expressed simply as % C X % O -%co where K (from the German Konstant) is the equilibrium constant for the reaction. Although mathematics is such a necessary and useful tool, it is also a potential pitfall. Mathematics in itself is an abstract science, which is not inhibited by consideration of mechanisms or materials.

Jan 1, 1948

By C. E. Sims

The carbon-oxygen reaction without doubt is the basic reaction in steelmaking. It is important on several counts: In the first place, carbon is the element that distinguishes steel from iron. It is the principal element controlling properties, and its control is of prime concern. Although the principal objective of the carbon-oxygen reaction is to oxidize excess carbon, the accompanying boil should not be underrated. The mechanical agitation, stirring, and mixing resulting from the boil are so useful in the distribution of heat and in promoting uniformity of composition in the bath that, were it not a natural accompaniment of the carbon-oxygen reaction, it is probable that something would have to be invented to replace it. The open-hearth operation, for example, with the bath heated from above by radiation, would be impracticable without the carbon boil. The electric-arc furnace is somewhat less dependent on it, but every melter knows how much easier it is to gain temperature with minimum damage to refractories during the boil than with a dead bath The motor action of the induced current of the induction furnace makes the carbon boil unnecessary but even there a severe oxidation has been found useful in giving greater freedom from porosity in certain steels. The quantitative aspects of the carbon-oxygen reaction have been given considerable attention by a large number of investigators, and the principles of physical chemistry have played an important part in these studies. Physical chemistry is the science of the mechanics and mathematics of chemical reactions. It is possible to study the mechanisms of reactions in a qualitative manner writhout reference to mathematics and thus obtain valuable concepts as to the manner in which the wheels go around. When it is desired to express quantitative relations in these reactions, however, resort to mathematics is not only convenient but necessary. Mathematics may also be regarded as the shorthand language of physical chemistry. A basic relation whose description requires numerous words may be expressed very simply by a mathematical formula or equation. A good example of this is the equilibrium constant for a chemical reaction. Expressed verbally, it is: When a chemical reaction has reached a condition of equilibrium, the Product of the concentration of the reacting substances on one side of the equation, divided by the product of the concentration of the reacting substances on the other side, gives a quotient that is a constant at constant temperature For the carbon-oxygen reaction C + O ^ CO this is expressed simply as % C X % O -%co where K (from the German Konstant) is the equilibrium constant for the reaction. Although mathematics is such a necessary and useful tool, it is also a potential pitfall. Mathematics in itself is an abstract science, which is not inhibited by consideration of mechanisms or materials.

Jan 1, 1948

By R. D. Mollison, C. F. Fogarty

Sulfur is widely distributed in nature. It is present in the earth's crust, the ocean, the meteorites that come to us from cosmic space and in practically all animal and plant life. According to Clarke,9 the earth's crust contains 0.06 pct sulfur. Large quantities of free or combined sulfur are found in coal, natural gas and petroleum. Mineral waters contain sulfates and hydrogen sulfide. Sulfur is rather plentiful in the crust of the earth; however, only under special circumstances can it be produced profitably. Sulfur is one of the cheapest raw materials used by industry; and, therefore, the economic feasibility of a given deposit is strongly dictated by the law of supply and demand on local as well as world-wide levels. The forms which are commercially important are elemental sulfur or brimstone, and the sulfides such as pyrite (FeS2), pyrrhotite (FenSn+1), chalcocite (Cu2S), sphalerite (ZnS), and galena (PbS); the sulfates such as gypsum (CaSO4,2H2O), anhydrite (CaSO4), and kieserite (MgSO4,H2O). Elemental Sulfur Elemental sulfur is found in many localities, generally in solfataras and gypsum type deposits. The solfatara deposits are found commonly in the neighborhood of active or extinct volcanoes as in Italy, Japan and Chile, or fumaroles associated with mineral springs such as the Mammoth Hot Springs in Yellowstone Park. Here the sulfur is deposited in tufas or other porous host rocks. This type of sulfur deposit probably results from the oxidation of hydrogen sulfide or the reaction of hydrogen sulfide with sulfur dioxide. Most of the world's supply of elemental sulfur comes from the gypsum-type deposits. Here the mineral occurs as either crystalline or amorphous sulfur in sedimentary rocks in close association with gypsum and limestone. This association is characteristic and occurs in almost all the great gypsum beds of the world, although sulfur is not always present in quantities of economic importance. Various theories have been advanced to account for this association. Bischof5 suggested that the sulfur came from hydrogen sulfide which resulted from the reduction of calcium sulfate by carbon or methane in accordance with the following reactions: CaSO4 + 2C= CaS + 2CO2 CaS + C02+ H2O = CaCO3 + H2S CaSO4 + CH4= CaS + C02+ 2H20 2H2S + 02= 2H20 + 2S All of the sulfur-bearing domes on the Gulf Coast have calcium sulfate in great quantity in the cap. They all show the presence of hydrocarbons. The oxygen for the final reaction could have been supplied by circulating ground waters. The principal objection to this theory is that temperatures of 700° to 1000°C are needed to reduce the sulfate to sulfide with carbon compounds. The geologic evidence is that the temperature of the sulfur-bearing domes of Texas did not exceed 100°C. Proponents of the theory say that geologic time or a catalyst replaced temperature. According to another theory the sulfur in the salt domes is the result of bacterial action. Sulfate reducing bacteria have been detected in sulfur cores and in the formation water issuing from salt domes. It has, therefore, been suggested that these bacteria converted the sulfate to sulfide which subsequently was converted to elemental sulfur.

Jan 1, 1960

By George A. Moore, Donald P. Smith

In spite of many investigations of the occlusion of hydrogen in iron, the nature of the process and the reasons for the accompanying effects upon the metal are still open questions. This is in large part due to three causes: (1) the difficulty of obtaining iron of adequate purity as starting material; (2) the occurrence of allotropic transformations, which complicate the effects; and (3) the fact that the body-centered cubic modification does not lend itself readily to crystallographic investigation. The present paper attempts a critical review and correlation of the somewhat scattered and disconnected existing observations, and an experimental determination of the extent to which the conclusions that appear to follow from these are applicable to iron of really high purity, studied under well-defined conditions. Review Although only a comparatively few investigations have so far been made on the pure system iron-hydrogen, there is a much larger volume of literature which throws some light on the problem but falls short of a place in the systematic investigations, either because no attempt was made to measure equilibrium conditions or because the metal used was not iron or the gas not pure hydrogen. Such results have been variously dismissed in the past as of no importance, or as too complicated to try to explain; or they have been explained in terms of any of a dozen or more pictures, each of which is contradicted by data from other sources. The present importance of these data thus arises from their very mass and diversity, which present a picture of occlusion as a phenomenon whose variability cannot be ignored. We have attempted to organize the literature into groups comprising similar experiments or data leading to similar conclusions, thus of necessity sacrificing accuracy of historical order. Lattice Occlusion.—Throughout this discussion, the term "lattice occlusion" will be used to denote the formation of a simple solid solution of a gas in a metal lattice, usually of interstitial distribution. The word

Jan 1, 1939

Jan 1, 1954

By E. J. Fasiska, H. Wagenblast

The dilalion of a ivon by interslilial carbon was measured by two independent techniques —dilatometric mesurements at 719 c and X-ray measurments of the urlil cell parameters a1 room temperature after quenching. The relative expansion per increase in cavbon content by both methods is (2.9 + 0.3) x 10-3 pev at. pcl C nrzd is temperature- independent within experimental error. This corresponds to (6.3 5 0.6) cu cm per g-atom for the partial gram-atomic volume of carbon in a iron-only slightly smaller than the atomic volume for iron in the same temperature vange. THE only previous quantitative study of the dilational effect of carbon dissolved in a iron was performed in 1934 by Burns1 which, at the time, generated some discussion of possible sources of experimental error.2 For a system of such widespread importance, we felt that a new investigation was merited. Both X-ray diffraction and dilation measurements were used to determine the expansion of the a iron lattice by dissolved carbon, avoiding as much as possible any previous experimental problems and deficiencies. The dilation method at solution temperature offers not only measurements which are free of residual strain but also, in conjunction with the room-temperature X-ray measurements, a method to detect any large temperature dependence of the partial gram-atomic volume of carbon. To insure that quenching strains did not affect the room-temperature X-ray measurements, wire specimens of constant carbon content but different diameter were examined for such an effect. SPECIMEN PREPARATION The material used for both experimental techniques was "Ferrovac E" iron received in the form of 19-mm-diam rod and stated as having the following impurity contents: C, Cr, Cu, Mn, P, and V, each in the range of 10 to 50 ppm; Co, O, Mo, S, and Si, 60 to 100 ppm; W, 200 ppm; Ni, 230 ppm; N, 4 ppm. The stock material was cold-swaged to 0.71 mm diam for the Debye-Scherrer X-ray camera specimens and portions were cold-rolled from 6.3 mm diam to 0.79- and 0.25-mm sheet for X-ray diffractometer and dilation measurements. The wires were annealed in wet hydrogen for 6 hr at 840°C and 15 hr at 720°C, and then quenched into 0°C water. A chemical analysis for carbon after this treatment gave 0.0046 + 0.0014 at. pct C. Three portions of these wires were subsequently held at 719°C in three different hydrogen + methane mixtures and then quenched, resulting in carbon concentrations of 0.0283, 0.0598, and 0.1067 at. pct C by chemical analysis. After carburizing, the wires were swaged to 0.48 mm and electroplated with silver to prevent carbon loss during subsequent heat treatment. The final heat treatment consisted of holding the wires at 72 1°C for 5 min in a He-2 pct H mixture followed by quenching into 0°C brine. The wires were held at room temperature for a few minutes to remove the silver plating using a phosphoric acid-hydrogen peroxide solution, and then stored in liquid nitrogen until the measurements were made. EXPERIMENTAL TECHNIQUE A) Dilation Measurement. The dilatometer consisted of a gas-atmosphere vertical tube furnace modified so that length changes of a ribbon-shaped specimen could be measured externally. This was done by installing a gas-tight mercury seal at the top of the furnace as shown schematically in Fig. 1. The specimen (21.0 cm long, 1.27 cm wide, and 0.25 mm thick) was suspended in the center of the furnace by 3-mm-diam quartz rods with the upper one passing through the cap of the mercury seal. Above the cap, the upper quartz rod was coupled to a lever exerting a load of about 25 g (-12 lb per sq in.) on the specimen and having a 10 times mechanical magnification. The vertical position of a marker at the other end of the beam was read with a traveling microscope with a precision of 0.01 mm. The temperature gradient of the furnace was meas-

Jan 1, 1968

By Walter C. Lawson

THE first plans were made in 1930 for the mining by open-pit methods of the low-grade disseminated ore body now known as the Morenci open pit. It was not until 1937, however, that final plans were completed and the decision reached to go ahead with the actual development. Many advances were made in open-pit mining equipment during that period of seven years, therefore the ways and means of attack actually used were very different from those originally contemplated. Diesel-operated bulldozers, big trucks, full-revolving electric shovels and electric churn drills constitute the major equipment finally purchased for this modern stripping operation. Neither the bulldozers nor the big trucks were considered in the early operating plans, for at that time bulldozers had not been used in mining operations and the trucks as yet were undesigned. The full-revolving shovel and the churn drills were not new developments in open-pit equipment, but both had undergone remarkable manufacturing transition, emerging far more efficient and far more dependable than their predecessors. Even the ordinary drilling steel had been fundamentally changed. It was now threaded so that the dulled cutting bits could be detached and replaced, thus eliminating the costly transportation of long bars to the drill shop for resharpening. The decision to use trucks in the preliminary stripping operations was based on the desirability of this type of transportation to economically prepare the pit for rail haulage, coupled with the success that the contractors had had with them on other big excavation jobs. There are at present no plans for the use of trucks beyond the preliminary work, inasmuch as rail haulage will give lower costs after roadbeds and benches are once established. For many years to come, both ore and waste haulage will be over favorable grades. The average length of ore haul between the pit and an assembly yard will be about two miles. From there the crushers will be 1 1/3 miles with a connecting track grade of 0.4 per cent. The upper ore benches of the pit will be reached from the yard by a series of four switchbacks over a ruling grade of 4.0 per cent compensated for curvature. Tracks to the dumps will be on 0.2 per cent grades.

Jan 1, 1938

By A. J. M. Ross, R. G. Wayland

The Homestake mine is situated in Whitewood mining district, in the northern Black Hills of South Dakota, in the city of Lead, Lawrence County. The entire property, comprising 557 lode claims with a total area of 3343 acres, is held under United States Patent. The older claims were 300 by 1500 ft. under local regulations, the newer ones 600 by 1500 ft. The Homestake was discovered April 9, 1876, by Moses and Fred Manuel, and Jake Harney, who were drawn into the northern hills, from the Custer placer district, by news of the discovery of rich placer deposits in Deadwood Gulch. They located a number of additional lode claims and, in a short time, the whole country was covered with locations. The Manuel brothers built an arrastre the following winter and took out $5000. The next year the Homestake lode was sold to Senator George Hearst and associates, who organized the Homestake Mining Co. Other companies were formed to exploit other groups of claims and at one time fivc companies were operating on this deposit, the Father DeSmet, the Dead-wood-Terra, the Caledonia, the Highland, and the Homestake Mining Co. These companies, however, have been merged into the Homestake Mining Company. The first stamp mill, known as the "Eighty Mill," commenced operation on July 12, 1878, and production has been nearly continuous since that time. Geology The orebodies of the Homestake are found in an intensely folded and altered bed of dolomitic limestone occurring in a series of ancient rocks believed to be of Archean age, belonging to the Keewatin series. The Keewatin series is estimated to be 20,000 ft. thick and is made up essentially of quartz mica schists, garnet schists, quartzites, slates, and some green schists, probably derived from basic igneous rocks. The dolomitic limestone bed has a thickness of 40 to 60 ft. The great width of ore, as much as 400 ft. in some of the stopes, is due to the folding, wherein the bed is repeated. In other cases the bed is stretched and pinched out. Dikes of Tertiary rhyolite cut across the country and, in places, sills overlie the

Jan 1, 1925

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Jan 1, 1938

By J. R. Bridge, D. A. Vaughan

The phase diagram of the Zr-H system over the range 0 to 65 atomic pet was determined by high temperature X-ray diffraction methods. Results show a eutectoid between a zirconium and the hydride phase. The eutectoid temperature was established at 560±10°C with a eutectoid composition of 42*3 atomic pet H. The hydride phase of the lowest hydrogen content is stable only above the eutectoid temperature, but is formed and retained in a metastable state during reaction of zirconium with hydrogen at temperatures below 560°C. One hydride phase is indicated that exists over the composition range 55 to 65 atomic pet H. RECENT increase in the industrial importance of zirconium has stimulated several investigations of the reaction of zirconium with hydrogen. Review of the literature on interpretation of absorption isotherms' ' shows that attempts were made to relate the observations to the room temperature hydride phases reported by Hagg.3 However, more recently Schwartz and Mallett' reported the existence of a new hydride phase, isomorphous with the lower hydride in the Hf-H system described by Sidhu.4 This phase was found adjacent to the metal in a diffusion gradient sample. In addition to the new phase, Schwartz and Mallett reported on only two of the five hydrides found by Hagg. Gulbransen" confirmed the existence of only three hydrides of

Jan 1, 1957

By H. H. Campbell

The following pages discuss some problems connected with the manufacture of steel by the open-hearth process. The methods employed necessarily enter into the domain of what is called theory; but the results are eminently practical. The determination of the various losses of thermal power and the investigation into the chemical reactions in the bath, are important to every manufacturer. It will be understood that definite figures concerning one furnace and one system, will not apply to all other furnaces and systems; but it is hoped that methods are developed, which are capable of general application and which will shorten the labors of others. The gas-calculations contain nothing entirely novel; but certain methods appeared to be very convenient and they are here elaborated in order that others may have a model to follow. The determination of the loss of iron by weighing the slag and finding the percentage of iron therein, is probably unusual. If so, the fact is to be regretted, since this is the only way that an accurate result can be obtained. The common method of estimating the loss in open-hearth work, is to subtract the weight of metallic products from that of the materials charged. Nothing could be more unsatisfactory, inaccurate and meaningless. Pig-iron, steel, wrought-iron and ore are charged into the furnace; complicated chemical reactions occur; the sand of the pig-iron, the slag from the wrought-iron, the gangue of the ore, all rise to the top ; the silicon, manganese and carbon burn and leave the metal; some of the iron oxidizes and goes into the slag; some of the ore is reduced and gives up metallic iron ; the recarbonizer is added, the mission of which is to waste itself; in the pouring of the steel, pit-scrap is made in the ladles, around the moulds and under the spout; the errors in weighing the products join hands to make accuracy impossible; and then the " loss" is determined by diffrence !

Jan 1, 1891

By R. F. Mehl, J. K. Stanley

THE recrystallization of cold-worked metals is studied ordinarily by determining the temperatures required for complete recrystallization to occur within a given arbitrary time period, usually within 15 min. to 2 hr. The results obtained are conventionally assembled in a three-dimensional diagram relating this temperature to the amount of cold-work (percentage deformation) and the resultant grain size, though sometimes other modes of representation are employed.1 Such three-dimensional diagrams are not complete, for the number of variables exceeds the number represented. The process of recrystallization is characterized by a time-rate, a fact that is not portrayed upon ordinary recrystallization diagrams. It is known that recrystallization consists in the formation of new nuclei and the growth of these nuclei, a process that continues until the matrix is completely consumed and the original set of grains entirely replaced by the new. This knowledge is old.2 Truly heterogeneous reactions invariably proceed by nucleation and growth; the decomposition of eutectoid solid solutions provides an example about which much is known,3 and freezing, originally studied by Tammann, provides the classic example. Although recrystallization is not a heterogeneous reaction .within the orthodox meaning of the term, the mechanism of the process is the same. As in eutectoid inversion and freezing, it should be possible to study the rate of isothermal recrystallization as a function of time, and it should also be possible to analyze the isothermal reaction curve into the component rates of nucleation and growth that determine them.* Other methods, not employing the rates of nucleation and growth, have been used to represent the rates of such reactions, but these in general have been artificial and have not led to progress.4,5? The theory of recrystallization is not in advanced state; if recrystallization data were obtained, in terms of the rate of isothermal recrystallization, and in terms of the rate of nucleation and the rate of growth of recrystallized grains, and in particular if the temperature coefficients of these rates were measured accurately, an adequate theory should be more readily developed.27 Such an effort requires proper experimental technique, but especially requires suitable methods of mathematical analysis to convert measurements made upon a surface of polish into values for the rate of nucleation and the rate of growth and to combine these into a rate of isothermal recrystallization. These methods are now

Jan 1, 1942

By W. N. Poundstone

The mining and ventilating system used in development work in the Pittsburgh Seam in northern West Virginia is discussed. The seam conditions and the nature of the accompanying methane gas are described. The type of equipment and the mining cycle will be discussed, showing how they are well suited for very gaseous development work. Face ventilation in development work is possibly the fastest growing problem of the industry. The coal mines of the future will be faced with the prospect of mining from under increasing depths of cover. Consequently, larger and larger amounts of methane gas probably will be found. The Pittsburgh Seam, in northern West Virginia, is an example of an area already faced with this problem. At the present time, most of the development work being done in this seam lies beneath 500 to 1200 ft of cover. The Pittsburgh Seam in this area has always been very gassy—even near the outcrop—and the recent development work has been accompanied with extremely large volumes of gas. In many cases, a single development section has liberated in excess of 1,000,000 cfm in 24 hr. This problem of heavy gas liberation was the chief concern, several years ago, when continuous mining equipment was first considered at Christopher Coal Co. All of us were apprehensive about the liberation that would accompany rapid extraction in a single working place. However, the experience during the past few years has shown that this ability to mine only one place at a time, is actually the key to working this type of coal. With all of the mining or advancement concentrated in one place, the ventilation can also be concentrated. By this it is meant that continuous mining permits the active working place to be ventilated with a maximum amount of fresh air, taken directly from the intake source without first passing another working place. Continuous mining (and a good ventilating system) also permits a much greater concentration of attention or vigilance to the actual working place. There are two things that are very important to the mining of coal having high rates of liberation. First, adequate volumes of air are necessary. Second, and perhaps more important, a mining and ventilating system must be used that will provide an uninterrupted flow of air to every portion of the working section. Liberations of this magnitude take only a few seconds of interruption for a dangerous accumulation of gas to occur. With adequate volumes of air available, the ability to concentrate ventilation more than offsets the concentration of gas emission that is inherent with continuous mining. The mining system used with continuous mining equipment at Humphrey Mine is similar to the system used at many mines in the area for development work. This system is designed to favor ventilation, realizing that other efficiencies are meaningless if the equipment must stop because of ventilation difficulties. This plan is especially well suited to minimizing ventilation interruptions. Basically, the overall plan of mining is to develop headings into virgin coal and encircle or block out large areas. These blocks are generally at least 2000 ft sq. The purpose of this blocking out is to bleed gas from the area before pillaring. Experience has shown this method to be quite effective, even in the most gassy areas. The gas in this field seems to migrate or flow readily from the solid coal into the outside return headings of the development work. The numerous clay veins and slips that are found in the area are extremely good avenues for gas flow. A block of coal, surrounded with development headings, usually bleeds off readily; and since it is cut off from the virgin coal, it is not subject to gas migration, through the seam, from this source. However, the outside return of the encircling development work, adjacent to the virgin coal, may liberate gas for years. This liberation from the outside ribs in the virgin coal is the reason split ventilation is used in development work. If split ventilation were not used, there would, in many cases, be a serious build-up of gas in the intake before it could reach the working face. Fig. 1 shows a typical development section having seven headings. The two outside places on each side are returns, and the three center headings serve as intakes. This section is equipped with a ripper-type continuous mining machine. An off-track loading machine is used to load from a surge pile on the

Jan 1, 1961

By C. W. Nicolson

THE Tri-State zinc and lead-mining district is in the northeast corner of Oklahoma, the southeast corner of Kansas and the southwest corner of Missouri. The area throughout which active mining has been conducted is about 45 miles long and about 5 miles wide, extending northeasterly from Commerce, Okla., to Alba, Missouri. Although the lead ores were mined on a very small scale in the vicinity of Joplin, Mo., as early as 1848, nothing of any importance was done in the district until 1870, since when both mining and smelting have been prosecuted with considerable vigor. In the beginning the lead ores only were exploited, but within a few years extensive deposits of zinc ores were found and since that time the production of zinc ore has far exceeded that of lead. Both the surface and mineral rights in Missouri and Kansas were under individual ownership by the time ore was discovered. Although some of these rights were purchased by mining companies, most of the mining has been done under leases covering small areas, usually 40 acres, although in the past many leases were given on much smaller tracts. In Oklahoma most of the mineral land had been alloted by the Government to various Indian tribes and although the title to some of these lands had been acquired by various white men before the discovery of the rich Picher field, the title to most of the land has remained with the Indian tribes and the leasing of the mineral rights has been done by the Federal Government for the benefit of the Indians. The Indian allotments were of 200 acres each and some of the mining leases covered entire allotments, although many leases were granted for only 40 acres or even less. Practically all of the leases granted in the past required the erection of a concentrating plant on each lease, a condition that has had a pronounced effect upon the mining and milling methods of the district, since the apparent ore reserves on each tract were too small to justify large

Jan 1, 1938