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By R. Philip Hammond

Monazite has had a Cinderella-like history. Although nearly go per cent pure rare-earth compound (rare-earth phosphate) it was sought at first not for the rare earths but for the sake of a minor constituent—thorium. The thorium, essential for the Welsbach gaslight mantle, was present in only small quantities and the principal constituents, the rare earths, were largely discarded. Gradually, however, the rare earths have developed uses of their own and today have left the thorium far behind in value. Occurrence Monazite was first produced commercially about 1886, in North Carolina, where it was collected in small sluices by farmers who found it in stream beds on their land. The deposits were later exploited on a larger scale, but were mostly abandoned in a few years, when monazite from Brazil came upon the market in far larger quantities. Domestic production ceased entirely in 1906. The Brazilian source is still active, together with Indian, Dutch East Indies, and Australian deposits. Several other localities in the United States have yielded monazite, but none of these has produced commercially as yet. Monazite occurs originally in pegmatite~ and gneisses, through which, unfortunately, it is scattered in highly dispersed form. All commercially useful deposits consist of transported monazite sands liberated by erosion and concentrated by the action of water, which has sluiced away lighter materials and concentrated the heavy (D = 5.0 to 5.2) grains of monazite, together with ilmenite, zircon, garnet, and other dense minerals. The Carolina deposits were in stream beds; most of the other deposits mentioned are on or near the seashore, where the action of the waves has served to concentrate the monazite. In most cases today, the sands are worked to obtain the ilmenite and zircon, as well as monazite. The minerals are separated by means of sluices, dry tables, and magnetic separators, and each is finally obtained nearly pure. No crushing or grinding is necessary. The concentrates are shipped in fiber bags. Composition of Monazite As Table I illustrates, monazite is the anhydrous orthophosphate of the cerium Table i.—Typical Analysis of a Monazite Sand (India). Per Cent Thorium oxide............................. 8.1 Cerium oxide.............................. 30.6 Lanthanum oxide........................... 15. 7 Neodymium oxide.......................... 10.5 Praseodymium oxide........................ 2. 9 Samarium oxide............................ 1.0 Europium. gadolinium, and terbium oxides.... 0.7 Yttrium oxide.............................. 0.4 Dysprosium, holmium, erbium. thulium, ytterbium. and lutecium oxides................. 0. 1 Silicon oxide............t................... 2.4 Calcium, aluminum, and iron oxides.......... 1.0 Uranium oxide............................. 0.3 Phosphorus pentoxide....................... 26. 2 a The values given for the rare earths following samarium are approximate. being based upon analyses of concentrated fractions derived from monazite. The composition given represents Travancore monazite carefully freed from other minerals. goup of rare-earth elements. A small amount of yttrium and terbium group phosphate is also present.* All the rare-

Jan 1, 1948

By R. Philip Hammond

Monazite has had a Cinderella-like history. Although nearly go per cent pure rare-earth compound (rare-earth phosphate) it was sought at first not for the rare earths but for the sake of a minor constituent—thorium. The thorium, essential for the Welsbach gaslight mantle, was present in only small quantities and the principal constituents, the rare earths, were largely discarded. Gradually, however, the rare earths have developed uses of their own and today have left the thorium far behind in value. Occurrence Monazite was first produced commercially about 1886, in North Carolina, where it was collected in small sluices by farmers who found it in stream beds on their land. The deposits were later exploited on a larger scale, but were mostly abandoned in a few years, when monazite from Brazil came upon the market in far larger quantities. Domestic production ceased entirely in 1906. The Brazilian source is still active, together with Indian, Dutch East Indies, and Australian deposits. Several other localities in the United States have yielded monazite, but none of these has produced commercially as yet. Monazite occurs originally in pegmatite~ and gneisses, through which, unfortunately, it is scattered in highly dispersed form. All commercially useful deposits consist of transported monazite sands liberated by erosion and concentrated by the action of water, which has sluiced away lighter materials and concentrated the heavy (D = 5.0 to 5.2) grains of monazite, together with ilmenite, zircon, garnet, and other dense minerals. The Carolina deposits were in stream beds; most of the other deposits mentioned are on or near the seashore, where the action of the waves has served to concentrate the monazite. In most cases today, the sands are worked to obtain the ilmenite and zircon, as well as monazite. The minerals are separated by means of sluices, dry tables, and magnetic separators, and each is finally obtained nearly pure. No crushing or grinding is necessary. The concentrates are shipped in fiber bags. Composition of Monazite As Table I illustrates, monazite is the anhydrous orthophosphate of the cerium Table i.—Typical Analysis of a Monazite Sand (India). Per Cent Thorium oxide............................. 8.1 Cerium oxide.............................. 30.6 Lanthanum oxide........................... 15. 7 Neodymium oxide.......................... 10.5 Praseodymium oxide........................ 2. 9 Samarium oxide............................ 1.0 Europium. gadolinium, and terbium oxides.... 0.7 Yttrium oxide.............................. 0.4 Dysprosium, holmium, erbium. thulium, ytterbium. and lutecium oxides................. 0. 1 Silicon oxide............t................... 2.4 Calcium, aluminum, and iron oxides.......... 1.0 Uranium oxide............................. 0.3 Phosphorus pentoxide....................... 26. 2 a The values given for the rare earths following samarium are approximate. being based upon analyses of concentrated fractions derived from monazite. The composition given represents Travancore monazite carefully freed from other minerals. goup of rare-earth elements. A small amount of yttrium and terbium group phosphate is also present.* All the rare-

Jan 1, 1948

By Henry F. Herley

The New Orient mine, owned and operated by the Chicago, Wilmington & Franklin Coal Co., has caused a great deal of comment and interest because of its unusual features and huge daily production. It is in Franklin County, Illinois, adjacent to the town of West Frankfort. The seam being mined is the Illinois No. 6 which in this locality is 9 to 12 ft. thick and lies approximately 500 ft. below the surface. Without fear of contradiction, it can be said that this is one of the largest coal mines in the world from a daily production standpoint. During 1928, New Orient produced 2,400,000 tons, which amounts to over 10,000 tons each day the mine operated that year. The mine is built for a capacity of 12,000 tons but has actually hoisted over 15,000 tons in one 8-hr, shift. This enormous production can perhaps be better visualized if it is realized that each day's operation depletes over two acres of coal. The general features of this mine have already been fully covered in a paper by George B. Harrington,' President of the Chicago, Wilmington & Franklin Coal Co. In a paper of the nature of Mr. Harrington's, it was unnecessary to stress any particular phase of mining conditions, consequently the ventilation problems were touched upon but lightly. In this paper an attempt has been made to describe some of the problems which have been encountered in providing adequate ventilation for the mine. Ventilating Conditions The acreage allotted to New Orient mine has a length, north and south, of approximately 6 miles, and a width, east and west, of 2 to 4 miles. A number of important considerations caused the hoist shaft, air shaft and surface plant to be located near the southeast corner of the property, instead of near the center, as is usual. During the initial phase of the mine development, the mine was ventilated through these shafts, although there was a full realization that at some future date other shafts would be required.

Jan 1, 1930

By Richard Klimpel

In this paper various formulae are developed which can be used to estimate stream flow rates or weight ratios given information on the stream components. The type and level of experimental error present in the stream component analyses does have an important bearing on the numerical values (and reliability) of the weight ratios calculated by the various formulae. A simple but theoretically sound method is shown for selecting appropriate estimation formulae for any given engineering operation. The derived formulae are applied to sets of experimental classification data for illustration purposes.

Jan 1, 1980

By A. J. Shaler, J. Prieto Isaza, John Wulff

TANTALUM metal has a number of unique properties which give it widespread application in modern technology and in research. In electronic apparatus involving high temperatures in vacuo some of the refractory metals become brittle. Tantalum retains its ductility at elevated temperatures, and this property, together with its low vapor pressure and its ability to absorb gases, make it important in this field. Its chemical inertness in the presence of acids, halogens, and other corrosive media, makes it useful in chemical apparatus and in neuro and orthopedic surgical applications. As an addition to tungsten carbide in steel-cutting grades of cemented-carbide tools, the carbides of tantalum and of its sister element columbium have found considerable use. The present-day method1 of manufacturing tantalum is to sinter a powder compact of the metal in vacuo. Because tantalum- columbium alloys are difficult to work and since tantalum ores almost always contain columbium, the two metals must be separated chemically, the products of the separation being generally in the form of potassium tantalum fluoride and potassium columbium oxyfluoride. These salts are used in fused-salt electrolytic baths from which coarse metallic powder is deposited as a sponge at the cathode. Finer powder can be made from the coarse product or from tantalum scrap by first submitting it to an embrittling heat treatment in hydrogen and then crushing it. The fine hydrogen- containing powder may subsequently be degassed in vacuo at a high temperature. Prompted by the success of others2,3 in the magnesium reduction of titanium and zirconium halides, one of the authors under- took4 an investigation of the thermo- chemistry of the reaction between solid magnesium and gaseous tantalum penta-chloride, a subject which had not previously been studied. He found that the heat of formation of tantalum pentachloride is approximately 364,250 cal per mol at temperatures lower than the melting point of magnesium. A value of 83 units was found for the standard entropy at these temperatures. With these values, it was shown that magnesium and tantalum pentachloride are capable of reacting exothermically at temperatures less than the melting point of magnesium, and that no great violence is to be expected when these substances are heated together. The exothermic nature of the reaction indicated that the process should be efficient and should not require much externally applied energy. Tantalum pentachloride is not commonlv made commercially, and any process using it therefore involves the subsidiary problem of producing and handling this substance. A series of experiments was carried out in which dried chlorine saturated with carbon tetrachloride was passed over heated tantalum, either in the metallic state or combined

Jan 1, 1947

By Richard W. Lodge

Mr. H. R. Batcheller, of the class of 1894, Massachusetts Institute of Technology, while experimenting with chlorine gas on a certain lot of roasted concentrates, met with the following difficulties: 1. A poor extraction of the gold. 2. A very large consumption of chlorine gas. 3. Inability to precipitate all of the gold from the solutioil containing the AuC1,. 4. The bullion obtained was very base. These difficulties were the same whether the chlorine was generated from H2SO47 MnO29 and salt, or whether H2SO, and bleaching powder were used. They may be accounted for partly by the presence of some arsenic left in the roasted ore, and partly by the presence of copper in the solution containing the AuCI3. It was therefore suggested to try the effect of bromine on a similar lot of ore. The use of this element is, of course, nothing new, but in the following experiments it seemed to present many advantages over chlorine. The material worked upon consisted of some concentrates containing 2.31 ounces of gold per ton, and 34.26 per cent. of arsenic, which would correspoild to about 74.4 per cent. Of

Jan 1, 1896

By Earl S. Greiner, Eric R. Jette

ALTHOUGH the mechanical and chemical characteristics of certain iron-nickel-silicon alloys have been investigated,1 the available literature shows no results of a systematic investigation of the constitution of this system. This paper describes the results of an X-ray investigation of the constitution of the iron-rich iron-nickel-silicon alloys at 600°C. Data on the constitution of the included binary systems obtained in other investigations have been correlated with the structure of the ternary alloys. Jette and Foote2 have presented a tentative constitutional diagram of the iron-nickel system following X-ray studies on quenched specimens. This diagram shows that the alloys at 600°C. containing from zero to approximately 4 atomic per cent nickel consist of a body-centered cubic (alpha) phase, the alloys containing 4 to 24 atomic per cent nickel consist of body-centered cubic (alpha) and face- centered cubic (gamma) phases, and the alloys containing from 24 to 100 atomic per cent nickel consist of a face-centered cubic (gamma) phase. These investigators recognized that it was not possible to retain the gamma phase in equilibrium by quenching alloys containing less than approximately 25 atomic per cent nickel and that high-temperature X-ray methods were desirable to determine the gamma-phase solubility limit. In a later investigation of the iron-nickel alloys, Owen and Sulley3 determined the alpha-phase solid solubility limit to be 3.5 atomic per cent nickel at 600°C. High-temperature X-ray methods showed the solid solubility limit of the gamma phase to be 14 atomic per cent nickel at 600°C. Since the high-temperature X-ray method should reveal equilibrium conditions in these alloys better than the quench method of other investigators, the results of Owen and Sulley pertaining to the gamma-phase boundary are to be preferred. As the result of an X-ray investigation of quenched iron-silicon alloys, Greiner and Jette4 have shown these materials to consist of a body-centered cubic (alpha) phase containing from o to 26.4 atomic per cent silicon at 600°C. The alloys containing from 26.4 to approximately 50 atomic per cent silicon consist of two phases at 600°C.; namely, alpha and eta. The eta phase corresponds to the stoichiometrical formula FeSi (33.4 wt. per cent Si).* The literature pertaining to the constitution of the nickel-silicon alloys has been reviewed by Ackerman,5 who found disagreements in the results of various investigators on several parts of the system. Subsequent data on the constitution of the nickel-silicon alloys were reported by Osawa and Okamoto.6

Jan 1, 1943

By F. V. Shallcross

Physical properties of thin films of CdS and CdSe formed by vacuum deposition onto glass sibstrates have been studied as a function of deposition and processing conditions. The crystallinity and surface features of CdS films were examined using electron microscopy and electron and X-ray diffraction techniques. The films were poly crystalline; the preferred orientation and crystallite size increased with film thickness, substrate temperature, and deposition time. The CdS films consisted primarily of hexagonal-phase material, in contrast to similarly prepared CdSe films which have previously been observed to contain mixtures of cubic and hexagonal phases. As-deposited CdS films showed no major dependence of Hall mobility on crystallite size or degree of preferred orientation. Hall mobility and carrier concentration in CdS and CdSe .films were measured at various temperatures; both parameters increased with temperature and yielded activation energies which depended on fabrication conditions. Surface-desorption phenomena and overcoating of the semiconductor with SiO affected the observed electrical properties significantly. THIN films of cadmium sulfide1,2 and cadmium sele-nide3,4 have been employed by various workers as semiconductors in the insulated-gate thin-film field-effect transistor, known as the TFT. These devices are most commonly made by vacuum deposition of all materials onto an amorphous substrate such as glass. A knowledge of the microstructure and electrical properties of semiconductor layers used in the thin-film transistor is essential in order to form a realistic model for the device and to improve its performance, reproducibility, and reliability. This paper will describe studies of the physical properties of vacuum-deposited CdS and CdSe films prepared under various conditions. Structural characteristics examined in- cluded phases present, crystallite size, nature of preferred orientation of crystallites, surface roughness, and structural homogeneity throughout the film thickness. Electrical properties measured were Hall mobility and conductivity and their dependence on temperature and ambient. Thin-film properties are affected by many fabrication parameters including purity and physical form of evaporant, deposition rate, film thickness, design and temperature of the evaporation crucible, geometry of the deposition chamber, nature of the residual atmosphere, composition and temperature of the substrate, and details of postdeposition processing. PREPARATION OF FILMS In this work the semiconductor films were deposited in a conventional oil-diffusion-pumped system with pressures in the 10-8 torr range. The CdS evaporant was obtained from the Eagle-Picher Co. as a high-purity coarse-grained crystalline powder; the CdSe was a high-purity sintered powder supplied by the Harshaw Chemical Co. The evaporation crucible was a resistance-heated molybdenum-wire basket coated with aluminum oxide and filled with a quartz wool plug at the top. The source to substrate distance was usually 10 cm. This region was enclosed by a Pyrex inner cylinder. The substrate was heated with an overlying Pyrex plate coated with tin oxide. The substrate temperature was controlled using a thermocouple attached to the lower side of the heater. This thermocouple was calibrated against another thermocouple attached to a dummy substrate and by observation of melting points of various metal films deposited in the system. The substrates were polished borosilicate glass plates and conventional glass microscope slides. Substrate preparation included cleaning with an ultrasonically agitated detergent bath followed by isopropanol-vapor de-greasing. Film thickness was measured interferomet-rically during and after deposition. STRUCTURE OF CdS FILMS Structural studies were performed on CdS films using electron diffraction, electron microscopy, and

Jan 1, 1967

By Archer E. Wheeler, Milo W. Krejci

The Boston & Montana Reduction Works at Great Falls, Mont., was formerly the reduction works of the Boston & Montana Consolidated Copper & Silver Mining Co., and continued as the reduction plant for the independent company until June 1, 1910, when the consolidation of a large number of the operating companies of Butte was effected. It then became merged in the Anaconda Copper Mining Co. as the Boston & Montana Reduction Department of the Anaconda Copper Mining Co. The history of copper converting at this plant, while not covering the entire period of the commercial use of the process in this country, does cover by far the larger part of it, and as the operation of and appliances for the process have undergone many changes during the time, it may, perhaps, be of some interest to put the record of these changes into permanent form. The plan followed in the preparation of this paper has been to give first a brief chronological record of the principal events and changes and then, even at the risk of some repetitions, to give more detaild accounts of some of these changes under separate headings. The headings for the complete paper are as follows: 1. General. Chronological Review. 10. Development of Different Classes 2. Mechanical Manipulation. of Converters After Class I. 3. Casting of Finished Copper. 11. Basic Lining. 4. Tamping of Linings. 12. Number and Size of Tuyeres. 5. Early Acid Linings. 13. Cast Copper Tuyeres. 6. Acid Linings With the Use of Ore. 14. Efficiency of Air. 7. Introduction of Flux Through the 15. Size of Converter Mouth. Tuyeres. 16. Height of Converter. 8. Bottom Blast. 17. Summary. 9. Disposal of Converter Slag, General Chronological Review. Ground was broken for the general concentrating and smelting plant in the spring of 1,891. The first departments to start operations were the concentrator in March, 1892, and the Brückner roasting and reverbera-tory smelting departments in April, 1892. The converter department

Jan 1, 1914

By W. D. France, H. l. Burghoff

FABRICATORS of copper and copper alloys have contended with the problems of reconversion during the past year in endeavoring to return to the full-scale production that is demanded of them. The problems have not been easy, for the industry, like so many others, has had to deal with strikes of long duration, and material shortages, particularly in the raw materials, copper, zinc, lead, and tin. Despite all these obstacles, it was possible to gear production to new peacetime records during the latter part of the year. This was made possible not only by the use of multiple shifts of personnel, but also by the improved production equipment, the development of which had been stimulated by wartime necessity. The work of installing new and better equipment is still continuing, and virtually every company is engaged in improving or planning to improve its processes.

Jan 1, 1947

By Eric R. Jette, Earl S. Greiner

Although the mechanical and chemical characteristics of certain iron-nickel-silicon alloys have been investigated,1 the available literature shows no results of a systematic investigation of the constitution of this system. 'This paper describes the results of an X-ray investigation of the constitution of the iron-rich iron-nickel-silicon alloys at 600°C. Data 011 the constitution of the included binary systems obtained in other investigations have been correlated with the structure of the ternary alloys. Jette and Foote2 have presented a tentative constitutional diagram of the iron-nickel system. following X-ray studies on quenched specimens. This diagram shows that the alloys at 600°C. containing from zero to approximately 4 atomic per cent nickel consist of a body-centered cubic (alpha) phase, the alloys containing 4 to 24 atomic per cent nickel consist of body-centered cubic (alpha) and face-centered cubic (gamma) phases, and the alloys containing from 24 to Ioo atomic per cent nickel consist of a face-centered cubic (gamma) phase. These investigators recognized that it was not possible to retain the gamma phase in equilibrium by quenching alloys containing less than approximately 25 atomic per cent nickel and that high-temperature X-ray methods were desirable to determine the gamma-phase solubility limit. In a later investigation of the iron-nickel alloys, Owen and Sulley3 determined the alpha-phase solid solubility limit to be 3.5 atomic per cent nickel at 600°C. High-temperature X-ray methods showed the solid solubility limit of the gamma phase to be 14 atomic per cent nickel at 600°C. Since the high-temperature X-ray method should reveal equilibrium conditions in these alloys better than the quench method of other investigators, the results of Owen and Sulley pertaining to the gamma-phase boundary are to be preferred. As the result of an X-ray investigation of quenched iron-silicon alloys, Greiner and Jette4 have shown these materials to consist of a body-centered cubic (alpha) phase containing from o to 26.4 atomic per cent silicon at 600°C. The alloys containing from 26.4 to approximately 50 atomic per cent silicon consist of two phases at 600°C.; namely, alpha and eta. The eta phase corresponds to the stoichiometrical formula FeSi (33.4 wt per cent Si)." The literature pertaining to the constitution of the nickel-silicon alloys has been reviewed by Ackerman,' who found disagreements in the results of various investigators on several parts of the system. Subsequent data on the constitution of the nickel-silicon alloys were reported by oSawa and okamoto.6

Jan 1, 1943

By Earl S. Greiner, Eric R. Jette

Although the mechanical and chemical characteristics of certain iron-nickel-silicon alloys have been investigated,1 the available literature shows no results of a systematic investigation of the constitution of this system. 'This paper describes the results of an X-ray investigation of the constitution of the iron-rich iron-nickel-silicon alloys at 600°C. Data 011 the constitution of the included binary systems obtained in other investigations have been correlated with the structure of the ternary alloys. Jette and Foote2 have presented a tentative constitutional diagram of the iron-nickel system. following X-ray studies on quenched specimens. This diagram shows that the alloys at 600°C. containing from zero to approximately 4 atomic per cent nickel consist of a body-centered cubic (alpha) phase, the alloys containing 4 to 24 atomic per cent nickel consist of body-centered cubic (alpha) and face-centered cubic (gamma) phases, and the alloys containing from 24 to Ioo atomic per cent nickel consist of a face-centered cubic (gamma) phase. These investigators recognized that it was not possible to retain the gamma phase in equilibrium by quenching alloys containing less than approximately 25 atomic per cent nickel and that high-temperature X-ray methods were desirable to determine the gamma-phase solubility limit. In a later investigation of the iron-nickel alloys, Owen and Sulley3 determined the alpha-phase solid solubility limit to be 3.5 atomic per cent nickel at 600°C. High-temperature X-ray methods showed the solid solubility limit of the gamma phase to be 14 atomic per cent nickel at 600°C. Since the high-temperature X-ray method should reveal equilibrium conditions in these alloys better than the quench method of other investigators, the results of Owen and Sulley pertaining to the gamma-phase boundary are to be preferred. As the result of an X-ray investigation of quenched iron-silicon alloys, Greiner and Jette4 have shown these materials to consist of a body-centered cubic (alpha) phase containing from o to 26.4 atomic per cent silicon at 600°C. The alloys containing from 26.4 to approximately 50 atomic per cent silicon consist of two phases at 600°C.; namely, alpha and eta. The eta phase corresponds to the stoichiometrical formula FeSi (33.4 wt per cent Si)." The literature pertaining to the constitution of the nickel-silicon alloys has been reviewed by Ackerman,' who found disagreements in the results of various investigators on several parts of the system. Subsequent data on the constitution of the nickel-silicon alloys were reported by oSawa and okamoto.6

Jan 1, 1943

By J. C. Jaeger

It frequently happens in engineering and mining situations that "bad" rock is encountered which consists of rock broken up into blocks a few inches or less in diameter by a network of intersecting joints. These joints may be open, or filled by veins of solid material, or covered with weathering products. Essentially, the material consists of an aggregate of small interlocking blocks. In such circumstances, major joint systems usually can be recognised and studied, but there are probably many minor planes of weakness which may cause the blocks to be of almost random shape. It is extremely difficult to determine the properties of such materials. Measurements on small specimens give the properties of the constituent rock and not the jointed material. At the other extreme, the material has occasionally been tested as loose aggregate in large triaxial pots, but this gives no information about the strengthening effect of the interlocking of the small blocks of rock. One simple approach, which has been much used, is to regard the rock as randomly jointed on a small scale and to apply soil mechanics theory to it. In this case, the normal and shear stress at failure are related by [ ] where the coefficient of friction p and the cohesion c will be those of the individual joints. Even in very bad rock, it is usually possible to drill core in small diameters of 1 to 2 in. which will contain a number of joints, both open and filled. The testing of such joints provides one simple method of determining some of the properties of closely jointed rock and will be discussed in detail in the next section. Calculations based on Eg. 1 with values of c and µ obtained in this way may be expected to give a lower limit for the strength of structures in rock.

Jan 1, 1970

By A. Blake Caldwell

The continental margins and ocean basins represent by far the largest unexplored frontier for discovery and development of mineral values. In April 1971, Deepsea Ventures, Inc., at a press conference in its Gloucester Point, Va. headquarters, announced what may become the first commercial deepsea venture--15,000 ft below the ocean surface. During the presentation, Deepsea's president, John E. Flipse, announced that studies made by company personnel had proven the feasibility of mining, transporting, and milling L million tpy of manganese nodules taken from the ocean floor, and that, based on current conditions and prevailing construction costs, a venture of this magnitude would cost about $200 million split evenly between mining and processing facilities. A subsidiary of Tenneco, Deepsea has tentatively reserved 1976 as the year in which it plans to mine, process and market the nodules.

Jan 1, 1971

By C. C. Whittier

CIVILIZATION'S PROGRESS, which has multiplied man's comforts, conveniences, a n d happiness, is based upon the extensive employment of natural minerals and sources of energy. Mineral resources are basic factors in modern economic development, machine industry, international trade and world power. A survey of mineral consumption shows that the United States leads the world in the production and consumption of energy materials, of metals, and of the large and diverse array of earth materials that fall in the nonmetallic mineral group. The use of nonrnetallic minerals exceeded both the metals and the fuels in the long period before the industrial age, but it is only in the last two decades that consumption of non- metals has kept pace with and approximated in value the output of metals. Although the data of production in the first half of the last century are meager and fragmentary, the record of the past fifty years-the period of most rapid growth-is available, and reveals an astounding growth.

Jan 1, 1933

By S. C. Lindsay, D. J. I. Evans

With each year that passes hydrometallurgical processes are being more widely used to recover base metals from ores and concentrates. Generally these processes involve liquid-solid separation of metal-bearing liquors from barren residues. This may be done by countercurrent decantation, thickening and filtration, or filtration or centrifuging only. Choice of method is governed by chemical and physical characteristics of the pulps; cost of labor, power, materials, and waste disposal; and even by the amount of capital available when building plans are under way. Since all these controlling factors change with time and location and with technological advances, the separation method must be re-evaluated when new plants or expansion programs are contemplated. At the Sherritt Gordon refinery in Fort Saskatchewan, Alberta, an ammonia pressure leaching process recovers nickel, copper, and cobalt from the nickel concentrate produced at Lynn Lake, Manitoba.' Pregnant liquors are separated from the barren leach residues in a thickener-filter liquid-solids circuit. The decision to use this type of separation was based on a summation of economic factors during the pilot plant and design stages. Although countercurrent decantation was not incorporated in the refinery flowsheet, the problems solved in thickening the leach residues and the experience gained in operating the commercial plant are pertinent to countercurrent decantation, particularly where it is applied to slow-settling leach slurries or slurries having a relatively high vapor pressure of a valuable, obnoxious, or poisonous vapor. The nickel sulfide concentrate is leached under pressure with air and ammonia to dissolve the nickel, copper, and cobalt and most of the sulfur, leaving a residue of iron and siliceous material to be discarded.2,3 During a subsequent distillation stage to recirculate part of the ammonia used for leaching, copper is recovered from the solution as a high-grade sulfide. After further purification to remove traces of copper and undesirable sulfur compounds, the nickel is precipitated by hydrogen under pressure at an elevated temperature. The cobalt, together with unreduced nickel, is precipitated as a mixed metal sulfide by hydrogen sulfide for eventual cobalt recovery. The end solution is then evaporated to produce a crystalline ammonium sulfate byproduct. As shown in Fig. 1, the nickel concentrate is leached in a continuous, two-stage, countercurrent circuit. In the first stage, or adjustment leach, the fresh concentrate is partially leached (60 pct) in the liquor produced in the second stage, or final leach. This system is necessary to produce a solution suitable for treatment in the copper sulfide precipitation step. Both stages are carried out at 170" to 180°F under a total pressure, with air, of 100 to 120 psig in large, horizontal, water-cooled autoclaves. The autoclaves are divided by overflow weirs into four compartments to give a certain amount of staging during leaching. In each compartment a relatively slow-speed (100 to 150 rpm) agitator maintains the nickel concentrate in suspension. Adjustment leaching, carried out in two autoclaves in parallel, is followed by a thickener-filter liquid-solids separation. Final leaching is done in two parallel trains of three autoclaves using aqueous ammonia to extract metal values from the adjustment leach residues. This too is followed by a thickener-filter circuit. Here the residues are repulped once with aqueous ammonia and twice with process water and refiltered after each repulping stage, to insure a maximum recovery of soluble metal, before being discarded to the tailings pond. The adjustment leach is followed by a seven-disk Dorr-Oliver American filter, with an agitator in the filter boot to keep the residues in suspension. Agitators have also been installed beneath the four ten-disk filters following the final leach thickener. Slurry Characteristics: A typical analysis of the Lynn Lake nickel concentrate, produced by differential flotation,' is given in Table I. The concentrate comprises 35 to 49 pct pentlandite, (Fe, Ni)S; 3 to 6 pct chalcopyrite, CuFeS,; 1 to 4 pct pyrite, FeS2; and 24 to 42 pct pyrrhotite, Fe1-2S (where x varies between 0 and 0.2) together with various siliceous minerals such as actinolite, hornblende, and talc. During leaching, the sulfur in the pentlandite, chalcopyrite, and part of the pyrrhotite is successively oxidized through the thiosulfate and poly-thionate radicals to sulfate and sulfamate." Simultaneously the nickel, copper, and cobalt are converted to soluble ammine complexes and the iron in the pentlandite, chalcopyrite, and part of the pyrrhotite is oxidized to a spongy hydrated iron oxide. The hydrated iron oxide is readily broken down by the agitation needed to sustain the concentrate in suspension and to maintain a satisfactory mass transfer of the oxygen from the air to the slurry. Table I shows typical chemical, screen, and

Jan 1, 1961

By D. H. Newland

New York has a small but not insignificant place in the oil and natural gas industries of the United States. It has had a continuous record as an oil producer since 1872, with an aggregate yield of about 104,000,000 bbl. The reported output for 1935 was 4,237,000 bbl., a gain of more than 10 per cent for the year and a total that has been exceeded only in the early period of flush production half a century ago. The industry has been steadily building up since 1920 with the successful practice of the water drive, which has given a new lease of life to pools that had been practically drained of oil recoverable by pumping. An additional output of 2000 bbl. or more per acre is being procured by this method. Altogether the fields in New York State cover about 55,000 acres. Their limits are well defined and it is unlikely that they will be extended in the future, although there is some prospect of finding additional supplies by deeper drilling. The oil from New York is all classed as Pennsylvania grade, for which the recent price has been about $2.50 a barrel. It is refined at Olean, Wellsville and Bolivar, in the oil district, and partly in Pennsylvania refineries. Exploration for natural gas, outside of the established districts, was considerable during the year. Altogether 59 wells were drilled, distributed over 13 counties, of which 33 were listed as producers and 26 were dry. At the close of the year, 13 wells were in process of drilling. The 33 producing wells had a combined estimated flow of 278 million cubic feet per day. The best results were obtained from exploration in Allegany County, where out of eight wells drilled to the Oriskany sandstone five were successful and showed a combined open-flow capacity of 107 million cubic feet. The Oriskany sandstone was encountered at a depth of 4500 to 4900 ft. In Steuben County, next east of Allegany County, two out of seven wells to the Oriskany proved productive, and one of these, in the town of Greenwood, on the Watkins structure, was probably the largest that has so far been opened in the state, with a reported yield of 35 million a day. In the central part of New York interest was awakened by the activity shown in exploring for gas in the Trenton limestone, in Camden, Florence and Rome townships, Oneida

Jan 1, 1936

By D. H. Newland

New York has a small but not insignificant place in the oil and natural gas industries of the United States. It has had a continuous record as an oil producer since 1872, with an aggregate yield of about 104,000,000 bbl. The reported output for 1935 was 4,237,000 bbl., a gain of more than 10 per cent for the year and a total that has been exceeded only in the early period of flush production half a century ago. The industry has been steadily building up since 1920 with the successful practice of the water drive, which has given a new lease of life to pools that had been practically drained of oil recoverable by pumping. An additional output of 2000 bbl. or more per acre is being procured by this method. Altogether the fields in New York State cover about 55,000 acres. Their limits are well defined and it is unlikely that they will be extended in the future, although there is some prospect of finding additional supplies by deeper drilling. The oil from New York is all classed as Pennsylvania grade, for which the recent price has been about $2.50 a barrel. It is refined at Olean, Wellsville and Bolivar, in the oil district, and partly in Pennsylvania refineries. Exploration for natural gas, outside of the established districts, was considerable during the year. Altogether 59 wells were drilled, distributed over 13 counties, of which 33 were listed as producers and 26 were dry. At the close of the year, 13 wells were in process of drilling. The 33 producing wells had a combined estimated flow of 278 million cubic feet per day. The best results were obtained from exploration in Allegany County, where out of eight wells drilled to the Oriskany sandstone five were successful and showed a combined open-flow capacity of 107 million cubic feet. The Oriskany sandstone was encountered at a depth of 4500 to 4900 ft. In Steuben County, next east of Allegany County, two out of seven wells to the Oriskany proved productive, and one of these, in the town of Greenwood, on the Watkins structure, was probably the largest that has so far been opened in the state, with a reported yield of 35 million a day. In the central part of New York interest was awakened by the activity shown in exploring for gas in the Trenton limestone, in Camden, Florence and Rome townships, Oneida

Jan 1, 1936

By V. B. Tare, H. Schmalzried

The use of solid electrolytes for determining kinetic paraneters at elevated tevnperatures is pointed out. The reaction rate constant k1 of the phase-boundary reaction during oxidution of iron to wiistite by CO2-CO gas mixtures has been deternined between 850 nnd 975C, using ZrOz(+CaO) as an electrolyte. Values are between 1.4 x 10-a and 5.2 x 10 ole per sq ctn atm. The tzain difficulty is due to mixed potentials arising from side reactions at the electrolyte inteyface. In a number of papers the calcium-doped zirconia electrolyte has been used for the determination of thermodynamic data from measured differences in oxygen activities (or potentials) between two electrodes. The purpose of this note is to suggest the use of this solid electrolyte for kinetic measurements as well. The principle can be seen from Fig. 1. A thin and compact phase II (electron conductor) is fixed on a plate of gas-tight, polished ZrO2(+CaO) (I), which separates two compartments with different oxygen potential. p, is a constant reference pressure of oxygen (1 atm). The electromotive force of this galvanic cell is given by E = RT5 In pep, and pe is the oxygen partial pressure at the interface electrolytephase 11. If phase I1 is in equilibrium with the surrounding gas phase, p, = DR. If pg changes sud- denly to a value pi, p, and therefore the electromotive force, E, change as a function of time according to the phase-boundary reaction rate at the gas phase I1 interface and the transport processes inside phase 11. It is assumed that local equilibrium is established at the boundary electrolytephase 11, that the gas phase shows no concentration gradients, and that the con-

Jan 1, 1967

By W. L. Fink, M. S. Hunter, R. H. Brown

Early workers attempted to study the structure of alloys by measurement of equilibrium electrode potentials in aqueous solutions containing ions of the metals from which the alloy was made.' The method was subject to such limitations (e.g., the difficulty in attaining electrochemical equilibrium at low temperatures) that it has not been widely used by metallurgists. Recently, Seltz and co-workers have introduced a greatly improved method for studying alloys by measurement of equilibrium electrode potentials in molten salts.2"4 The mathematical treatment is the same, of course, as for equilibrium potentials of amalgams in aqueous solutions.5 This method will probably find extensive use, since it makes possible not only the determination of phase fields of equilibrium diagrams but also the determination of certain thermodynamic quantities which can be used advantageously in metallurgical calculations. However, the method presents difficulties. With many metallic and alloy electrodes, reversibility is not readily obtainable. Also, the difficulty of obtaining suitable material from which to make the cells is increased as the temperature is increased. Moreover, the necessity of carrying out measurements in a vacuum requires additional apparatus and introduces considerable difficulty, especially at the higher temperatures. Apparently, no consideration has been given heretofore to the metallurgical use of irreversible electrode potentials that exist when a specimen is immersed in a suitable aqueous solution at room temperature. The apparatus and the method required for such measurements are very simple, and if the results of such measurements could be demonstrated to be reproducible they might be very valuable in studying the structure of alloys. The method would not have the scope of that developed by Seltz and his co-workers because no thermodynamic quantities could be calculated from the data. However, the utility and the simplicity of the method might warrant extensive use for the determination of phase fields and similar applications. Theory of Irreversible Potentials A brief review of the theory of irreversible potentials will be given before showing how to interpret the potential readings in terms of alloy structure. It is known that heterogeneity of a metal surface in an electrolyte will produce points of different potentials, with the result that current flows between these points and electrochemical reactions occur. The points at which oxidation reactions are localized are known as anodes, and those at which reduction reactions are localized are known as cathodes.6, 7, 8 For the benefit of those who are not familiar with the terms anode and cathode as applied to a primary cell, the potential difference between anode and cathode of such a cell can be measured when

Jan 1, 1941