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By George Smith

TWELVE years ago, the Director of the United States Geological Survey addressed to the Secretary of the Interior a letter calling attention to the government's need for liquid fuel for naval use and pointing out that the rate of increase in demand was more rapid than the increase in production.1 This letter, in a way, inaugurated the policy of public oil-land withdrawals, which was well founded in its primary purpose of protecting the oil industry and highly desirable in its immediate effect of checking the over-development of that day in California. Unfortunately, however, through delays in legislation, this policy may be regarded now as having outlived both its intent and its usefulness. In 1908, the country's production of oil was 178,500,000 bbl., and there was a surplus above consumption of more than 20,000,000 bbl. available to go into storage.: In 1918, 10 years later, the oil wells of the United States yielded 356,000,000 bbl.-nearly twice the yield of 1908-but to meet the demands of the increased consumption more than 24,000,000 bbl. had to be drawn from storage. Nor is this all of the brief comparison. In 1918, our excess of imports over exports of crude petroleum was nearly 33,000,000 bbl. whereas in 1908 we exported 3,500,000 bbl., which was net, as we had not begun to import Mexican oil. In this period, the annual fuel-oil consumption of the railroads alone has increased from 16,871,000 to 36,714,000. bbl.; the annual gasoline production from 540,000,000 gal. to 3,500,000,000 gal. This record may be taken not only as justifying the earlier appeal for Federal action, but as warranting deliberate attention to the oil problem of today.

Jan 1, 1920

By R. Schuhmann, G. W. Powell

The concept of local equilibrium is examined and, in particular, the applicability of the concept to two-phase binary diffusion couples is discussed. It is concluded that, if binary solid solutions are treated thermodynamically as ternary solutions, vacancies being the third component, then recent experimental observations of nonequilibrium interface compositions (i.e., compositions different from the phase diagram values) are consistent with a state of complete dynamic equilibrium at the interface. CLASSICAL approaches to diffusion and to other irreversible processes often utilize a postulate of "local equilibrium". That is, one assumes even in the presence of gradients, fluxes, and time changes of properties, a) that the Second Law can be formulated locally, and b) that thermodynamic equations of state among intensive properties are identical with those for equilibrium phases. A direct consequence of this assumption, for example, is that one would calculate the total entropy of a nonequilibrium phase simply by integrating the entropy density (eu per unit volume) over the volume of the phase, assuming that entropy density is the same function of energy and particle density as for equilibrium phases. In the study of diffusion and of diffusion-controlled phase transformations, metallurgists take this concept of local equilibrium for granted and utilize it automatically. In fact, experimental evidence of all kinds is overwhelming that "local equilibrium" is a valid limiting law, approached more and more closely as gradients and rates of change approach zero. On the other hand, we have neither experimental nor statistical thermodynamic proof that this principle of "local equilibrium" should remain rigorously valid at high gradients and for rapid processes. Theoretically, in fact, one would expect deviations because interactions between adjacent volume increments of material affect the evaluation of entropy. Also one observes experimentally structural and small energetic differences between equilibrium and nonequilibrium phases. The purpose of this paper is to present a thermodynamic framework for the study and correlation of deviations from strict local equilibrium in isothermal diffusion and related processes. This procedure, in effect, preserves the principle of local equilibrium by thermodynamically assigning the deviations from static equilibrium properties to a defect component. Although this theory is entirely phenomenological, the possibility does exist of correlating the theory with experimental observations of defects under favorable circumstances. The most immediate application appears to be to the equilibria at the interfaces in two-phase binary diffusion couples. A recent pertinent work by Eifert et al.1 has shown that the concentrations of aluminum in the a(fcc) and B(bcc) phases at the 0-8 interface in Cu:Cu-12.5 wt pct A1 diffusion couples are greater than those given by the phase diagram. It is postulated by these authors that the supersaturation of the o phase at the interface provides the driving force for the a-to-B lattice transformation; the excess free energy of the a phase, ?Gaxs, arising from the greater-than-equilibrium aluminum concentration is about 3 cal per g-atom. On the basis of the schematic free energy-composition diagram shown in Fig. 1, Eifert et al. concluded that the thermodynamic situation at the interface is one of the partial equilibrium; that is, = for the more mobile aluminum whereas will be reexamined in the latter part of this paper. THERMODYNAMIC PROPERTIES OF DEFECTS A rigorous analysis of the thermodynamics of defects requires an added degree of freedom in the Phase Rule sense, because the standard formulations of solution thermodynamics (partial molal properties of components, free energy minimization, equality of chemical potentials, and so forth) involve the implicit

Jan 1, 1970

The next meeting of the Institute, the 113th meeting, will be held in Arizona in the latter part of September, 1916. All papers to be presented, at this meeting must be published in the September Bulletin or previously. Manuscripts must, therefore,' be in the hands of the Secretary of the Institute not later than July 1. In case manuscripts are given by authors to members of technical committees, or others, they must be in the hands of such persons sufficiently in advance so that they may be actually in the hands of the Secretary of the Institute by the date mentioned. In the past, the Secretary has received urgent requests for special consideration regarding manuscripts that come in after the closing date. In view of the obvious unfairness of this, the Committee on Papers and Publications has instructed the Secretary not to accept for presentation at the Arizona Meeting any papers received later than July 1, 1916.

Jan 3, 1916

By Donald W. Gentry

Many firms in the minerals industry are facing enormous capital-equipment requirements for existing operations, planned expansion programs, pollution control systems, etc. Yet, because of existing economic conditions, mining companies find it increasingly difficult to obtain reasonable financing for the acquisition of large, high-cost capital equipment. One way of obtaining the use of mining and other major pieces of high-cost capital equipment is through leasing. The popularity of this approach is evidenced by the growing number of leasing companies, equipment manufacturers, and financial institutions now offering this service to their customers. Indeed, leasing has become a billion-dollar industry, and many commercial banks have developed sizeable portfolios in this area. "Should we buy or lease?" This question eventually comes up whenever a mining company needs additional major capital assets. Unfortunately, many buy-or-lease decisions are made on an emotional basis-rather than on a proper financial evaluation that would yield the…

Jan 9, 1975

By W. R. Webster

Opinions still differ widely concerning the requirements, chemical and physical, which should be expressed in specifications for steel rails, in order to secure results satisfactory to both manufacturers and purchasers.

Jan 1, 1902

By Gordon I. Gould

The treatment of quicksilver ores to extract the metal, for centuries one of the fundamentally simpler metallurgical operations, has undergone few if any material changes during the past iew decades other than improvement and change of type of equipment used. Of almost universal application and as the seldom deviated from process, the roasting method is still considered superior to chemical metallurgy. Likewise, roasting of the crude ore without previous beneficiation continues to be standard practice, although some successful operations have employed concentration prior to roasting. The roasting process has been carried out in a variety of equipment, devised for different tonnage capacities, to treat "special" ores, and to satisfy an inventive notion of the particular builder, but during the past 25 years there has been one outstanding change in roasting equipment. This change, though neither originating in nor confined to the United States, has probably been developed and applied to a far greater extent in this country than in any other mercury-producing country of the world. The change from manually or gravity operated furnaces, mostly huge brickwork affairs justified largely by simplicity, lack of power and mechanical requirements, and occasionally by excellent metallurgical results, to mechanical furnaces, began actively during World War I under the stress of requirements for in- creased production, a shortage of labor, 2nd other factors to be brought out later. During the twenties the change to mechanical furnaces became nearly complete at American mines with the development of several types, the rotary furnace predominating. During the thirties, and the period of low prices in the early part of this period, few changes were made other than mechanical improvements and an almost complete acceptance of two types: the rotary furnace and the hearth or Wedge furnace. These two types have been developed to a high degree of metallurgical efficiency, have proved to be mechanically simple and have far greater flexibility and lower operating costs than pre-World War I furnaces. Of the two types the rotary is the more popular, about 30 rotaries having been in operation in the United States in 1943 as compared with about six hearth-type furnaces. The units of smaller capacity for roasting mercury ores have almost without exception been indirectly fired, such distinction being commonly accepted as the difference between retorts and furnaces, which are fired directly. The difference between indirect and direct firing obviously permits of quite different conditions surrounding the ore being roasted in relation to the chemical reaction to take place. In the indirect-fired unit the ore is contained within the body of the retort in a stagnant if not completely oxygen-impoverished atmosphere. In the direct-fired furnace the ore is in contact with the gases of combustion, which may easily (if not too easily) be supplied with an excess of

Jan 1, 1944

By H. R. Hanley

ELECTROLYTIC zinc produced from sulfate solution and, with pure lead anodes is always contaminated with a small and varying percentage of lead. The purpose of this investigation is to determine the characteristics of several lead alloys and their influence on the products of electrolysis and power consumption. The study of alloyed anodes has been a matter of interest for some years. Tainton, Taylor and Ehrlinger prepared a highly interesting paper1 on this subject a year ago, in which the effects of silver-lead and some ternary alloys of lead-silver-tin were described. The present paper describes a study of various combinations of 10 metals. The general plan of the work provides for the fabrication of the alloyed anode, its adequate conditioning by preparatory electrolytic operation, the production of cathode zinc and its analysis, the determination of the anode polarization, and other features. A list of the anodes tested, showing composition and polarization at various current densities together with the lead assay of the cathode zinc, is shown in Table 1.

Jan 1, 1930

By H. Majima, E. Peters

The oxidation rates of pyrite, pyrrhotite, chalcopy-rite, chalcocite, covellite, bortzite, galem, sphalerite, and stibnite have beet2 carefully compared at 120 oC, using aqueous phosphate solutions buffered at pH 2.7, 7.1, and 11.2 as zvell as in 1.0 M NaOH and in am~onia-containing solutions. Under conditions of these studies, variations in rates of more than a factor of two per unit of mineral surface area were not observed for different minerals in phosphate buffered solutions, except that pyrrhotite showed unusually rapid oxidation rates In acid solutions, and stibnite showed very rapid oxidation rates in basic solutions. In caustic solutions, oxidation vates varied considerably, the most rapid being for pyrite and the slowest for sphalerite. In the presence of ammonia, only copper minerals showed more vapid oxidation rates in neutral solutions. Oxidation rates were measured on the basis of oxygen-consunzption rates per unit surface area of exposed mineral, using equivalent surface areas, mineral mesh sizes, pulp densities, agitation, and oxygen pressure. OXIDIZING pressure leaching of sulfide minerals has been a commercial method of treating concentrates of nickel, cobalt, and copper for over a decade, and recently the treatment of lead and zinc concentrates,' and even the recovery of sulfur from pyrrhotite by such processes, have been shown to be technically feasible.' Furthermore, the leaching of uranium ores by solutions acidified through the oxidation of pyrite and other sulfides present in the ore is commercially practicable.3 5 The mechanisms by which sulfide minerals oxidize in aqueous environments are not yet understood. However, certain generalities can be made for systems containing no unusual reagents, in which oxygen is the oxidizing agent. In acid solutions the oxidation of many sulfide minerals leads to the formation of elemental sulfur.8'7 The attack of some sulfides, notably galena (PbS), sphalerite (ZnS), and pyrrhotite (FeS), at temperatures below about 110°C leads to an almost quantitative conversion of the sulfide mineral to elemental sulfur according to the equation: On the other hand pyrite (FeS2) and copper minerals do not yield elemental sulfur quantitatively. Not more than 50 pct of the sulfur in pyrite is converted to the elemental form in acid oxidation, and this percentage is lowered by higher temperatures and possibly higher oxygen pressures.8'9 Copper minerals sometimes yield elemental sulfurlo'" but, since sulfur can reduce cupric ions with the precipitation of CuS or Cu2S, it is not likely that elemental sulfur is obtained in good yield. In acid solutions sulfur that is not converted to the elemental form always appears as sulfate salts or sulfuric acid. Sulfide minerals that yield elemental sulfur nearly quantitatively on oxidation in acid solutions tend to generate H2S when the conditions are not oxidizing. However, although it has been suggested that H2S is an essential intermediate in the mechanism of oxidation," this is doubtful because it is oxidized very slowly by oxygen. In basic solutions elemental sulfur is never formed, as predicted by thermodynamical considerations, summarized in the form of a potential-pH diagram in Fig. 1. However in neutral and basic solutions, unstable forms of sulfur not shown in the diagram appear during oxidation, notably thiosulfate (SOT-) and polythi-onates (S,O;-, x = 2 to 6).l3,l4 On prolonged oxidation only hexavalent sulfur as sulfate (SOi-) or sulfamate (NHzSO;) is found to remain, the latter appearing only in the presence of ammonia. The oxidation kinetics for thiosulfate by oxygen are the subject of a separate paper,'5 and were studied on the presumption that thiosulfate may, in fact, be a primary oxidation product for sulfide minerals, at least in neutral and basic solutions. A survey of the literature indicated that comparative oxidation rates for different sulfide minerals were needed to establish the role of the mineral structure and its thermodynamic properties on the oxidation rates and mechanisms.

Jan 1, 1967

By W. H. Geis

THE following pages summarize the causes that led to the suggestion of unit operation of the Paloma field, the organization of committees, preparation of the Paloma Operators Agreement and the reasons for rejection of the plan.

Jan 1, 1942

By J. Rogers, H. F. A. Hergt, K. L. Sutherland

IN 1938 Ralston4 reviewed the many attempts to find a satisfactory collector for the separation of cassiterite from its ores and in 1944 Dean and Ambrose2 summarized some further attempts. Generally, soaps and amines are effective but nonselective collectors. We have discovered that reagents containing either the polar group -SO4- or _S03- are excellent collectors for cassiterite and promise to be selective.1 The response to these reagents of cassiterite and of minerals commonly associated with it was studied, using the captive-bubble technique. Using these fundamental data, the practicability of separation and concentration of tin was investigated by flotation tests in a 2000gram Denver cell. EXPERIMENTAL METHODS Reagents All inorganic reagents were of Analar grade. The preparation and purification of sodium cetyl sulphate, cetyl trimethyl-ammonium bromide, laurylamine and cetylamine have been previously described.5 The other collectors were commercial surface-active agents, which were used without purification. Tests Captive-bubble Tests and Cylinder Flotation Tests have been previously described.5-10 The full lines shown in the figures relating solution composition to contact (flotation) distinguish solutions in which contact (flotation) is possible from those in which it is not. The curve is derived by successive approximation and the accuracy is ±0.2 pH units and ± 5 mg. per liter of collector or depressant. Solution compositions for which it was shown experimentally that contact or flotation is possible are marked by a circle, those for which it is not possible, by a cross, and those for which it is doubtful by a cross within a circle. It is assumed that at all other solution compositions within (without) the curve, contact or flotation is possible (not possible). After testing in the collector solution, the mineral was removed, washed, and tested by the captive-bubble method in water, or floated in a cylinder with frother only. In this way the composition of solutions in which a mineral was conditioned but in which properties of the collector solution prevented contact or flotation can be defined. The composition of solutions in which conditioning was possible lie between the full and broken curve, and the experimental results are indicated by a square. The curves show the limits of composition of solutions in which flotation in a cell would be possible but many factors other than those considered in these tests determine recovery and grade of a given mineral in practice. Flotation Tests in 500 and 2000-gram Denver Submachines.--Melbourne tap water, containing 12 parts calcium, 6 parts

Jan 1, 1947

By J. E. Hilliard

A procedure is described for determining, from measurements on a section, the moments of any degree n (i.e., the mean value of Dn, where D is a linear dimension) of the size distribution of particles (or grains) in an opaque sarnple. The analysis is applicable to particles of alnzost any shape and to any mixture of shapes. However, if absolute values of the wloments are required, it is necessary to know what shapes are present and the relative frequency of their occurrence. In addition, certain shape-dependent parameters have to be evaluated before the formulas can be used. The measurement required is the distribution of intercept lengths. This can be determined either visually or with an automatic scanning instrument. Corrections me derived for the bias due to instrumental end effects. The proposed analysis has the following advantages over existing ones: 1) Confidence limits are easily estimated for the measured properties or, conversely, the number of counts required to achieve a given accuracy can be determined. 2) The analysis is not restricted to particles of a special shape. 3) The error resulting from any known degree of departure of the actual from the assumed particle shape can be estimated. 4) The computations are simple and, apart from a change in constants, are independent of particle shape. 5) The number of particles per unit volume can be determined by a simple counting procedure. MANY procedures have been described for determining the size distribution of particles from measurements on a section (or plane of polish). They differ from one another in the property measured on the section (radius, intercept length, profile area) and in the method used for the numerical solution of the integral equation relating the property to the particle size distribution. However, all existing analyses share at least two of the following disadvantages. 1) They are limited to a particular shape of particle (usually spherical). 2) It is very difficult to determine how the statistical sampling error is propagated into the computed size distribution. The investigator thus has no means of knowing the reliability of his result and, what is of equal concern, he is unable to estimate how many measurements are required to obtain a result of the required accuracy. 3) It is also difficult to assess the error resulting from any deviation between the actual and assumed particle shape. The foregoing limitations stem from the complex relationship between the particle size distribution and the distribution of the property measured on the section. As will be shown, they can be avoided by defining the size distribution in terms of discrete parameters

Jan 1, 1969

By Ikuya Takase

INTRODUCTION Since the occurrence of the first oil crisis, coun-tries of the world, especially oil-importing countries have made sustained and vigorous efforts to lessen the dependency on oil as a source of energy supply. The adoption of "Principles of Coal Policy" by the IEA Ministerial Governing Board Meeting in May, 1979 was the first formal action taken by major energy consuming countries. At the Venice Summit in June, 1980, it was agreed that production and use of coal should be doubled over the next ten years. In fact, the world coal use in 1980 showed around a 10 percent increase over the previous year. Recently, we have seen an indication that the balance of oil supply and demand in the short term have eased. But I believe that it remains vital that we continue to encourage the development and introduction of alternative energy sources. Because, from the medium and long range viewpoint the recovery of the worldwide economy will lead us to increased oil requirements and thus we will be faced with the cyclical, structural tightening situation between the supply and demand of oil. Moreover, we are still convinced that the constraint of the supply capabilities of the Middle-East nations may be increasing in the long-term, since there still remains political uncertainties among these nations. Consequently, above all, coal is viewed as an alternative energy resource available for immediate expansion of use and is given as high a priority as nuclear power. In Japan, we regard coal as the most reliable alternative energy resource to replace oil. According to the "Alternative Energy Supply Targets" approved by the Cabinet in November, 1980, the level of coal imports is estimated to approximately double by 1990, while our domestic coal production will remain nearly at the same level. The transition from oil to coal is found in the recent import levels of coal---73 mil¬lion tons in 1980, a 23 percent increase over the 59 million tons imported in 1979. There was an upsurge in steaming coal imports, reflecting the transition in feedstocks---7.2 million tons in 1980, four times over the previous year's amount. Henceforth, from the medium to long range view, the demand for coal, especially that of steaming coal is forecast to continue to grow. The timely expansion of supply capabilities is our utmost concern and should be one of the most significant goals of our comprehensive policy. The Overseas Coal Investigative Committee, a privately organized advisory panel to the Director-General of the Natural Resources and Energy Agency of the Ministry of International Trade and Industry (MITI), investigated means to secure a stable supply of overseas coal. The panel presented its interim proposals in August, 1981, recommending the diversification of coal import sources, extensive use of low rank coal, as well as enhanced international cooperation between coal producing and importing countries. THE CONTENTS OF THE COMMITTEE'S REPORT Four Points for Major Consideration In order to ensure a stable supply of overseas coal, Japan needs adequate policy measures consistent with the characteristics of coal resources and environmental requirements, giving consideration to Japan's status and the role she is expected to play in the areas. From the above, great importance should be attached to the following four points: All the components of the "Coal Chain" (Namely, the development of mine sites, construction of railroads, port loading facilities, coal shipping vessels, port receiving facilities, including coal centers and international transport facilities etc.) should be reviewed and reformed with steps taken to assure efficiency consistent with the entire coal chain system. The complete formation of a coal chain system requires such lengthy lead times and huge amounts of investment that necessary measures should be undertaken well in advance utilizing long-range projections of future demands and various economic surveys. Policy planning should be conducted taking into account of harmonizing stability and economics of the supply structure. For ensuring the long-term stability and expansion of the coal trade, international cooperation on a bilateral and multi-national basis should be encouraged. Mutual understanding and close relationships are essential to facilitate the formation of the supply system and to promote the extensive use of coal. Direction and Problems Related to Supply Stability Expansion of Supply Capabilities. World coal imports in 1979 amounted to 229 million tons, of which Japan's share amounted to 59 million tons, or one fourth of the entire amount. The imports of European and Asian countries accounted for 83 million tons and 7 million tons respectively. According to the examination of the Investigative Committee, Japan's coal requirement is estimated to be between 140-150 million tons by 1990, nearly the same level as announced in the Provisional Long-Term Energy Supply and Demand Outlook in 1979. This fore¬cast is-to be revised in April, 1982. Japan's demand is expected to be met through fiscal 1985; however, by 1990, the supply is estimated to fall short of demand, particulary, in the field of steaming coal. For the expansion of supply capability, first, mine development should be accelerated. The proposed

Jan 1, 1982

By E. D. Gardner

Introduction Oil shale deposits have been exploited in various countries throughout the world, but generally with government aid. The oil-shale industry of Scotland perhaps is the oldest and best-known; the largest was conducted in Manchuria by the Japanese during World war 11 as a source of liquid fuels for military uses. In general, foreign oil-shale deposits that have been exploited are much lower grade than those in the western United States. Considerable interest began to be shown in western oil shales in 1916; the peak of activities was in 1923. The catlin operation, near Elko, Nevada, perhaps was the nearest approach in this country to an oil-shale enterprise on a commercial scale. Over 100 companies were formed, ostensibly for exploiting the oil shale; a large number of them, however, proved to be stock promotions only, which gave the embryo industry a black eye. The Bureau of Mines operated an experi-mental oil-shale retort plant near Rifle, Colorado, from September 1926 to June 1927 and again from April 1928 to July 1929, after which the plant was dismantled. By this time the East Texas oil fields had come ill and the country lost interest in substitute liquid fuels. During World War II the Nation again became concerned about the magnitude of its petroleum reserves. Congress (April 1944) directed the Bureau of Mines to build and operate demonstration plants to produce synthetic liquid fuels from coal, oil shales, and agricultural and other products; a five-year Program was authorized. *' a part of this program the Bureau of Mines has built, at Anvil Points near Rifle, Colorado, a retort plant and develOped an experimental mine to supply the plant with oil shale. An important part of the mining work at Rifle is to devise methods and select practices for mining the oil shale on a commercial scale at the lowest practicable cost. The product to be mined has a relatively low value, a fact that must be kept in in mind. The combined aim of those in charge of the mining and those in charge of retorting is to demonstrate that the shale oil can be produced at a cost per barrel corresponding to the current quotation for crude petroleum —or at least very close to it. Plans call for an uninterrupted flow of broken oil shale from the lace in the mine, through crushers, through the retorts and thence to the disposal dump. The disposal of the spent shale in the Ride area should present no unusual problem. Mining research has consisted so far of Paper studies of the general phases of the probleml determination of the widest Span that the roof Stone will stand safely unsupported, and drilling problems. underground development has not proceeded far

Jan 1, 1949

By W. M. Bertholf

IN 1945 tests were made in the coal washery of the Colorado Fuel and Iron Corporation, at Pueblo, Colo., to determine the value of the Humphreys spiral. So far we have demonstrated that it is of definite value to us in rewashing a portion of our table middlings; and we are fairly certain that this is not necessarily the only place in which it can be used to advantage. Because of manpower and material shortages, experimental work has been discontinued for the present. Three of the spirals are being installed for use in rewashing the middlings, and testing and experimental work will proceed when this installation is completed. All evidence secured so far points to the fact that the spiral can make an effective separation of heavy material below 8-mesh; but that it is ineffective in removing larger, heavy material. This, of course, will limit its use to fine coal or a classified feed containing no heavy material larger than 8-mesh. In considering the results of our tests, it should be noted that the feed was our table middling, and that any real separation of this material is a "moral victory," as there is little material that could be properly called coal and practically no heavy rock, the consequence being that previous attempts to clean the middlings have not been at all successful. Several articles dealing with the spiral and its use in treating heavy minerals have already been published,1 but for the benefit of those who have not seen these we include a brief description of the spiral and of the way it operates, taken from Bulletin 4 of The Humphreys Investment Co.: The Humphreys Spiral Concentrator consists of a spiral conduit of modified semicircular cross section. Ore pulp is fed to the top and, as it flows downward, the heavier particles concentrate in a band along the inner side of the pulp stream (Fig. I). Outlets for removal of products are located at the lowest points in the cross section of the conduit. Wash water, added at the inner edge of the stream, flows outwardly across the concentrate band. The width of concentrate band removed at the outlets is controlled by adjustable splitters. Concentrate is usually removed from the upper portion of the spiral and middling from the lower portion. Tailing is discharged from the lower end. Tests are usually made in closed circuit, since this provides a maximum of information with a minimum amount of sample. Fig. 2 shows the spiral set up for closed-circuit testing, and gives a good idea of the general arrangement of such an installation. The small cyclone separator is used to provide clean wash water without introducing additional water into the circuit.

Jan 1, 1946

By D. S. Flett, D. W. West

The solvent extraction of chromium 111 has been studied for the system Cr 111, H,SO., H,O/RNH/RNH., xylene, where the primary amine used was Primene JMT. Rate studies have shown that extremely long equilibrium times are required, ranging from 1 hr at 80°C to 20 days at room temperature. Heating the solution prior to extraction increases the rate of extraction. The variation in the amount of Cr 111 extracted is an inverse function of the acidity of the aqueous phase. Thus, the slow rates of extraction appear to be connected with the hydrolysis of the Cr I11 species. Extraction isotherms for the extraction of Cr 111 have been obtained for two sets of experimental conditions, namely at 60°C and for a heat-treated solution cooled to room temperature. The separation of Fe 111 from Cr 111 and Cr 111 from Cu 11 in sulfate solution by extraction with Primene JMT has been studied and shown to be feasible. A survey of the literature relating to the solvent extraction of chromium showed that, although many systems exist for extraction of Cr VI, only a very few reagents have been found to extract Cr 111. The extraction of Cr III by di-(2-ethyl hexyl) phosphoric acid has been reported by Kimura.' A straight-line dependence of slope —2 was observed between log D,, and the log mineral acid concentration at constant extractant concentration. Since the slope of this plot reflects the charge on the ion extracted, it must be concluded that a hydrolyzed species of Cr III is being extracted. Carboxylic acids generally do not form extractable complexes with Cr III but di-isopropyl salicylic acie does extract Cr 111. Simple acid backwashing of the organic phase, however, failed to remove the chromium. Similar difficulty in backwashing was found by Hellwege and Schweitzer8 in the extraction of Cr I11 with acetyl-acetone in chloroform. The extraction of Cr 111 from chloride solutions by alkyl amines has been reported4-' but the maximum amount of extraction achieved in these studies did not exceed 10%: From sulfate solutions, however, Ishimori" has shown that appreciable amounts of Cr I11 were extracted by amines. The amines used were tri-iso-octyl amine, Amberlite LA-1 (a secondary amine, Rohm & Haas) and Primene JMT (primary amine, Rohm & Haas). The efficiency of extraction with regard to amine type was primary>secondary> tertiary. Appreciable extraction of Cr I11 was recorded for Primene JMT as the aqueous phase acidity tended to zero. The major difficulty with Cr I11 in solvent extraction systems stems from the nonlabile nature of the ion in complex formation. This accounts for the slow rate of extraction generally experienced and the difficulty encountered in backwashing the Cr I11 from the organic phase in the case of liquid cation exchangers. Consequently, the possibility of extraction of Cr I11 as a complex anion is attractive since the backwashing problems should be minimized in this way. From published data, it appeared that the extraction of chromium from sulfate solutions of low acidity by primary amines afforded the best chance of success for a useful solvent extraction system for Cr iii This paper presents the results of a study of the extraction of Cr I11 from sulfate solution by Primene JMT and examines the application of such an extraction procedure for the recovery of chromium from liquors containing iron and copper. Experimental Chromium solutions were prepared from chrome alum in sulfuric acid and sodium sulfate so as to maintain a constant concentration of sulfate ion of 1.5 molar. Solutions of Primene JMT were prepared in xylene and the amine equilibrated with sulfuric acid/sodium sul-fate solutions, of the same acidity as the chromium solution, until there was no change in acidity between the initial and final aqueous phases. The solutions of Primene JMT conditioned in this way were then used for the equilibration experiments. Equilibrations at 25°C were carried out in stoppered conical flasks shaken in a thermostat; equilibrations at all other temperatures were carried out in stirred flasks in a thermostat. After equilibration, the phases were separated and analyzed for chromium. In the tests on the rate of extraction, small samples of equal volume of both phases were withdrawn from time to time and the chromium distribution determined. The chromium analyses were carried out either coloi-imetrically using diphenyl carbazide, or volu-metrically using addition of excess standard ferrous ammonium sulfate and back titration of the excess iron with potassium dichromate. The oxidation of Cr 111 to Cr VI in the case of the raffinate solution was effected by boiling with potassium persulfate in the presence of silver nitrate and, for the backwash solution, by boiling with sodium hydroxide and hydrogen peroxide. Results Preliminary experiments indicated that extraction results were effected by the age of the chromium solution, higher distribution coefficients being obtained with solutions which had been allowed to stand for some time. Consequently a stock solution of chrome alum, 10 m moles per 1 Cr I11 in 1.4 M Na,SO,/O.l M &SO,,

Jan 1, 1971

J. Chipman (Massachusetts Institute of Technology, Cambridge, Mass.)—The fact that the experimental work has been applied to copper rather than iron and that the paper is presented to the Iron and Steel Division, I regard as rather significant. It shows the unity of metallurgy and the fallacy of trying to cut it up by metals. This result for the solubility of sulphur in molten copper correlates with Professor Schuhmann's finding that the published data on the other side of the copper-sulphur miscibility gap are also in error. I should like to ask the author to say a little bit more about the sulphur capacity of the slag. T. Rosenqvist (author's reply)-—I hope that Dr. Chipman will find the derivation of the expression for sulphur capacity more clearly explained in the printed version of the paper than in the oral discussion at the meeting. I feel that this quantity, which actually is the ratio of two activities, can be measured more easily than the individual activities. Even if the ratio CaO/CaS is chosen as the standard state, the expression can be used for any slag, even for slags completely free of lime, and it represents a way to put the desulphurizing power of all slag constituents into one bag. Some doubt has been expressed as to whether oxygen ions really exist in calcium oxide and in molten slags. From a thermodynamic view point that question is of minor importance. The term oxygen ion activity, or any activity for that matter, is defined rigorously by the equation: activity = exp u/RT, where u is the change in free energy connected with the transfer of one mol of ions from the standard state into the slag. Whatever happens to the ion in the slag is of no concern to the thermodynamicist. Regardless of whether the ion is "free" in the slag or not, or whether it is present in a very small amount, its activity can always be expressed, and for a thermo- dynamic calculation that is all we need. However, ionic activities will only be of some real value if they are simple functions of the slag composition, or can be measured easily. Concerning the real nature of the oxygen in the slag, my feeling is that the oxygen atom has a rather multiplex nature depending on how strongly it is tied by covalent forces or polarized by the other atoms or ions present. The oxides of iron, cobalt, and nickel differ from calcium oxide and blast furnace slags as to the amount of free electrons that can give rise to electronic conductivity. In slags we know that the conductivity is mostly ionic. The fact that reversible emf's can be obtained with oxygen electrodes in certain salt melts, indicates a significant amount of oxygen ions in these melts. But extended work, e.g. polaragraphic studies and measurements of transference number; are needed to obtain quantitative information about the real structure of the slags. D. E. Babcock (Republic Steel Corp., Youngstown, Ohio)—-With reference to the ion, it might be well to remember Dr. Moses Gomberg. All of his life he had no use for the ionization theory and he contributed greatly to the field of chemistry on the assumption there was no such thing as ions. I do not think we have to worry about whether the oxygen is ionic or not. I think one thing specifically should be brought to your attention and this I think is one of the important contributions of Dr. Rosenqvist. He pointed out what we know as oxygen potentials or what is described as oxygen potentials. I have used this concept for a long period of time and I want to state that if this concept is properly applied, it vitiates much of what we have in the literature, or makes our usual ideas regarding oxidation seem primitive. That one thing is more valuable than almost all the rest of the discussion as a fundamental basis on which to build a reasonable in-

Jan 1, 1952

By R. Y. Williams

IN the United States, fully 98 per cent. of the anthracite and bituminous coal tonnage obtained from underground operations is mined by the room-and-pillar system. Under this system, the total cost of the coal f. o. b. railroad cars contains as its greatest single item the money paid for "labor." Each labor dollar in an. average bituminous mine may be subdivided into 85 c. paid for work done inbye the gathering turnouts (including all work at the face), and 15 c. outbye that point (including all work in and under the tipple). In an average anthracite mine, the corresponding figures are 70 c. and 30 c., the larger breaker force accounting mainly for the difference between these and the bituminous figures. The next largest single item after "labor" is usually "supplies and power;" and a division of this item inbye and outbye the gathering turnouts shows somewhat the same relative proportions as has been noted under the case of "labor". During the past 10 years, the chief advances made in the coal industry have been to obtain economies through complete mechanization covering that portion of the work which lies outbye the gathering turnouts. These results have been accomplished by applying scientific principles to railroad yard layout, to cleaning and sizing machinery, to dumping facilities, to roller-bearing haulage equipment, and to heavy-rail, well-ballasted trackage. But these improvements, while gratifying in their resulting economies, apply only to 15 to 30 per cent. of the important cost items. Obviously, then, the big problem before the engineers of the coal industry today has to do with the methods of mining and the layout inbye the gathering turnouts. Four years ago, Weston Dodson & Co., Inc., determined to have an exhaustive study made of the conditions which must be met in order to gain complete face mechanization, and in order that such a mining layout would be based on, correct underlying principles. The result of that study, which was made by the writer, led to the adoption of a method of longwall mining wherein the. roof is worked on the caving system and is supported as an overhang along the face by steel jacks.

Jan 1, 1928

By Nicholas J. Grant, Italo S. Servi

SPECIAL polishing and etching techniques were developed during an investigation of the high temperature mechanical properties of high purity aluminum (99.995 pct Al).* Electrolytic polishing was done successfully in the following electrolyte: 5 ml perchloric acid (72 pct), and 95 ml glacial acetic acid. No special precautions need be taken during the preparation of the electrolyte since no appreciable heat of mixing is evolved. Although the electrolyte is not an explosive, it is recommended that Jacquet's safety rules' be followed during the polishing operation. A voltage of 25 to 60 v gives a good polish in about 2 min at room temperature after preparation on 3/0 metallographic paper. Most of the grain boundaries are visible under the microscope after polishing. Since the current is controlled essentially by the resistance of the bath, it is necessary to keep the anode-to-cathode distance as constant as possible. Accordingly, polishing of irregularly shaped pieces will be difficult. A cooling bath and a stirring system are advisable in order to keep the temperature of the bath uniform and constant. Coarse-grained samples can be macroetched in a few seconds by lowering the voltage below 10 v. This is done after electrolytic polishing, without removing the sample from the bath, Fig. 1. The specimen can be repolished in less than 1 min by raising the voltage above 25 v. The "galvanic etching" technique, which has been described elsewhere,' was found to be helpful not only for macroetching, but also for microetching coarse-grained specimens. In fact, the different orientations of adjacent grains provide good contrast at the grain boundaries, when the sample is observed under polarized light. If the specimen is only partially etched, Fig. 2a, the grain boundaries can be located without completely destroying the appearance of the surface of the specimen. The unetched surface appears black under polarized light. Excellent color contrast is obtained by using a "sensitive tint" plate in the optical system of the microscope. In this case, the unetched surface has a magenta color, while the etched part of the sample assumes different colors varying from green to brown, according to the orientation of the grains. Etch pits were produced on high purity aluminum by using the technique suggested by Lacombe and Beaujard." Good results also were obtained by substituting 70 pct nitric acid for the fuming nitric acid recommended. This gave an etching reagent of the following composition: 70 ml nitric acid (70 pct), 50 ml hydrochloric acid (37.5 pct), and 3 ml hydrofluoric acid (48 pct). An example of the results is shown in Fig- 2b. The outline of the etch pits is revealed sharply if the specimen is observed under polarized light, as shown in Fig. 2c. These metallographic techniques are not suitable for the examination of commercially pure (2s) aluminum. References 'P. A. Jacquet: Metal Finishing (Nov. 1949) 47, p. 62. 21. S. Servi: Metal Progress (1950) 58, p. 732. 3 P. Lacombe and L. Beaujard: Journal Inst. of Metals (1947) 74, p. 1._________________________

Jan 1, 1952

By D. M. Wyslouzil

Standard testing methods are described that are presently used for the selection of grinding equipment. Correlation between laboratory batch grinding tests and pilot plant continuous tests are established by means of particle size distributions and flotation results. Conventional and autogenous grinding circuits are discussed showing the relationships of the controllable circuit parameters.

Jan 1, 1982

By Narendrakumar A. Chevli

Exploratory work was conducted in the fabrication of integrated circuitry, specifically linear amplifier circuits, by three general methods: 1) monolithic diffused silicon; 2) a combination of metal thin-film and monolithic diffused silicon; and 3) a hybrid of metal films and diffused silicon on an alunina substrate. In these linear amplifier integrated circuits the followzng conditions were desired: very high-frequency response, high voltage gain, and good thermal tracking stability of electrical characteristics. The resulting circuit designs imposed problems of isolation between elements, layout and smallness of size of active elements, and close tolerances on electrzcal characteristics of the passive elements. Interconnection problems for specific designs resulted from the small dimensions involved and the topography of the hybrid fabrication techniques. The desired integrated-circuit characteristics were achieved with the technologies of categories 2 and 3 above. Solutions to the problems imposed by these characteristics lay in the ability to isolate czrcuit elements of small size while providing a layout designed to minimize element-to-element variations. Sufficient freedom in the formation of passive elements was achieved by uniting the metal film and the monolithic silicon technologies. The most satisfactory designs were based on the beam-lead interconnection and isolation technique. SINCE the advent of integrated circuits, major emphasis has been on fabricating digital integrated circuits. Linear circuits require high performance, high voltage, and tighter tolerance components which are not always compatible with the capability of process technology available for fabrication of these circuits into integrated form. Fortunately the growth of newer and improved processes and materials for fabricating integrated circuits has been an accelerated one. This has now made possible the translation of stringent performance requirements of the linear circuits into microminiature integrated circuits of the same performance. In the exploratory work of fabricating high-performance Linear Integrated Circuits—LIC, the following objectives were formulated: i) fabrication of high-frequency transistors such as the type 2N918 isolated on a single silicon substrate; ii) fabrication of medium-frequency transistors having a very high gain at low collector currents such as the types 2N930/2N2484 isolated on a single substrate ; iii) fabrication of tight-tolerance, high-valued resistors having low temperature coefficients of resistance and stable thermal tracking characteristics, these resistors to be fabricated on an active or passive substrate; iv) simultaneous fabrication of complementary transistors—pn and pnp-on the same silicon substrate; v) fabrication of newer active elements such as MOS, FET transistors along with the conventional active and passive elements on the same silicon substrate. State-of-the-art assessment f all the available processes, materials, and technology to meet above objectives indicated that economic fabrication of LIC cannot be achieved by a single technology for all types of linear circuits. Where design and performance of a given linear circuit can be modified and tolerated to the extent of a particular technology, then alone is it possible to fabricate a LIC using a single process technology such as all diffused, planar technology. In order to evaluate this economic breakpoint with design and performance compromise in fabricating LIC, it is essential that a thorough understanding be obtained of techniques, potentials, and limitations of all the various process technology and materials

Jan 1, 1967