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By Arnold S. Epstein

Tlze green electroluminescence occurring at liquid-nitvogen temperature in epitaxial gallium phosphide diodes is exarnined using the donor dopants silicon and sulfur. Zinc is used as the p-type diffusant. Two tt~ain peaks are found, namely til 0.56 and 0.535 p. The intensity of the gYeen peak occurring at 0.56 is found to oary as -4"' wlzere Jf is the forward current density and to first order appears to be dependent on the concet~tvation of ionized donovs. Tile vadintive lifetinze fov this process is -10-'sec. The intensity of the 0.56-p lu~ninescence is nt least several ovdevs of magnitude greate,, at liquid-nitvogen temperature than that noted jor the 0.538 radiation for current densities up to about 35 amp per sq cm. The variation oj- the intensity of. the 0.538-p peak with current density caries according to the donor dopant. With sulfur as the donor one has a J12 dependence, whereas when silicon is the donov a J1.5 dependence is noted. Tl~e above can be fitted to a In molecular process (in first order) such as a band to band recombination. The constant B fir band to band vecombination) is found from our experitt~etlt to be of the order of 2 CZI cm per sec, zcl~ereas for tlze impurity vecombination peak (0.56 p]) tile A cotzstor~t is of the order of. 7 x 10-' cu cm per sec. The structuve o/. the diodes at liquid-nitvog-en tett~peruture is oj tlze double injection type, and by carefi~lly selecting. the thickness of the structure one can regulate the onset of the 0.538-p radiation. The diode clzavaclevistics follow an I-Vx laiv where x is >1. Llregatiue resistance in these structures con be correlated with saturation of tlze 0.56- peak. ThE development of high-purity, large single crystals of epitaxially grown gallium phosphide is the ultimate aim of the studies to be reported. While a number of papers and reviews' have been presented on properties of gallium phosphide grown from gallium solution and from the melt, less attention has been paid to the properties of epitaxial gallium phosphide grown from the vapor. In the studies to be reported we have examined the effects of shallow donor impurities, primarily silicon and sulfur, at liquid-nitrogen temperature, on both the electrical and green electroluminescent properties of carefully characterized single-crystal epitaxial Gap. I) EXPERIMENTAL PROCEDURES A) Material Preparation and Properties. The samules used in this investigation were single-crystal n-type epitaxial gallium phosphide. he single crystals were synthesized from the elements by vapor transport and epitaxial deposition on single-crystal gallium arsenide substrates. Typical transport agents used were chlorides. The growth procedures are described in more detail in Ref. 2. The samples were grown in the (111) orientation and had thicknesses up to 480 . Following the growth, the GaAs substrate was removed from the epitaxial Gap by etching in nitric acid. The Hall effect and resistivity of these n-type samples were measured as a function of temperature and analyzed for impurity content and compared with spectroscopic emission analysis. The results are given in greater detail in Ref. 3 but a summary is noted in Table I. In Table I, AED denotes the donor ionization energy, Nd is the donor impurity concentration, lvA is the acceptor impurity concentration, NI is the total impurity concentration, Rip vs temperature is the measured Hall mobility-temperature relationship from liquid nitrogen to about 400"K, n(77"K) is the measured carrier concentration at liquid nitrogen, and R/p(77'~) is the measured Hall mobility at liquid nitrogen. Good agreement is noted between electrical and emission analysis for the major donor impurity, silicon, in the two materials where it is a major constituent. In the case of the two samples SC90-6 and AP138-3(111) B which were sulfur-doped the ionization energy found from the electrical data is in good agreement with that reported for sulfur.4 The acceptor impurities are not known, although from the presence of magnesium in the samples as indicated by emission analysis and its known role as an acceptor in GaP,4 magnesium could be present as an acceptor. Similarly, since silicon is known to be an amphoteric impurity4 it may also be present as an acceptor in the Gap.* The *A small band has been noted at 0.625 11 in samples SC90-6, SC76-4, and SC77-4, suggesting according to Ref. 5 that sillcon could be present as an acceptor In these samples since these authors have found this peak to represent a donor-silicon emission. presence of calcium deduced from emission analysis is not correlatable with the electrical analysis and its presence as an electrically active impurity should be questioned. B) Sample Preparation and Diode Fabrication. The original slices were of the order of 2 sq cm in area witi the (111)B face up. The material was cleaved and sectioned and the best pieces selected (i.e., those which visually appeared to have the least strain and defects). The samples were polished, lightly etched, and cleaned in trichloroethylene. Zinc was diffused in a closed tube at 800°C to form a p-n junction. Diodes were made from these samples. The depth of junction varied, but did not exceed 10 p depth. The back side of the slice was lapped back and a low-resistance n-type contact was formed (at 600°C in forming gas) to an Au-Mo tab with a hole in the middle for

Jan 1, 1968

By E. Gregory, C. G. Goetzel

The outstanding elevated temperature properties of materials made from sintered aluminum powder have been well established in recent years.1,2 and considerable investigation has been carried out on the structures which appear to be responsible for this type of strengthening.2,3 The maximum operating temperature of such materials is severely limited, however, by the low melting point of the aluminum matrix; and, therefore, considerable interest was aroused in methods of introducing the

Jan 1, 1959

By H. H. Hausner, H. S. Kalish

IN recent years zirconium and beryllium have become of great interest because of their special properties. Zirconium is known for its remarkable ability to absorb the gases oxygen, nitrogen and hydrogen, has extensive use as a getter in electron tubes and has indeed become the primary metal in the manufacture of photoflash bulbs. Beryllium is of interest because it is light metal and as such could supplement aluminum and magnesium in light metal applications. The late development of zirconium ductile at room temperature produced by both the iodide and calcium reduction methods has stimulated frequent articles on this metal in the recent literature. Beryllium is so closely akin to zirconium crystall-ographically that some investigators are of the opinion that beryllium should be ductile at room temperature if it were pure enough. The crystallographic relationship of beryllium and zirconium, the interest created in Be-Zr alloys where the zirconium is believed to function as a remover of solid solution gas in beryllium and thus increase the ductility of the beryllium rich alloy, and the amenability of these metals to powder metallurgy methods stimulated this approach to an investigation of the system Be-Zr. Preliminary work showed that a zirconium compact melted when pressed in contact with a beryllium compact and sintered at 1250°C, without any apparent final bond between the two. A search of the literature revealed nothing pertinent about the Zr-Be system or about any zirconium - beryllium alloys. In 1936 Misch³ vaguely identified the compound ZrBe2 and reported that it has a deformed cubic structure. Two patents," , were issued to Mach-lett Laboratories in 1943 and in 1946 regarding the addition of small amounts of zirconium to beryllium in order to improve the ductility of beryllium so that it may better be used for X ray windows. In considering the alloy formation of beryllium with other metals Raynor thought it unlikely that zirconium would have any solid solubility in beryllium. From this indefinite information nothing could be ascertained about the possible use of Zr-Be alloys or the use of these metals intimately. A brief preliminary study of the system Zr-Be by powder metallurgy methods was undertaken to provide regions for more intense studies of Zr-Be alloys and as a guide to a formal phase diagram determination. The investigation described in the following pages was completed in less than three weeks. The usefulness of this rapid method to facilitate phase diagram studies and new alloy investigations will be shown. Materials and Procedure Zirconium powder was produced from crystal bar stock of high purity supplied by Foote Mineral Co. The crystal bar was converted to hydride at 730°C, crushed, and the hydride decomposed in purified argon at 850°C. 60 pct of the powder passed through a 325 mesh screen, 40 pct of the powder was —140 mesh, +325 mesh and the average particle size of the total was 8 to 12 microns. The beryllium powder was used as re-

Jan 1, 1951

By M. R. Geer, H. F. Yancey, P. S. Jacobsen

Two growing problems confront the preparation engineer—still further restrictions on stream pollution and a greater proportion of fine coal as more and more continuous miners come into use. The de-watering screens, centrifuges, and settling ponds that sufficed a few years ago must often be supplemented by more effective equipment, and in some instances the finest solids are now being recovered by vacuum filtration, once considered too costly in many coal washeries. Unfortunately not all slurries can be readily filtered. Some are virtually unfilter-able, and others do not permit the high cake rates needed to hold costs within reason. Often, however, these difficult slurries can be rendered filterable by flocculation. Starch and lime have long increased settling rate in thickeners and can also aid filtration. More recently there have been other flocculants, primarily synthetic polymers or gums. Reports of their great effectiveness prompted the U. S. Bureau of Mines to test their use in filtration as part of its program on recovering and cleaning fine coal. The object of the present work was to compare some of the newer flocculants with starch and lime and to test the reaction of different types of slurries to flocculation. Three natural slurries, three synthetic coal-clay mixtures, and five flocculants were tested, all with a laboratory filter leaf. Slurries and Flocculants Tested: First of the slurries was the thickener feed from the washed coal section of the Michel colliery of Crow's Nest Pass Co. Ltd., Michel, B.C. As shown by the screen and ash analyses in Table I, practically all this slurry was finer than 28 mesh, and about half the solids were finer than 200. Substantially all material coarser than 200 mesh was clean coal, but the ash content of 20.7 pct in the finest size indicates a moderate amount of impurity. This coal is medium-volatile bituminous in rank. Slurry was also obtained from the Black Diamond washery of Palmer Coking Coal Co., King County, Wash. This underflow of a 1/2-mm vibrating slurry screen is a waste product discharged to a settling pond. As shown by the data in Table I it contained about 20 pct material finer than 200 mesh, which analyzed 77.5 pct ash, indicating a high proportion of clay. The coarser sizes were also high in ash content because of the presence of bone and shale. Black Diamond coal is on the dividing line between bituminous and subbituminous rank. The third slurry, from the washery of Roslyn-Cascade Coal Co. in Kittitas County, Wash., was the underflow of a battery of 8-in. cyclones that is wasted with the coarser refuse from the plant. In both size and ash content this slurry was similar to the Black Diamond, but since it was a cyclone-underflow product, the fraction finer than 200 mesh undoubtedly contained a much smaller proportion of finely divided clay than was present in the Black Diamond slurry. The Roslyn-Cascade coal is high-volatile A bituminous in rank. Initially the slurry samples were stored in the laboratory at a concentration of 40 pct solids. A progressive change in filtration and flocculation characteristics during storage was noted, however, presumably because of progressive disintegration of the clay. After careful testing demonstrated that the slurry solids could be dried and then repulped without changing the original filtration characteristics, this procedure was adopted. The flocculants used were Separan 2610, Kylo 27, Jaguar MD-A, Idaho potato starch, and lime. The lime was used as a slurry, the Separan 2610 as a 0.10 pct aqueous solution, and the other flocculants as 0.50 pct aqueous solutions. The starch was causti-cized with sodium hydroxide before use. As some of the flocculants are reported to deteriorate on storage, new batches of flocculants were prepared every two days. Test Procedure: Fig. 1 diagrams the filter leaf apparatus employed. This consists of a test leaf having an effective area of 0.10 sq ft., a 60°, 8 1/2-in. diam cone to hold the slurry sample, a variable-speed electric stirrer, vacuum gage, bleed line for controlling vacuum, filtrate flask, moisture trap, and vacuum pump. Two filter cloths were selected—Saran SA 603, a monofilament, coarse-weave cloth, and polyethylene PO-801 HF, a monofilament, fine-weave cloth. The Saran was selected to provide maximum cake rate without regard to clarity of filtrate and the polyethylene to provide the best quality of filtrate without regard to cake rate. The test charge for the filtering vessel consisted of 800 g of solids (previously soaked for 24 hr) and

Jan 1, 1960

By R. A. Morse, P. M. Bridges, L. E. Wilsey, Howard N. Hall, P. L. Terwilliger

Theoretical and experimental investigations of a constant pressure gravity drainage system are reported. Experimental data are presented to show that recovery to gas breakthrough by gravity drainage is inversely proportional to rate. The gravity drainage reference rate, which is numerically equal to the so-called "maximum theoretical rate of gravity drainage" is shown to have no particular significance from a recovery standpoint. Before this rate can be used as a basis of comparison for recoveries, it is necessary that the relative permeability and capillary pressure characteristics and displacing fluid viscosities be identical for the systems compared. A method is presented by which accurate prediction of the performance of a gravity drainage system can be made. Close agreement between experimental and calculated drainage performance shows that steady state relative permeability and static capillary pressure data can be used to describe fluid displacement behavior. The very wide range of liquid recoveries before gas breakthrough which result from production rate variation alone demonstrates the importance of this factor in planning depletion of a gravity drainage reservoir. Calculated results are presented which show that little additional recovery can be expected from a high pressure gravity drainage system between the times of gas breakthrough and attainment of such high gas/liquid ratios as to make further pressure maintenance impractical. INTRODUCTION It bas been recognized for some time that gravity forces play an important part in the recovery of oil from some types of reservoirs. Field experience has shown that under certain conditions, gravity drainage can result in very high oil recov- eries. Qualitative reasoning has led most engineers to the general conclusions that: (1) Where gravity drainage is important, the reservoir pressure should be maintained by gas injection at the crest of the structure to prevent shrinkage of the oil in place and to keep a low viscosity so the oil can drain at the fastest possible rate. (2) Recovery by gravity drainage is rate sensitive. A survey of the literature indicates that while considerable work has been done on the effects of gravity in oil production problems, no satisfactory method of calculating the performance of gravity drainage reservoirs has been reported.1,2,3,4,5 In the absence of any proven method of calculating reservoir performance, the level at which pressure should be maintained and the rate of production for most efficient operation has been open to debate. The limits and general character of the recovery us rate relationships are apparent from the following: As rates of production approach zero, oil will drain by virtue of its own weight fast enough that the saturation distribution is always approximately the same as the original static capillary distribution. That is, at the gas-oil contact the liquid saturation goes from 100 per cent to a value of perhaps 10 to 30 per cent in a very short distance, so that as production continues. a relatively sharp gas-oil contact moves down-structure, leaving a very low residual oil saturation in the originally oil saturated zone. At very high rates of production, the oil that drains by virtue of its own weight is negligible and recovery will approach that of a horizontal gas drive, leaving a much higher residual oil saturation. At intermediate rates of production. recovery should be between these extreme*. Despite the lack of quantitative methods, tentative agreement had been reached on the question of optimum producing rate. It has been generally concluded that rather sharp decrease in recovery would occur at rates of production above the "maximum rate of gravity drainage" and hence this rate should not be exceeded. The "maximum rate of gravity drainage" is defined as the rate of production from a 100 per cent

Jan 1, 1951

By L. E. Wilsey, R. A. Morse, P. L. Terwilliger, Howard N. Hall, P. M. Bridges

Theoretical and experimental investigations of a constant pressure gravity drainage system are reported. Experimental data are presented to show that recovery to gas breakthrough by gravity drainage is inversely proportional to rate. The gravity drainage reference rate, which is numerically equal to the so-called "maximum theoretical rate of gravity drainage" is shown to have no particular significance from a recovery standpoint. Before this rate can be used as a basis of comparison for recoveries, it is necessary that the relative permeability and capillary pressure characteristics and displacing fluid viscosities be identical for the systems compared. A method is presented by which accurate prediction of the performance of a gravity drainage system can be made. Close agreement between experimental and calculated drainage performance shows that steady state relative permeability and static capillary pressure data can be used to describe fluid displacement behavior. The very wide range of liquid recoveries before gas breakthrough which result from production rate variation alone demonstrates the importance of this factor in planning depletion of a gravity drainage reservoir. Calculated results are presented which show that little additional recovery can be expected from a high pressure gravity drainage system between the times of gas breakthrough and attainment of such high gas/liquid ratios as to make further pressure maintenance impractical. INTRODUCTION It bas been recognized for some time that gravity forces play an important part in the recovery of oil from some types of reservoirs. Field experience has shown that under certain conditions, gravity drainage can result in very high oil recov- eries. Qualitative reasoning has led most engineers to the general conclusions that: (1) Where gravity drainage is important, the reservoir pressure should be maintained by gas injection at the crest of the structure to prevent shrinkage of the oil in place and to keep a low viscosity so the oil can drain at the fastest possible rate. (2) Recovery by gravity drainage is rate sensitive. A survey of the literature indicates that while considerable work has been done on the effects of gravity in oil production problems, no satisfactory method of calculating the performance of gravity drainage reservoirs has been reported.1,2,3,4,5 In the absence of any proven method of calculating reservoir performance, the level at which pressure should be maintained and the rate of production for most efficient operation has been open to debate. The limits and general character of the recovery us rate relationships are apparent from the following: As rates of production approach zero, oil will drain by virtue of its own weight fast enough that the saturation distribution is always approximately the same as the original static capillary distribution. That is, at the gas-oil contact the liquid saturation goes from 100 per cent to a value of perhaps 10 to 30 per cent in a very short distance, so that as production continues. a relatively sharp gas-oil contact moves down-structure, leaving a very low residual oil saturation in the originally oil saturated zone. At very high rates of production, the oil that drains by virtue of its own weight is negligible and recovery will approach that of a horizontal gas drive, leaving a much higher residual oil saturation. At intermediate rates of production. recovery should be between these extreme*. Despite the lack of quantitative methods, tentative agreement had been reached on the question of optimum producing rate. It has been generally concluded that rather sharp decrease in recovery would occur at rates of production above the "maximum rate of gravity drainage" and hence this rate should not be exceeded. The "maximum rate of gravity drainage" is defined as the rate of production from a 100 per cent

Jan 1, 1951

By Paul T. Allsman, E. W. Newman

TRENCHING, sampling, and core drilling in Stillwater and Sweetgrass Counties, Mont., by the Bureau of Mines have delimited over 5,000,000 tons of chromite ore containing more than 20 per cent chromic oxide. The Benbow and Mouat-Sampson mines have been developed and are fully equipped for mining and milling 500 tons and 2000 tons a day, respectively.

Jan 1, 1944

By J. Randel Hill

The 64th Texas Legislature passed the "Texas Surface Mining and Reclamation Act," Chapter 131, Texas Natural Resources Code (subsequently referred to as "the Act"), at a point in time when little surface mining had taken place within the state. Thus, enactment of regulatory control governing mining operations in our state has, for the most part, preceded widespread, intensive mining activity. I should point out that the statute applies only to the extraction of coal, lignite, uranium and uranium ore. A recent opinion rendered by the Attorney General's office has stated that extraction of the named elements, when it occurs incidental to the extraction of other materials, e.g., clay, is not not an activity subject to the Act. An important theme of the Act, frequently overlooked in other environmentally oriented legislation, is recognition of the Act's affect on the mining industry. The Act states that "the extraction of minerals by surface mining operations is a basic and essential activity making an important contribution to the economic well-being of the state and nation" and, in reference to reclamation being accomplished contemporaneously with mining, provides a recognition that "the extraction of minerals by responsible mining operations is an essential and beneficial economic activity." This legislative recognition is, of course balanced against the need for proper mined land reclamation, the rights of surface owners, the need to guard against unreasonable degradation to land and water resources and numerous other actions or events that the Legislature wanted protected. Another rather pervasive general theme that is established in the Act is the concept that the agency is entitled to obtain whatever information, or take whatever action, that appears reasonably necessary to effectuate the purposes of the Act. This concept, coupled with the detailed requirements placed on mining operations in the portions of the Act dealing with Permit Applications, Reclamation Plan and Reclamation Standards, easily insures that surface mining activities can and will be regulated to the extent necessary. Section 131.102(b)(2) is probably the most relevant provision in the Act which deals with the preclusion of mined lands becoming waste lands. This portion of the Act states that the surface mining operator shall: ". . . restore the land affected to the same or a substantially beneficial condition. ." In this language the Legislature had made it abundantly clear that the abandoned or orphaned lands found in some of the Eastern states, will not be tolerated in this State, and provided the Commission with a degree of latitude to determine what condition would be appropriate in each individual mining situation. I bring this area of the Act to your attention because it is the area which has received the most inquiries and concern by operators, i.e. what does "substantially beneficial" constitute? The Commission's staff has spent a considerable amount of time wrestling with the statutory language "substantially beneficial" to determine the legislative intent and provide operators with guidance of what they can expect. In this regard, the most definitive criteria in our opinion lies in the Act's legislative hsitory. The Legislature had before it basically three reclamation standards namely: House Bill 656, considered to provide the most stringent reclamation standard and identical to Senate Bill 66; House Bill 1717 which was supported by industry spokesmen and was considered to contain the least stringent reclamation standard; and Senate Bill 55 which was adopted by the Legislature. During the Bill's initial hearing before the House Environmental Affairs Committee, the House sponsor of the Senate Bill 55, which was the Bill eventually adopted, made the following statement: (I am quoting verbatim from the Committee's transcript although substituting the speaker's reference to the authors names with the Bill's numbers.) "An example of the differing approaches of the four bills can be seen in the area of reclamation standards and this is critical. House Bill 656, talking about restoring the surface of the land, House Bill 656 has this statement: 'At least fully capable of supporting the use to which it was capable of supporting prior to any mining or any higher or better use.' In other words you have to restore it to the level it was prior to the mining. Senate Bill 55: 'Restore the land to the same or substantially beneficial use.' Substantially beneficial use. (Emphasis his) House Bill 1717 says: 'Restore insofar as practical to appropriate beneficial post-mining use.' So that House Bill 1717 said to, 'restore insofar as practical to appropriate beneficial use. I think that's too weak, whereas I think the House Bill 656 that would call you to restore it to at least the use it had prior to the mining may also be too tight the other way. I think the Senate Bill 55 approach is down the middle of the road which says that you do restore it to the 'same or substantially beneficial use,' is a proper way to go there." Therefore, the conclusion that we have drawn from the legislative history of the bill is that the extent of reclamation required by "substantially beneficial" may be something other than the use it was prior to

Jan 1, 1979

By H. B. Treweek, V. R. Degner

Current mineral industry trends toward handling the high tonnages of lower grade ore and tailings retreat lead to a continuing need for large volume flotation cells. The benefits which accompany the larger cell flotation circuit include reduced capital cost, less mill floor space, reduced operational complexity, and less maintenance, provided the metallurgical performance and solids suspension capability of the cell are not compromised. This study reviews development considerations pertinent to large mechanical air induction type flotation cells from the standpoint of cell internal hydrodynamic characteristics and metallurgical performance. While the importance of process related factors such as chemical usage, pH control, solids size and loading, and circuit arrangement cannot be denied, this study will emphasize the relationship of cell size (volume), mechanism geometry (impeller diameter), and mechanism operating conditions (rotor speed and submergence), to air transfer, liquid circulation, liquid "rise velocity" and mechanism power draw. Specific hydraulic performance maps for large capacity 300 and 500 cu ft flotation cells will be reviewed in terms of the relationship between the operational variables and the air and liquid flow conditions within the cell. Metallurgical results, obtained under plant operating conditions for 300 and 500 cu ft cells, are included to illustrate the metallurgical performance similarity of flotation cells which follow hydrodynamic scale-up criteria set forth in this investigation.

Jan 1, 1976

By Ralph Hultgren

FEW phase diagrams of alloys composed of two transition metals have been adequately studied, probably because of the high melting points involved. Transition metals are the elements that have inner shells incompletely filled with electrons. They comprise groups IIIa to VIIIa of the periodic table, including more than half of all metals. We have chosen to study two systems whose comparatively low melting points allowed the alloys to be melted in a molybdenum resistance furnace. The nickel-palladium system proved to consist of a simple series of solid solutions, but iron-palladium manifested several remarkable features. The main characteristics of the latter diagram were decisively established, but lack of time prevented precise determination of phase boundaries. The gamma to alpha transformation in this system is unusual and warrants further study. Grigorjew1 determined the liquidus and solidus of the iron-palladium system by thermal methods. He found a minimum melting point, but no eutectic. He also found that palladium lowered the gamma to alpha and raised the gamma to delta transformation temperatures of iron, with a complete series of solid solutions existing between gamma iron and palladium. His measurements also indicated a compound or super-lattice near the composition FePd3. Jellinghaus2 found that annealing at 500° C. greatly increased the magnetic coercive force of an alloy of composition FePd. X-ray dif-fraction photographs showed that a tetragonal ordered phase had formed during the anneal.

Jan 1, 1939

By J. Steininger

The Hallimond tube flotation of sphalerite and pyrite with sulfhydryl collectors has been found to be inhibited near neutral pH in the presence of copper salts. Alkalimetric titration studies of the reactions between collector and activator indicate that this effect is apparently related to the formation of basic copper collector complexes. The conditions of formation of these compounds and their stability are in good agreement with the depression observed in flotation experiments. The general procedure employed in the flotation of zinc sulfide minerals requires activation of the mineral surface by heavy metal ions, usually copper, which react more easily than zinc with the common short-chain ionic sulfhydryl collectors.' Commercially, zinc flotation is carried out under alkaline conditions (pH 7 to 10.5), but small-scale experiments indicate that zinc sulfide minerals can also be activated and collected under acid conditions. Selectivity, however, becomes poor at low pH and undesirable materials such as pyrite, silicates and carbonates tend to report in the float. Several years ago, Wark and Sutherland~, measured the contact angles of air bubbles on copper-activated sphalerite immersed in various sulfhydryl collector solutions. When represented, as in Fig. 1, on pH-sodium cyanide diagrams, the results are characterized by 'islands' of non-contact near neutral pH and

Jan 1, 1969

By Chas. H. Behre, Arbiter. Nathaniel

Two outstanding factors characterize most undertakings in the mineral industries: (1) mineral deposits are not equally distributed over the earth but are localized by natural processes, and (2) the mineral industries are largely based upon wasting assets. Neither of these factors is invariably true, for a few mineral materials, such as water, are essentially world-wide and others are replaced periodically by processes not unlike crop production. Indeed, with some, such as the salts in the sea, the supply is cyclic in short or long periods, whereas others, like water, though locally or periodically in short supply, are essentially inexhaustible. But to the extent that most minerals are limited to certain areas and are "permanently" consumed, any industry founded upon them, by implication, demands great care in planning for the most effective extraction-the essence of wise and conservative expenditure. Several less unusual yet also truly fundamental factors in the economics of the mineral industry are those involving (1) the various kinds and properties of mineral materials, which influence their use; (2) their geo- logic and geographic availability; and (3) the techniques unique to their discovery, exploration, and utilization. This chapter is designed primarily as a brief background for later ones and as a summary of the several un- usual or at least special factors and of their effect upon the economics of the mineral industry. The social and political and especially the economic aspects of the industry are the main subjects of this volume and are dealt with in extended fashion in subsequent chapters. Fundamental Characteristics of Mineral Deposits DEFINITIONS Minerals are naturally occurring compounds of nonliving matter, each technically defined as having (1) a chemical composition that may vary

Jan 1, 1959

By H. F. Hebley

In recent years, especially in the last decade, great interest has been shown and many advances have been made in the preparation and cleaning of coal. In the major coal-producing countries, the percentage of tonnage cleaned has been increasing ever since 1924. As separating media, both liquids and gases are used, these generally being water and air respectively. Some systems, instead of obtaining separation by the velocity of the medium in which the coal is cleaned, depend on the density of water mixed with sand, or coal dust and shale, or with chemicals such as calcium chloride. In studying the results of coal-cleaning equipment, it will be observed that the efficiency of the cleaning apparatus lowers as the size of the coal decreases. This inability to obtain any marked improvement in the fines has been partly responsible for the installation of dedusting equipment, to remove the fine sizes from the raw coal prior to cleaning. When considering the possibility of installing dedusting equipment, many factors must be taken into account. Very often, but not always, both the ash and sulfur content of the coal increase as the coal size decreases. When bituminous coal, containing soft powdery fusain, is subjected to a wet washing process, the porous fines of the fusain remain in the small coal or in the wash water and delay the dewatering of the washed coal and increase the difficulty of clarification in settling tanks or thickeners. When a dedusted coal is cleaned by a wet process, the sludge recovered from the settling tank often runs so high in ash that the sludge can be discarded without further treatment and still the loss is small. Where treatment of the sludge is desired, however, froth flotation may be used to advantage if the size of the feed is below 1/10 in. Dust from the deduster can be treated in a similar manner. Fusain, which is usually found in the fine sizes, has often a much larger ash content than other coal. Illustrative of this condition is a table of ash contents for the various petrographic constituents of Illinois coal (No. 5 bed) as given by Mitchell' (Table 1).

Jan 1, 1934

By Arthur Notman

SacRamento Hill is a mass of granite porphyry intruded along a fault between Paleozoic sediments and pre-Cambrian schists in the Bisbee district, Cochise County, Arizona. The intrusion invaded both walls of the fault to a large extent, and the accompanying extensive mineralization of the Paleozoic limestones is the locus of the great high-grade copper orebodies of the Bisbee mines. Prior to 1909, although the presence of ore in the masa of the hill itself had long been suspected, systematic exploration had not been attempted. A few shallow pits on the surface here and there had disclosed some chal-cocite with associated carbonates as stringers in a mass of strongly brccciated, silicified, and iron-stained porphyry. The workings in the surrounding limestones had penetrated the porphyry in a dozen or SO places for some distance from the contact but had disclosed no ore. However, the rock had been largely altered to quartz and sericite and very thoroughly impregnated with pyrite and traces of the copper sulphides. A close geological study of the conditions, both surface and underground, strengthened these suspicions, and plans for prospecting the hill were made in 1909. Reference to the accompanying illustrations, Figs. 1 and 2, will give an idea of the general appearance of the surface. The mineralization is more intense in two main zones, one at the west end and the other at the east end of the hill. The outcrop of the hill is elliptical and approximately 3,000 ft. long by 1,400 ft. wide. The Sacramento shaft, which is the main hoisting shaft of the mine and situated at the east end of the hill, as shown by the accompanying map (Fig. 3), offered a convenient base for prospecting that end of the hill, while the workings from the Holbrook shaft offered a similar opportunity at the west end. The choice of level for the first work was determined by analogy with the most favorable depth for enrichment below surface obscrved in the other disseminated deposits of the Southwest.

Jan 1, 1916

By John D. Roach

DURING an investigation of the yttrium-hydrogen system aimed at producing solid yttrium hydride specimens containing various amounts of hydrogen, it was observed that yttrium containing approximately 2 wt pct H exhibited a tendency to crack and crumble to a powder on standing in air at room temperature. It was also observed that longer hydriding times, at a given temperature, increased this susceptibility to powdering without an increase in hydrogen content, also that moisture in the air is necessary for the observed effects to occur. Even if cracking did not occur, there was a continual formation of a light gray powder on the as-treated surface of the hydrided yttrium and this reaction continues until the entire hydrided piece has been reduced to a powder. Storing the hydrided specimens in the absence of air or removing the surface either by machining or grinding were effective means of preventing this disintegration of hydrided yttrium. In an attempt to determine the reason for this powdering phenomenon, the surfaces of a number of as-hydrided yttrium specimens were examined by X-ray techniques. In all cases the X-ray pattern obtained showed the major phase to be yttrium hydride (YH2) as would be expected since the specimens contained 2 to 2.2 wt pct H. In some cases a trace of yttrium oxide was observed. There was also a third phase present on the surface of these hydrided specimens which could not immediately be identified. This unknown phase was a face-centered cubic material, NaC1-type structure, with a lattice parameter of 4.855 and a calculated density of 5.914 g per cc. Very slight hand polishing of the surface of the hydrided yttrium specimens completely removed both the unknown phase and the traces of oxide so that only the yttrium hydride pattern remained. Based on the X-ray patterns the quantity of the unknown phase on the surface of the hydrided yttrium appeared to be directly related to the susceptibility of the material to powdering. Work at the Denver Research Institute on the yttrium-nitrogen binary system showed that yttrium nitride (YN) is a face-centered cubic material with a lattice parameter of 4.878A and a density of 5.890 g per cc. They also noted that this compound rapidly disintegrated to a powder on standing in air. The unknown pattern observed in the above specimens corresponds very closely to that of the nitride—fcc structure, 4.885 parameter, and density of 5.914 g per cc. The presence of this thin film of nitride on the surface of the hydrided specimens probably accounts for the observed powder formation and crumbling. The nitride reacts with the water vapor in the air (verified by private communication from Dr. C. Huffine, General Electric Co.) to yield yttrium oxide and ammonia. Ammonia is readily detected when hydrided yttrium specimens were allowed to stand in bottled moist air. The powder formed on the surface of the hydrided specimens was shown by X-ray analysis to be yttrium oxide. This reaction appears to occur primarily at the grain boundaries since discrete particles of yttrium hydride separate from the specimens during this powdering process. The reaction of yttrium nitride with water vapor is believed to be as follows: 2YN + 3H2O - Y203 + 2NH3. Despite the fact that this nitride is present only as an extremely thin surface film, if the above reaction is not prevented by removing this film from the surface either by machining or grinding, the reaction continues until the entire hydrided piece has been reduced to a powder. To account for this continuation of the reaction, it is believed that the following reactionalsooccurs: 2YH2 + 2NH3 -2YN + 5H2. The nitride produced by the latter reaction reacts in turn with water vapor. The reaction therefore becomes autocatalytic and continues until the hydride has been consumed and the entire piece reduced to oxide powder. The amount of nitride required to initiate this reaction is quite small and this nitrogen contamination can occur from a number of sources—hydrogen gas employed, minute leak in the hydriding apparatus or even from degassing of the reaction vessel itself. Longer hydriding times increase the possibility of nitrogen contamination and this is especially true when a dynamic gas system is employed in the hydriding process. The production of stable, solid hydrided yttrium is dependent on the complete absence of nitrogen contamination during processing. If such contamination does occur, powdering of the hydrided product can be prevented by removing the nitride from the surface e.g. grinding or by preventing access of air to the pieces e.g. sealing in wax or plastic. The author wishes to express his appreciation to General Electric Co. for sponsoring this research and for permission to publish the results of work under Subcontract AT-93.

Jan 1, 1962

By Robert T. Howard, Morris Cohen

THE purpose of this paper is to direct attention to the lower part of the austenite transformation diagram, or TTT curves, where considerable uncertainty still exists as to the blending of the bainite and martensite reactions. The dissimilarities between these two low temperature trans- formations have been summarized recently by Troiano and Greninger.1 Of particular importance to the present work is the fact that martensite formation, unlike bainite formation, is not suppressed by the fastest quenching rates attainable. However, most of the investigations in this direction have been concerned primarily with the start of the martensite transformation [(M,)] during cooling, rather than with the quantitative aspects of the subsequent reaction on either further cooling or isothermal holding. Several years ago, Cohen2 suggested a form of transformation diagram which reconciled, at least schematically, the isothermal characteristics of the bainite transformation with the insuppressible nature of the martensite transfoi mation. In essence, the diagram consisted of a family of horizontal lines (representing the progress of the austenite-martensite reaction during quenching) which were interrupted in point of time by the bainite family of C-curves extending down from higher temperatures. This picture received later support by metallographic3 and dilatmetric4,5 studies, but the techniques employed were not sufficiently critical to substantiate some of the details. Elmendorf6 and Grange and Steward7 have shown that the Greninger-Troiano metallographic techniques may be used not only for [M,] determinations, but for studying the course of further austenite decomposition. In fact, the latter investigators have observed the amount of martensite formed as a function of temperature below [M,] in fourteen commercial steels. In the present paper, the Greninger- Troiano technique has been combined with the lineal method of Howard and Cohen9 to provide a unique, quantitative treatment of the austenite-martensite reaction. Furthermore, isothermal transformations have been similarly measured on holding at temperatures above and below M,, thus permitting a fairly detailed presentation of the lower part of the conventional austenite transformation diagram. EXPERIMENTAL DETAILS Materials The steels, listed in Table I, were selected for study because they exhibit a satisfactory range of M, temperatures and have not received as much attention as the lower carbon grades. They were prepared as 30 lb induction furnace heats in the laboratories of the Vanadium-Alloys

Jan 1, 1947

By L. L. Wyman

SINCE the observations of Heyn,1 relative to the embrittlement of copper after having been heated in hydrogen, this subject has received considerable attention from later investigators. The published works of Archbutt2 and of Bengough and Hill3 give the reasons for this embrittlement-the formation of steam by the reaction between cuprous oxide and hydrogen. From Ruder,4 Pilling,5 Moore and Beckinsdale,6 Bassett and Bradley,7 and from Smith8 can be obtained quantitative data concerning the action of hydrogen and other reducing gases on copper samples having various oxygen contents. This problem has been discussed from a practical standpoint by Fuller9 who calls attention to some of the instances of this embrittlement encountered in the manufacturing field. The examples he cites may be considered typical cases of copper embrittlement which were incident to the process of manufacture. In many cases, such difficulties are overcome by changes in the manufacturing process.

Jan 1, 1931

By John S. Johnson, Thomas Fraser

SIZING is the process of separating mixed particles into groups of particles all of the same size, or into groups in which all particles L range between certain definite maximum and minimum sizes. In coal preparation, sizing is generally accomplished by passing the coal over screens. Separation by differential settling in air or water currents has been adapted to the special field of separating very fine sizes, and these processes are in commercial use to a relatively small extent in the coal industry. Separation with screens is a very old industrial practice. Agricola 1 described the use of screens for ore treatment in the middle ages. In the literature of the British coal industry references were made to the screening of coal as early as 1589, but the practice of extensive sizing for the market did not become general until the last half of the nineteenth century. In America, the practice of sizing developed first in the Pennsylvania anthracite region, beginning with the use of rakes2 in the mine working places to recover coarse coal. This mining procedure left the fines in the mine. Preparation outside the mine started with the installation of stationary cast-iron plates with 4 to 6-in. square holes. The run-of-mine coal was dumped upon the platforms, the large pieces of rock were picked out by hand, and the large lumps of coal were broken with hammers. The term "breaker," which still applies to the anthracite-preparation plant, originated with this practice, but the term is no longer descriptive of the entire function of the plant. In 1884, the first power-operated anthracite coal breaker3 was erected by Gideon Bart at his colliery at Wolf Creek near Minersville, Pa. This plant utilized a system of rolls for breaking the coal and revolving screens for sizing. The plant was driven by a steam engine. It could handle

Jan 1, 1943

By J. W. Pamplin

SOME 40 miles east of Tampa is the center of the Florida pebble phosphate deposits. These are of Pliocene age and consist of several members of the Bone Valley formation.' Physically the phosphate-bearing formation, locally called the “matrix," varies in thickness from nothing to about 25 ft., usually averages 10 ft., and consists mainly of clay, quartz and phosphate pebble, the latter particles varying in size from colloidal to one inch diameter. The pebbles range in color from dark gray, through white, to cream, and in hardness from that which must be broken with a hammer to that which can be scratched with the fingernail. They assay from 66 to 80 per cent bone phosphate of lime (called "B.P.L." in the trade) or tricalcium phosphate (Ca3P2O8) and are secondary apatites. They form from 15 to 50 per cent by weight of the matrix. Over the matrix lies a varying thickness (5 to 40 ft.) of overburden composed of quartz and clay. Briefly, mining consists of two operations2 in open pits about 200 ft. wide by ½ mile or more in length. In the first step overburden is removed by large electric draglines at the rate of about 700 cu. yd. per hour. This is followed closely by hydraulic mining of the matrix at the rate of about 300 cu. yd. per hour. This matrix yardage is moved from an improvised sump in the floor of the pit to an ore-dressing plant, some- times a mile distant, by one, two or three "pit-cars" (pumping units) working on a 12-in. pipe line called the "rock line" to distinguish it from the high-pressure water line feeding the hydraulic giants, which is known as the “hydraulic line." This 700 yd. of overburden and 300 yd. of matrix-1000 yd. in all- amounts to about 1500 tons of material moved each hour. The over- burden is dumped into the mined-out pit alongside the pit being mined. The matrix moves to the ore-dressing plant at the rate of about 7 ½ long tons in 4000 gal. of water per minute-a ratio of approximately one to two by weight, or one to six by volume. This constitutes the "mill heads," but in the pebble district it is called the "matrix."

Jan 1, 1938

By L. F. Bishop

The ore bodies of the Butte district1 are found in many different vein systems having many different structural characteristics; some are narrow with self-supporting ore but with weak walls; some are wide with weak or strong ore and weak walls; some of the veins dip steeply and others do not; some have well defined walls, and others, in the "horsetail" area, are mined to sample limits. Consequently, many types of stoping methods are used in mining these ores. The stoping methods used in the Anaconda Copper Mining Company's properties are the square-set and cut-and-fill. The square-set method is the principal stoping method used because, generally speaking, the ore and walls are weak, the ore is high grade, and good extraction is required. These square-set stopes may be classified as conventional, vertical slice, slot, timber rill, and Mitchell slice types. The conventional type square sets are those of various shapes and sizes, mined by horizontal slicing to the boundaries of the stopes. The rock is slid to the chute and the filling is moved by gravity. The ore and waste may be handled with a scraper when local conditions require it. The vertical-slice square-set system is the type used in narrow veins that are mined in vertical panels. The slot stopes are stopes in wide veins that employ a slot across the vein instead of a con- ventional chute to handle the ore. The timber rill is a type of square set in which the ore is mined as in inclined cut and fill but the square-set timber is used. The Mitchell slice is the type used for some broken or heavy ore blocks, or for pillar extraction between two converging slot stopes. The cut-and-fill method is used where the ore will stand without much support although the walls may be weak. The principal type of this method is the horizontal cut-and-fill, with mechanical scraping. The inclined cut-and-fill, or rill, stopes are used in some veins too narrow for scraping. The production from the various methods in use for the second six months of 1944 are shown in Table I. This paper deals mainly with the vertical slice and slot types of square-set stoping, because of their effect on production locally and their potential possibilities here and in other districts, with sufficient reference to conventional square-setting for comparison.

Jan 1, 1946