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By C. S. Samis, J. C. Mitchell

Sodion activity data have been obtained for the Na-A1 system for sodium concentrations in aluminum between NN, = 25 . 10-and 300 x 10'. This concentration intert-a2 encompasses those sodium concentrations nor1)zally encountered in aluminum reduction cell operation. The sodium activity data were measured by a two-phase equilibration of sodium between a lead and an aluminam rich phase. The Na-Pb system was emplojed as a reference for the determination of the actiz7itj 0.f sodium. The activity of sodiin in aluminuwz exhibits large positi2.e deviations frorn ideality and a strong dependence, on concentration below NN, = 100 x 1K6. The inteated data indicate that the activity of aluminium is equal to its mole fraction over the range of miscibility of the Na-A1 sgstem. The data on the Na-A1 binary have been combined with experimental data on the cryolite-A1 system at 1025°C to obtain the activities of Na F and AlF, in liquid cryolite oz2er the cornposition 1-ange encountered in aluminum cell operation. The results are in agreement with activities calculated from the NaF-AlF, phase diagram. ALUMINUM is produced commercially by the electrolytic reduction of aluminum oxide dissolved in molten cryolite. There is considerable controversy over the actual mechanism of the discharge processes, but sodium potentials in the systems appear to play an important role in the reduction mechanism. The metal-salt reaction involving NaF and aluminum to produce A1F3 and sodium is responsible for the presence of sodium in the aluminum metal phase. Additional sodium may be produced from the simultaneous deposition of sodium and aluminum at the cathode as a result of a cathodic overvoltage. runert' has suggested that sodium gas at atmospheric pressure would be the result of reaction between cryolite and aluminum at 1000°C. Subsequent investigations have shown that production of sodium at atmospheric pressure does not occur. These later investigations can be conveniently separated into two categories. The first involves sodium, aluminum, and cryolite, in which the sodium activity was measured. The second includes a lead phase for sodium activity measurement. Jander and errmann,' studied the reaction: at 1090°C in alumina crucibles under an atmosphere of dry, oxygen-free nitrogen. The equilibrium constant for the reaction was expressed in terms of concentration. Their results in Fig. 1 show an increase in sodium content of the aluminum with increasing NaF/A1F3 weight ratio. Pearson and waddington3 performed similar experiments at 1000°C. Their results are included in Fig. 1. Dewing and ollinshead have measured the sodium content of aluminum as a function of the NF/AF, ratio at 1025"C, Fig. 1, and ewin' measured the sodium content of the aluminum in a system involving the solid reactants NaF, cryolite, and liquid aluminum. This reaction is different from those discussed above. Two solid phases, NaF and Na3A1F6, and a liquid aluminum phase were present. The sodium concentration in the aluminum was determined by the temperature. Dewing's measurements covered the temperature range 679" to 896°C. Omo, Matsushima, and 1t02" investigated the equilibrium 6NaF ential thermal analysis. Stokes and Frank6 determined sodium activities by

Jan 1, 1970

By W. R. Ingalls

THE paramount subject of interest and concern at the present time is the readjustment in economic conditions following the cataclysmic disturbance produced by the war and the misconceptions leading to an orgy of extravagance that prevailed during two years following the armistice he, time is too short for me to undertake to review the nature and extent of the upheavals occurring between August, 1914, and October, 1920. Bulky volumes will be written about them. . But I shall have to refer to some of the results in order to outline a prognosis. It is the future, not the past;' that is of most interest to us. Let me be so bold as to say, without further preface, that I am not optimistic as to the near future. .We shall, indeed, have revivals in trade, but they will be delusive if their nature be not 'understood. We shall build hopes and expectations upon political maneuvers and events, only to find in the end that they were folly. In the meanwhile fundamental economic influences will continue to exert their steady and irresistible pressure. The new administratiow at Washington has no magic wand with which to kindle the fires in our idle steel furnaces, or create a million new houses for the people; nor can the premiers of Europe put into motion the spindles of the cotton and woolen mills, or by any incantations compel the people of the Orient to buy goods. The people of the Orient, and of, Europe, and of the two Americas are in the grip of the same economic forces. The readjustment has proceeded further in some parts of the world than in others. In the United States I do not think we, have gone more than over the threshold. I shall tell you why 1 think thus, but in telling you I shall be limited, in view of the immensity of the subject, to a series of bald statements, without much elucidation.

Jan 1, 1921

By J. B. Dilworth

OUTCROPS of coal have bees discovered is many localities is the Philippine archipelago, and practically all of the larger islands contain deposits of this mineral. Very little prospecting has been done to determine the value of the various coal-bearing areas, but so far as known, the largest and most promising fields are found : (1) is northern Cebu; (2) is the small island of Batan, a part of the province of Albay is southeasten Luzon; (3) is the somewhat larger island of Polillo, off the east coast of Luzon, and (4) is southern Mindoro, sear the small coast tows of Bulalacao. Northern Panay, south-central Cebu, and various localities is southern Luzon, Masbate, Negros, and Mindanao also afford evidences of the existence of coal-beds, the extent and value of which have not yet bees proved. The general position of these islands and districts is shows on the map of a portion of the Philippine Islands, Fig. 1. Some of these coal-fields have been known for many years (coal was discovered is Cebu 1827 and is Batas is 1842),1 and several futile attempts were made by the Spaniards to operate mines is these districts. But owing to many circumstances, chief among which were indifferent management, the political unrest of the islands, natural difficulties of transportation, and those inherent in the mining of steeply-inclined and somewhat irregular seams, no considerable output was ever obtained from any of these mines, and the fuel required is the many departments of industrial and political life has continued to be drawn largely from Australia and Japan. These conditions exist to a great degree at present, and though much interest is the coal-deposits of the Philippines

Jan 1, 1909

By C. C. Furnas

IT is well known that particles of different sizes are not distributed evenly throughout the average charge in an iron blast furnace. Just how great the disparity in particle size in different parts of a single plane in a furnace may be is indicated by the results of some recent investigations1 conducted by the Bureau of Mines on a furnace operating on Lake ores. The wide variations found in gas velocity, gas composition, and temperature from the periphery to the center of the upper charge column were caused by the great variation in particle size of the raw materials used and were also greatly influenced by the methods of charging. This paper summarizes the results of an investigation of the influence of different methods of charging and of the treatment of raw materials upon the size distribution of the solid particles in the blast furnace. A more complete report will appear later as a Bureau of Mines technical paper.

Jan 1, 1929

By Charles S. Barrett

THE experiments reported in this paper have been fruitful in disclosing the mechanism of the deformation of iron in compression. They have established the nature of "deformation bands," "etch bands," or "X-bands," that have been a recognized but little understood feature in the structure of cold-worked metals since the early days of metallography, and have shown the role of the bands in the development of preferred orientations by cold-working. The work has also shown the relation of the orientation of individual grains to the preferred orientation of the aggregate. Some of the methods previously used in the determination of the indices of slip planes and slip directions are shown to be untrustworthy in the presence of deformation bands. The conclusion is reached that many slip planes and slip directions must operate during each stage in the compression of a single crystal, and that theories failing to take account of this require revision. In conducting the experiments a method of compression has been used by which extreme reductions can easily be reached, even to the limit set by the metal's capacity to deform without fracture. The work is a portion of a research program on the plastic properties of iron and steel. It is being used as a foundation for studies of orientations resulting from recrystallization and is being extended to other metals and other types of deformation. PREVIOUS WORK The previous experiments are few and have given confusing results. Ono1 compressed a polycrystalline alpha-iron specimen between two flat plates of a testing machine and found that severe deformation oriented the crystals into a duplex preferred orientation, one set of crystallites having a cube diagonal of the body-centered cubic lattice parallel to the compression axis, and another set having a cube axis parallel to the compression axis. We shall speak of this structure as a. double fiber texture of the type [111] + [100]. Wever2 also made an X-ray determination of the texture

Jan 1, 1938

By E. H. Jr. Dix

THE consideration of alloying elements for aluminum has led to a series of investigations of the equilibrium relations between aluminum and those alloying elements. Therefore, the aluminum end of the aluminum-antimony diagram has been studied. The general form of the aluminum-antimony equilibrium diagram has been worked out by Campbell and Mathews1 and by Tammann.2 Campbell and Mathews described principally the beginning of solidification. They found the curve of beginning of solidification to rise gradually from the melting point of pure aluminum to a maximum at about 67 per cent. aluminum. After a slight lowering of the curve at a little greater antimony concentration the curve again rises to a maximum at 18.4 per cent. aluminum, which corresponds to the compound AlSb. The curve then drops to the melting point of pure antimony. Tammann explained the maximum occurring at about 67 per cent. aluminum as the result of the slow formation of the single compound AlSb. The space lattice of the compound AlSb, according to Owen and Preston,3 is face-centered cubic, the antimony atoms being intermeshed with an identical aluminum lattice. Very little, if any, work has been done on aluminum alloys containing small amounts of antimony.

Jan 1, 1930

By J. R. Thompson

It is common practice, and certainly good business as all of us know, to take care of plant operating equipment. Machinery of any type requires periodic inspection and planned maintenance. With this thought in mind a plant operator should at the end of every shutdown period make regular belt inspections and plan for later appropriate care and maintenance. The points mentioned below are understood well by all of us but are sometimes forgotten because belt conveyors are comparatively easy to operate. Maintenance of any conveyor belt is dependent upon the fundamental characteristics of the two component parts-cover and carcass.

Jan 6, 1950

By R. J. Wysor

MORE than two years ago, in making efficiency tests on our hot-blast stoves, I was surprised to discover a marked difference in temperature as indicated by a pyrometer inserted near a stove on blast, and the regular recording instrument situated near the bustle pipe. A special hole was then provided at the junction of the hot-blast main and the bustle pipe, and portable pyrometers with bare fire ends were used, both at this point and in the stove necks. I had occasion to make a number of such tests on various stoves on the same furnace, the difference in temperature as shown by the two pyrometers varying chiefly with the temperature of the blast, and the distance of the stove from the furnace. However, this difference was always great, often averaging above 100° F., for the entire period of a stove on blast. Later, experiments were made with similar results on another group of stoves. The pyrometers used were properly standardized and checked against each other before and after each test. However, there was still a slight doubt as to the accuracy of the results obtained, as subsequently explained. But I have obtained corroboration of the magnitude of heat losses from blast-furnace hot-blast mains from two independent sources. I have learned from H. A. Brassert, Superintendent of Blast Furnaces, South Works, Illinois Steel Co., that he has recently clone some experimental work similar to my own, and found temperature drops of the same order of magnitude. Also, C. R.. Lyle, of the Armstrong Cork Co., has made some interesting theoretical calculations, based oil the thermal conductivity of fire brick, for the particular conditions of several of our tests; and his theoretical interpolations, all facts being considered, check our actual observations fairly well. I understand that Mr. Lyle expects to publish the results of his investigations.

Jan 10, 1915

By Robert C. Freas, William H. Lane, David J. Krohn

Maysville, Kentucky, is the location of Dravo Lime company's new 9 070 mt(10,000 tons) per day limestone mine and 2 727 mt (3000 tons) per day calcination plant. This complex has been designed as a unit, and capitalizes on recent technological advances. Geologically the Dravo facility is.located on the eastern flank of the Cincinnati Arch, with the high calcium limestone being found at a depth of approximately 274 m (900 ft). A systems approach has been employed in designing and equipping the mine. This allows for maximum production while maintaining flexibility and versatility. All hydraulic drilling, large LHD equipment, and an extendable mine conveyor system are utilized in a five-part mining cycle. A modular concept modifies the room and pillar system to optimize ventilation. The limestone is calcined in three 5.18 x 61.87 m (17 x 203 ft) KVS rotary kilns with a design capacity of 909 mt (1000 tons) per day of lime per kiln. The kilns are coal fired and equipped with preheaters. Lime storage is provided by three 57 m (186 ft) high concrete silos with a combined capacity of 40 909 mt.

Jan 1, 1976

By Robert Stefanko

Roof bolting in coal mines has progressed very rapidly in the last decade, and today this method of support is in general use. There are many theories concerning the functions of roof bolts, but the importance of beam building is indisputable. Proper tension in the bolts minimizes shearing along bedding planes and creates a thick, competent beam from individually weak layers. Bolting must be accomplished immediately upon exposure of the roof, and bolt tension must be maintained if roof failure is to be prevented. Seams are being mined today with roof bolt support where conventional timbering was not effective1. The widespread use of continuous mining equipment was made possible by roof bolts which permit long supported spans free of obstructions.2 Since adequate anchorage is the key to successful bolting, better methods for determining the efficiency of anchorage are continually being sought. Attempts have been made to measure bolt loads, thus assessing anchorage efficiency by employing sensing devices between the bolt head and roof. 3,4,5 None of the techniques appears to be very accurate, and all have at least one serious deficiency.

Jan 5, 1962

By Cleland N. Conwell

Intermittent coal mining has been conducted in Alaska for over a century. The first report of coal in Alaska was by the Veechy expedition of 1826 and 1827. Whaling ships used coal from Corwin Bluff near Cape Beaufort during the early and latter parts of the 19th century. The first coal mine in Alaska-and probably the oldest in the Pacific coast of North America-was opened by the Russians at Port Graham on the southwest tip of the Kenai Peninsula. The mine was operated from 1855 until 1867 when the United States took possession of Alaska. From 1880 to 1915 coal mining was carried on intermittently at several localities including Unga Island, Herendeen Bay, Chignik Bay, Kachemak Bay, and several points along the Yukon River. Small coal mines along the Yukon River provided fuel for the river steamers traveling from St. Michaels to Whitehorse. The area of sustained coal production began with the completion of the Alaskan Railroad from Anchorage to the Matanuska coal field in 1916 and to the Nenana field in 1918. Coal production continued to increase until 1953, at which time the oil and gas fields in Cook Inlet were developed. Oil and gas eventually replaced the Matanuska coal as a means of providing heat and power. The military in the Anchorage area shifted from coal to oil in 1967 causing a decrease in production. The increased demand for electric power in the Fairbanks area offset the decline and coal production started to increase. In 1969-1970 the Golden Valley Electric Assn. (GVEA) constructed a mine-mouth power plant 70 miles southwest of Fairbanks near Healy and a power line to Fairbanks. Location of Coals in Alaska Coals are found in all geographical subdivisions of Alaska. Coal in Alaska ranges in age from Carboniferous to Tertiary, and grade from lignite through anthracite. Fig. 1 shows the locations of Alaskan coal fields. The only fields that have been developed extensively are the Matanuska and Nenana. Fig. 2 illustrates the annual production of coal in Alaska and the ratio of underground to strip mining.

Jan 1, 1973

By M. H. Richman, E. S. Meieran

An analytical method is presented which enables the electron diffraction patterns from a twinned region to be indexed. The method has only been applied to (112) twins in bcc lattices, but can easily be adapted to other types of twinned lattices. Calculations of all twin spots, including those superimposed on matrix spots, is made possible by this method. SINCE the advent of transmission electron microscopy, the analysis of selected-area electron diffraction patterns has become very important in the interpretation of electron micrographs. Frequently, as in the case of some martensites, twinned areas are observed and give rise to complex diffraction patterns, which so far can be analyzed only for the simplest orientations of the thin foil specimen with respect to the electron beam. In order to simplify the analysis of twin patterns of more complex orientations, an analytical method was devised which is capable of predicting the positions of all reflections from both matrix and twin regions for all possible foil orientations. Although the method has only been applied to the case of bcc metals twinned about a (112) plane, it is equally applicable to other Bravais lattices. This method has been successfully applied to selected-area electron diffraction patterns of Fe-Ni and Fe-Ni-C martensites and drawn tungsten wire. PROCEDURE Imagine the reciprocal lattice corresponding to a bcc material, with each point hkl representing the crystallographic plane (hkl). Since the extinction conditions require that for this lattice, only reflections where h + k + 1 = even integer are allowed, the three dimensional reciprocal lattice is actually fcc. Since in real space twinned regions and matrix regions are mirrored across a (112) plane, the twinned reciprocal lattice is derived from the matrix reciprocal lattice by a rotation of 180 deg about a (112) direction. While it is possible to calculate how a point hkl will shift under a twinning transformation to a new point htktlt using only the reciprocal lattice based on the orthonormal vectors [100], [010], and [001], the calculations are greatly simplified if a new orthonormal coordinate system containing the twin axis is introduced. The twinning operation then becomes a simple rotation of 180 deg about a principal coordinate axis (in this case the twinning axis), and a retransformation back to the original reciprocal space will give the position htktIt of the twinned reflection.

Jan 1, 1963

By S. Sumski, M. B. Panish, R. T. Lynch

The liquidus isotherms in the gallium-rich corner of the Ga-Al-P phase diagram have been determined from 1000" to 1200°C and at I100°C the corresponding solidus isotherm was obtained. A simple thermody-namic treatment which permits calculation of the solidus and liquidus isotherms is discussed. A technique which was previously used for the growth of GaxAl1-xAs was used for the preparation of solution epitaxial layers of GaxAl1-xP and ALP. An approximate value of 2.49 i 0.05 ev for the band gap of Alp at 300°K was obtained and the ternary phase data were used to estimate a value of 36 kcal per mole for the heat of formation 0f Alp at that temperature. The Gap-A1P crystalline solid solution is one in which there exists the possibility of obtaining crystals with selected energy gaps, within the limits imposed by the energy gaps of Gap and Alp. Such crystals are of considerable interest because of their potential value for optoelectronic and other solid-state devices. Furthermore, it has been amply demonstrated for GaAs and GaP,'-7 that device, or bulk materials grown from gallium solution generally have more efficient radiative recombination than materials prepared in other ways. This presumably due to the lower gallium vacancy concentration in such material.= Small crystals of GaXAl1-xP and A1P have been grown from solution,8-10 and A1P has been grown from the vapor," but neither have previously been grown by liquid epitaxy. In this paper we present the ternary liquidus-solidus phase diagram of the Ga-A1-P system in the region of primary interest for solution epitaxy, and discuss the thermodynamic implications of that phase diagram with particular reference to the liquidus and solidus isotherms in the gallium-rich corner of the GaxAl1-xP primary phase field and to the A1-P system. Several measurements of the absorption edge of GaxAl1-xP crystals have been made and the width of the forbidden gap of A1P has been estimated from these measurements. EXPERIMENTAL The differential thermal analysis technique used to determine the liquidus isotherms and the optical measurements used in this work are similar to those described previously12 for the Ga-Al-As system, ex- thermocouples in the thermopile for added sensitivity. The materials used were semiconductor grade Ga, Gap, and Al+ The composition and temperature range at which DTA studies could be done was quite restricted. The upper temperature was limited by the chrome l-alumel thermopile to about 1200°C, and the highest aluminum concentration to about 5 at. pct by low sensitivity caused by the reduced solubility of Gap with increasing aluminum concentration in the liquid. DTA studies were not possible at 1000°C and below because of the low sensitivity caused by low solubility of Gap in the Ga-A1-P system. The cooling rate for these studies was about 1°C per min. No heating studies were done because of limited sensitivity. Supercooling probably does occur, but our experience with other 111-V systems indicates that it is no greater than about 10 to 15.c. Solid solubilities were determined by analyzing epitaxial layers of GaxAl1-xP grown from the liquid, with an electron beam microprobe. The layers were grown on Gap seeds by a tipping technique in which the layer is grown over a short-temperature range (20" to 50°C) on the seed from a solution of known composition. The tipping technique reported by Nelsson1 for GaAs could not be used, particularly for solutions containing appreciable amounts of aluminum, because of the formation of an A1203 scum on the liquid surface. A system was therefore designed, which would effectively remove the oxides mechanically, so that uniform wetting and crystal growth could occur. This tipping technique has already been described in detail." The best control over the composition of the re-grown layer was obtained when the tipping was done at a temperature which corresponded to the temperature of first formation of solid for the solution being used. Generally, therefore, a solution was prepared by adding the amounts of Ga, Gap, and A1 required to yield a solution which would be completely liquid above the tipping temperature with solid precipitating below that temperature. For most of the work reported here, the 1100°C isotherm of the ternary was used. It was generally necessary to heat the solution to 50" to l00. C above the tipping temperature to dissolve all of the Gap in a reasonable length of time. The epitaxially grown layers were used both for optical transmission measurements to aid in the estimation of the way in which the absorption edge changed with aluminum concentration, and for the electron beam microprobe analyses to provide data for the determination of the solid solubility isotherm. RESULTS AND DISCUSSION Liquidus Isotherms in the Ga-A1-P Ternary Phase Diagram: Thermodynamic properties of the system. The only thermal effect studied in this work was that

Jan 1, 1970

By George J. Clark

One of the major problems of operation in the anthracite industry is the disposal and handling of refuse—not because of its complexity but because of the quantity and type of material involved. It is the purpose of this paper to describe the kinds of refuse, methods of disposal, quantities of material to be handled and equipment used, together with present day application at specific operations in the Northern, Eastern Middle, Western Middle and Southern anthracite fields. For the purpose of this paper, refuse is considered to be any material that has no present or foreseeable future value and that must be handled and disposed of in the process of mining and preparing anthracite for market. Included in this classification are tunnel rock, mine rock, cleaner plant refuse, breaker refuse, old timber, ashes and silt. Disposal Methods Old timber is disposed of either by burning or by depositing on the refuse bank. Burning is preferred because timber on the refuse bank is a potential fire hazard. Ashes are deposited on a separate bank, mixed with other refuse, or flushed into old mine workings. In many places, the latter practice has caused considerable difficulty in preparation of coal mined from these areas. In depositing ashes on the surface, it is wise to refrain from mixing them with material containing coal as such contamination may prevent reclamation of the coal in future years. Tunnel work, mine rock, cleaner plant and breaker refuse compose the bulk of the material to be disposed of and handled, and are referred to collectively as "refuse" in this paper. Waste material in or adjacent to the coal beds may be removed at the working face wherever possible. This can be done in flat or lightly pitching beds, and in the Northern field represents a sizable percentage of this type of refuse handled. In the other three coal fields, this method of disposal cannot often be used. Refuse not removed at the working face is taken to the surface and generally is deposited on banks; occasionally it is crushed and flushed into old mine workings. Breaker refuse often is used for constructing berms for silt-retention basins. Disposal Problems The problem of handling refuse is different for each operation, owing to topographical conditions, quantity of material to be handled, anticipated requirements and types of equipment in use elsewhere at the operation. Preparation plants with limited refuse-disposal areas, excessive grades to reach the required elevation and long hauls to disposal areas not readily accessible require the selection of equipment to best meet the conditions. The quantity of refuse to be handled from a given amount of raw material varies considerably throughout the four fields. In mine coal, this varies from a low

Jan 1, 1949

By D. J. Jr. McAdam

RESULTS of a general survey of corrosion-fatigue phenomena at the Naval Engineering Experiment Station were presented in five previous papers.1-5 In these papers references were given to the work of Haigh in 1917.6 The five papers mentioned gave a general survey of the behavior of metals when tested to failure under simultaneous corrosion and cyclic stress. As a result of this survey the fourth paper gave a tentative analysis of the corrosion-fatigue process. According to this analysis, if the initial stress is below the endurance limit but above the corrosion-fatigue limit, the corrosion-fatigue process is divided into two periods. The first period is the formation of pits. As the initial stress is below the endurance limit, the pitting is assumed to be due to corrosion, not to fatigue. The corrosion pitting, however, is not the ordinary pitting of stressless corrosion, but is an accelerated pitting due to the effect of the cyclic stress on the corrosion. As the pit progresses, both the actual stress and the effective solution pressure increase. The increase of actual stress is due to increasing stress concentration at the bottoms of the pits. The increase of effective solution pressure is due to the increase of actual stress. The mutual intensification of stress and solution pressure continues until the actual stress at the bottoms of the pits surpasses the endurance limit. The second period of corrosion-fatigue then begins. In this period the process is merely fatigue accelerated by the corrosion. The cracks advance at a continually accelerated rate until the specimen breaks.

Jan 1, 1930

By Martin A. Moyers

THE nation's effort to win the war speedily is reflected in current trends in coal utilization, as in all other fields of our lives. In all industries, wherever coal is used for the production of heat and power the emphasis is on getting the most useful result with the least expenditure of matt.ria1. In addition to carrying its own share of the load, increased as it is by the demands of war industry, coal has had to fill in for the other fuels, mainly petroleum products, whose distribution from their more distant sources has been crippled by lack of shipping. Thus, the outstanding note in the utilization of coal this year is not the development of new methods of burning or handling coal but the extraordinary job that the industry has done in producing enough coal to serve all needs.

Jan 1, 1943

By George M. Fowler

DURING 1937 the subject of mining geology was probably given more attention and more mining geologists were usefully employed than at any previous time. Of the many contributing factors the most important were: (1) a higher degree of prosperity in many countries, (2) a. better understanding of geologic phenomena, and (3) the apparently diminishing reserves of several important minerals. Mining companies have come to look upon geology with a growing appreciation of its aid in the more effective exploration and exploitation of mineral deposits. Most of the larger and more active companies have one or more geologists permanently attached to their staffs and some have well organized and efficiently managed geological departments. Even the smaller companies, who feel they cannot afford to employ a geologist on a permanent basis, are seeking the advice of competent men in this field with increasing frequency. One of the most significant trends has been the growing tendency to base exploratory work on more thorough geologic studies instead of empirical "hunches,"on which so much off the work in the past has relied. Likewise, mining companies are apparently more willing to expend larger sums on the basis of geologic possibilities in a district.

Jan 1, 1938

By R. C. Gould, A. M. Skov, L. F. Elkins

Comparison of long term decline in oil production during cyclic waterflooding or pressure pulsing of part of the Driver Unit with steady injection-imbibition flooding in the Tex Harvey area led to large expansion of flood in the Driver Unit on the steady injection basis. While the flood has been successful, the major problem has been attainment of satisfactory oil production rates in most of the wells. Large volume fracture treatments of low capacity wells were unsuccessful in achieving sustained increases in production. A two-section area in the Driver Unit has already recovered 620 bbl of oil per acre by waterflood but other areas have not performed so well. Sun Andres water containing 300 to 500 ppm H,S is sweetened to 0.5 to 1 ppm H,S by extraction with oxygen-free flue gas. This prevents contamination of gas produced in the area and apparently it has reduced corrosion in minimum investment, thin-wall, cement-lined water dktribution systems. Cement-lined tubing in injection wells has mitigated corrosion as effectively as thick polyvinyl chloride films have, and at less cost. Introduction As reported in the literature the Spraberry field of West Texas has presented unusual problems for both primary production and waterflood ing. Earlier information from the Spraberry Driver Unit included conception and evaluation of cyclic waterflooding or pressure pulsing in a nine-section pilot test as an aid to extraction of oil from the tight matrix rock and as a boost to normal capillary imbibition forces An additional 5 years' operation in that area, and performance of expanded steady injection water-flood, now covering a total of 68 sq miles, are reported herein. In addition, since the Driver Unit is one of the largest waterfloods in areal extent in the U. S., many operating experiences are presented for the benefit of engineers concerned with operation of other Spraberry floods or with other waterfloods where this reservoir technology and/or water handling technology may be adaptable in part. These include: (1) attempts to improve producing well capacity through large volume fracture treatments, (2) long-term performance of water treating plants utilizing oxygen-free flue gas to extract H,S from sour San Andres water, (3) performance of thin-wall cement-lined pipe in water distribution systems including comparison between those sections carrying raw San Andres water and those carrying treated water, and (4) comparison of performance of various lining materials and subsurface equipment in water supply and water injection wells. These experiences are reported without regard to whether results are good, bad or indifferent. Since the operations reported are limited to the techniques, materials, and equipment actually used in the Driver Unit, no comparison is possible with results of other approaches used in other Spraberry floods or in waterfloods generally under different conditions. However, an attempt is made to quantify these experiences as much as possible in the space available to permit other engineers to select those parts applicable to eheir problems. Background The Spraberry, discovered in Feb., 1949, is a 1,000-ft section of sandstones, shales and limestones with two main oil productive members—a 10- to 15-ft sand near the top and a 10- to 15-ft sand near the base, having permeabilities of 1 md or less and porosities of 8 to 15 percent. Extensive interconnected vertical fractures permitted recovery of oil on 160-acre spacing from this fractional-millidarcy sandstone, but they made capillary end effects dominant. Primary recovery by solution gas drive is less than 10 percent of oil in place, with most wells declining to oil production of a few barrels per day when reservoir pressures are still in the range of 400 to 1,000 psi. Partial closing of the fractures with declining reservoir pressure is believed to be the cause of such low production rates at these relatively high reservoir pressures. In 1952 Brownscombe and Dyes proposed that displacement of oil by capillary imbibition of water from the fractures into the matrix rock might significantly increase oil recovery from the Spraberry, overcoming otherwise serious channelling of water through the fractures." A pilot test conducted by the Atlantic Refining Co. during 1952 through 1955 indicated technical feasibility of the process; but low oil production rates averaging I5 to 20 bbl/well/D failed to create significant interest in large-scale waterflooding at that time." Humble Oil & Refining Co. conducted a highly successful 80-acre pilot test during 1955 through 1958 with

Jan 1, 1969

By Charles P. Williams

BY PROFESSOR CHARLES P. WILLIAMS, ROLLA, MISSOURI. During the fall of the year 1873, attention was redirected to the occurrence of lead ores in Southwestern Arkansas (chiefly in Sevier County), and somewhat extensive explorations of the deposits have since been made in the hope of finding the ores sufficiently argentiferous to be profitably worked. How far the expectations have been realized I am not authentically advised, but samples of the galena ore, yielding 62.09 per cent. of lead, gave on assay at the rate of 15 3-10 ounces of silver to the ton of ore. This was the highest result obtained by myself, though I am informed that higher yields have been obtained by others. Among the samples of ores from this locality, forwarded to me in January last, was one specimen which I at once recognized as stibnite, and, on notification, other specimens of the same from Sevier County were forwarded me. The first specimen of the several received contained 11.51 per cent. of gangue, 57.62 per cent. antimony, 4.57 of bismuth, with small amounts of arsenic and iron. The latest result from a portion of another hand specimen I append in full, with duplicate estimations of the arsenic, bismuth, and gangue. The analyses were all conducted by Mr. C. R. Winters, under my direction, and in the case of those given below the ore mas separated as closely as possible from the gangue before analysis. The results are for the mineral freed from hygroscopic moisture, and are as follows: I. 11. Mean. Sulphur,.. 28.618 .. . 28.518 Antimony,.68.576 .. . 68.676 Arsenic,..6 47 .474 .497 Bismuth,..521 .498 .509 Iron,.......762 .. ..762 Gangue,..944 .948 .946 99.868 99.808 This result indicates that the ore is stibnite.

By M. S. Seltzer

High temperature steady-state creep rates have been determined jor lead sulfide single crystals whose defect concentrations were fixed by equilibration under controlled sulfur pressure. The activation energy of creep, Qc , for undoped lead sulfide, is a function 01 composilion, decreasing from 2.9 to 2.2 ev as the carrier concentration increases from 9 x 1016 to 8 1018 electrons cm-3 for lead excess crystals, and increasing from 1.7 to 2.3 ev as the concentration of holes increases from 4 x 1017 to 1 x 1018 cm-3 in sulfur excess material. For five different composilions, Qc for undoped and bismuth-doped crystals has been found to be equal to Qpb + Qs, the self-diffusion activation energies for lead and sulfur in PbS. It is well-established1 that high-temperature steady-state creep of pure metals is a diffusion-controlled process, where the activation energy of creep is equal, within experimental error, to the activation energy of self-diffusion. The relationship between the activation energy for steady-state creep and those for self-diffusion in binary compounds is more complicated, however, because two different diffusing species must be considered, and becayse the activation energies may be influenced by compositional variations and by foreign atom additions.2-4 In some cases experimentally determined creep activation energies are correlated with those for self-diffusion of the slower-moving species, but such agreement is by no means universal. Interpretation of experimental results is difficult because few investigations include measurements of creep rates and self-diffusion coefficients of both diffusing species on single crystals of similar composition and foreign atom concentration. The objective of this investigation, therefore, is to determine the influence of stoichiometric defects and foreign atoms on steady-state creep and self-diffusion for a well-characterized binary compound. Lead sulfide, a compound semiconductor which crystallizes in the NaC1-type structure, and whose homogeneity range includes compositions on either side of the 1:l atom ratio, was chosen for study in this investigation. The pressure-temperature-composition relations for PbS are available,5,3 and deviations from stoichiometry may be monitored by electrical measurements.7 Single-crystal specimens are available to allow observation of effects due to bulk phenomena without interference from grain-boundary effects. These crystals have been employed to determine steady-state creep rates under compressive stress for "pure" and bismuth-doped PbS as a function of sulfur pressure and temperature as well as crystal orientation and applied stress in order to establish the relationships between defect concentrations and creep rates. EXPERIMENTAL PROCEDURES Crystal Growth. Lead sulfide crystals, prepared by the Bridgman method, are grown in evacuated quartz crucibles, filled with almost equal atomic proportions of high-purity (99.999 pct) lead and sulfur, and heated to a temperature above the melting point of PbS (about 1127°C) so that the lead and sulfur react to form molten PbS. The crucible and melt are dropped through the hot zone of the crystal-growing furnace at the rate of 1 cm per hr. The maximum melting point of PbS is slightly on the lead-rich side of the 50:50 composition; hence crystals grown from a near stoichiometric melt are usually n-type semiconductors containing excess lead atoms. Typically the lead excess concentration in solid solution with the PbS is 3 x 1018 atoms cm-3. Crystals containing either 1/20 or 1/2 mole pct Bi2S3 were prepared by addition of the foreign atoms prior to crystal synthesis. Preparation of Specimens of Controlled Stoichiom-etry. Since it is difficult to grow crystals of desired composition, the process of crystal growth and control of stoichiometry are separated into two distinct operations. Equilibration of as-grown PbS to a desired composition is most easily accomplished by first annealing the n-type crystals under high sulfur pressure (about 1 atm) at temperatures above 700°C. This process serves to put excess lead precipitates into solution, yielding 0 -type crystals upon quenching to room temperature. Inter diffusion occurs readily in crystals so treated, and the methods described by Bloem may then be employed to obtain crystals of controlled stoi-chiometry. For the creep measurements made in this study, this involves heating crystals in mixtures of H2 and H2S The equilibrium constant for H2S is given by: Thus the sulfur partial pressure is obtained from knowledge of the H2/H2S ratio and Kh2S for the temperature in question. Fig. 1 shows the p-T-x diagram for PbS. It can be seen that, within the stability limits for single-phase lead sulfide, desired compositions may be obtained by equilibrating under a specified sulfur pressure and temperature. Characterization of Crystals. The principal methods for evaluating PbS crystals include measurement of electrical properties and mass-spectrographic analysis. The measured electrical parameters include Hall coefficient, conductivity type, and electrical resistivity Bloem7 has shown that there is a 1:l relation between the defect concentration and carrier concentration obtained. Hence, if the contribution to the carrier con-

Jan 1, 1968