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By Frederick Laist

IN the course of the past 75 years the treatment of copper ores has undergone the most profound changes. To a lesser degree, this is true of all the nonferrous metals, but the rapid increase in the demand for copper due to the phenomenal growth of the electrical industry, and the discovery of vast new ore deposits in Michigan, Montana and Arizona, provided an exceptional incentive for improvements in smelting practice and for large-scale operations. Because these must perforce be carried on in regions where labor was scarce and wages high, the need for mechanization and larger smelting units soon became apparent. At a later date the porphyry coppers were discovered, with ores so low in grade that enormous tonnages had to be treated daily if they were to be made to pay at all. In some instances these ores were associated with, or overlain by, oxidized ores, which could not be concentrated mechanically and, of course, could not be smelted directly. This led to the development of the copper-leaching process. While the principles of the various smelting and leaching processes are for the most part of European origin, and have long been known, modern practice is essentially American and was evolved on this side of the Atlantic. The ores of copper may be divided into three general classes; viz, native copper, sulphide and oxidized ores. By far the greater number of commercially important ore deposits come under the classification of sulphides. Commercial deposits of native copper are limited to the Lake Superior

Jan 1, 1947

By S. W. Zanolli

The history of labor relations in the coal industry of the United States is a study of its collective bargaining. This study of collective bargaining is largely the history of the United Mine Workers of America and its contractual relations with the various coal mining employers who have produced this country's coal over the years under a free enterprise system. There have been other unions in the picture from time to time and some coal miners have mined coal without representation by any union. Even today some 25% of the nation's coal is produced outside of the collective bargaining relationship with the UMWA. However, more than 100,000 coal mine wage employees - well over 75% of the total in the industry - are covered by labor agreements negotiated for them by the UMWA. Practically all of these work in bituminous mines.

Jan 12, 1972

By Frederic L. Kadey

Perlite, as a volcanic glass, has been recognized since the Third Century, B.C. (Langford, 1978). The precise details of discovery often become lost in antiquity, and the variations among the stories pertaining to the more recent discovery of perlite as a material of commerce are no exception. Credit in the United States is given to a dentist who, while experimenting with tooth enamels about 1941, discovered that perlite-the rock-intumesced when subjected to heat. At about the same time it is reported that the chief geologist of Silver and Barytes Ores Mining Co. attempted to put out a picnic bonfire on the shores of Milos Island, Greece by throwing beach sand on it. The ensuing pyrotechnic display immediately conjured up in that man's mind the possibility of a new use for the volcanic rock that constituted most of the island. Very little was done with this discovery either here or abroad until after World War II. Today the name perlite is applied to both the hydrated volcanic glass, generally of rhyolitic composition, and to the lightweight aggregate that is produced from the expansion of the glass after it has been crushed and sized. Petrologically, it is defined as a glassy rhyolite that has a pearly luster and concentric, onionskin parting. Occurrences of perlite are restricted to several Tertiary to Quaternary age rhyolitic belts that trend in a generally north-south direction around the world. Commercially suitable deposits generally occur as domes of several hundred feet in height, although glassy zones in welded ash-flow tuffs and others associated with dikes and sills also have been reported. Mining is by ripping and blasting from open pits. Because of weight considerations, perlite usually is shipped to the local market area for subsequent expanding. In the United States, New Mexico leads in production with Arizona, California, Nevada, Idaho, and Colorado following in approximately that order. The principal use for expanded perlite is as a lightweight insulating aggregate in cryogenics, in plaster, concrete, and in loose fill insulation. Expanded perlite is also used in horticultural applications, and after subsequent milling and classification, as a filter aid. The United States is the world's largest producer and consumer of perlite. Table 1 shows the world production of perlite and Table 2 shows the perlite mined, processed, expanded, and sold or used by producers in the United States. Geology Composition and Morphology Any discussion of perlite must take into consideration its dual nomenclature, for it is known by the same name as both the naturally occurring rock and, after processing and expansion, as the lightweight aggregate of commercial significance. In its naturally occurring form, perlite is a rhyolitic glass that contains from 2 to 5% combined water. While perlite also can occur as andesitic or dacitic glass, these latter types are of negligible commercial significance. Table 3 lists the chemical composition of a few typical perlites (Anderson, et al., 1956; Langford, 1979). What sets perlite of commercial significance apart from other volcanic glasses is the fact that under the proper conditions of preparation-crushing and sizing-it will, when rapidly introduced into a flame of sufficient temperature, expand or "pop." All of the elements of composition contribute to the expansibility of the rock. The role of the combined water, however, is the most significant because it is believed not only to produce a fluxing effect in the softening of the highly siliceous glass prior to expansion, but it is also responsible for the explosive force of expansion through volatilization during heating. The current theory of the origin of the water in perlite is now less con-

Jan 1, 1983

By P. M. Blair, D. W. Peaceman

The shape and position of the gas-oil transition zone during downdip displacement of oil by gas has been calculated using flow equations which include the effects of gravity, relative permeability, capillary pressure and compressibility of the fluids. The calculations treat the problem in two space dimensions, and results are compared with data from a laboratory model tilted at 30° and 60° from the horizontal on displacements near and above the maximum rate at which gravity segregation prevents channeling of the gas along the top of the stratum. The good agreement between calculated and experimental results demonstrates the validity of the tecbnique as well as that of the flow equations. INTRODUCTION Knowledge of the fluid distribution and movement in an oil reservoir is important in producing operations and estimation of reserves. The history of the oil industry has included steady progress in improving the accuracy of calculations which provide the required knowledge. The earliest method of calculating reservoir performance consisted of material-balance equations based on the assumption that all properties were uniform throughout a reservoir.l For many reservoirs such a simple formulation is still the most useful. However, when large pressure and saturation gradients exist in a reservoir, the assumption of uniform values throughout may lead to significant error. To reduce these errors, Buckley and Leverett2 introduced a displacement eqation which considers pressure and saturation gradients. Methods available at that time permitted solutions to the Buckley-Leverett equation in one space dimension; these solutions have been very useful in solving many problems related to the production of oil. However, the one-dimensional methods are not adequate for systems in which saturations vary in directions other than the direction of flow. An example of such a system is the case of gas displacing oil down a dipping stratum in which the gas-oil contact becomes significantly tilted. Of course, the Buckley-Leverett displacement method cannot predict the tilt of the gas-oil contact. Recent improvements3,4 of the one-dimensional Buckley-Leverett method achieve some success in predicting the tilt of the gas-oil contact at sufficiently low flow rates. However, at rates high enough that the viscous pressye gradient nearly equals or exceeds the gravity gradient, even these improved one-dimen,sional methods incorrectly predict the shape and velocity of the contact. Further progress in estimating such fluid movements in a reservoir appears to require consideration of the problem in more than one space dimension. The recent two-dimensional method of Douglas, Peaceman and Rachford5 appears adaptable to calculate changes with time of the saturation distribution in a vertical cross-section of a reservoir. The movement of saturation contours should represent the moving fluid contacts and include the effects of crossflow due to gravity, as well as variations in the rock and fluid properties. The nonlinear nature of the equations used in the method has prevented proof of the validity of the solutions. Douglas, Peaceman and Rachford made some comparisons with experiment but did not include cases in which gravity was important nor cases involving displacement by the nonwetting phase.For these reasons, a test of the two-dimensional method for a case in which these factors are included would be very desirable. The test selected was a comparison of calculated results with those from a carefully controlled laboratory experiment on a model with measured physical properties. The model selected was one in which gas displaced oil down a tilted, rectangular sand pack. The model can be thought of as representing a vertical cross-section taken parallel to the dip of a reservoir. The displacement thus simulates gas displacing oil downdip that might result from gas-cap expansion or gas injection. This report outlines the calculation method used

By Jack A. Simon, M. E. Hopkins

GENERAL GEOLOGY Coal is defined as a combustible rock that had its origin in the accumulation and physical and chemical alteration of vegetation. Coal can be ignited and burned like the wood that was man's earliest fuel, but coal gives more heat than the same amount of wood and has many industrial uses. Unlike wood, coal is not generally found on the surface of the ground but is mined from the solid rock of the earth. Before taking up the occurrence, formation, and the somewhat unique character of coal in the rock sequence, let us briefly consider the general character of all rocks in the crust of the earth. Relatively little is known about the very earliest history of the earth, although a number of logical theories have been developed. Manned exploration of the moon and the rocks being returned to earth will, we hope, provide some answers to questions concerning the earth's origin and history. The period of earth history with which we concern ourselves here begins after great areas of water had evolved on earth and substantial land areas of once molten (igneous) rock existed. Weathering and other processes that attacked the surface of the rocks reduced them to small particles. Water provided by rainfall transported this material, ultimately, to large bodies of water where it was deposited. Thus was initiated the geologic sequence of sedimentary rocks that lie above the once molten igneous rocks. The crust of the earth is not completely stable, and throughout the geologic past portions of the crust have moved laterally and vertically. Even today, many coastal areas are slowly rising or sinking. More sudden earth movements are recognized by the earthquakes they cause. Throughout geologic history, rises in sea level or the sinking of the land areas have many times permitted the oceans to cover much of what are now the areas of the continents. Only relatively small parts of the present continents appear to have been above sea level throughout geologic time. Great

Jan 1, 1973

By F. R. Hensel

Up to the present time few attempts have been made to produce hard nonmagnetic materials by heat treatment of austenitic steels. The usual result has been to cause them to pass into the martensitic stage, thus destroying to a great extent the typical austenitic properties, since this involves a transition of a portion of the iron from a face-centered to a body-centered type of atomic arrangement. High-strength nonmagnetic materials such as might be provided by properly hardening austenite are required in the electrical industry for different machine parts. In Europe nonmagnetic retainer rings for restraining the end-turns of the rotor windings in turbo-alternators have been developed as a special application of high-strength austenite. In testing1 a 28,000-kva. three-phase Siemens turbo generator running at 3000 r.p.m. at full load current, the losses in the short-circuit test were 450 kw. for the magnetic ring and 286 kw. for the nonmagnetic, and the difference should be attributable to the magnetic ring. The differences in temperatures during the same test are given in Table 1 and these show the advantage of a nonmagnetic over a magnetic retainer ring.

Jan 1, 1931

By W. P. Sykes

ThiS investigation was undertaken primarily to establish the relations existing between temperature and mechanical properties in molybdenum, nickel, and an aluminum-copper alloy. Mlolybdenutn (m.p. 2500" C.) was chosen because it is partly similar to tungsten and partly similar to the common ductile metals. Also it is known to furnish, by proper treatment, a desirable material to use in studying relation of grain size and physical properties. The molybdenum used was of the quality that is drawn into wire 0.003 in. in diameter for use as filament supports in incandescent lamps; Chemical analysis shows less than 0.1 per cent. of impurities. Nickel belongs to the same class as iron. Its melting point is 1450" C. and an allotropic change at about 370" C. results in a loss of magnetism above that temperature. This feature made nickel doubly valuable for the purposes of these tests. The nickel used was obtained from the Driver-Harris Co. as 0.090 in. (2.3-mm.) wire, annealed; analysis showed 99.8 per cent. nickel and 0.150 per ccnt. iron. Aluminum is one of the low melting-point metals. Some tensile tests at clevated temperatures have been reported by Bengough but the possibility of learning more with the low temperature and sensitive apparatus available rccommendcd this metal. The samples marked A1 arc an aluminum-copper alloy that contains 3 per cent. copper, 0.42 per cent. iron, and 0.21 per cent. silicon. The presence of the copper somewhat coniplicates the analysis of the results; but the action of copper in aluminum has been studied so that its influence might have been foretold, in part at least. The material and analyses were furnished by the Aluminum Castings Co. The nickel wire, which was deformed at 400" C., was drawn under a bath of molten lead and through a die, which also was immersed in the bath. A thermocouple was suspended in the molten metal to indicate the temperature. Hot oil was uscd as the heating bath for drawing the

Jan 1, 1921

By I. Cornet

INTRODUCTION WITH the greatly expanding use of magnesium during the war, it appeared necessary to the War Metallurgy Committee that the notch sensitivity of magnesium alloy extrusions be further investigated and the influence of various factors upon notch sensitivity be noted. Accordingly, the National Defense Research Committee of the Office of Scientific Research and Development placed a research contract with the University of California, supervised by the War Metallurgy Committee. The work discussed herein was done under "Restricted" Project NRC-21, reported in Dec. 1943 1; it has been released for publication by the O.S.R.D. SCOPE OF THE INVESTIGATION The notch sensitivity of various magnesium alloy extrusions was determined under axial tension, and also under several conditions of nonaxial tension. Hardness, grain size and other metallographic features were observed; stress-strain data were obtained, and the chemical compositions of the alloys were determined, in order to correlate these quantities with the notch sensitivity. Notch sensitivity under axial tensile load was determined for a few specimens which had been cold worked to various degrees by tensile prestraining. Magnesium alloy extrusions studied included Dowmetal 0, X, J, and M. For comparison, extrusions of aluminum alloy 24S-T, cast bars of aluminum alloy I22-T2, and cast bars of magnesium alloy C were also tested, The specified chemical composition of these alloys is given in Table I. All bars tested were within specification limits of composition. Investigation of the tensile notch sensitivity of various magnesium alloy extrusions, under conditions of axial and eccentric load, showed little or no correlation with stress-strain or other conventional data. Since the many uncontrolled variables present might mask significant relationships, one alloy was selected for intensive study. Magnesium 0 alloy extrusions were subjected to experimental heat treatments, and the changing hardness, tensile strength, microstructure, and notch sensitivity observed. EXPERIMENTAL TECHNIQUES AND PROCEDURES Tensile Testing Bars used for axial loading were machined with 3/8 in.- and with 1/4-in. minimum diam, and included specimens with 6o° V notches (Fig I and 2). Each V-notched specimen was roughed out carefully and then finished with a honed tool. These V-notched bars were sampled frequently, sectioned, polished, and examined at 500 X magnification to control

Jan 1, 1948

By C. L. Mantell

Although so common and well known a metal, tin is really a less abundant element than many of those less familiar and usually ranked with the scarce or rare elements, such as cerium, yttrium, lithium, beryllium, titanium, zirconium and vanadium. The color of tin is white, with a slightly bluish tinge. When it is compared with nickel, the latter metal is brown. When placed alongside of tin, chromium is definitely blue. Tin is whiter than silver or zinc. Exceedingly thin films of tin show various shades of brown by transmitted light. The metal has a brilliant luster, and when mirror-polished, has high light reflectivity. The luster depends to a large extent upon the pouring temperature at which the metal is cast. If the temperature be too high, iridescent colors may show on the surface. These are the result of oxide film formation. If the pouring temperature be too low, the surface is dull. Small amounts of foreign metals, such as lead, arsenic, antimony and iron, decrease the luster of tin and impart a yellowish tinge to the metal. The structure is decidedly crystalline. The cast metal is a mass of crystals. When a bar of tin is bent, it emits a characteristic creaking sound. This is called the "cry" of tin, resulting from the grinding of the crystals one against the other during the bending of the metal. Tin metal may lose its crystalline structure by cold working, but grain growth occurs rapidly under the influence of heat. Metal which has been cast at a low temperature may become amorphous as the result of mechanical work. If such material be heated to temperatures well below the melting point, say at 110° C. for a half hour or for a few minutes at 150" C. recrystallization occurs. If the surface of tinned plate, tin foil, or tin meta1 in cast form be etched with hydrochloric acid containing a little free chlorine, attack occurs at the intererystalline faces. The surface shows patterns resembling the frost flowers on window panes in winter. The etched appearance is called moire metallique. Fine dendritic surface crystals of tin may be obtained by casting the metal on a surface of polished steel. In commercial tin plate, the intercrystalline boundaries are shown by fine grooves or channels, .which result from the method

Jan 1, 1929

By Paul M. Tyler, Herbert R. Mosley

Strategically situated in almost the heart of the leading fertilizer-consuming area of the United States, Tennessee long has ranked second only to Florida as a phosphate-producing state. Since 1932 its share of the national output of phosphate rock has increased steadily, and in 1937 its production mounted to an all-time record. More significant even than the increase in tonnage are the forward strides in technology. The Tennessee Valley Authority's research program has led to quasicommer-cia1 operations using hydroelectric power to manufacture concentrated phosphatic fertilizer that is used to further the farmer education program designed to streamline the fertilizer business and halt the appalling waste of farm land by soil erosion. Even more stimulating to chemically minded imaginations is the production of elemental phosphorus by a private company that not only has succeeded in extracting it from the phosphate rock in electric furnaces but actually has contrived to capture it and to transport it safely in tank cars. New values have been created for low-grade phosphate deposits, and the economic life of reserves has been lengthened while the waste of former years goes back into the mills for recovery of its values by modernized methods. Tennessee's phosphate-mining industry dates from the discovery of blue rock in Lewis County in December 1893. Its known reserves are of the order of 101,500,000 tons, which compares with the production of 825,099 tons in 1937; that is, 21 per cent of the phosphate-rock output of the whole nation. The total output reported from 1894 until July 1. 1938, was approximately 19,000,000 tons. Offcial estimates of reserves are overly conservative and evidence submitted before a joint Congressional committee in November 1938 places "probable" reserves at more than 6,000,000,000 tons.

Jan 1, 1942

By Arthur F. Taggart

Some years ago, A. M. Gaudin and one of the authors published a paper showing removal of tar acids from solution by sulfides preferentially as compared to gangues (specifically by galena as compared to quartz).' The underlying phenomenon was classed as adsorption, and the paper went on to develop the general thesis that so far as water-soluble frothing and collecting agents in flotation are concerned, the phenomenon of adsorption is one of controlling importance. Adsorption was defined in that paper as "a process of rearrangement of a system, which results in establishing a difference in concentration, as between the interfacial layers and the bulk of the phases, of a substance or substances initially uniformly dispersed in one or several of the phases." The paper went on to develop the relation between adsorption and surface cnergy according to Gibbs' equation (which may be thrown into the form U/c = KdT/dc, where U = excess concentration in surface layer, c = concentration, T = surface tension, and K is a constant), and pointed out that, according to this equation, degree of adsorption and change in surface tension vary directly. The present paper offers a somewhat different definition for the term adsorption; and sets up, in sweeping terms, the generalization that simple chemical reaction underlies the functioning of the flotation reagents which control mineral collection, when these reagents are soluble in and act from solution in the water of the pulp. Adsorption According to the modified definition, adsorption means concentration at an interface between different phases in a heterogeneous system (thus far the definition runs as before), by the action of some mechanism, of which nothing is properly implied in the word, and concerning which the user of the word is probably in entire ignorance. Thus defined,

Jan 1, 1930

By Herbert R. Mosley, Paul M. Tyler

Strategically situated in almost the heart of the leading fertilizer-consuming area of the United States, Tennessee long has ranked second only to Florida as a phosphate-producing state. Since 1932 its share of the national output of phosphate rock has increased steadily, and in 1937 its production mounted to an all-time record. More significant even than the increase in tonnage are the forward strides in technology. The Tennessee Valley Authority's research program has led to quasicommer-cia1 operations using hydroelectric power to manufacture concentrated phosphatic fertilizer that is used to further the farmer education program designed to streamline the fertilizer business and halt the appalling waste of farm land by soil erosion. Even more stimulating to chemically minded imaginations is the production of elemental phosphorus by a private company that not only has succeeded in extracting it from the phosphate rock in electric furnaces but actually has contrived to capture it and to transport it safely in tank cars. New values have been created for low-grade phosphate deposits, and the economic life of reserves has been lengthened while the waste of former years goes back into the mills for recovery of its values by modernized methods. Tennessee's phosphate-mining industry dates from the discovery of blue rock in Lewis County in December 1893. Its known reserves are of the order of 101,500,000 tons, which compares with the production of 825,099 tons in 1937; that is, 21 per cent of the phosphate-rock output of the whole nation. The total output reported from 1894 until July 1. 1938, was approximately 19,000,000 tons. Offcial estimates of reserves are overly conservative and evidence submitted before a joint Congressional committee in November 1938 places "probable" reserves at more than 6,000,000,000 tons.

Jan 1, 1942

The problem of surface support in coal mining is naturally divided into three branches: 1. Surface covered with improvements of such value as compared with the value of the underlying coal, or with such elements of danger to mining, that absolute support is essential. 2. Surface with improvements of less value than the underlying coal such that moderate settlement may be permitted, but destructive settlement must be avoided, either by reason of danger to human life or unwarranted property damage. 3. Surface of relatively small value as compared with the underlying coal where destructive settlement may be permitted. First Problem In the first case it is evident that the original support must be maintained either (a) by leaving ample pillars and confining the coal recovery to a very conservative first mining, (b) by so supporting less conservative first mining by filling or flushing that the gradual deterioration of the pillars may be prevented and subsidence avoided, or (c) by incompressible support as masonry either as an adjunct to insufficient pillars or in place of the original coal support. a. From tests made by the Scranton Engineers Club, it appears safe to figure on 2000 Ib. per sq, in. as the safe squeezing strength of coal pillars in place, provided that these are, as usual, not higher than their least horizontal dimension; and from this figure the percentage of pillar to be left for various depths may be easily calculated. For safety in this

Jan 1, 1930

By C. L. Mantell

Although so common and well known a metal, tin is really a less abundant element than many of those less familiar and usually ranked with the scarce or rare elements, such as cerium, yttrium, lithium, beryllium, titanium, zirconium and vanadium. The color of tin is white, with a slightly bluish tinge. When it is compared with nickel, the latter metal is brown. When placed alongside of tin, chromium is definitely blue. Tin is whiter than silver or zinc. Exceedingly thin films of tin show various shades of brown by transmitted light. The metal has a brilliant luster, and when mirror-polished, has high light reflectivity. The luster depends to a large extent upon the pouring temperature at which the metal is cast. If the temperature be too high, iridescent colors may show on the surface. These are the result of oxide film formation. If the pouring temperature be too low, the surface is dull. Small amounts of foreign metals, such as lead, arsenic, antimony and iron, decrease the luster of tin and impart a yellowish tinge to the metal. The structure is decidedly crystalline. The cast metal is a mass of crystals. When a bar of tin is bent, it emits a characteristic creaking sound. This is called the "cry" of tin, resulting from the grinding of the crystals one against the other during the bending of the metal. Tin metal may lose its crystalline structure by cold working, but grain growth occurs rapidly under the influence of heat. Metal which has been cast at a low temperature may become amorphous as the result of mechanical work. If such material be heated to temperatures well below the melting point, say at 110° C. for a half hour or for a few minutes at 150" C. recrystallization occurs. If the surface of tinned plate, tin foil, or tin meta1 in cast form be etched with hydrochloric acid containing a little free chlorine, attack occurs at the intererystalline faces. The surface shows patterns resembling the frost flowers on window panes in winter. The etched appearance is called moire metallique. Fine dendritic surface crystals of tin may be obtained by casting the metal on a surface of polished steel. In commercial tin plate, the intercrystalline boundaries are shown by fine grooves or channels, .which result from the method

Jan 1, 1929

By Charles G. Maier

It has long been supposed that when crystalline materials are comminuted the energy used in the production of increasingly smaller grain sizes is not entirely dissipated as heat but that a certain portion is "stored" as a part of the internal energy of the material. This portion usually has been called the "surface energy" of the particles. The practical interest of the Bureau of Mines in this subject in connection with the energy requirements of crushing processes has led to the author's attempt to measure the "stored" energy in finely divided calcite by heat-of-solution methods1.t The experiments on calcite showed that "storage" of energy could not be proved for this material, because fine grinding caused a lack of chemical homogeneity evidenced by loss of carbon dioxide and subsequent adsorption of water on the surfaces of the calcite particles. When thermochemical correction was made for composition changes the corrected heat of solution was less for fine material than for coarse. Continuation of the experimental work into the problem of comparing work and heat in the deformation of metallic crystals, where the calorimetric difficulties were less, showed, however, that in the case of copper and aluminum a real discrepancy between work and heat could be shown. Similar results had previously been obtained by Farren and Taylor2 and Hort3 and more or less simultaneously with the author's work by Rosenhain and Stott4 and by Taylor and Quinney9 The results obtained by the different investigators were not satisfactorily consistent, but the experiments of Taylor and Quinney constitute by far the best figures obtained to date. The previous paper1 presented evidence to show that if energy is stored in the surfaces of crystals the densities of fine crystals should differ

Jan 1, 1936

By Robert M. Grogan

Fluorspar is the commercial name for fluorite, which is the mineral having the composition CaF2, calcium fluoride. Its valuable properties are due to its content of fluorine, and it is the only important commercial source of that element. The name is derived from the Latin fluere, to flow, because the mineral melts easily and is a good flux. History The mineral has been known since Greek and Roman times, when it was used for drinking cups and ornamental slabs. Various peoples including the Chinese and the American Indians have carved ornaments from large crystals. Its usefulness as a flux was known to Agricola, who wrote about it in 1546.1 Mining began in England about 1775 15 and at various places in the United States during the period 1820 to 1840.28 Substantial production was achieved first in the period 1888 to 1900 in consequence of the development and widespread adoption of the basic open hearth method of making steel, in which fluorspar is used as a flux. After that, production and usage was stimulated by growth in the steel, aluminum, chemical, and ceramic industries and accelerated by World Wars I and II. The organic fluorides called "Freons" entered the picture in 1931, and the use of anhydrous HF as a catalyst in the manufacture of alkylate for high octane fuel blends began in 1942. The development of the froth flotation process in the late 1920's, a differential flotation scheme for separating fluorspar from galena, sphalerite, and other minerals in the 1930's, and the application of heavy-media concentrating methods to the treatment of low-grade ores in the 1940's were outstanding technological contributions that enabled increased production of fluorspar concentrates. Composition and Properties Fluorite in its purest form contains 51.1 pct calcium and 48.9 pct fluorine. Substitution of small percentages of cerium and yttrium for calcium have been noted.4 Mechanical inclusions of gases and fluids such as petroleum and water, and of other solid minerals such as pyrite, marcasite, and chalcopyrite are common. The fluorspar of commerce contains attached and admixed mineral impurities, chiefly calcite, quartz, barite, celestite, and various sulfides. It is interesting that the purest commercial form in which the mineral is sold, acid grade concentrate, contains a minimum of 97 pct CaF2, and as such is of comparable purity to many reagents used in chemical laboratories. Fluorite has a marked tendency to occur in large, well-formed crystals sometimes six to ten inches on a side. It crystallizes in the isometric system, frequently forming cubic and octahedral crystals or combinations thereof. The mineral also occurs in massive and in earthy forms, and in crusts or globular aggregates with radial fibrous texture. Crystalline fluorspar exhibits a great array of colors, from colorless and water clear to yellow, blue, purple, green, rose, red, bluish and purplish black, and brown. The colors are often arranged in alternating bands parallel to cube faces. They may be altered by exposure to X-rays, heat, ultraviolet light, and pressure, and are caused by a variety of factors including the presence of trace impurities and displaced ions in the lattice. Sometimes the changes induced by X-rays can be reversed by ultraviolet radiation. The mineral has a hardness of 4, and is the model of that hardness on the Mobs scale.

Jan 1, 1960

By K. A. Semlak, F. N. Rhines

NFILTRATION is a term used to designate that i- process by which the pores of a metal powder are filled with a relatively low-melting liquid metal through the action of capillary forces. This is accomplished in practice either by heating the porous body in contact with the solid infiltrant metal above the melting point of the latter, or by preheating the porous body separately and then dipping it into the liquid metal. The liquid, as it sweeps through the porous body, replaces the gases progressively, thus yielding a relatively dense product in a short time.' Liquid-phase sintering, which is related to infiltration, is a process by which a mixture of two or more metal powders is sintered at a temperature between the liquidus and solidus of the ultimate alloy.' According to Cannon" liquid-phase sintering can be divided into three stages which he calls liquid flow, accommodation, and solid sintering. The largest density increase occurs during the first stage, where the lower melting component melts and, driven by capillary forces, flows among the particles of the higher melting component, where, after dissolution of the bonds between the solid particles, it moves them into close packing. This happens so quickly that little has yet been learned of its mechanism. A study of the rate of capillary rise of a liquid metal in a higher melting metal-powder compact may be expected, therefore, to contribute not only to a firmer understanding of the process of infiltration as such but also to a more extensive knowledge of what occurs during the initial stage of liquid-phase sintering. Theoretical Basis In order to derive a mathematical expression of the rate of infiltration, it has been assumed that a powder compact consists of a great many parallel capillary tubes and that the rate of rise of a liquid in an average capillary channel represents the rise in the entire compact. For a straight capillary, assuming that Poiseuille's law obtains for the non-stationary state and that wetting is very rapid, Ligenza and Bernstein' have derived the following differential eauation of motion where h is the height of rise of the column of liquid at time t, R, is the radius and 1 the length of the capillary, t) and 7, the viscosities of liquid and air, respectively, p and p, the density of the liquid and air, respectively, y the liquid-gas surface tension, 0 the liquid-solid contact angle, and g the acceleration due to gravity. The term on the left of Equation [I] represents the rate of change of momentum of the contents of the capillary tube. On the right the terms represent, respectively, the forces due to a) surface tension, b) viscous resistance, c) gravity, and d) end-drag effect. Equation [I] is not amenable to explicit solution, but for a tube of sufficiently small radius, the rate of rise may be slow enough so that the rate of change of momentum and end-drag terms may be neglected. The validity of this simplification was established by Ligenza and Bernstein' by graphical differentiation of observed data obtained from organic liquids rising in glass tubes. The solution of this simplified case is:

Jan 1, 1959

By J. Gurland

The wmk is concerned with the estimate of the degee of continuity of a particulate phase dispersed in a matrix. The first section is a verieu: of the parameters nzeasurable by quantitative rnetallogvaphy, namely the contact area and, under certain conditions, the number of contacts between particles of one phase. In the second section, the frequency of particle contacts is related to the degee of continuity of a randomly embedded phase orz the basis of the lattice-percolation model of Hamrnersley and others. THE extent of continuity of the constituent phases may greatly influence the structure-sensitive properties of phase mixtures, particularly if the phase properties differ significantly. An example from the literature1 is shown in Fig. 1. The marked decrease of the electrical resistivity of sintered silver-alumina bodies near 25 pct by volume of silver presumably occurs because the more conductive phase changes from a discontinuous to a continuous structure. Other example of electrical- and thermal-conductivity transitions are cited by kingery In view of these observations, a knowledge and understanding of the connectivity of the microstructure may be of considerable practical importance. This study is concerned with one aspect of the genera1 problem, namely the estimate of the degree of continuity of a particulate phase dispersed in an opaque matrix. The first section reviews the parameters measurable on a polished cross section by auantitative metallography, such as the contact area and under certain conditions, the number of contacts between particles of one phase. In the second section, an attempt is made to relate the frequency of particle contacts to the degree of continuity of a randomly embedded phase. For the purpose of this discussion, the aggregate has two constituents: the particulate phase and the matrix. The latter is considered to be homogeneous. The term "particle" is used with the meaning of "grain", i.e., a minute unit of matter which is usually a single crystal of a readily distinguishable substance within the confines of a simply connected boundary. While many of the concepts which are used here to describe the structural variables characterizing the microstructure of phase mixtures are qualitative and ill-defined, they are presented with the intent of stimulating further work of a more general and rigorous nature. I) PARTICLE CONTACT, CONTIGUITY, AND MEAN FREE PATH 1) Measurement of Contiguity. The fraction of the total internal surface of a phase a shared with particles of that same phase in a two-phase mixture of and $ is indicated by the contiguity ratio:3 whereis the area of the interface between o particles, and Sap is the area of the interface between a particles and matrix P, per unit volume of mixture. The contiguity ratio ranges from 0 to 1 as the distribution of the a phase changes from a completely dispersed to a completely agglomerated structure. The interfacial areas may be obtained from simple intercept measurements on a random plane, after Smith and Guttman where and N are the numbers of intercepts between a random line of unit length on a plane of polish and the interparticle and interphase interfaces, respectively. The equations are valid for any distribution of particle sizes and shapes.

Jan 1, 1967

By R. W. Kraft, L. D. Graham

The process of' spheroidization, or more properly coarsening, of Al-CuAl,eutectic alloy specimens with various initial microstructures was studied by quantitative metallographic and X-ray diffraction techniques. By measuring the rale at which specimens with a very fine dispersion of phases (produced by quenching molten droplets of the alloy in water) coarsened it uias determined that the rate-controlling mechanism for coarsening was diffusion, probably of aluminum in the aluminum-rich phase. The lamellae in specimens with a high degree of microstructural and cr-ystallog/uphic anisotropy (produced hy unidirectional solidification of ingots) thickened during heat treatment by recession of the CuAl, platelets from jaulted regzons, yet the specinlens retained a very high degree of. anisotropy after prolonged heat treatments at a temperature within 8°C of the eutectic temperature. In such specimens the crystallographic orientation relationship between the phases remained constant and no change in the crystallographic substructure occurred. Based on these observations a model was developed for the coarsening—or rate of' thicken-ing—oj- the lamellar structures which predicts that the rate of decrease of interface area is proportional to the square of lamellar interface area. Experiments with degenerate and very coarse lamellar microstruc -tures preduced by extremely slow unidirectional solidification) indicate that initial microstructure is a most important factor governing the final micro-structure after heat treatment. The particle size and shape of dispersed phases are important parameters affecting the properties of a wide variety of two-phase materials. As is well-known, varietythe dispersed-phase particles tend to coarsen at appropriately high temperatures because the interface energy of the system is reduced by the concomitant reduction in interface area. The phenomenon of

Jan 1, 1967

By Richard H. Olson

"Rarely in our technological society does the discovery of a new class of inorganic materials result in such a wide scientific interest and kaleidoscopic development of applications as has happened with the zeolite molecular sieves." The foregoing, the opening sentence in a landmark volume on zeolite molecular sieves by D. W. Breck (1974), is, if anything, an understatement. Zeolites were recognized as a new group of minerals in the 1750s, but it was not until 1930 that the first analysis of the crystal structure of a zeolite mineral was made. In the late 1940s research workers at Union Carbide Corp. began a program of zeolite synthesis and study which has resulted in one of the major research achievements of all time. Naturally, with the vast research and development efforts devoted to the synthetic molecular sieves, Union Carbide became concerned in the mid-1950s about its position should minable deposits of natural analogues be discovered. Zeolite minerals have diverse origins, and even a brief discussion of these is beyond the scope of this paper. The early work on zeolites was confined to igneous rock occurrences (e.g., amygdules and veins) which were formed by "space-filling;" these crystals tend to be euhedral, thereby rendering them appealing to both mineralogists and collectors. During the first year or so of Union Carbide's exploration (which began in mid-1957) attention was devoted solely to such igneous occurrences. A landmark paper by Bramlette and Posnjak (1933) heralded the potential significance of the occurrence of zeolite minerals as alteration products of vitric ash and similar materials. In the summer of 1958, full attention was directed by Union Carbide to the search for deposits of this type in the western United States. Since then, such exploration has been continu-

Jan 1, 1975