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By H. D. Keiser

Minor industrial minerals included in this chapter are: the alum minerals, bromine, calcium chloride, epsomite and other natural magnesium salts, iodine, meerschaum, quartz, industrial crystals other than quartz, and nonfuel gases (air, helium, carbon dioxide). Alum Minerals The natural alums comprise a group of hydrated double sulfates, the most important of which are potash alum, KAI(S04)2.12H20, the "alum" of popular usage; ammonium alum, (NH4)AI(SO4)2, known mineralogically as tschermigite; and soda alum, NaAI(SO4)2.12H20. Kalinite, KAI(SO4)2.11H20, and mendozite, NaAl(SO4)2, 11H20, are fibrous monoclinic alums, distinct from the isometric species potash alum and soda alum.4 Alunite, KAI3(S04)2(OH)6, also known as alumstone or alum rock, has been used as a raw material in the manufacture of alum since early times. All the natural alums are highly soluble and occur as surface evaporation products in arid regions or in sheltered places. Potash alum, together with the other natural alums, commonly occurs as an efflorescence or crevice filling in argillaceous rocks and brown coals that contain disseminated pyrite or marcasite. The mineral is derived by the action of sulfuric acid, formed during the weathering of the sulfide, upon alkali-rich aluminum silicates. Ammonia alum is found chiefly in lignite or broad-coal beds and bituminous shales. Alunite is most commonly associated with acid volcanic rocks, where the rock has been largely altered and alunite formed owing to the presence of sulfuric acid solutions or vapors. Aluminum sulfate, which for most uses is the essential ingredient of alum, may be found in saline residues resulting from the evaporation of natural water and may be formed by the action of acid waters upon aluminous rocks. A deposit of natural potash alum occurs in an irregular network of veins associated with sulfur in rhyolite in Esmeralda County, Nevada, about 35 miles west of Tonopah and 10 miles north of Silver Peak. Alum was recovered at a plant operated on the property between 1920 and 1923 by crushing the ore to ¾ in., grinding to minus 80-mesh, and counter-current leaching; the resulting alum solution was then filtered and crystallized. Alunite was of much interest during World War I as a source of potash and during World War II as a source of alumina. The wellknown deposits at Tolfa, Italy, are veins in trachyte and have been the basis of alum manufacture there since the middle of the fifteenth century. Pure alunite is insoluble in water and in common acids, but if it is heated to 500°C it loses its water of hydration, and the residue consists largely of anhydrous potash alum, part of which is readily soluble in water or acids. If the heat is increased beyond 500°C, most of the sulfur combined with the alumina is released as oxides and the residue consists of potassium sulfate and alumina. Thus, either potash alum (and aluminum sulfate) or potassium sulfate and alumina may be made. In the

Jan 1, 1960

By Craig E. Saporito

INTRODUCTION Freeport-McMoRan Inc. has been very active recently with two major discoveries and its restructuring activities. This paper describes Freeport-McMoRan's businesses, the two major mineral discoveries, and exciting opportunities within the oil and gas operations. BUSINESS ACTIVITIES Freeport-McMoRan is the largest and one of the lowest cost fully integrated U.S. phosphate fertilizer producers. It is the second largest domestic Frasch sulphur producer. Freeport- McMoRan will become the largest domestic producer of Frasch sulphur when its Main Pass Block 299 sulphur deposit reaches full production in 1993. Furthermore, it is the largest transporter of sulphur produced by others. Its oil and gas activities rank among the largest U.S. independents in terms of production and proved reserves. The copper/gold operations in Indonesia are among the world's lowest cost. When expansion operations reach full capacity levels in 1992, the Indonesian copper/gold complex will be the fifth largest copper operation in the world. Operations are divided into three business segments that include: 1. Agricultural minerals, incorporating sulphur, phosphate rock and phosphate fertilizer activities; 2. Energy, including oil and gas activities; and 3. Metals, incorporating copper, gold and silver operations in Indonesia. In early 1989, Freeport-McMoRan announced the discovery of two world-class ore bodies; a sulphur deposit off the coast of Louisiana on Main Pass Block 299, and a copper/gold deposit -- the Grasberg in Indonesia -- approximately two miles away from the existing Ertsberg East operations. As a result of these major discoveries, Freeport- McMoRan decided to carry out a restructuring program. Its purpose was to sell $1.2 to $1.5 billion of non-strategic assets. Debt levels and associated interest expenses will be significantly reduced, and general and administrative expenses will be reduced, which will place Freeport- McMoRan in an excellent position to fund the development of the Main Pass Block 299 sulphur discovery, the Grasberg discovery, and oil and gas discoveries. This restructuring program also will allow Freeport-McMoRan to achieve the greatest future value for shareholders by focusing on its principal businesses (Figure 1). Strategic Restructuring • Sell $1.2 - $1.5 Billion Of Non-Strategic Assets • Significantly Reduce Debt • Significantly Reduce G&A • Fund Development Of Main Pass & Grasberg • Stronger Company; Positioned For Future Growth • Focus Is On Principal Businesses: - Sulphur/Phosphate Fertilizers - Indonesian Copper/Gold - Oil And Natural Gas Figure 1 - Strategic Restructuring AGRICULTURAL MINERALS Main Pass Block 299 Discovery The Main Pass Block 299 discovery has a proven reserve of 67 million long tons of recoverable sulphur. This is the largest known Frasch sulphur deposit in North America. The discovery increased Freeport-McMoRan's sulphur reserves more than five-fold, and is synergistic with the company's phosphate fertilizer assets. The

Jan 1, 1990

By Arthur F. Taggart

RECENT jig practice has shown such marked departures from the pronouncements of the textbooks, particularly as to particle size recovered and size range of feed, as to make it desirable to reexamine the mechanism of jig action. This paper presents the results of such a study. The general conclusions of the paper are: I. A jig bed is a bi-functioned as well as bi-parted body. The upper layer comprises a plastic stream moving slowly in a substantially horizontal direction from feed lip to tail board. It serves to rough out tailing and light middling and to pick up heavy middling and lift it out of the jig box. The lower layer acts as the ultimate separating means by absorbing concentrate and rejecting heavy middling. 2. The separating function of the lower layer is performed in three definitely different ways, depending upon the relative sizes of the grains presented to it and those composing it. EXPERIMENTAL The experimental work consisted of close and long-continued visual observations of operating beds in a plunger jig, eccentric driven, and in determinations of the settling rates of various metal spheres through a quartz bed under various conditions of operation. Falling velocities were measured by an ingenious method devised by A. C. Dorenfeld, a student in the Mining Department at Columbia. Spheres of different metallic alloys, Y8-in. diameter, were cast with a short piece of fine copper wire frozen in to serve for suspension. A short piece of black cotton thread was looped to the top of the wire to serve as an indicator. The set-up for a test is shown in Fig. I. The thread should be boiled, if necessary, to make it freely water absorbent. The piece of clean plate glass D is supported rigidly at the proper height in a vertical position. The white scale E is similarly supported behind the glass. At the beginning of a test, D is filmed with water by holding it (best with clean rubber finger cots) under running tap water. It is then clamped in approximate position and C, already wet, is laid across it and drawn straight and vertical with the upper end at or near the top of D, and the ball A slightly above the top of the expanded bed. The water film holds the string to the glass. For a test the string is released, its upper end position noted just after the top of the ball becomes submerged, when the corresponding time is read, and thereafter simultaneous readings of position and time are taken as desired. Results of the visual studies of the bed are given at the pertinent places in the following discussion. Results of the settling tests are summarized in Figs. 2 and 3. DEFINITIONS The name bed as used herein refers to the entire mixture of solids and water filling the jig box. A layer is a stratum of a bed composed of particles of substantially the same specific gravities. A granular product is long-range when it approximates a crushed or ground product limited as to upper size only; a shorlrange product is one closely sized. A bed is loaded when operating with continuous feed

Jan 1, 1943

By J. O. Brittain, E. Lautenschlager

An investigation was conducted on fine grained airon wire to measure the influence of the temperature of deformation on strain aging near room temperature. Specimens were deformed various amounts at 77°, 195°, or 273°K and aged. The strain aging was followed by either internal friction or return of the yield-point measurements. The results show that strain aging occurs in three stages. During the first stage there is small, almost immediate return of the yield point. The solute carbon concentration, as mesured by internal friction, remains constant in stage I but is lower than the concentration in the unstrained condition. In the second stage, the solute concentration decreases while the magnitude of the yield point increases. In the third stage, the solute atoms continue to drain from the solution, the yield point approaches a maximum, and the strain-hardening coefficient and flow curve increase. The kinetics of the strain aging reaction are not the same for the two sets of measurements since the internal friction results lag behind the yield-point measurements. However, the strain-aging kinetics measured at 44° and 64°C showed no effect due to the difference in initial deformation temperature; nor were the strain aging kinetics influenced by low-temperature anneals at 77°, 195°, and 273°K. 1 HE object of this investigation was to measure the effect of initial deformation temperature on the strain aging of a-iron by tensile tests (i.e., return of the yield point) and internal friction methods, to correlate the results of the two measuring methods, and to measure the effect of low-temperature annealing (<273°K) after low-temperature deformation upon strain aging. The experiments were performed on fine-grained a-iron wire containing 0.02 wt pct c.l According to Thomas and Leak,&apos; return of the yield point and internal friction are similar measures of strain aging since both are dependent on solute atoms leaving the solid solution. The decrease in internal friction as a function of aging time is indicative of the removal of solute atoms from the solid solution, while the return of the yield point as a function of the aging time gives the rate of arrival of solute atoms at the dislocations. According to Cottrell and Bilby,3 during aging the solute atoms create an "atmosphere" which locks the dislocations and causes a return of the yield point on subsequent testing. It has been shown that after low-temperature neutron bombardment, a-iron goes through a stage of recovery at low temperatures which can be attributed to the annealing of iron interstitials&apos; and/or vacancies.4 If, after low-temperature deformation, there is an interaction during a low-temperature anneal between mobile point defects and the solute atoms (i.e., carbon atom interaction with vacancy or iron interstitial), it is possible that some solute atoms will be found at defect sites other than dislocations. Such changes in the sinks for the carbon atoms might be expected to alter the strain-aging kinetics sufficiently to be detected by either inter-

Jan 1, 1962

By OTTO HERRES

TO operate the bituminous coal industry in the United States in 1929 cost $770,237,000, of which $30,739,000 was paid for purchased power and $34,947,000 for new machinery and equipment. Equipment aggregated 3,124,000 hp. A mining industry that spends $65,000,000 a year for power and machinery is likely to be fairly well mechanized, and when the machinery in use takes three million horsepower to drive it, the probabilities are that mechanization has been in progress in at least some of the mines for quite a few years. Mechanization in its broadest sense implies machine cutting, power drilling, mechanical loading, electric haulage, mechanical sizing and cleaning, and lesser applications of machinery to mining operations. But the introduction and development of mechanical loading has been the feature of coal mining recently and its extraordinary progress is causing great changes within the industry. First, let us look at the records. The quantity of coal loaded mechanically in bituminous mines was:

Jan 1, 1933

OFFICERS AND DIRECTORS President and Director AUGUSTUS B KINZEL, &apos;60, New York City Past President and Director GROVER J HOLT, &apos;59, Ishpeming, Michigan President-elect and Director HOWARD C PYLE, &apos;61, Los Angeles, Calif

Jan 1, 1958

By H. K. van Poollen, H. C. Bixel

A treatment is given of the transient pressure behavior of a well located at the center of a circular region surrounded by a radial discontinuity. On either side of the discontinuity, the values of permeability, viscosity, compressibility and porosity are uniform but may be different from those on the other side of the discontinuity. The results are obtained by solving a pair of finite difference equations. The numerical solution to these equations is obtained using a digital computer. The results are compared with previously published, approximated analytical solutions to the same problem. Solutions, presented graphically, show pressure decline for constant rate fluid production. The range of variables studied include dimensionless time from &apos;0.001 to 100 and storage capacity ratio from 0.001 to 1,000. The well behaves as if it were in an infinite reservoir for dimensionless times less than 0.25. Reservoir properties near the well can be estimated in the usual manner. An overlay technique is used to match an experimental curve with one of the theoretical curves. It is possible to estimate the distance to a discontinuity by substituting the actual time t and the corresponding dimensionless time tD at which a match occurs into the equation a = (0.000264 tk1/tD , µ1 cI)I/2 where kI/ I µI cI is the diffusivity near the well, and may be estimated from data taken at early time. Several buildup curves are computed. These curves show that for early shut-in times, correct values for transmissibility are obtained from conventional analysis. However, erroneous values of static reservoir Pressure are obtained unless data at large shut-in times are taken. INTRODUCTION A mathematical treatment of the transient pressure response of a well located at the center of a region bounded by a circular discontinuity is given. Within a region (Fig. 20) the properties of both the rock and the fluid are considered to be constant on either side of the discontinuity. While these properties are considered constant, they may be different on opposite sides of the discontinuity. A discontinuity of this type could be a fluid-fluid contact or a sudden change in rock characteristics such as thickness, porosity or permeability. Analytical solutions to this problem are available. 1-3 However, they are so involved that they are of little practical use. An approximate solutionl is available but the range of times over which it is valid has not been specified. A numerical solution to a pair of finite difference equations is used to obtain the solution given in this paper. PREVIOUS WORK One of the first solutions to the problem was published by William Hurst.1 Hurst considered unsteady-state flow of fluids through two sands in series with different mobilities in each sand. He used Laplace transforms to obtain a solution for a single well located at the center of the circle enclosing the first of the two sands. In this case, the solution for the pressure change in Region I (Fig. 20) is2

By Howard N. Eavenson

TWO months ago, just after the coal code hearing in Washington, one of our leading liberal weeklies printed a study of the coal industry made by an economist in the Administration, and on the outside cover bad it featured as "Coal-A Dying Industry." There are, of course, different opinions as to the accuracy of this characterization and I want to present some of the facts about the outlook for the bituminous industry for a short time ahead. In view of what has happened in the industry within the recent past it would be futile to attempt to make any prophecy about what is likely to occur in the future. We all know that a prophet is not without honor save in his own country, but it is likely that anyone undertaking this role about this industry would soon find himself in no man&apos;s land. One can, with some slight degree of safety perhaps, outline present conditions and tendencies and draw some inferences as to what the future may hold.

Jan 1, 1933

By T. Leffers, A. Grum-Jensen

The development of texture in copper and brass (15 pct Zn by weight) rolled at room temperature and in copper rolled at -196°C has been followed by determination of pole figures for various degrees of reduction. The concurrent development in microstructure has been investigated by transmission electron microscopy. For low deformations, the texture in brass, and in copper rolled at -196°C, is the same as the texture in copper rolled at room temperature. The difference in texture does not show until 50 pct reduction. At the same reduction at which the difference in texture appears, mechanical twinning starts in brass and low-temperature rolled copper. Nevertheless, Wassermann&apos;s twinning theory is found to be incompatible with the present resulls. All fcc metals and alloys develop, by heavy rolling, one or the other of two types of texture, classified for convenience as copper type and brass type, or possibly a &apos;(mixed" texture representing an intermediate stage between the two types. The pure fcc metals, except silver, develop copper-type texture by rolling at room temperature. Silver and many alloys, including brass with more than 10 pct Zn, develop brass-type texture.&apos; By rolling at low temperatures a transition in texture from copper type to brass type has been observed for copper of commercial purity.2&apos;3 It is generally accepted that there is a correlation between the type of texture developed and the stacking fault energy. Metals and alloys having fcc structure develop brass-type texture when rolled at room temperature if the stacking fault energy is low, whereas those with higher stacking fault energies have copper-type texture.2 Thus, the difference in stacking fault energy must cause a difference in deformation mechanism responsible for the difference in texture. Of the numerous theories advanced concerning the nature of this difference in deformation mechanism, four seem to be of current interest. Smallman and Greeen,2 Dillamore and Roberts,4 and Dillamore5 refer to the fact that cross slip more easily takes place in a material with a higher stacking fault energy and suggest that the copper-type texture is developed by deformation with extensive cross slip whereas the brass-type texture is developed by deformation without cross slip. Haessner6 has advanced the theory that the copper-tye texture is developed by a combination of normal {111} slip and slip on other planes, mainly 1100). Thus his theory, like the theory above, proposes an additional deformation mode for the formation of the copper-type texture. Contrary to this, wassermann7 and Ahlborn et al.8 believe that the copper-type texture is obtained by normal slip. In their opinion mechanical twins will change a copper texture into a brass texture. For this reason it is suggested that the brass-type texture is developed when, in addition to normal {111}(110) slip, mechanical twinning is present. None of these theories are, however, supported by direct experimental evidence. In a recent experiment Hu et al.9 have followed the development of rolling texture in copper and brass. The texture of copper and brass was found to be es-

Jan 1, 1969

By E. E. ELLIS

THE zinc deposits under development by the Universal Exploration Co., a subsidiary of the United States Steel Corporation, are close to Jefferson City, Tenn., a small town about 30 miles northeast of Knoxville, Tenn., and are served by the Southern Railway. The first zinc mining in this district was in the old Mossy Creek mine at the north edge of the town, opened for oxidized ores in 1871 and later worked for sulfide ores. An oxidized zinc ore deposit (carbonates and silicates) was opened near New Market in 1900 and worked through the war period by the G1&apos;8sselli Chemical Co., producing around 25,000 tons of oxidized ore. In recent years a sulfide deposit has been found and developed but is not producing. About 1% miles south of this a small body of sulfide ore was developed by open cut, but the operation was unsuccessful. The Universal Exploration Co. entered the district in 1926 and, after extensive exploration, has been operating an oxidized ore-body since Janual:y, 1928, and has been developing a sulfide ore body since July, 1928.

Jan 1, 1929

Report of the Americanization Society, New York Section During the past two months the Americanization Committee has held social meetings of various kinds for foreign-born women, as a preliminary to future effort along the lines of Americanization work. At the same time, a thorough investigation was made as to the work being done in New York by organizations devoted to this interest. The committee will be very glad to help any other committees being formed, in mining centers, with advice and information that has been gathered together as to classes and meetings of all kinds best suited to the needs of a foreign-born population. The work has been so extensively taken up in New York that for the present it would seem to be, for this committee, the most profitable and interesting work to continue the social meetings and to undertake the care of one or more immigrant families, to be friend and adviser in joy and sorrow, work and play, and in this way do some fundamental Americanization work. Respectfully submitted, LAURA G. BURGER, Chairman.

Jan 6, 1918

By J. David Lowell

For his contributions to the field of mining geology, a striking example being his brilliant inte.rpretation of the complex geologic history of the San Manuel District (Pinal County, Arizona) which resulted in the discovery of the Kalamazoo orebody, and for his lecture, "Copper Resources in 1970." On a low desert ridge six miles south of Cairo lie the remains of the world&apos;s earliest known mining town, Maadi of predynastic Egypt. Copper artifacts, including ingots and an ax head which was spoiled in casting, indicate that copper ore was smelted in Maadi, and radiocarbon dating has placed the activity at least as early as 3300 B.C. This is the oldest documented date for the use of smelted copper, the first industrial metal used by man. Copper was mined and smelted almost as early in Asia Minor and on the island of Cyprus, but the greatest development of the budding copper industry was in Egypt, where specific historical records show that about 10,000 tons of copper metal were produced in the period from 1850-1580 B.C. Contrast this production of 35 tons per year with the present world production of about 7 million tpy. Evolution of the Copper Industry The copper ore mined by the ancients was high grade, and the copper produced was expensive. The copper industry began with narrow high-grade veins, but has evolved to the point where massive earth-moving equipment can be operated in huge, low-grade open pits. Indian pits dug before 3000 B.C. in the Lake Superior district were in ore which averaged 15% Cu. His- torical research done by Arthur Brant has shown that copper cost in the Middle East in 1840 B.C. in terms of 1970 labor dollars was about $25 per lb. The copper mined in northern Europe in 1540 in the time of Georgius Agricola averaged about 8% Cu, and the cost in 1970 labor dollars was about $10 per lb. Average ore grade had dropped to about 6% Cu in 1890, and the cost of copper in the U.S. in 1970 dollars was about 45¢ per lb. Butte, Mont., was a good example of the efficiently operated vein mines of this time. In 1906, Daniel Jackling made a dramatic entrance into the copper scene with the Bingham Canyon open-pit copper mine and proved that more profit was possible mining 2% porphyry copper ore on a

Jan 1, 1971

One of the best known of the early mining districts of Nevada was that at Eureka, where gold was first produced in 1864. While the most productive period for the district was during the early 1900s, production was maintained until World War II. During this time it is said that the Eureka district produced as much as $200 million from over 3,200 km (2,000 miles) of tunnels and workings. The Windfall Mine was discovered in 1902; and a 100 ton cyanide plant was operated there during the periods 1907 to 1912 and 1932 to 1940. Since 1974, however, Windfall Venture has been operating a unique heap leaching facility on the site of the old Windfall Mine. Gold at the Windfall occurs primarily in the Cambrian Hamburg dolomite which has been "sanded" and in which the original cementing material has been destroyed. The gold is micron sized and is accompanied by anomalous amounts of arsenic and mercury; however, the ore is low in base metals which distinguishes it from the typical Eureka district ores. Mining the ore causes it to break down into very fine sizes, approximately 50% minus 150 microns (100 mesh). Conventional heap leaching by spraying proved to be impossible; and extensive test work on alternate methods, aided by the United States Bureau of Mines, was conducted using 9 m (30 ft) high columns and then large tonnage heaps. The leaching procedure adopted was to build 10.6 m (35 ft) high heaps on a 50 mm (2 in.) asphalt pad covered with a layer of gravel for drainage assisted by perforated pipe drains and gravel-packed sumps. A berm is constructed around the top of each pad and cyanide solution is allowed to “pond” on top of the heap. The resulting percolation is at the rate of 24 liters per sq m per hr (0.6 gal per sq ft per hr), a figure about 2.4 times the average used in other heap leaching operations. The dolomite furnishes its own protective alkalinity and no lime or caustic is used in the solution which contains 0.4 kg per mt (0.8 lb per st) of NaCN. Pregnant solution from the heaps averages about 0.7 g Au per mt (0.02 oz per st) with a cyanide content of about 0. 2 kg per mt (0.4 lb per st) and a pH of plus 9. Addition of NaCN brings the pH of the leach solution up to 11 to 12. Carbon adsorption of the gold was originally done in six enclosed columns mounted in a trailer but five conventional columns have been substituted as the size of the operations has increased. Carbon stripping is with hot caustic, cyanide and 10% ethanol solution. The

Jan 1, 1981

By O. N. Carlson, H. A. Wilhelm, H. E. Lunt, J. M. Dickinson

On the basis of data obtained from microscopic examination, melting observations, cooling curves, X-ray analyses, and resistance measurements, phase diagrams have been proposed for the Th-Cb and Th-Ti alloy systems. Both are simple eutectic systems and have no terminal solid solubility or intermediate phases. The eutectic between thorium and columbium occurs at a composition of about 8 wt pct Cb and a temperature of 1435°C. The Th-Ti eutectic occurs at 1190°C at the composition 12 wt pct Ti. No change was observed in the transformation temperature of thorium in either system or in the titanium transformation. RECENT study of thorium and its alloys has been promoted because of the possibility of employing this metal in nuclear reactors. Their corrosion resistant properties, nuclear characteristics, and high melting points put columbium and titanium among the many metals being employed in the study of thorium alloys. Since a knowledge of the phase relationships would be important in the application of such an alloy, investigations were undertaken to propose phase diagrams for the Th-Cb and Th-Ti systems. Experimental Procedures Thorium metal sponge was specially prepared for use in this investigation. Carbon in a quantity less than 0.04 wt pct was the principal impurity. There was also less than 0.01 pct each of iron, calcium, zinc, aluminum, and nitrogen in the thorium. Columbium, both as a powder and sheet metal, was obtained from the Fansteel Metallurgical Corp. The manufacturer&apos;s specifications indicated that the metal contains less than 1 wt pct total impurities. An analysis of the metal showed approximately 0.18 pct C in the powder and less than 0.05 pct C in the sheet. The titanium used was commercial sponge, reported to be 99.5 pct Ti. An analysis showed that this metal contained 0.2 pct Fe. Preparation of Alloys—Since the metals used in this investigation are reactive and might become contaminated on melting in a refractory crucible, the alloys were prepared by arc melting. The titanium sponge was employed in the form of small lumps while the columbium additions were made either as pressed pellets of powder or as clippings from sheet. The alloying material and the thorium sponge were melted together under argon in conventional arc melting equipment employing a tungsten electrode and a water cooled copper crucible.

Jan 1, 1957

By W. R. Opie, O. W. Mole

By confining the electrolytic reduction of TiCl4 to the interior of a porous basket-cathode the electrolyte between the anode and the cathode can be kept free of reduced chlorides of titanium eliminating undesirable reactions of reduced titanium chlorides with brickwork or oxygen in the cell atmosphere. Semiwalls are not needed. Operating conditions are given and discussed. Titanium yields based on TiCl4 introduced are 93 pct. Cell voltage and amperage characteristics are adaptable to multiple cathode-series cell urmngements. EXPERIMENTS conducted in the National Lead Co., Titanium Division, Research Laboratories showed that titanium metal could be deposited in an electrolytic cell in which titanium tetrachloride was introduced through a tubular cathode.&apos; The reduced chlorides as formed were confined to the vicinity of the cathode. They were reduced to form a cocoon-shaped growth of sponge titanium metal at the end of the cathodic tube below the surface of a sodium chloride-strontium chloride electrolyte. No diaphragm was needed.&apos; Although high-purity, coarse crystalline metal was produced in the cocoon growth, the yields of metal removed from the cell, based on the amount of titanium introduced as TiCl4, were usually only 40 to 60 pct. The growth of the cocoon deposits was away from the cathodic tube for introduction of TiC14 toward the anode following the flu lines. The reduced chlorides of titanium diffused through the deposit and were reduced to titanium electrolytically within the deposit or on the outer surfaces. Deposition within the pores of the cocoon was detrimental to further deposition because it plugged the passages used by the reduced chlorides to diffuse away from the point of titanium introduction. As plugging due to deposition in the pores proceeded, the reduced chlorides in the center of the cocoon would force their way out by forming a channel and would escape from the vicinity of the cathode without being reduced to metal. Some work had been done previously1, 2 which indicated that if the end of the cathodic tube for introducing TiC14 was surrounded by a screen connected to the tube so that it too was cathodic, growth could be made to occur within the screen. Direction of growth was observed to be from the screen toward the point of TiCl4 introduction. Through a series of design modifications a cathode evolved which consisted of an introduction tube surrounded by a perforated metal basket as shown in Fig. 1. Modifications of this design are described in Refs. 3, 4, and 5. This basic cathode designa" was incorporated in electrolytic cells containing graphite anodes and constructed of high-silica brick refractory for containing the electrolyte (see Fig. 2). The inner crucible was surrounded by insulating brick and the entire unit contained in a welded steel shell. Suitable cooling chambers with inert gas atmospheres were devised so that the cathode could be removed from the cell without exposing the deposit to air while hot. Various alkali and alkaline earth chlorides were used as electrolytes.

Jan 1, 1961

By W. R. Ingalls

Jan 1, 1922

By W. R. Ingalls

Jan 1, 1922

By Reuben B. Ellestad, Fremont F. Clarke

Lithium chemical plant extraction methods are discussed with reference to 1) base exchange with alkali sulphates; 2) processing based on roasting with lime; 3) miscellaneous methods; and 4) application of the Lithium Corp. process to extraction of lithium from run-of-mine, low grade spodumene ore, or concentrates. IN the early days of the lithium industry most of the production was from lepidolite, zinnwaldite, and amblygonite. Nearly all the early extraction processes described in the literature involve heating the finely ground mineral with sulphuric or hydrochloric acid. On subsequent water leaching most of the bases present in the mineral (especially aluminum) are dissolved as sulphates. As a result, the leach solution required extensive chemical purification before the lithium could be precipitated as carbonate. Following the remarkable growth of the lithium industry to its present size, zinnwaldite and amblygonite ores must be considered of minor importance only. Attention is now focused on spodumene, abundant enough in North America to be a major source of supply, and there are important supplies of lepidolite and petalite in Africa. The extraction processes described below all apply to spodumene, although several will also operate on other lithium minerals, such as petalite. Base Exchange with Alkali Sulphates: A distinct advance was made with the disclosures of Wadman and von Girsewalt. In these methods the finely ground silicate ore (spodumene or lepidolite) is intimately mixed with an excess of alkali sulphate (usually K2SO4) in at least a 1 to 1 proportion, and the mixture was heated to a relatively high temperature. Base exchange results, with the formation of lithium sulphate. A water leach dissolves the lithium sulphate, together with the excess potassium sulphate. Successful operation of this type of process requires very thorough grinding and mixing, as well as careful temperature control. The use of K2SO4 is objectionable from cost considerations since purification of lithium carbonate requires the use of potassium carbonate, if the K2SO4 is to be recovered and recycled. The lower solubility of K2SO4 as compared with Na2S04 is also objectionable, since it limits the concentration of the Li2SO4 solution to be precipitated by K2SO4. Early laboratory-scale investigation of this process by Lithium Corp. was not encouraging. Other related base exchange processes are those of Lindblad, Wallden, and Sivander3 and Sivander, Gard, Villestad, and Wallen4. The former covers the reaction of lithium silicate minerals with a sodium sulphate solution, at 100" to 300°C (under pressure), while the latter involves the extraction of silicate minerals with molten sodium sulphate. Both these processes would seem to be difficult and expensive to operate.

Jan 1, 1956

By R. W. Fenn, H. A. Lepper, W. R. Hibbard

A. J. Shaler—I should like to congratulate the authors on the presentation of this paper, which we have been awaiting a long time. The view they have taken of the sintering process, namely that voids are comparable to particles of a second phase capable of dissolving to a slight extent in the metal phase, is an interesting but dangerous one. Pines has given a first-order solution of the problem and Has predicted a decrease in the concentration of pores near the surface. The authors of the present paper have experimentally demonstrated the second-order effects, that is, the diffusion of the space phase between voids of different sizes, and also the movement of atoms from highly curved parts of a void to less curved regions of the same void. I have recently calculated the rate of vapor-phase transport within odd-shaped pores in copper at 850 °C and found that probably at that temperature volume flow is the more rapid shape-changing mechanism. The authors of the present paper have found that at 1000°C, vapor-phase transport is dominant. There is no disagreement here, I think. The dominant phenomenon can easily be different in different temperature ranges and with different pore shapes: I used a cylinder going to a sphere, not a tricuspid going to a "triple cuspidor." But there is some danger in the other art of the explanation, that is, in the study of the diffusion of vacancies from a pore to its neighbors and to the outside. A vacancy is very different in dimension from an atom. When it moves, it carries a field of elastic strain. This has to be taken into account. A concentration gradient of vacancies can cause them to diffuse. But in the absence of such a gradient, they can be made to diffuse by a field of stress. What happens in some of our experiments, and it is most noticeable in the shrinkage of synthetic cylindrical pores, like the tubes we have been working with, may be broken down into the following steps. (1) The presence of a surface establishes a vacancy concentration gradient, as Dr. Kuczynski and the present authors have shown. (2) Vacancies then diffuse in order to decrease this gradient. (3) In so doing, they cause an elastic field to be built up in such a direction as to oppose the diffusion, so that it slows down until it reaches a steady-state rate. (4) The steady-state flow is due to the fact that the surface tension acting on curved surfaces applies a stress to the system which itself mechanically causes vacancy diffusion. What I have said is that the diffusive types of flow of the authors and of Dr. Kuczynski are transient phenomena which soon stop if the pores are large. We are then left with a mechanical problem only, and our researches have not yet disclosed just what the mechanism of flow is; it may be a slip process, or it may take place by a vacancy diffusion of the type Nabarro has de-

Jan 1, 1951

By D. G. Westlake, D. T. Peterson

The saturation solubility of thorium dihydride in thorium was studied by saturation of samples and subsequent analysis. The solubility increased from about 1 at. pct at 300°C to above 20 at. pct at 800 °C. Over this temperature range the log of the solubility was a linear function of the reciprocal absolute temperature for thorium of good purity. The heat of solution of thorium dihydride was found to be 7.9 kcal per atom of hydrogen in crystal bar thorium and 6.6 kcal per atom of hydrogen in Ames thorium, The important effect of hydrogen on the physical and mechanical properties of many metals is receiving increasing recognition. The basic physical and chemical data necessary to help explain the observed effects of hydrogen on the mechanical proper ties of metals are all too often not available. The solubility of hydrogen in thorium metal was determined to provide a portion of this basic data for the thorium-hydrogen system. The absorption of hydrogen by thorium metal and the formation of thorium hydrides was studied by several investigators, beginning in 1891, and their work is summarized in Gmelin&apos;s Handbuch.1 No effort was made to determine the extent of solid solubility in the metal in these early investigations and the impure metal available made interpretation of the results uncertain. Nottorf2 reported the results of a careful study of pressure-composition isotherms for the thorium-hydrogen system. The principal interest in this work was in the composition and dissociation pressures of the thorium hydrides. Mallett and campbel13 reported the pressure-composition isotherms for the thorium-hydrogen system up to the composition of thorium dihydride. The saturation solubility of thorium dihydride in thorium was reported to be 13 at. pct at 650°C and 23 at. pct at about 900° C. Mallett and Campbell used thorium metal which had been prepared by the calcium reduction of thorium tetra-fluoride or thorium oxide. The results obtained with thorium of these two types agreed within the experimental error. PROCEDURE AND MATERIALS Procedure—The method used to determine the solubility was to saturate a sample of thorium with hydrogen and analyze a portion of the saturated sample. This method was chosen rather than a determination of pressure-composition isotherms since it was much less time consuming and could be applied at temperatures at which the equilibrium hydrogen pressure was too low to measure. The

Jan 1, 1960