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By Robert Franke

(Butte Meeting, August, 1915.) IN view of the prominence which the conical mill has attained in the fine-crushing field within the few years since its introduction, the following comparison with its more mature forerunner, the Chilean mill, based on extensive tests, is submitted in the interest of the milling profession. Soon after designing the concentrating plant of the Miami Copper Co. in 1909, the Hardinge conical mill made its appearance in the milling forum. Its possibility as a suitable crushing device for the plant was well recognized, but in view of the lack of commercial demonstration, at the time, as to capacity, efficiency for desired product, and the still more uncertain factors of cost of maintenance and power consumption, it was deemed that the immediate adoption of this machine throughout the plant would be a hazardous undertaking. For these reasons it was decided to equip the majority of the imme diately required units of the plant with Chilean mills, the fine-crushing proficiencies of which were better known, and one section with Hardinge mills, to serve as a test unit for the guidance of future installations and replacements. Thereby, after 1.5 years' operation with both types of mills, a thorough test as to metallurgical efficiency and cost economy has been obtained. The conical mill used in these tests is the 8-ft. Hardinge pebble mill, having a cylinder 22 in. in length. The cylindrical portion of this mill is lined with cast-iron liner plates, and the conical extensions with silex bricks bound together by cement. Each liner plate carries a projecting lifter, the function of which is to increase the height of drop of the lifted material. Danish No. 5 pebbles, obtained from the coast deposits of Denmark, are used for the grinding charge. The Chilean mill used is a fast-running, 3-roller, 6-ft. Saturn mill, with screens of 0.037-in. opening. The feed to these mills is the oversize of Callow screens having 0.029-in. openings, which follow rolls crushing to 0.5 in.

Jan 7, 1913

By W. B. Heroy

ONLY through the mineral fuels can large amounts of energy be transported to great dlstances and stored for long periods for future use. Coal has the advantages over oil of greater safety of handling and smaller losses in storage. But oil is, in the present stage of technical advancement, the more economical source of liquid fuel for internal-combustion motors. No method for direct use of coal in such motors has been developed that can compete with petroleum products. The automoblle engine and the airplane motor are designed to make the most effective use of gasoline.

Jan 1, 1944

By William F. Campbell

One of the deepest coal operations today is the Springhill No. 2 mine of Cumberland Railway & Coal Co., subsidiary of Dominion Coal Co. Ltd. Mining is now conducted at a slope distance of 14,000 ft, with 4400 vertical ft of cover. The record of Springhill No. 2 can be said to contain the history of bumps in the Province of Nova Scotia. The Springhill coal field forms part of the Cumberland field of Carboniferous age. There are seven mineable fields in the area, numbered in the order they were discovered. Mining has been carried on in all but the No. 4 and 5 seams, but present operations are confined to the No. 2. Fig. 1 shows a vertical section through the seams.

Jan 9, 1958

By J. L. Huiatt, G. M. Potter, R. B. Tippin

The US Bureau of Mines and Great Salt Lake Minerals and Chemical Corp. have developed a froth flotation process for concentrating potassium salts from Great Salt Lake solar evaporites containing about 6% K2O. The crude evaporites, which were predominately halite (NaCl) with smaller amounts of kainite (KCl.MgS0, 2.7Hp0) and schoenite KeS0,MgS04.6H,0), were conditioned in a saturated brine solution., thus converting nonfloatable kainite to the floatable mineral schoenite. Schoenite was then selectively floated with a medium-molecular-weight fatty acid. Continuous small-scale pilot-plant testing indicated that 80% of the potassium could be recovered from the crude evaporites in flotation concentrates assaying about 13% K2O.

Jan 1, 1976

By Per-Martin Sandgren, Alrik Anttila

LKAB's ores have specific mineralogical properties that make them especially suitable for the production of supergrade concentrates. Conditions are particularly good for this purpose at Malmberget, where a concentrate for high-purity sponge iron production has been produced for many years. This product assays approximately 71.5% Fe and 0.20% SiO2. Potential exists for still further improvement. In recent years, the production of fractioned concentrates has been started. The material lies within the size range 74-125 µm and the approximate chemical analysis is 71.4% Fe and 0.30% SiO2. Other special products are under discussion. Malmberget ores are also suitable for the production of high- purity direct reduction pellets with a SiO2 content below 1%.

Jan 1, 1983

MEN AVAILABLE Engineering Manager, many years' experience in design, construction and operation of industrial plants and mining properties, requiring a knowledge of mechanical, electrical, civil and mining engineering. Have directed many men and engineers working on foregoing projects. Domestic and foreign experience. Now available. M-702. Mining Engineer, 36, married. Thirteen years' experience underground mining operations; exploration, development, mine evaluation, cost estimation and job evaluation. Registered Professional Engineer. Employed. Available reasonable notice. M-697. Mining Engineer, B.S. plus 2 years' pre-law. Three years' experience; completed training program all phase open pit and underground. Last 2 years sintering, nodulizing and wash plants. Varied pre-professional job experience. Veteran, 32, married, 2 children. Available immediately. Will consider any location. M-703.

Jan 1, 1952

By E. C. Wright

The following article is based on observation of college graduates entering the steel industry in technical work made during the Past 25 Years, the first five of which were spent as a college instructor in two engineering schools, and the last 20 in the employ of a large steel company that has hired hundreds of engineering graduates for steel-mill operations. The college graduates encountered during this period have come from many colleges representing schools in Eastern States, Midwestern Universities, many Southern colleges, and many smaller colleges and normal training schools mostly in western Pennsylvania and Ohio. The college training of these students for engineering work naturally has varied widely and the educational qualifications of the entrants have been in many ways different. It was found at an early date that graduates of standard engineering colleges were much more adaptable than graduates in science from nontechnical schools. The engineering students seemed to be more suited to actual work in steel plants and in general were better able to grasp a knowledge of the operations they observed. However, although the graduates of engineering schools have had somewhat better training in physics, mathematics, and engineering, it has been a general and continual observation that most of the students employed have had inadequate training in the fundamental sciences. Since this discussion relates entirely to metallurgical engineers it should be emphasized that students taking metallurgical engineering courses in college seem to be poorly trained in organic chemistry-physics, physical chemistry, thermodynamics, and any higher form of mathematics than simple calculus. It has been noted frequently that young engineers faced with problems in a mill that involve some mathematics generally flounder badly, and that they have little conception of physical chemistry. Another common deficiency lies in the young graduate's lack of knowledge of where to look for the more detailed literature on any subject. He reverts instinctively to some college textbook whose coverage is usually very elementary. It is recommended that such textbooks contain a bibliography of the source literature. and that students be taught to use the original data. Many of the students had had previous courses in college dealing with metallurgical work such as steel melting, metallograhy, etc.r but it was found that their grasp of these subjects was extremely sketchy. It was soon realized that an ordinary engineering graduate could be taught more about steel melting and manufacturing processes in a few weeks in a plant than he could learn in a college course on such subjects. A similar statement may be made regarding the ability of students to conduct laboratory work. Their lack of technique and skill in handling equipment and setting up experiments was soon apparent. It became neces-

Jan 1, 1948

By E. C. Wright

The following article is based on observation of college graduates entering the steel industry in technical work made during the Past 25 Years, the first five of which were spent as a college instructor in two engineering schools, and the last 20 in the employ of a large steel company that has hired hundreds of engineering graduates for steel-mill operations. The college graduates encountered during this period have come from many colleges representing schools in Eastern States, Midwestern Universities, many Southern colleges, and many smaller colleges and normal training schools mostly in western Pennsylvania and Ohio. The college training of these students for engineering work naturally has varied widely and the educational qualifications of the entrants have been in many ways different. It was found at an early date that graduates of standard engineering colleges were much more adaptable than graduates in science from nontechnical schools. The engineering students seemed to be more suited to actual work in steel plants and in general were better able to grasp a knowledge of the operations they observed. However, although the graduates of engineering schools have had somewhat better training in physics, mathematics, and engineering, it has been a general and continual observation that most of the students employed have had inadequate training in the fundamental sciences. Since this discussion relates entirely to metallurgical engineers it should be emphasized that students taking metallurgical engineering courses in college seem to be poorly trained in organic chemistry-physics, physical chemistry, thermodynamics, and any higher form of mathematics than simple calculus. It has been noted frequently that young engineers faced with problems in a mill that involve some mathematics generally flounder badly, and that they have little conception of physical chemistry. Another common deficiency lies in the young graduate's lack of knowledge of where to look for the more detailed literature on any subject. He reverts instinctively to some college textbook whose coverage is usually very elementary. It is recommended that such textbooks contain a bibliography of the source literature. and that students be taught to use the original data. Many of the students had had previous courses in college dealing with metallurgical work such as steel melting, metallograhy, etc.r but it was found that their grasp of these subjects was extremely sketchy. It was soon realized that an ordinary engineering graduate could be taught more about steel melting and manufacturing processes in a few weeks in a plant than he could learn in a college course on such subjects. A similar statement may be made regarding the ability of students to conduct laboratory work. Their lack of technique and skill in handling equipment and setting up experiments was soon apparent. It became neces-

Jan 1, 1948

By P. W. Gilles, B. D. Pollock

THE pioneering work of Steinitz1 and Steinitz, Binder, and Moskowitz2 has shown conclusively the existence at high temperature of two additional phases in the molybdenum-boron system and thus brings to a total of six the number of structures appearing in this system. To the structures Mo2B, MOB, and Mo2B5 they have added MO3B2, a new -MOB form, and have shown that MOB,, which has the same range of composition as Mo2B5, is only a high temperature structure of the latter. This solid solution, interestingly enough, includes neither of the compositions corresponding to the stoichiomet-ric compounds, MOB, or Mo2B5, but rather at all temperatures has intermediate values of composition. These workers have also, in the course of their work, measured melting points, transition temperatures, eutectic and peritectic points in the system and have shown that Mo3B2, because of its dispro-portionation at low temperature to Mo2B and MOB, is stable only in a limited high temperature range. During the course of the present work on the vaporization properties of the molybdenum-boron compounds, a few transition temperatures were observed. When the report of the other workers appeared, it was decided to repeat, in part, their study of the system. As a result, considerable evidence has been obtained that substantiates the specific kinds of melting processes they report as well as the general features of their diagram. However, a marked difference was found between the temperatures they report and the ones observed in this study, with the latter being higher. The purposes of this paper are to present the evidence obtained in this laboratory that verifies their diagram of the system, to give some important temperatures in the system, to compare them with those previously published, and to seek an explanation of the difference. Samples The metal starting material was 400 mesh molybdenum powder with a purity stated by the manufacturer to be 99.9 pct. The initial treatment, designed to remove volatile contamination, consisted of heating in a vacuum for 10 min to a temperature of from 800" to 1000°C during which a loss of 0.3 to 0.4 pct occurred. An assay following this treatment showed it to be 99.4 pct pure, with the principal impurity probably being oxygen. The boron starting material was obtained from the Cooper Metallurgical Laboratories and the Fair-mount Chemical Co. as 325 mesh powder with manufacturers' analyses of 99 pct or better. Initial treatment consisted of heating in molybdenum in a vacuum at about 1700°C for 10 min. During this time a loss of 3.5 pct occurred. An assay following this treatment showed the different samples to have purities ranging from 95.5 to 99.0 pct with iron and carbon as the principal impurities. Following the initial treatment, the elements were combined to form stocks of Mo2B and MOB by heating pressed mixtures in a vacuum to 1100" to 1200°C to accomplish reaction and to 1500" to 1900°C for a few minutes to evaporate the more volatile impurities. Analysis of the two compounds for boron by a modification of the method of Blumenthal3 and for molybdenum by the lead-molybdate method indicated them to have purities greater than 99 pct. The individual samples to be studied had compositions in the Mo2B-MOB range and consisted of mixtures of the stock compounds. Procedure As is usually the case in high temperature work the selection of containers for the samples posed some problems. For vapor pressure studies tantalum crucibles, allowing little contact with the pressed samples, were used and some of the observations made during these experiments are pertinent to the study of the phase diagram. Most of the experiments, however, were performed in graphite containers, as were those of the previous authors. Two kinds of spectroscopic grade graphite crucibles were used. One was a % in. cylinder, 3/4 in. high, containing seven 3/16 in. holes drilled 1/2 in. deep into which were packed samples of the different mixtures weighing 250 to 500 milligrams. The other, consisting of separate crucibles, was prepared by drilling 3/16 in. holes, 1/2 in. deep into 1/4 in. graphite rods % in. long. The 7/8 in. cylinder was heated directly by induction while the small crucibles were packed in a tantalum heating element for induction heating. All heating was done in a high vacuum system in which the pressure was generally less than 1x10-5mm and never rose above 2x10-5mm when the samples were hot. The general pattern of the heating in graphite was to heat rapidly to a temperature somewhat below the desired one, then to raise the temperature slowly. The samples were held for 2 to 5 min at the maximum temperature, which in all cases was far higher than that needed to produce reaction. The short time was employed to reduce possible contamination by the crucible material and to reduce composition changes that would occur because of vaporization. After examination following the heating, the samples were reheated to a higher temperature. Temperatures were measured with a Leeds and Northrup disappearing filament optical pyrometer, certified by the National Bureau of Standards, by sighting through a window at the top of the vacuum

Jan 1, 1954

By Robert Laurich

Chuquicamata pit was opened in 1915 with steam shovels and steam locomotives brought down from the Panama Canal excavation project. With expansions in the early years, more steam locomo¬tives were brought into the mine. IMPROVED LOCOMOTIVES During the period 1927 to 1937, electric locomo¬tives were purchased and main line and bench tracks were electrified. Third rail was installed up to the working areas. At first, the locomotives were equipped with batteries for service at the shovels, but charge life was too short and they were con¬verted to use the third rail and a reel with 3000 ft of trailing cable for service in the loading area.

Jan 11, 1959

By I. E. Rosenzweig

GEOPHYSICAL prospecting by earth-resistivity methods is frequently applied to investigation of structural problems in geology. Fig. 1 indicates a scheme of the general arrangement used in these methods of measurements. The battery (or generator) E is connected with two "current electrodes" II and 12. The current of intensity J, supplied by this battery, passes through the earth between these elec- FIG. 1.-GENERAL ARRANGEMENT OF APPARATUS. trodes. A potential difference U will be measured between two other electrodes V1 and V2, called "potential electrodes." According to the configuration of electrodes (Fig. 1), the resistivity of a homogeneous soil results from the formula p = 2pcaU/J [1] where c=1/a/b11 - a/b12 ? (a/b21-a/b22) [2]

Jan 1, 1938

By Malcolm J. McPherson, Michael Hood

Sunnyside Mines, owned and operated by the Kaiser Steel Corporation, are situated near the city of Price, Utah. The complex comprises three adjacent mines, named simply Nos. 1, 2 and 3, all connected underground. Two seams, the upper and lower Sunnyside have been worked. These dip at about 10 percent to the north-east. The surface cover is variable due to the mountainous nature of the topography. The Sunnyside upper seam varies from 5 1/2 ft (1.7m) to 9 ft (2.7m) In thickness whilst the lower seam remains at about 6ft (1.8m). The separation between the two seams has ranged from 7 to 45 ft over the mined area (2 to 14m). Longwall mining has been practiced at Sunnyside for over 20 years due to difficulties of roof control encountered when using the roan and pillar system. Number 3 mine is bounded on the north and south sides by mines Number 1 and 2 respectively. Whilst current production is concentrated into Number 1 mine, much of the future of the complex lies in the further development of deeper reserves in Number 3 mine. Workings in this latter mine were curtailed in 1978 due to difficulties in ventilation. Present developments are ventilated partially from the neighboring Number 2 mine where no workings are in progress. The layout of Number 3 mine is illustrated on the schematic Figure 1. Trunk airways extend down dip from the surface at No. 2 Canyon and the Water Canyon for a distance of some 9,600 ft. (2930m). The area between the two sets of trunk airways has been worked extensively in both seams as have the corresponding reserves on either side in the connected adjacent mines. At the present time exhausting fans are sited at the top of a shallow shaft in No. 2 Canyon and an 8 ft (2.4m) diameter shaft sunk to a depth of 1013 ft (310m) closer to the current developments (Figure 1). The current airflow system, even with an additional 116,000 cfm (55m3/s) entering from No. 2 Mine, is adequate only for the development work now in progress but will be unable to support new longwall faces further downdip. The basic ventilation problem of this mine may be stated quite simply. In a situation where all intake and return airways pass through extensive old workings, a ventilation system design was required that would be effective, efficient and economic for the foreseeable future of the mine. ORGANIZATION OF THE PLANNING PROCEDURE The procedure followed during the study is illustrated on Figure 2. Initial ventilation surveys established the current state of the airflow system and provided the necessary data for setting up a Basic Network File in a computer store. The data in this file was a mathematical model of the ventilation system of the mine. The basic network was analysed by a ventilation network analysis program in order to correlate the measured and computed airflows and to establish the basic network as a true representation of the mine as it stood at the time of the surveys. The network model could then be extended to simulate the future development of the mine and alternative ventilation designs investigated. The remaining sections of the paper outline the work involved in each of these main phases of the planning procedure. VENTILATION SURVEYS Conduct of Surveys Two types of measurements were conducted simultaneously throughout the air-carrying routes of the mine: (i) Airflow measurements were made by anemometer traverse or smoke tube at 221 selected stations. Anemometer traverses were repeated at each station until at least three gave results to within 5 per cent. (ii) Pressure drop measurements were made across ventilation doors, regulators and, wherever possible, across stoppings. Additionally, frictional pressure drops were measured along airways where such pressure drops were significant (above 0.01 inches of water gauge or 2.5 Pa over a 100m distance). The trailing hose method was used to determine these frictional pressure drops. This involved laying out 100m of abrasive resistant plastic tubing (3 mm internal diameter) with a 4 ft. pitot-static tube facing into the airflow at either end and a low range pressure gauge connected into the line. The trailing hose method was preferred to the alternative barometer technique for this study because of (a) the relative ease of access between measuring points and (b) the greater accuracy within individual airways. The anemometers used were Davis Biram Type A/2-3" (30 to 5,000 ft/min) and Airflow Developments AM-5000 digital (50 to 5,000 ft/min). The pressure gauges employed were Dwyer magnehelic instruments. These were preferred to liquid in glass manometers because of their portability and dependability under adverse mining conditions. A checklist of the equipment used in the survey is given in Appendix 1. The instruments were calibrated before and after the surveys in the mine ventilation laboratory at the University of California, Berkeley. The survey occupied two teams, each of three men, for ten working days. The work consisted

Jan 1, 1982

By D. D. Dunlop, J. R. Welker

The growing interest in the use of CO, in crude oil recovery increases the need for data on the effect of CO, on hydrocarbon physical properties. Data are presented on the solubility of CO, in various dead oils, the swelling changes in CO2-oil solutions and the effect of CO, on dead oil viscosity. This latter property shows the most pronounced effect, with viscosity reductions up to 98 per cent of the uncarbonated viscosities. An empirical method of estimating the viscosity of carbonated oils is presented. The apparatus and procedures used are described in sufficient detail to allow others to make similar studies. INTRODUCTION The effect of dissolved carbon dioxide on the swelling and viscosity reduction of specific hydrocarbon oils has been observed and recorded by a number of investigators.'- me object of this paper is to offer a means of predicting these effects for crude oils free from natural gas, using the dead state viscosity and gravity of the crude oils. The CO, solubility and swelling of numerous crude oils were determined in a visual cell at various pressure levels. The viscosity of the oils carbonated to various pressure levels was then determined by measuring the pressure drop across a capillary tube. From these data, the physical properties were correlated empirically. The resulting correlations allow the prediction of CO, solubility, swelling and viscosity reduction if the dead state gravity and viscosity of the oils are known. SOLUBILITY AND SWELLING MEASUREMENT EQUIPMENT AND PROCEDURE A high pressure visual cell was installed in a constant temperature cabinet. A test gauge was attached at the top of the cell for pressure measurement, and a line was run through the cabinet wall to a wet test meter which was used for volumetric measurement of the gas. The first step in making a test run was to put the oil in the cell up to a level about half to two-thirds of the total volume. This required about 50 to 65 ml of oil. carbon dioxide was then bubbled up through the oil for a time during which the pressure of CO2 in the cell was kept above 800 psia. Saturation of the oil with CO2 at this pressure and ambient temperature was confirmed by slowly bleeding CO2 through a valve to the atmosphere. If the oil was completely saturated with CO2, bubbles of gas would form in the oil at the first small decrease in pressure. If the oil was under-saturated, no bubbles formed until the pressure was decreased to the saturation pressure existing in the oil. If this saturation pressure was lower than that desired, more CO2 was bubbled through the oil until the desired level was reached. After saturation at ambient temperature was completed, the cabinet temperature was adjusted to the desired level and the cell was allowed to reach temperature equilibrium. After temperature equilibrium was reached, the pressure was again decreased slightly, and the oil again checked for full CO2 saturation at the cell pressure. The pressure now had changed because of the difference in solubility of the CO, in the oil at higher temperatures and the expansion of CO2 as the temperature increased. The outlet tube from the cell was then connected to the wet test meter and the CO2 was allowed to flow slowly out of the cell and through the wet test meter at ambient temperature and pressure. The water in the wet test meter had previously been saturated with CO2 at ambient temperature and pressure by allowing CO2 to flow continuously through it lor a period of several hours. The gas flow was stopped at several pressures during the run and the cell was allowed to come to equilibrium; this made possible the measurement of solubility and swelling data at the intermediate pressures. The volume of the oil in the cell was recorded at each of the equilibrium pressures in order to obtain swelling data. DATA AND RESULTS The solubility of CO2 in the oil was calculated by the relationship V — V, where R. = solubility of CO, in crude oil, cubic feet of CO, measured at 60F and 1.0 atm/ bbl of dead state oil at the temperature under which solubility was measured, V, = volume of gas released from the cell between the saturation pressure and zero pressure, corrected to 60F and 1.0 atm, cu ft, V, = volume of CO: contained in the gas space above the oil, corrected to 60F and 1.0 atm, cu ft, and V, = volume of the dead oil in the cell in bbl at the temperature of the run. The volumetric data of Sage and Lacey' were used to calculate V., from the volume of CO2 at high pressures. The swelling factor was calculated as where V, is the volume of the C0,-

By Zay Jeffries

From the title of this chapter the reader could expect an attempt to out- line the anticipated shape of things to come, mineralwise. We have no crystal ball and if we possessed one we could claim no expertness in its use. In the first place no one can tell the future status of man. No one has any way of knowing to what extent peace will prevail, nor to what extent changes may occur in national sovereignties or forms of government or in international relationships. So future man is an uncertainty. Nor can we predict new developments that may result in significant changes in man's status or in the mineral industry or both. If, for example, this chapter had been written in the middle 1930's, nearly everything that has happened since in the fields of atomic energy and space technology would have been missed. Yet what vast changes these I have made in the status of man! Also the changes in the mineral industry have been important. A writer would have been bold indeed had he prophesied that uranium would play such an important role. But we need not confine our foggy vision to these fields. The steep rise in the use of aluminum, titanium, and germanium reflects the unpredictable in what may be thought of as the more normal pursuits. This should not discourage one from using the past and currently observable trends as bases for limited predictions. To do this, however, it is desirable to make certain assumptions about man's status without pretense that these assumptions have a high probability of fulfillment: 1. Only minor changes will occur in the geographical boundaries of the nations of the world. 2. World War III will not take place in the near future. 3. As a consequence of (2), man will not destroy himself by wanton use of atomic weapons. 4. Disarmament will take place, if at all, gradually rather than all at one time. Under the above assumptions the world will enjoy a period of relative peace even though the status may be one of an armed truce. The assump-

Jan 1, 1964

By AIME AIME

THE autumn is the time that nearly all the special groups within the broad field of the Institute's activitives chose for their own special meetings. The big annual meeting in New York in February has its own special advantages, but to realize them involves sacrificing others. A meeting of a smaller group with the subjects brought up for discussion much more closely limited to a single field of interest has some advantages that a big general meeting cannot possibly have. And so the custom has gradually developed of having these smaller meetings in the autumn, at con¬venient places, so the men will not have to travel too far from the job to be present. Sometimes the meetings have for their field of interest a single phase of mineral technology, and are called divisional, and at other times they cover a diversity of topics that are locally important in that geographical area, and are then called regional meetings. Of the five meetings to be held this fall, four are divisional and one regional. Two of the divisional meetings are to be held in the same place at the same time, but with programs so arranged that they do not conflict.

Jan 1, 1930

By K. L. Komarek, P. F. J. Landler

Synthetic polycrystals of wustite were reduced ilz H2-H2O mixtures over limited roncentration ranges wiltun the wustite. field and the weight changes were continuously followed with a McBain quartz spiral balance. The reduction was. found to be controlled by a combined surface plus solid-state diffusion reaction. The solid-state diffusion had an activation energy of 38 kcal. Self--diflusioities of iron decreased with itzcreasing vacancy concentration. The activation energy of. the surface reaction runs different tor- different samples. The surface reaction-rate constan increased with increasirzg vacancy concentration. THE reduction of the oxides of iron has been studied for many years. Edstroem' has summarized the early work and has provided much information on the reduction of magnetite and hematite by hydrogen and carbon monoxide. More recent summaries are those by smeltzer2 and Themelis and Gauvin.3 Most investigators have reported that the iron metal which forms the outer layer during gaseous reduction is rather porous. According to Kohl and Engel14 the formation of such a porous iron layer depends on the properties of the underlying wiistite layer, on the reaction of the gas with the wustite surface, and on the transport of matter through the wustite layer. McKewan, Quets, Wadsworth, and Lewis, and Knacke 10 have found that, if a porous iron layer is formed, a surface reaction between gas and wustite at the bottom of the pores controls the rate of reaction. Seth and ROSS 11 and Warner 12 have pointed out that the influence of the gaseous pore diffusion through the porous iron layer cannot be neglected. It has further been shown that the wiistite layer formed during reduction is dense and that transport of matter across the layer occurs only by solid-state diffusion of iron ions.13,14 The solid-state diffusion rates observed by Edstroem and Bitsianis 14 and the surface reaction rates observed by Quets eta1.' show that an interaction of the two steps in controlling the reaction rate has to be considered. In this investigation the reduction of wustite was studied with respect to the interaction of the two steps, isolated from any other effects, by reducing wustite within the wustite field from higher to lower oxygen concentrations with H2-H2O gas mixtures. A similar study with CO-CO2 mixtures has been performed by Levin and wagner.15 Fused synthetic wustite polycrystals were reduced in steps of 0.4 wt pct from 24.4 to 23.2 wt pct 0 and over a temperature range from 700" to 1050°C. A few tests were also conducted with reduction steps from 24.4 to 23.6 wt pct 0 and 24.5 to 23.2 wtpct0. The Fe-O phase diagram is shown in Fig. 1 where the composition of the gas phase in equilibrium with the condensed phases is plotted as pct H2 vs the temperature. A careful study of the literature led to the conclusion that the fully drawn equicomposition curves (in wt pct O) in the wustite field used by Edstroem 1,16 and other authors needed some correction. Based on results by Darken and Gurry17 (shown as open circles) and on some of our own data, four corrected curves for 23.2, 23.6, 24.0, and 24.4 wt pct O were calculated (drawn as dashed lines in Fig. 1) which should replace the fully drawn equicomposition curves. MATERIALS AND APPARATUS Materials and Specimen Preparation. Wustite was prepared from iron sulfate (Fisher Scientific Co., New York) which had a purity of over 99.92 pct, with small amounts of manganese, copper, and zinc adding up to 0.03 pct. From the aqueous solution iron oxalate was precipitated and decomposed to magnetite according to Economos. 18 The magnetite powder was pressed into cylinders and sintered in vacuum at 900°C for several hours. The sintered compacts were placed in a platinum crucible of 2.5 cm diam which was fitted into a high-purity alumina crucible and then inserted into the center of the graphite heating element of an electric resistance furnace.lg The furnace was evacuated to below 1 p Hg and the magnetite sample was slowly heated. The evolution of gases during heating deter-

Jan 1, 1967

By K. I. Savage, S. C. Sun

This paper describes a process developed to recover coal, clays and pyrite from coal wastes. The process consists of fine grinding followed by coal and pyrite flotation which leaves the clays in the flotation pulp. A bituminous coal refuse containing 10% sulfur and 30% carbonaceous material was treated by this method to yield a coal product containing 4% sulfur, 10% ash; a pyrite product containing 45% sulfur (84% FeS2), 1% carbonaceous material; and a clay product containing 2% sulfur (3.5% FeS2). The coal yield was about 89%. The pyrite yield was about 77%. The process steps may be entirely flotation, or gravity separation (hydrocycloning) may be used to increase the pyrite : coal ratio in the flotation feed. Cost estimates for the process show a profit of $2.28 per ton of low pyrite grade refuse, but these do not include labor, maintenance, overhead and plant depreciation. The development of this process consisted of three parts: (1) exploratory tests, (2) op-timazation tests and (3) confirmatory tests. The objectionable qualities that sulfur imparts to coal have been commented upon from early times, and they have become more objectionable as the uses of coal have grown. In whatever form coal takes — raw, carbonized or gasified —the sulfur content remains objectionable, and therefore its compounds are removed as completely as possible. It has long been known that sulfur occurs in coal in different forms. In 1861, sulfur was said to exist in the state of sulfuric acid in combination with a base; in combination with iron as iron pyrites; as bisulfides of iron; and in combination with the organic elements of coal.' Pyritic sulfur is a term loosely used to cover the sulfur associated with iron in its various forms. The mineralogically recognized forms are pyrite (FeS2), pyrrhotite (Fe 1-x S) and marcasite (FeS2). The particle sizes of pyrites vary widely. Isolated grains of marcasite smaller than 15 microns have been found disseminated through coal.2 Hair-like "veins" of pyrite filling cracks in vitrain have been found. At the other extreme, lumps or nodules of pyrites large enough for removal by hand picking have been encountered. Organic sulfur, unlike pyritic sulfur, does not exist as discrete particles, but is instead intimately associated with the coal structure and thus it is impossible to remove it or reduce its concentration by physical or mechanical means.2 In the preparation of coal for its various markets, the pyrite minerals (pyrites) are separated from the raw coal feed. This separation process concentrates the pyrites in the tailings or other waste products. It would be desirable to recover these pyrites for three reasons: (1) Pyrites are potential sources of sulfur and iron. In 1967, for the fifth consecutive year, Free World consumption of sulfur exceeded production.3 Propelled by the shortage, the domestic price of sulfur has risen from $24 to $38 per long ton (bright). (2) The refuse, when placed in piles, becomes ignited. The pyrites (FeS2) bum, giving off SO,. Thus, the pyrites are a cause of air pollution. (3) Also, the pyrites undergo chemical reaction when exposed to air. The refuse is leached by waters which result in stream pollution due to the water-soluble iron and acidic reaction products. Coal refuse also contains coal minerals and clay minerals. Therefore, any process for recovering the pyrites must successfully separate them from the coal and clay minerals. In the study discussed here, ten different bituminous coal refuse samples were successfully upgraded in pyrite content. These samples represented a wide variety of coal waste materials from Pennsylvania and other states. The variabilities of the sulfur and coal contents are shown in Table I. The extremes are Sample J, a high sulfur-low coal, and Sample B, a low sulfur-high coal. Definitions of some of the symbols or terms used in this report are given below: Mesh size—Tyler standard mesh screen sieves with an opening based on the square root of two. Fe —Indicates iron, as determined by a stannous reduction-dichromatic oxidation method. S—Indicates sulfur, as determined by the ASTM "Eschka" method for sulfur in coal.

Jan 1, 1969

By G. Gutierrez, D. A. Elgillani, M. C. Fuerstenau

The zero-points-of-charge of apatite, calcite, and fluorite are pH 6.4, 10.8, and 10.0, respectively. Scheelite is negatively charged above at least pH 3. In this article, the flotation responses of these minerals in the presence of potassium oleate and sodium silicate are described and compared with electrokinetic data. Colloidal silica appears to be the species principally responsible for calcite depression, while silicate anion is the species responsible for fluorite depression. Additions as high as 1 x 10-3 mole/liter silicate have no effect on the flotation responses of apatite and scheelite. Selective flotation of nonmetallic minerals is difficult to achieve with fatty acids or soaps by themselves. As a result, specific reagents are added to aid these separations, and one of the reagents commonly employed for this purpose is sodium silicate. Flotation separations of various calcium-bearing minerals such as fluorite from calcite1-3 and scheelite from calcite2,4 and apatite,2,5 for example, almost always involve the use of sodium silicate. The mechanisms by which sodium silicate functions as a depressant are still not understood, probably for a number of reasons. For one thing, the dissolution process of sodium silicate is complex, giving rise to a number of ionic and colloidal species.' Moreover, the type and concentration of these species depend on the ratio of Na2O to SiO2, the concentration of sodium silicate, and the pH of the system.' At the present time, it is not known which species, colloidal silica or silicate anion, is responsible for depression. If colloidal silica is the species that is adsorbing, then adsorption must occur by electrostatic attraction between the colloid and the mineral surface. Silicate anion, on the other hand, may adsorb either physically or chemically. The objective of this paper is to determine first the active species of sodium silicate and then the conditions under which this species will adsorb and function as a depressant. EXPERIMENTAL MATERIALS AND METHODS Pure samples of apatite (Durango), calcite (Iceland-spar), fluorite, and scheelite were used in this investigation. Pure potassium oleate was used as collector, while reagent-grade HC1 and KOH were employed for pH adjustment. The sodium silicates used were samples obtained from the Philadelphia Quartz Co. In one series of experiments, various sodium silicates containing different ratios of SiO2 to Na2O were added to calcite systems. These sodium silicates contained SiO2-to-Na2O ratios of 3.75 to 1, 3.22 to 1, 2.40 to 1, and 1.60 to 1. All other experiments were conducted with the sodium silicate containing the ratio of 3.22 to 1, which is the one that is normally used in industry. Flotation experiments were conducted with 21/2-g charges of 48 x 150-mesh material in conductivity water with an apparatus and technique described previously. Electrokinetic experiments were conducted with both a Zeta Meter and streaming potential apparatus. Particle size was 48 x 65 mesh for the streaming potential experiments. EXPERIMENTAL RESULTS The first series of experiments involved flotation of scheelite in the absence and presence of sodium silicate. As shown in Fig. 1, flotation response was not affected with even the relatively high addition of 1 x 10-3 mole per liter sodium silicate. Interestingly though, no flotation was effected below pH 6 with this collector addition. The responses of apatite to flotation under these same conditions are given in Fig. 2. Similarly, no depression was obtained in basic media under these conditions. Similar experiments were conducted with fluorite, and in this case, depression was noted above about pH 11 with 1 x 10-3 mole per liter sodium silicate (Fig. 3). When calcite was floated with these same levels of addition of sodium silicate, essentially no flotation was possible above pH 7 (Fig. 4). The effect of collector addition with a constant addition of sodium

Jan 1, 1969

By H. L. Gilbert, W. W. Stephens

Production of anhydrous zirconium tetrachloride by direct chlor- ination of a zirconium oxide carbon mixture in a silica-brick-lined chlorinator is described. Theory and thermodynamics of reactions are discussed. A pilot-model chlorinator and full-scale production equipment are described and operating data are included. ANHYDROUS zirconium tetrachloride required as a starting material in the Kroll process for production of ductile zirconium has been produced in this country principally by chlorination of the carbide or "carbonitride" made by reduction of zircon sand concentrates with carbon in the arc furnace. This process and the equipment used have been fully described.'.' It is well known that zircon or badde-leyite ores may be chlorinated directly with chlorine in the presence of carbon, and this one-step approach would seem at first glance to be preferable to the two steps involved in the carbide-chloride operation. As previously discussed1 considerations leading to adoption of the longer process were: 1—Chlorination of the carbide proceeds rapidly at temperatures below 500°C, whereas temperatures above 900°C were considered necessary for chlorination of zircon-carbon mixtures. 2—The highly exothermic nature of the carbide-chlorine reaction makes it self-sustaining, while heat must be supplied continuously in direct chlorination of the ore. 3—Silicon was thought to be chlorinated along with zirconium in the direct chlorination of zircon, leading to high chlorine consumption. In production of carbide in the arc furnace, silicon is driven off as silicon monoxide and does not enter the chlorinator. 4—For efficient direct chlorination, the ore must be finely ground and intimately mixed with carbon, and the mixture briquetted. 5—Direct chlorination requires a much larger chlorinator for a given production capacity than chlorination of carbide. Recently it has become necessary to produce large quantities of zirconium metal from a chemically purified zirconium oxide. Since the cost of the latter is high, the relatively high losses encountered in production of carbide in the arc furnace could not be tolerated, and a graphite resistor furnace5 was developed for production of carbide, which was then chlorinated in equipment previously used for chlorinating arc-furnace carbide. This method of operation was quite satisfactory, and losses in the carbid-ing step were minimized. However, operating costs were relatively high, and the process did not lend itself particularly well to large-scale operation because of the multiplicity of small units required and the hand labor needed to load, unload, and maintain the furnaces. To chlorinate the carbide, a vertical-shaft chlorinator was used in which the charge was heated with a central split graphite-rod resistor.' Operation of this chlorinator was somewhat less satisfactory with the resistor furnace carbide than it had been with the arc-furnace carbide due, principally, to the differences in physical properties of the carbide. The arc-furnace carbide is obtained as a fused metallic-appearing mass which can be crushed to -1/4 in. with production of a minimum of fines, whereas the resistor-furnace product is lightly sintered and produces a large proportion of fines in crushing and handling. These fines tend to pack in the chlorinator and promote channeling. which results in poor chlorine efficiency and low capacity. Data based on production of 22,000 lb of chloride from resistor-furnace carbide in this equipment are shown in Table I. Necessity for increasing production of chloride from about 2,000 to 15,000 lb per week led to further investigation of possible methods for direct chlorination of the oxide or oxide-carbon mixtures. Direct chlorination of the pure oxide presents much less difficulty than chlorination of zircon sand or oxide ores. The oxide is easily ground to —200 mesh, and no silica is present to cause excessive consumption of chlorine or contamination of the product. Theoretical Considerations The principal chemical reactions involved in chlorination of mixtures of zirconium oxide and carbon may be written as follows: ½ ZrO2 (c) + C(c) + Cl2(g) = ½ ZrCl,(g) + CO(g) [I] 1/2 ZrO, (c) + CO(g) + Cl2(g) = ½ ZrCl,(g) + CO2(g) 121 ½ ZrO2 (c) + ½ C(C) + Cl2(g) = 1/2 ZrCl4(g) + ½ CO2(g) [3]

Jan 1, 1953

By F. R. Morral, K. T. Aust

The preferred orientation and earing characteristics of ZS aluminum were studied. An empirical correlation was obtained relating earing behavior and variation of mechanical properties for face-centered cubic metals. Strain-ratio mecsurements for ZS were found to be in good agreement with Hill's theory of plastic anisotropy. DIRECTIONALITY in sheet metals may be revealed by earing in a cupping test, or by the variation of mechanical properties of tensile specimens taken at different angles to the rolling direction. However, no simple correlation appears to exist between earing and variation in mechanical properties in metals and alloys studied.1-5 Aluminum of commercial purity (known as 2S, with a specified minimum of 99.0 pct Al) cast by the direct casting process was chosen in the present investigation since ears at 45° or 0°, 90° can readily be obtained. Preferred orientation is often the principal cause of uneven metal flow, such as earing, and variation in mechanical properties. Consequently, the preferred orientation characteristics of 2s aluminum were initially studied using both X-ray diffraction and micrographic techniques. The variation of mechanical properties with angle to the rolling direction was next determined in an effort to clarify the apparent lack of correlation of earing behavior with mechanical properties for face-centered cubic metals. Strain-ratio*5,8 measurements were finally conducted to determine first, if the maximum values of the strain ratio occurred at the earing positions, and second, if Hill's theory of plastic anisotropy7 is applicable to other face-centered cubic metals such as aluminum. Detailed treatments, working, and heat treating are not given in this paper since this study is not concerned with the methods to produce earing, but to correlate earing with other properties and characteristics of the material. The percentage of earing was measured using the formula specified by the x—Y Aluminum Association, -------- X 100 = pct earing, where x is the height of the ear and y is the height of the valley from the bottom of the cup. Preferred Orientation Characteristics of 2S X-ray Studies: Beck and coworkers8 have determined that the rolling texture of 2s after 95 pct cold reduction may be approximately described by four equivalent ideal orientations near (123) [121]. Also, the recrystallization or annealing texture of 2s aluminum consists of four components of the (123) [l21] type, retained from the rolling texture, and of a (100) [001] or cube texture component." Fig. 1 illustrates the typical appearance of deep drawn earing cups with the corresponding X-ray diffraction patterns. The X-ray patterns were taken with copper radiation using the structure-integrating method'" in which the specimen is scanned during the X-ray exposure. The rolling direction was vertical and the rolling plane was perpendicular to the horizontal X-ray beam. It was found that an increase in the retained rolling texture component resulted in a greater 45" ear height, while an increase in the recrystallization texture component (i.e., cube texture) caused greater 0°, 90° earing. X-ray diffraction studies of 2s cold rolled to final thickness followed by a final anneal have shown that the rolling texture, and also the retained component of the rolling texture after annealing, are increased with greater cold-rolling reduction. The preferred orientation characteristics of 2s sheets given an intermediate anneal between cold rolling followed by a final anneal were found to depend on the position of the intermediate anneal during cold rolling. For instance, three identical samples of 2s homogenized ingot, each 1 in. thick, were given the following cold-rolling and annealing treatments: 1—50 pct reduction, intermediate anneal, 96 pct reduction to 0.020 in. and a final anneal; 2—75 pct reduction, intermediate anneal, 92 pct reduction to 0.020 in. and a final anneal; and 3—90 pct reduction, intermediate anneal, 80 pct reduction to 0.020 in. and a final anneal. The intermediate and final annealing treatments consisted of a 70°F per hr heating rate, held 6 hr at 800°F and air cooled. Typical X-ray patterns after each of these treatments are shown in Fig. 2. It was evident that after treatment 1, the retained rolling texture component predominated; after treatment 2, the retained roll-

Jan 1, 1954