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By Robert C. Emmett, Donald A. Dahlstrom

FOR many years gravitational classification has been employed as a basic tool in beneficiation of minerals and coal. While improvements have been made to increase efficiency and fields of application, the basic flow pattern has remained relatively unchanged in most gravitational classifiers. Feed slurry is introduced into a settling pool wherein the coarser solids settle against either an upward or horizontal fluid current, or a combination of both, and are withdrawn in a concentrated underflow stream. The finer solids below the classification point possess too low a settling velocity and thus are primarily swept out through a weir overflow by the bulk of the fluid. Because of its simplicity, efficiency, and low power and maintenance costs, gravitational classification finds a wide acceptance for separations in the range of 20 to 325 mesh.

Jan 10, 1953

By C. W. Lawr

THE ores mined by the Santa Gertrudis Co. at Pachuca, Mexico, are mainly silver-bearing; they also yield some gold and carry a little copper. Strong cyanide solutions are used to dissolve the silver and gold, and the mechanical loss of cyanide at the tailings filter has been considerable. Prior to the year 1923, the pulp, after agitation, was given a 35 to 37-min. wash with barren solution in a Butters-type leaf filter; the discharged slime cake was repulped and pumped into eight Merrill self-sluicing slime presses in which the slime was given a further wash with barren solution for 25 to 35 min., followed by a 10-min. water wash. At that time the barren solution titrated around 0.350 per cent. free KCN and 0.500 per cent. total KCN. (Aero brand cyanide is used.) It can readily be seen that a 10-min. water wash would leave considerable cyanide in the filter cake, which of course was a total loss. This averaged 0.522 kg. (1.15 lb.) KCN per ton of solution. As the daily discharge to. the dam was 1600 tons1 of slime of a 2: 1 ratio of liquid to solid, the value of this mechanical loss of cyanide was an important item and its recovery held alluring possibilities.

Jan 1, 1929

Occasionally it is interesting, and sometimes useful, to review the past for early references to our industry, and to learn of the trials and travail passed through before it arrived where it now is - and the results of such a review follow. Some time ago one of our modern playwrights and poets, Arthur Guiterman, turned to coal, with the following result : Afar in the Carboniferous time I grew in Paleozoical slime, A lepidodendron with boughs on my stem And lepidostrobusea grew out of them. My roots in the mud of the ages I spread And up to the heavens I vaunted my head, I throve in the heat of tropical sun, And now I am coal at two dollars a ton.

Jan 1, 1935

By C. Chu

An investigation has been made of the radial heat-wave process using a mathematical model in two-dimensional cylindrical coordinates. This model considers combustion, convection and conduction inside the reservoir, but only conduction in the bounding formations. From a study of the general features of the process, an important phenomenon has been revealed, namely, the feedback of heat into the reservoir on the trailing edge of the heat wave. The effects of various process variables on the performance characteristics of the process have also been investigated. It was found that up to the time when the combustion front reaches a given point, the per cent heat loss, provided it is not higher than 40 per cent, is approximately directly proportional to the square root of thermal conductivity arid fuel content, but inversely proportional to the square root of gas-injection rate and oxygen concentration. The effecr of reservoir thickness is more pronounced, since halving the thickness doubles the per cent heat loss. The most decisive factor in determining the center-plane peak temperature is the fuel content of the reservoir. Within the temperature range investigated, doubling the fuel content doubles the peak temperature in the early stage, but the rate of decline of the peak temperature is high. Reservoir thickness is also a very influential factor. The peak temperature is lowered when the thickness is reduced; however, the effect of thickness becomes less pronounced when the thickness is high. Reduction of oxygen concentration increases the peak temperature in the early stage but lowers it afterwards because of the higher rate of decline of the peak temperature. Increase in gas injection rate or decredse in thermal conductivity geives a higher peak temperature which stays high for a longer period. The propagation range of the heat wave is chiefly governed by the fuel content of the reservoir. An increase of 0.2 1b/cu ft in the fuel content increases the propagation range by 100 per cent. The propagation range is more than doubled by doubling the gas injection rate, or reservoir thickness, or by reducing the thermal conductivity by 50 per cent. Comparatively, oxygen concentration has less effect on the propagation range. INTRODUCTION Several investigators have conducted theoretical studies of a radial heat wave. Vogel and Krueger1 studied a system with a moving cylindrical heat source of constant temper- ature, considering conduction in the radial direction only. Ramey2 included conduction in the vertical direction in his studies. Bailey and Larkin2 attacked a more general problem where initial well heating, vertical heat losses and arbitrary frontal velocities were included. In all these studies, however, conduction was considered to be the only means of heat transfer. Bailey and Larkin in a later paper included the effects of convection in a study involving both linear and radial geometries. Vertical heat losses were neglected in the radial case. Katz5 studied a similar problem in a one-dimensional radial model, using a heat-loss coefficient to account for vertical heat losses. Selig and Couch6 mployed a cylindrical model and investigated two limiting cases. In one case they considered no heat loss from the reservoir whereas in the other they assumed a constant temperature at the interface between the reservoir and its bounding formations. Thomas' studied a more general case but assumed a permeable bounding formation so that the convection effect is not confined to the reservoir. In the present work a more realistic and more generalized model is used. It involves a two-dimensional cylindrical system with combustion, convection and conduction inside the reservoir, but only conduction in the bounding formations. The purpose is to establish the temperature distribution both inside and outside the reservoir, to study the general features of the radial heat wave process, and to investigate the effects of various process variables on the performance characteristics of the process. THEORY We fist consider a circular porous reservoir of thickness H extending vertically from y = — H/2 to y = + H/2. The reservoir extends from a well bore radius r, to an external radius re. A stream of oxygen-containing gas is introduced into the reservoir through the wellbore. The oxygen-containing gas reacts with the fuel contained in the reservoir and forms a combustion front wherever the prevailing temperature can support the combustion. It is here assumed that this combustion front constitutes a cylindrical surface source of heat having an infinitesimal thickness in the radial direction and extending vertically throughout the whole thickness H. This is designated as Region I. We next consider a Region II corresponding to the upper and lower formations bounding the reservoir, extending from y = — - to y = — H/2 and from y = + H/2 to y = + m. Since r, is very small, we may assume that the two bounding formations have the same dimensions, symmetric with respect to the center plane of the reservoir. In this way, we may take the upper half of the system alone into consideration. In contrast with

By C. E. Mills

Studies of ground movement and subsidence resulting from mining operations cover a broad field. It is also a very important consideration and one that eventually affects nearly every mining operation of any extent. The damage to surface buildings, removal of mine surface plants and replacements of main hoisting shafts must reach an astounding expenditure were these cost figures available over a period of years. Were the subject one of mathematical formula and dependent only on the angle of draw of the walls or country rocks, the problem would be relatively simple. Consideration must be given to depth and extent of workings; structural conditions of the orebodies and enclosing country rock; physical properties of these same rocks, including schistosity, bedding, jointing, slips, dikes, faults, and other structural weaknesses. The method of mining, extent of openings, supporting pillars, and amount of moisture or water underground are other pertinent factors. With such a large number of variable factors, it is apparent that the subject of subsidence is one that must be based largely on experience and results at other mines where conditions are somewhat comparable. In presenting this paper, it is the intent to describe the progressive results of past ground movements at the United Verde, to bring out physical conditions largely responsible for this movement, but to refrain from theorizing on the ultimate extent of subsidence resulting from future mining operations. Geology and Structure1 The ore deposits of the United Verde are of the massive sulfide, schist-replacement type. A structural anticline formed by the intrusion of diorite between bedding planes of steeply dipping and severely folded greenstones and porphyry localized the deposit of sulfide. The mineralized zone is of great horizontal extent varying from 200,000 to 400,-000 sq. ft., and extends from the surface to the lowest levels at a steep dip of from 50° to 75. The irregular interfingering of the sulfide with

Jan 1, 1934

By R. Silent, N. A. Rousselot

The first producing wells completed in the Kettleman Hills arca were noteworthy for their high gas-oil ratios. As a result they became the object of criticism, and controversies arose based on their alleged lack of gas conservation. Ultimately protracted hearings ensued in the District Court of the area, and diverse rulings and subsequent modifications have been handed down affecting the permissible gas-oil ratios. When the Kettleman North Dome Association was formed in April, 1931, and the control of the major portion of the North Dome area vested therein, it was decided to produce only those wells which had a relatively low gas-oil ratio. Among the wells having the highest gas-oil ratio were the Milham Elliott No. 1 (the discovery well) and the Continental Elliott 12-8. drilled as an offset to it. Under the numbering system adopted by the Kettleman North Dome Association, these wells are now known as 88-2P and 1-12P, respectively. Milham Elliott No. 1 was originally drilled to 7236 ft., then redrilled to 7108 ft. The upper portion of the Temblor Horizon produces with a very large gas-oil ratio; production which actually consists of light crude oil with an accompanying large.volume of gas. Little was known as to the location of the Temblor formation at that time but it is now generally accepted that its top was encountered at 6180 ft., giving 928 ft. of penetration. Initial production was estimated at 4000 bbl. of oil and 80 to 90 million cubic feet of gas per day, giving a gas-oil ratio in excess of 20,000 cu. ft. of gas per bbl. of oil. This ultimately increased to a ratio of about 48,000 at the time the well was killed when it was producing about 1100 bbl. of oil and 52 million cubic feet of gas, with a flow pressure of 1200 pounds. The Continental Elliott 12-8 was drilled to a depth of 6876 ft. with the top of the Temblor at 6100, giving a penetration of 776 ft. The estimated initial production of this well was 7000 bbl. of oil and 130

Jan 1, 1933

By J. C. Febles

The use of iron for the precipitation of copper was known at least as early as the fifteenth century. Both Paracelsus and Basil Valentine refer to it in their writings, as early as 1500 A. D. It was used in Peru for this purpose prior to 1637, and at Rio Tinto, Spain, as early as the sixteenth century. The statement has been made repeatedly that in the early history of the mining industry at Butte, the practicability of this method of recovering copper from solution was overlooked, and that enormous quantities of copper-bearing water were allowed to go to waste, the copper in which might easily have been recovered at small cost; and that this oversight on the part of the mine operators was due to ignorance of this method of recovering copper. As a matter of fact, very little copper-bearing mineral was encountered in the mines of Butte until a depth of 400 or 500 ft. had been reached, and in many cases much greater depths were necessary to reach the copper-bearing zone. The water encountered in the upper levels (although in most cases quite highly mineralized) contained little or no copper, and it was only after considerable areas of copper-bearing ore had been uncovered and developed that copper sulphate began to appear in the mine water in any considerable quantity. In fact, the first water that was observed to contain copper carried it in such small amounts as to be of little or no importance. It was only after years of underground work had opened extensive areas of stopes, drifts, and other underground workings, these being subsequently filled with waste, nearly all of which contained small copper values, which became oxidized by exposure to the air and were acted upon by the slowly percolating mineral water, that the recovery of copper from mine water became commercially important.

Jan 1, 1914

By Chester T. Sims, Robert I. Jaffee

The thermoelectric behavior of the Pt—Pt-Re thermocouple and the resistance of rhenium to attack by certain molten metals is discussed. In addition, data are presented on the stress-rupture behavior of drawn wire, the tensile characteristics of rolled sheet, the variation of Young's modulus with temperature, and the effect of specimen size and fabrication method on the work harden ability. Mechanical properties of thoriated rhenium are discussed. This includes data on the effect of thoria in rhenium on tensile properties, ductility, work hardening, and recrystallization. RECENT work by the authors', has described methods of fabrication and some of the physical and mechanical properties of rhenium. Rhenium was established as a high melting, dense, refractory-type metal with favorable mechanical properties. In addition, Todd and co-workers' and others" have studied such properties of rhenium as the work function, specific heat, and the resistance of rhenium to the water cycle. Revelation of these and other properties has led to serious consideration for application as electrical contacts, high temperature thermocouples, and wear resistant materials. chanical properties reported previously,' several additional examinations have been conducted. The stress-rupture behavior and the Young's modulus of rhenium have been investigated at elevated temperatures. Tensile data have been obtained for rolled sheet, and a study of the relative work hardening characteristics of rod, wire, and sheet has been conducted. Variation of Modulus of Elasticity With Temperature—The Young's modulus of a % in. diam annealed rhenium rod was determined from room temperature to 880"C (1620OF). The rod, approximately 6 in. in length, was activated in a transverse vibration apparatus suspended in a furnace. The resonance frequencies of the rod were measured and used to calculate the moduli values. The driven frequency was 569 cycles per sec, and a protective helium atmosphere was used. The data, plotted in Fig. 1, show that the modulus decreases in an approximately linear manner with temperature over the range tested.

Jan 1, 1957

By N. C. J. Ros

The paper deals with pressure gradients occurring in flowing and gas-lift wells, a knowledge of which can be applied to the determination of optimum flow-string dimensions and to the design of gas-lift installations. The study is based on a pressure-balance equation for the pressure gradient. It appears that a pressure-gradient correlation of general validity must essentially consist of two parts-—one part being a correlation for liquid hold-up and the other part being one for wall friction. Dimensional analysis indicates that both liquid hold-up and wall friction are related to nine dimensionless groups. It is shown that in the field of interest only four groups are really important. On the basis of these four groups a restricted experimental program could be selected that nevertheless covered practically all conditions encountered in oil wells. This experimental program has been carried out in a laboratory installation. Three essentially different flow regimes were found. The pressure gradients in these regious are presented in the form of a set of correlations. Comparison of these correlations with a few available oilfield data showed excellent agreement. INTRODUCTION Prediction of the pressure drop in the flow string of a well is a widely known problem in oilfield practice. Accurate data on the pressure gradient of a simultaneous flow of gas and liquid in a vertical pipe are especially useful for the determination of optimum flow-string dimensions. It is well known that with moderate gas and liquid flows such a vertical string acts as a "negative restriction". The pressure drop decreases (1) when the throughput through a given pipe increases, and (2) when at a given throughput the cross-sectional area is decreased. The reason is that, with increasing velocities, the flow becomes more agitated so that the gas slips relatively more slowly through the liquid. With the resulting increase in gas content in the string, the static head decreases. When the area becomes very small, however, the high velocities entail great wall friction, which causes an increase in pressure drop. For a given flow, therefore, minimal pressure drop is obtained by using a certain cross section. This means that, in principle, each well can be provided with an optimum flow string for minimum pressure drop and, hence, maximum possible production rate. The procedure for the selection of the optimum string has been discussed by Gilbert.' A necessary tool in the procedure, however, is accurate knowledge of the pressure gradient to be expected for various values of the governing variables. Another application of pressure-gradient data lies in the field of gas-lift practice: they provide a means of determining the optimum gas-injection rate, optimum injection pressure and optimum injection depth. Much work has already been done in the study of the pressure gradient of vertical gas-liquid flow. Poett-mann and Carpenter2 presented a pressure-gradient correlation based on measurements in wells. This correlation has been found to provide accurate predictions in high-pressure wells and in high-production wells for flow through both tubing and annuli.2-5 However, when their method is checked on low pressure-low production wells or on wells with viscous crudes, serious discrepancies are found. As we shall see in the next section, this is due to the fact that their correlation factor, representing all irreversible energy losses, is given as a function of only one correlation group. Some important variables, such as gas-liquid ratio and liquid viscosity, are not incorporated in this group so that their specific effects are not accounted for. To study also the mechanism of vertical gas-liquid flow outside the ranges covered by the Poettmann-Carpenter publication and extensions, a laboratory investigation has been carried out. This study is founded on a pressure-gradient equation that is based on a pressure balance. To reduce the number of test runs required, a dimensional analysis has been carried out, followed by a selection of relevant dimensionless groups. These groups guided a subsequent experimental study, and with their aid the experimental program could be minimized while still covering the majority of the situations encountered in oilfield practice. In this paper the choice of a formula for the pressure gradient is discussed first. This is followed by a brief description of the experimental setup. Subsequently, the dimensional analysis is discussed and the relevant dimensionless groups are selected, resulting in the experimental program required. The general relationships of pressure gradient and liquid hold-up are then described; various flow patterns and a certain flow instability (so-called "heading") are discussed and a set of correlations is presented which shows a good agreement with the measurements and a few available field

By Seymour Fiekowsky, Alvin Kaufman

Taxes are compulsory charges levied by a government for its support. They are usually paid to support the general services provided by government rather than special services (such as safety inspection). The latter are normally supported by user charges often called license fees. Taxes are used by national governments not only to raise money but also as a part of fiscal policy. As such, taxes are used to stimulate or deflate the economy, as an incentive to save or invest, as a means of allocating national resources, and as a means of redistributing income. In our discussion, we will deal only with those facets of the subject that relate specifically to the mineral industry. In doing so we will deal with taxes levied on all industry in a generalized way and only insofar as it affects our industry, but at some length on those portions of the tax system related directly to the mineral industry. It is not our intent to provide a "cookbook" for computing taxes, but rather to present some of the policy issues that bedevil those who must develop our tax policies. MINERAL TAXES The mineral industry is subject to the full range of taxes levied by governments. These include taxes on income, property, and sales, as well as excise and severance taxes. The latter are somewhat similar to a royalty in , that such taxes are levied either ad valorem or per unit of output. Severance taxes most commonly are charged to oil and gas output, although coal, salt, sulfur, and iron ore production also have been taxed in this manner. The major governmental advantage of the severance tax is the administrative ease of collection. On the other hand, it poses an addition to cost independent of profitability. As a consequence, the severance tax can cause premature abandonment if mineral product prices do not rise sufficiently to cover it. Such a rise may not occur if differential tax rates are levied by the various states. Property taxes normally are levied on all property owners, including mineral owners. The major difficulties in this kind of tax, in so far as mining is concerned, are erratic valuation coupled to the inherent problems involved in assessing a property where the extent and richness is chiefly unknown. The impact of these taxes, including state income taxes, is reduced somewhat, as they are usually deductible from gross income as a business expense with a consequent lowering of national income taxes. The net cost of severance, property, sales, and state or local

Jan 1, 1976

By Otto H. Henry

The purpose of this investigation was to determine the equilibrium diagram of the lithium-magnesium pair as a first step in studying the possible usefulness of these alloys as ultra-light structural materials. Review of the Literature The behavior of lithium towards magnesium was first investigated by Masing and Tammann.(1)† In order to prevent oxidation the alloys were made in iron tubes under an atmosphere of hydrogen; temperatures were measured with a glass-protected thermocouple. These investigators found that lithium and magnesium form two series of solid solutions separated by a miscibility gap between 85 and 95 per cent magnesium; that the alloys with 81 and 95 per cent magnesium showed a homogeneous structure under microscopic examination, while the alloy with 89 per cent magnesium contained two distinguishable crystallites; that the curve indicating the beginning of crystallization rises from the melting point of lithium to that of magnesium; and that no compounds of lithium and magnesium are formed. The equilibrium diagram was not plotted because no definite data were obtained for determining the solidus and the position of the miscibility gap in the solid state. The difficulties encountered in this investigation were: (1) that it was necessary to heat them as high as the melting point of magnesium in order to obtain homogeneous melts; at such temperatures the alloys attacked the glass protecting the thermocouple; and (2) that at temperatures above 400" C. the lithium united with the hydrogen to form lithium hydride, thus contaminating the alloys. By applying the same methods as those used in the lithium-magnesium system, Masing and Tammann determined the equilibrium diagram of the

Jan 1, 1934

By Alden B. Greninger

THE time-honored description of the growth of metal crystals to form polycrystalline aggregates is. one in which two important steps are considered: (1) nucleation, and (2) dendritic growth, each dendrite starting from its individual nucleus and resulting (upon slow cooling, assuming no solid phase changes) in a macrograin. This picture of the process of crystallization is incomplete, and it is with the hope of enlarging upon it that the following summary and correlation of experimental results are given. MOSAIC STRUCTURE For an exact definition of the mosaic structure of metal crystals-if, indeed, one can be found that will hold for all metals-one must await the results of much experimental work in this field. The writer's investigations have been. confined almost entirely to copper and a few of its alloys. The following terms are proposed, and will be used in this report: Macromosaic Structure1.-Large-scale mosaic structure; more specifically, mosaic structure of a scale large enough to produce splitting of Laue spots on back-reflection Lane X-ray patterns2. The deviation from exact parallelism of neighboring macromosaics varies from a few

Jan 1, 1935

By Gilbert Doan

AN extensive program of investigation is being carried out at Lehigh University in the study of arcs and arc welds of high-purity iron1, spon-sored by the Engineering Foundation. The part of that program reported in the present paper deals with welds made of high-purity iron in an argon atmosphere and for comparison with them welds made of the same iron in ordinary air. Welds of commercial steel also were made in argon and in air. The primary purpose of the study is to discover the basic physical constants of iron welds when not contaminated either by impurities in the iron or by the action of oxygen and nitrogen of the air during welding. Upon these constants can be founded such future studies as will determine what effects the various impurities and alloy elements present in steel have upon its welding characteristics, and what influence is exerted by the action of oxygen and nitrogen. The welding of steel involves such a multitude of variables, both of composition and of procedure, that development in the fabrication of this most important metal has necessarily been slow, wasteful, and in many instances discouraging. In the present investigation, the simplest possible condition has been selected; namely, iron practically free from contamination and a nonparticipating atmosphere, the inert gas argon. This simplification reduces the number of variables to a point where more rigid control of the system is possible. Although this study is significant for the contributions it makes to the science of steel fabrication, yet it is hoped that it will not be without value also in increasing knowledge of the nature and behavior of iron and steel in general. From the standpoint of open-hearth practice, and to

Jan 1, 1936

By W. I. Duvall, D. E. Stephenson

A theoretical solution is given for the energy that is radiated outward when either a cylindrical or spherical cavity located underground in a uniform stress field is suddenly created or enlarged. The method of derivation shows that the stress field in the solid rock surrounding the opening does work on the rock because of elastic displacements that result when the size of the cavity is increased. The amount of this work is sufficient to account for both the increase in the strain energy in the rock surrounding the opening and the seismic energy that radiates outward. Thus, the source of the radiant seismic energy is mainly the gravitational potential energy and not the strain energy stored in the rock. The amount of the radiant seismic energy is directly proportional to the volume of the rock removed from the opening or relieved of stress. Seismic energies from rockbursts are compared with earthquake energies. Also, the amount of gravitational potential energy released by underground explosions is calculated and found to be small compared to the seismic energy generated by the detonation of the explosive. A review of the early literature on rockbursts shows that a number of investigators calculated the amount of energy released by rockbursts. 1-5 However, none of these papers give the formula used to make these calculations or a reference to the derivation of any formulas. The general impression that one obtains from these early papers is that the main source of the seismic energy released by rock-burst is the strain energy stored in the rock before it is fractured. However, a few of the early papers appear to have considered the solid rock at a distance from the mine opening as a possible source of the seismic energy. Recently Black and starfield7 gave a theoretical solution for the strain energy in a stressed plate with and without a circular hole. Also, Press and Archambeau8 gave the theoretical solution for the seismic energy released when a spherical cavity is created in rock subjected to a three-dimensional stress field. Both of the above theoretical papers start with the condition of no opening and calculate the strain energy before and after the opening is suddenly formed. Neither of these papers appear to have calculated the work done by the applied stress field as the cavity is enlarged. The rockburst problem associated with deep mining is concerned with the failure of the solid rock surrounding an underground opening. Therefore, it seems appropriate to consider theoretically the problem of suddenly enlarging the size of an existing opening. The purpose of this paper is to present the theoretical solution for the energy that is available for release as seismic energy when an underground circular tunnel or spherical cavity is suddenly enlarged in diameter. To keep the mathematics as simple as possible, a uniform radial applied stress field is assumed and the rock is assumed to be isotropic, homogeneous and perfectly elastic.

Jan 1, 1965

By F. Hass, N. W. Lord

This paper gives the results of experiments conducted in the metallurgical laboratory of the Ohio State University with the objects of determining: First, the calorific powers of a number of coals in general use in Ohio; and second, how far ordinary analytical methods could be used as a basis for computing these values. Incidentally a test of the performance of the calorimeter was involved. The chemical work has been carried on in the department for some time, so that the whole investigation has extended over three or four years. The Mahler calorimeter was purchased from L. Golaz in Paris, and is practically identical with the one described and figured by Mahler in his monograph "Contribution a l'Etude des Combustibles," from the Bulletin de la Société d' Encouragement pour l'lndustrie Nationale. A figure and description is also given by William Kent in The Mineral Industry for 1892, page 97. There were furnished with the instrument three thermometers covering a range of from 7°.5 C. to 31° C. Thermometer "A" (17°.5 to 31°) was carefully calibrated by reading the ends of a thread of mercury in sixteen positions covering the whole scale, supplementing this by readings of longer threads and deducing the errors of scale by the method published by Prof. Holman in the Technology Quarterly of September, 1887. The maximum error of a single reading was found to be 0°.0042 C. Thermometer "B" (13° to 25°) was compared directly with " A " over the scale common to both, and a variation was found of 0°.0145 C. for 7°.5 (or 0°.002 for l°) of the scale. Thermometer " C" ('7°.5 to 19°.0) was omitted from the cornparison, as it was rarely used, being only required where measurements were made at low temperatures. From the

Jan 1, 1898

By P. K. Strangway, H. U. Ross

Briquets consisting of pure artificial magnetite, pure artificial hematite, and mixtures of the two were reduced by hydrogen in a loss-in-weight furnace at temperatures in the range 500° to 1000° . The rate of reduction of the pure hematite briquets increased continuously with increased temperature. In contrast, the pure nmgnetite briquets exhibited a pronounced rate ninimutn at about 700°C. Metallographic studies of partially reduced briquets rerlealed that, at this temperature, the he.matite samples reduced in a topo-chemical manner while the magnetite ones reduced uniformly throughout, and after partial reduction their cross sections contained a mixture of iron and unreacted wustite grains. No iron shells could be detected on the surfices of any of these uwstite grains. X-ray diffraction investigations indicated that these grains had a rzinimum lattice parameter when they had been formed at the rate rninimum temperature. Also, it was found that an activation energy of 41,000 cal per mole zoas required for reduction when only these wustite grains were present. Thus, it is suggested that the overall reduction rate of the rnagnetile su?nples at temperatures in the range influenced by the rate nzinirnum phenomenon was limited by the rate qf iron ion diffusion in the unreacted wustite grains. THE rate minimum phenomenon, which has often been observed when reducing iron oxides at a temperature of about 700°C, is one of the most interesting, yet unresolved, problems in the field of reduction kinetics. Basic principles of chemical kinetics and 'In some instance, a second rate minimum has been observed at about 900°C. Since most investigators are in agreement that this minimum is directly related to the transformation from a to y iron (which takes place at 911°C) and since it was not encountered during the present reduction tests, it will not be referred to in this vaver. fundamental laws of diffusion all agree that, as the temperature is increased, the rate of reduction should also increase. However, with certain ores, it has been found that their reduction rate actually decreases with an increase in temperature up to some value X where a minimum reduction rate is reached. With further temperature increases beyond X the rate becomes more rapid again. Temperature X is usually referred to as the "rate minimum temperature", while the overall type of behavior constitutes the "rate minimum phenomenon". This phenomenon has been reported by numerous investigators. They have found rate minima during the reduction of both artifiial' and natural374 magnetites and artificia15j6 and natural5" hematites. Rate minima have been observed when reducing high-purity material2 or low-grade ores,3'4 when studying particles in the micronsize range5 or relatively large agglomerates,g10 and during reduction with either hydrogen7 or carbon monoxide.11"2 Previously, this phenomenon has been attributed to many factors; these include sintering and recrystallization of the iron formed during reduction374 changes in microporosity of the ore upon redction,"" formation of dense iron shells around retained wustite grains,11716 and chem-isorption,17 to name only a few. However, most investigators who have reported a rate minimum merely speculated as to what seemed to influence it and they did not examine the fundamental causes. Consequently, the present experimental study was initiated in order to evaluate the basic factors which could be associated with this phenomenon. MATERIALS AND METHODS The experimental techniques, followed during this investigation, are similar to those which have been described previously.18 The chemically pure magnetic powder was prepared by partially reducing Fisher reagent-grade hematite with a gaseous mixture of carbon monoxide and carbon dioxide in a rotating-drum furnace. Three-quarter-inch diam cylindrical briquets which weighed about 12 g were formed from this magnetite powder and pure hematite powder. All of the briquets were sintered while they were slowly raised through the 1200°C hot zone of a vertical tube furnace. An argon stream was continually flushed through this furnace in order to prevent oxidation of the magnetite briquets, while in the case of the pure hematite briquets sintering was carried out in air. The sintered hematite briquets had a density of 5.06 g per cu cm while the density of the sintered magnetite briquets was 4.27 g per cu cm. The sintered briquets were reduced by purified hydrogen in a loss-in-weight furnace at temperatures in the range 500" to 1000°C. In all instances, the critical reducing gas velocity was exceeded and, in order to ensure that the results were reproducible, duplicate briquets of each type were reduced under each set of experimental conditions. A continuous record of the weight loss during reduction was obtained with the aid of a Statham transducer. The present experimental setup was capable of detecting a change in weight as small as 10 mg. Since a weight loss of over 2 g usually occurred during each reduction test, an accuracy of better than 0.5 pct of the total weight loss could be achieved. RESULTS AND DISCUSSION Reducibility Tests. In the first set of experiments, pure hematite and pure magnetite briquets were used.

Jan 1, 1969

By C. K. Stoddard, R. G. Knickerbocker, E. T. Leidigh, R. R. Lloyd, K. L. Mattingly

DURING July 1941, a study was initiated at the Boulder City Experiment Station of the Bureau of Mines on proposed methods for the production of magnesium metal. The major emphasis was placed upon development of a process that required minimum reliance upon the sale or utilization of by-products to meet economic competition from processes already in operation. It was felt that only through the development of such a process could the nation's vast resources of dolomite and low-grade magnesite that are contiguous to large blocks of firm power be properly utilized. During the course of exploratory tests on electrolytic and electrothermic processes, it was noted that fused magnesium chloride would dissolve appreciable quantities of magnesium oxide in the presence of small amounts of boric oxide. The use of such a solution in an electrolytic cell employing a graphite anode and a steel cathode caused the deposition of magnesium at the cathode and the evolution of carbon oxides at the anode with minimal amounts of chlorine The original results were sufficiently encouraging to justify further investigation on an enlarged scale, since the process seemed to present advantages over other proposed processes 1.2 for the direct use of magnesium oxide in a fused chloride electrolyte. When work on a larger scale was initiated it was found that the addition of boric oxide to the electrolyte resulted in dispersion of metal and constantly decreasing current efficiency. However, by this time solubility studies had shown that magnesium oxide was sufficiently soluble in magnesium chloride melts containing no boric oxide to effect the same anode reactions, and development work was continued. Over two years of development work have been carried out, and considerable work remains to be done. It is desired to emphasize the fact that many of the difficulties met require a long period of continuous operation before they become serious enough to affect operation of the cell. ACKNOWLEDGMENTS This paper is one of many reporting on various aspects of the Bureau of Mines' program initiated in August 1939 by passage of the Strategic Minerals Act the scope of which was greatly expanded by subsequent legislation. Some of these papers are published as war minerals reports. others as bulletins, technical papers, reports of investigations

Jan 1, 1945

By D. V. Doane, G. A. Timmons, W. G. Scholz

Molybdenum of high purity can be produced by direct dissociatiott of commercial molyhdenm disulfide in vacuo at 1600° to 1700°C (2910° to 3090°F). The Product is lower in oxygen than commercially available molybdenzdm powder. Analyses of ingots arc-cast from commercial molybdenum powder, hydrogen-re-cluced from animonium molybdate, and from thermally dissociated molybdenum disulfide indicate that the levels of chemical impurities in these ingots are similar. Equipment now in operation will produce 100-lb hatches of powder product. The paper describes development of processing equipment, control of processing varzahles, handling of the product, and evaluatiotl of the melal produced. MOLYBDENITE (molybdenum disulfide) can be decomposed by heat in the absence of oxygen to produce elemental molybdenum and sulfur, which is evolved as a gas. The temperatures required for the dissociation are above 1370°C (2500°F); the sulfur must be continuously withdrawn to permit the reaction to proceed to completion. This is accomplished by continuous evacuation of the thermal dissociation chamber and condensation of the gaseous sulfur in another part of the system. Cognizance of the fact that the dissociation takes place in two steps is important in controlling the process. Basically, the molybdenite dissociation process has two potential advantages as a method of produc- ing pure molybdenum: 1) The materials entering into the process contain little or no oxygen. Since the process is carried out in vacuum at high temperature, the quantities of interstitial oxygen, nitrogen, and hydrogen in the product should be very low. 2) The process is more direct than the commercia1 method of producing high-purity molybdenum. In the conventional process, molybdenite is roasted to molybdic oxide, the oxide is purified first by sublimation, then by conversion to ammonium molybdate, and finally, the molybdate is reduced in a hydrogen atmosphere (usually in two steps) to the metal lic molybdenum powder. This paper presents a description of the stages in scaling-up of the dissociation equipment and an account of attempts to evaluate the molybdenum produced by thermal dissociation, rather than a report of a fundamental study of the dissociation reaction. Since little has been written on the subject, it is appropriate, before detailing the development of the process, to review briefly the research that has been conducted over quite a period of years. LITERATURE SURVEY The first accounts of the possibility of thermal dissociation of the mineral molybdenite were re-

Jan 1, 1962

By H. H. Haung, J. D. Miller, E. F. Pereira

The chemistry of copper extraction from ammoniacal solutions by hydroxyoxime extractants was studied Equilibrium measurements were made by shakeout experiments with subsequent analyasis of the aqueous and/or organic phases The kinetic experiments were carried out in a single drop reaction cell in order to establish the details of the intrinsic reaction kinetics for this system. Equilibrium measurements Indicated that the extraction involves complete displacement of ammonia ligands from the coordination sphere of the cupric ion by the extractant molecules The extraction reaction has the following stoichiometry

Jan 1, 1981

By William A. Johnson

THE mathematical analysis of diffusion curves in solid metals is Carried out ordinarily by analogy with the flow of heat in a continuous medium and no account is taken of the fact that the materials involved are composed of discrete particles that move discrete distances at irregular intervals. It is possible to treat the problem on the basis of simple assumed atomic mechanisms, in which case, because of the small scale of the elementary process compared to the gross effects observed experimentally, the two procedures lead to the same expression for the variation of concentration with distance. Thus, for engineering purposes, the usual methods are quite satisfactory. If, on the other hand, our purpose is to go beyond the mere collection of data, however desirable this may be, it is necessary to recognize and understand the factors that are of fundamental importance. One factor that has not hitherto been considered when dealing with solid metals is the difference in atomic weights of the isotopes of a single metal. While all the atoms of a given element are alike chemically, their weights may vary by a small but significant amount, and atoms of different weights may have different diffusion rates. With gases this variation in isotopic weight produces a change in the rate of diffusion by a factor inversely proportional to the square root of mass. While, except for the lightest gases, this is not a large effect, it is, for example, sufficient to permit a considerable concentration of one isotope at the expense of others. If metals exhibit a similar phenomenon, some modification of the analysis of the diffusion process will be required, since the different isotopes of a given metal will have different probabilities of moving and the heat-flow analogy will contain a fundamental error. This situation cannot be rectified by using a diffusion coefficient based on the average probability of moving, and it can be shown that even when the diffusion coefficient is independent of composition, the diffusion curve will not agree with the simple theory except in the rare cases where only one isotope exists; e.g., gold. If, however, the mass effect in the solid state were no larger than in the gaseous, the errors arising therefrom in the analysis of ordinary diffusion curves would be quite negligible. Nevertheless, our desire to obtain all possible information concerning the details of the diffusion process, and the possibility of diffusion in the solid state as a means for separating isotopes are cogent reasons for undertaking an experimental study to determine whether isotopes of different masses diffuse at different rates. EXPERIMENTAL PROCEDURE If isotopes of different masses diffuse at different rates, the ratio of the concentration of one relative to another will vary with the distance from the diffusion inter-

Jan 1, 1946