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By George H. Ashley

The Legislature of the Commonwealth of Pennsylvania at its last session passed a new act dealing with barrier pillars, which may have a wide interest in other states. In the past the laws of Pennsylvania have required that the superintendent of a mine "shall not permit the mining of coal within 50 ft. of any abandoned mine containing a dangerous accumulation of water, until said danger has been removed by driving a passageway to tap and drain off said water, as provided for in this act: Provided, That the thickness of the barrier pillars shall be greater aid shall be in proportion of one foot of pillar thickness to each one and one-quarter feet of water head, if in the judgment of the engineer of the property and that of the district inspector it is necessary for the safety of the persons working in the mine." Thus it has happened that a thickness of several hundred feet has necessarily been left in pillars in mining. It has seemed to many in the mining industry that this left an unnecessary amount of coal in pillars, and did not provide that the pillar be left equally on the two sides of the mine. As a result the General Assembly of 1927 by Joint Resolution authorized the Governor to appoint a Commission of "seven prominent citizens, of whom four shall be recognized mining engineers, one shall be a hydraulic engineer, one a geologist of recognized standing in his profession, and one a State mine inspector from the bituminous coal mining district, to investigate and report upon barrier pillars in the bituminous coal region." The Governor appointed the following Commission: Morris Coulter, Clearfield Bituminous Coal Corp., Indiana, Pa.; A. E. Roberts, Monroe Coal Mining Co., Revloc, Pa.; George T. Lewis, Westmoreland Coal Co., Irwin, Pa.; Morris Knowles, hydraulic engineer, Pittsburgh, Pa.; Thomas A. Mather, State Inspector of Mines, Tyrone, Pa.; A. B. Jessup, Anthracite Coal Operators Association, Jeddo, Pa.; George H. Ashley, State Geologist, Harrisburg, Pa. Mr. Coulter was elected Chairman and Mr. Ashley, Secretary. This Commission held meetings in Harrisburg, Johnstown and Pittsburgh. It obtained and considered the laws and experiences of other states and European countries. Some of its members conferred at length with the directors and other members of the U. S. Bureau

Jan 1, 1930

By Daniel R. Hull

IN 1026 Genders' reviewed the existing theories of this subject and stated his views in support of the gas-pressure theory. Again, in 1937, the subject was thoroughly reviewed by N. B. Vaughan,3 and by Phillips and Brick,2 so that no resume is called for here. The purpose of this paper is to describe certain observations made in the course of mill work, and to point out that they mostly tend to confirm the gas theory of Genders. VAPOR SEGREGATION There is, however, one type of inverse segregation that can be accounted for by considering the volatility of one of the constituents of an alloy. The most familiar case is ordinary brass, which is subject to a zinc enrichment of a few tenths of a per cent at the surface of a chill casting. This has been noted in 70-30 brass by Genders, and a typical example of it is given in Table I, which represents a [ ] cylindrical billet 7 in. in diameter by 5; in. long. After lathe-turning 1/32 in. from the surface, the remaining distance to the center was sampled at six equally spaced intervals. The lead, which is essentially the same throughout, will be mentioned later. Consider a brass-mill mold, either round or rectangular in cross section, standing several feet high. It may require a minute or two for pouring. Before it is full, the metal in the lower end has partly solidified and contracted somewhat away from the mold. The initial shell of solidification follows not far behind the top of the column, even if the central portion is liquid for a long way down. There is, then, a space between metal and mold that is filled with zinc vapor. The vapor has no exit, because the liquid at the top of the rising column is not only in contact with the mold but keeps up a fresh supply of zinc vapor, which has, perhaps, already begun to condense in the lower portion. The cycle is short. Within a minute or two after the mold is full the bar has cooled enough to condense all the zinc. Some of it may condense on the mold; it might be expected that most of it would condense there, but the mold at that time is well coated with a velvety carbon residue from the oil dressing, overlain by fluffy zinc oxide that commenced covering the inside of the mold as soon as pouring began. The clean skin of the freshly cast brass offers a preferred surface for condensation. Reabsorption is quick and inevitable. A simple experiment indicates that a surprisingly large quantity of zinc vapor is trapped in the space between mold and

Jan 1, 1941

By S. K. Asunmaa, W. D. English, N. A. Tiner, W. A. Cannon

This paper discusses the reaction of metal surfaces with fluorine. Fluorination reactions result in the formation of metal fluoride films which are "passive" toward further reaction of the metal with fluorine. These films are very adherent, and do not easily detach from the substrate metal by mechanical flexing or thermal shock. Exposure of passive films to a humid atmosphere produces hydrated metal fluorides which cause secondary fluorination reactions upon reexpo-sure of the metal surface to fluorine. The surface films formed range from 10 to 30A in thickness and they pow at the expense of surface oxide films. The apparent film formation is completed rapidly in 15 to 30 min on stainless steel and nickel surfaces. On copper and on Monel surfaces, the film at first grows rapidly, then increases slowly over an extended period of time. Passive films are formed at all fluorine pressures in the range from 0.1 to 1.4 atm at room temperature. ALL metals react when exposed to fluorine. These reactions generally produce surface films which consist of metal fluorides. The rate of reaction is largely determined by the extent to which these films are protective. Although there is an extensive literature concerning reactions of oxygen with metals, there are very few investigations reported concerning fluorine-metal reactions. Brown, Crabtree, and ~uncan' investigated the kinetics of the reaction of gaseous fluorine with copper metal which had been freshly reduced in hydrogen. The reaction rate was independent of pressure over the range from 6 to 60 torr. A logarithmic rate law was obeyed in the temperature range from 25" to 300" ~. There was some deviation at higher temperatures which could have been the onset of a parabolic law. The calculated film thicknesses ranged from about two molecular layers, 10A, for 5 hr exposure at room temperature to thirty-five molecular layers for 5 hr exposure at 200" . The authors concluded that no single mechanism could explain all the observations. O7Donnell and spatkowski2 studied the reaction of fluorine with copper at 450°C at pressures from lo to 133 torr. The reaction was found to be pressure -dependent and followed a logarithmic rate law. It was not entirely diffusion-controlled, and fluorine was thought to be the migrating species in the reaction. Miscellaneous metal-fluorine reactions were investigated by Haendler et ~1.~ Reaction products were identified but no rate data were determined. Air Prod- ucts and Chemicals, Inc., have conducted an investigation of reactions between fluorine and various metal powders at room temperature and 85° C. Fluoride film thickness as a function of time of exposure was reported on the assumption that the reaction takes place between fluorine and metal to form the normal metal fluoride. Surface areas of the powders were only estimated so the relative film thicknesses may not be exact. The data showed reaction rates which were generally logarithmic in character, the rate of film growth virtually ceasing after a few hours exposure time for some alloy powders. The effect of moisture on fluoride films was also investigated by measuring additional reaction with fluorine after exposure of passivated powders to atmosperic moisture. The fluorination of iron was studied by 0'~onnell~ at temperatures from 225" to 525" ~ and at pressures ranging from 20 to 200 torr. In all ranges, the reaction followed a logarithmic rate law and was dependent on the square root of the gas pressure. The author concluded that fluorine gas passes through pores in the film. As the film grows, the blocking of pores leads to a rapid decrease in reaction rate; hence a logarithmic rate law is observed. Jarry, Fischer, and Gunther' investigated the mechanism of the reaction of fluorine with nickel at about 600" to 700°C. On the basis of the metallographic examination of fluoride scales growing on the nickel and from separate radioautographic data, it was claimed that fluorine is the migrating species in the reaction. This is in sharp contrast to the growth of oxide films on nickel where it has been shown that nickel ions migrate through the scale to the gas-solid interface to react with oxygen. Few investigations have been reported of the reaction of fluorine with metal oxides. Such investigations should be of great significance for a better understanding of passivation in view of the ubiquitous oxide films on technical alloys. Haendler et al.3 studied the reaction of fluorine with oxides of copper, tin, titanium, zirconium, and vanadium. Copper (I) oxide reacted as follows in the temperature range 150" to 300"~: temperature above 300" ~ was required for the CuO to react to form additional copper fluoride. Ritter and smith7 also investigated the reaction of fluorine with copper (11) oxide. An oxide powder comprised of spherical particles with a fairly high surface area was reacted with fluorine, starting at room temperature and increasing to 100° C over a period of 3 or 4 hr. The initial reaction was slow until the fluoride film thickness reached about to or 15R at which time the reaction rate accelerated, then decreased again. Most of the kinetic data was obtained during this final phase of reaction. The authors conclude that the film grows slowly at first until the stresses developed in the distorted lattice are sufficient to rupture the initial

Jan 1, 1969

By Waldemar Lindgren

I. INTRODUCTION AT the time of the discovery of America the old world had a scant supply-of the precious metals. Both the northern and the southern part of the new continent proved wonderfully rich in gold and silver and its treasures were eagerly looted; though the looting has lasted four centuries, the nines of its mountain chains are far from being exhausted. Even the later discoveries in Australasia and eastern Siberia could not rob the Western Hemisphere of its position as the greatest gold and silver producing region of the world, though finally the developments in a narrow and circumscribed area in South Africa wrested from the Americas their supremacy in the production of gold. Nevertheless the history of the two parts of the great western continent has been strikingly different. At first the Spaniards extracted vast treasures of silver from Mexico, Peru, and Bolivia, while Colombia and some placer deposits in Peru yielded a smaller quantity of gold. A couple of centuries later, a stream of gold began to flow from Brazil, the silver production from the countries mentioned above continuing strong in the meanwhile. Later on, the yield of South America diminished, but to offset this there began a wonderful series of discoveries in North America. The gold fields of California astonished the world; and when the cream of these had been skimmed off there began a no less amazing development of the Central Cordilleran gold and silver districts, which soon wade the United States the greatest producer of the precious metals. Aided by ever improving technique, extensive exploration, and a system of railroads, the yield was maintained and increased. Still later followed the discoveries of the gold fields of the arctic region and silenced those who had maintained that the zenith in gold production had passed. Recently the province of Ontario in eastern Canada

Jan 4, 1916

By H. Kenyon Burch

PaQe Introduction.............................................................. 708 Plant Sites................................................................ 709 Type of Construction...................................................... 710 Mine Plant............................................................... 710 Dual Arrangement.................................................... 711 Underground Haulage............................................. 711 Tipples........................................................... 712 Underground Pockets............................................. 712 Automatic Measuring and Loading Devices......................... 712 Shafts ............................................................. 716 Ore and Spillage Skips............................................ 716 Automatic Hoists................................................. 716 Man Elevator..................................................... 717 Crushing Plant....................................................... 718 Storage Bin........................................................... 720 Sampling Plant....................................................... 720 Motors and Other Equipment.......................................... 721 Compressor Equipment................................................ 721 Concentrator............................................................. 722 600-Ton Test Mill..................................................... 722 The 15,OO0-Ton Concentrator...................................... 726 Grinding Section.................................................. 726 Floor Arrangement........................................... 726 Marcy Ball Mills............................................. 729 Performance of Crushing Machines............................ 730 Flotation Section.................................................. 780 . Flow-Sheet with Callow Flotation Cells....................... 731 Flow-Sheet with the Inspiration Flotation hfachines............. 731 Flotation Air Supply.......................................... 733 Concentrates Filter Plant.......................................... 733 Drag Classifiers................................................... 733 Tailing Settling System........................................... 735 200-Ft. Dorr Thickener ...................................... 736 General Equipment and Supplies.......................................... 737 Water Supply......................................................... 737 Power Supply......................................................... 737 Transformer Stations.................................................. 738 Shops and Railroad Facilities.......................................... 739 Conclusion................................................................ 740

Jan 1, 1917

By T. W. Lippert

CUBA fancies herself the "pearl of the Antilles" and, by many, Jamaica is called "blessed." But far to the southward lies what is seemingly the Caribbean's most glittering jewel, the sparsely-settled, Spanish-speaking United States of Venezuela, indeed blessed by nature to a lavish degree. Not a large country, Venezuela is leaping from the donkey to the airplane under the impact of its natural wonders. Angel Falls, dwarfing Niagara and seldom seen by man, is hidden in the cold, primitive and unexplored Guiana highlands along the southeast border. A few hundred miles northwest are the low and torrid coastal plains from which gush unlimited black-gold streams of oil. About midway are the Llanos-low-lying, savanna-type grasslands, beneath which large deposits of bauxite are as yet barely touched by the explorer's diamond drill. And jutting starkly upward 2000 ft from a surrounding expanse of savanna is a small mountain (see front cover), 11 miles long and 1 mile wide. It is, or was, La Parida.

Jan 2, 1950

By J. A. Herbst

During the last decade it has been established that conventional mineral-processing control strategies based on classical control theory result in significant increases in plant throughput and operating-cost savings. It has, however, also been recognized that conventional strategies have important limitations for complex multivariable mineral-processing systems. These limitations center around the fact that single-input/single- output control linkings often result in highly undesirable interactions between controllers. During the last few years new and promising approaches to solving this problem have emerged. These approaches are based on the use of on-line dynamic models to make predictions which are useful for control decision-making. This paper presents a brief summary of the state-of-the-art for mineral-processing control in 1984. This summary is followed by a review of recent developments in model-based control strategies including those in optimal control, self- tuning regulators and decoupling control. Expected trends for the future in the control of mineral-processing operations are discussed.

Jan 1, 1984

By C. A. Heiland

The following summary is written for the benefit of the practical operator in the nonmetallic field who wishes to know what geophysics has done and may be expected to do in his line of work. His problem is quite different from that of the geophysicist who has operated with various or all methods and has followed the literature, and who is assumed to be familiar with the geologic possibilities and limitations of each method. This article is not written for the latter, although he may be interested in the four or five hitherto unpublished surveys described. To the operator, on the other hand, geophysics is only secondary. His problem is to determine which geophysical method is best suited to his special needs. If he wanted to know, however, which method could be used to locate a certain material of given physical properties, building stone, for instance, he would have to wade through a tremendous amount of geophysical literature, bibliographies and articles, before he could find what he wanted. Therefore, the purpose of this summary is to present the geological problems first and then to discuss the comparative merits of the geophysical methods that can be, or have been, applied. Choice of Geophysical Methods in Oil, Civil and Mining Engineering In the first two of these fields, the geological problems are not nearly so complex as in the metal and nonmetallic mining fields. The selection of the correct geophysical method in these fields is not nearly so difficult for the operator. For oil prospecting, his problems have been discussed exhaustively by E. DeGolyer.(1) † In civil engineering (foundation and ground-water work), the usefulness of electrical methods has been so well established that there is hardly any choice of other methods at present. The situation may be changed in the future with the perfection of the seismic reflection method for shallow depths. In the mining field the operator and often the geophysicist himself finds difficulty in determining which method is best suited for a given

Jan 1, 1934

By R. J. Charles

Previous study of simple impact systems indicated that energy required for fracture and size reduction of brittle materials is greatly dependent on the type of loading that is employed. In this regard it was postulated that fracture and size reduction of a brittle specimen might be accomplished by a high velocity impact at an energy level at which a low velocity impact would leave the specimen relatively undamaged. The finite time required to propagate energy away from the point of loading of an impacted object to other parts of the object and to its supports may permit a concentration of energy at the point of impact if the rate of loading is high. Localizing of energy at the point of impact could quickly initiate fractures that would propagate through the impacted material along with the traveling stress waves. As the cracks form, the initially absorbed strain energy would be released and portions of it travel ahead of the crack tips as stress waves. These secondary stress waves, combined with the initial stress waves derived from the impact, would produce high localized strain conditions in front of the fracture zone. The fracture zone would propagate and the specimen shatter. High rates of loading are brought about by short impact times, in turn obtained by employing high velocity projectiles that are of small mass compared to the impacted object.

Oct 1, 1956

By Richard McCaffery

CONTENTS PAGE 1. Research on Blast-furnace Slags (A Progress Report). By Richard S. McCaffery 5 2. Determination of Viscosity of Iron Blast-furnace Slags. By Richard S. McCaffery, Clarence H. Lorig, Ira N. Goff, Joseph F. Oesterle and Oscar O. Fritsche 27 3. Effect of Magnesia on Slag Viscosity. By Richard S. McCaffery, Joseph F. Oesterle and Oscar O. Fritsche 55

Jan 1, 1931

By W. H. Basssett

THE amount of oxygen present in refined copper bears an important relation to the effects of various impurities on physical properties of copper, as well as the effects of reducing gases at higher temperatures. It seems fitting at this time, when the effects of reducing gases on copper are being discussed, to describe methods that have proved satisfactory for the determination of oxygen and sulfur, and to present some results obtained by investigation of these methods in the authors' laboratory. The procedure for the determination of sulfur is closely interrelated with that for oxygen and has, therefore, been included. It was first proposed by Hamper that oxides in copper could be accurately determined by the loss in weight sustained by finely divided copper when reduced at red heat in pure hydrogen, or by the weight of water produced. Hampe's method was later modified by Archbutt,2 who established the accuracy of the method and demonstrated that equally accurate results were obtained by noting the loss in weight or by weighing the water formed. The determination of oxygen by heating in carbon monoxide has been proposed by West.3 In our hands this method has given slightly lower results than obtained by heating in hydrogen.

Jan 2, 1926

Jan 1, 1958

By Kittitep Fuenkajorn

Ring tension tests, permeability tests, and microscopic fracture studies have been performed to investigate the damaged zone induced by drilling (diamond, percussion, and rotary) in the borehole walls. Specimens are drilled with three different hole sizes (38, 76 and 102 mm diameter) in Pomona basalt and Grande basaltic andesite. The thickness of the damaged zone ranges from 0.0 to 1.7 mm. A larger drill bit induces more wall damage than a smaller one. Different drilling techniques show different damage characteristics (intensity and distribution). Damage characteristics are governed not only by drilling parameters (bit size, weight on bit, rotational speed, diamond radius, and energy), but also by properties of the rock. The weaker rock tends to show more intense damage than does the stronger one. Cracks within grains or cleavage fractures are predominant in coarse grained rock (larger than 0.5 mm grain size) while intergranular cracks are predominant in fine grained rock (smaller than 0.01 mm grain size). The influence of the damaged zone on the permeability of the rock around the hole is investigated by permeability tests.

Jan 1, 1984

THE decades immediately before and after the end of the nineteenth century (1890-1910) were a period of increased activity in mineral industry education. One reason for this, undoubtedly, was the rapid increase in mineral production in the decade 1880-1890; pig iron and copper production tripled; coal, lead, and zinc output more than doubled. Most of the other mineral substances followed the same general trend. Aluminum production began in 1886; petroleum output, which in 1888 was less than it was in 1882, almost doubled in the next three years. Gold alone showed no appreciable change until its discovery at Cripple Creek in 1891, followed by the Klondike in 1896, brought to boiling a public interest in minerals that had been simmering for some years previously. The first cyanide plant in the United States was erected at Bodie in 1892, and the first chlorination plant at Cripple Creek* the next year. Silver- lead smelting had already greatly developed, and the metallurgy of copper was almost transformed. The hearth area and smelting capacity of copper reverberatory furnaces more than quadrupled between 1878 and 1894; matte converters were first erected at Butte in 1884. Copper production of the United States in 1899 was 20 times that of 1872. While it was the increased technology used in mineral production that really made the field attractive for educated young men, undoubtedly they did not realize that, and were impressed mainly by the quantitative increase in output. Another factor was the increased general interest in engineering education; three times as many men took engineering degrees in the United States in 1890 as in 1880; 1892 showed almost a 56 per cent increase over 1890. Industry had come to recognize that technical training was worth while. The mineral industry lagged somewhat at first; the total number of mining degrees

Jan 1, 1941

By Andrew Mayer

Early in 1942 National Lead Co. was requested by the War Production Board to construct and operate a plant for the Government to produce magnesium by the ferrosilicon process which had been developed by Dr. E. M. Pidgeon in the laboratories of the Canadian National Research Council. A contract with the Defense PlantCorporation was concluded in May 1942 and Magnesium Reduction Co., a wholly owned subsidiary of National Lead Co., was formed to carry out this project. The capacity of the plant was rated at I0,000,000 lb. of magnesium per year, equivalent to an average production of about 14 tons per day. The Process The process, in brief, is as follows: The raw materials are dolomite and ferro-silicon, 75 per cent grade. The dolomite is calcined, the calcine and ferrosilicon are ground and mixed and the mixture is briquetted. The briquets are charged into tubular retorts of chrome-nickel steel set horizontally in a furnace with the open ends projecting outside the front wall. The retorts are then closed and evacuated. Magnesium is liberated according to then reaction 2(MgOl CaO) + Si = 2Mg + zCaO, Si% It is distilled from the charge and con- densed on a removable sleeve in the throat of the retort. Sodium and potassium, if present, are also liberated, distilled and condensed on a "sodium condenser" in the end of the retort. At the expiration of the distillation period the retorts are discharged and the cycle of operations is repeated. For the rated daily capacity of 14 tons of magnesium there are required approximately 170 tons of dolomite, equivalent to about 85 tons of calcine, and 16.5 tons of ferrosilicon. The retort residue, a bulky powder which at present is waste, amounts to about 87 tons. Choosing the Site The investigation to select the location of the plant was conducted by the Research Laboratories of National Lead Co. This work included geologic and economic surveys of a number of districts, examination of dolomite samples by chemical, spectrographic and petrographic methods and large-scale tests of dolomite from several of the more promising localities. in the last-named tests 2-ton samples were put through the ferrosilicon process in the pilot plant of the Canadian National Research Council, under the guidance of Dr. Pidgeon. The conclusions drawn from the investigation, in regard to the quality of dolomite to be used in the ferrosilicon process, were: First, the dolomite should contain not less than 21 per cent MgO and not more than 2 per cent acid-insoluble material. Second, the dolomite should

Jan 1, 1944

By J. L. Taylor, P. Duwez

The phase boundaries in the ternary system Ti-Cr-Al have been established at 1800° and 1400°F for alloys containing more than 60 pct Ti. The martensite transformation temperature has been measured for the titanium-rich alloys. THE studies of binary alloys of titanium with the transition elements which have been published so far1-0 ndicate clearly that the solubility of these elements is always much greater in the high temperature body-centered cubic form of titanium (ß phase) than in the low temperature hexagonal form. In this category of alloying elements are iron, nickel, chromium, manganese, vanadium, molybdenum, tungsten, columbium, and tantalum. Although studies of the nontransition elements have been rather limited, early work on titanium binary alloys'" has shown that most of them were not very soluble in the a form, with the exception of aluminum, for which the solubility in a is about 25 pct.13, 12 In addition to this large solubility in a, aluminum is also soluble in ß titanium to the extent of about 35 pct and the transformation temperature from ß to a is raised with aluminum content. This effect is also typical of aluminum, in contrast with that found for the transition elements which lower the ß to a transformation temperature. Therefore, it may be anticipated that tprnarv titanium alloys with aluminum and any one of the transition elements will constitute a class of ternary alloys having characteristic features absent in alloys involving two transition elements. Chromium was chosen as a typical transition element for the present study because ternary alloys of Ti-Al-Cr commercially produced have been found to possess very interesting physical properties (MST-3 pct A1-5 pct Cr of Mallory-Sharon).'" Binary Systems The binary systems Ti-A1 and Ti-Cr have been established recently by several investigators. The data used in this investigation were taken from the complete diagram of Bumps, Kessler, and Hansen." This diagram agrees quite well with earlier investigations." For the Ti-Cr system, the phase boundaries at 1800" and 1400°F were taken from refs. 6 and 7. The binary system Cr-A1 has been studied recently by Bradley." This system is rather complex and contains not less than seven intermediate phases. The present study was limited to the titanium corner of the ternary system (less than a total of 40 pct Cr plus Al) and none of the phases present in the Cr-A1 binary alloys were found in the ternary alloys investigated. Experimental Technique Microscopic observation and X-ray diffraction measurements were used to identify phases and de-

Jan 1, 1954

By I. Fatt, D. N. Saraf

A method is described for measuring two- and three-phase relative permeabilities in sandstones or sand packs using a nuclear magnetic resonance (NMR) technique to determine fluid saturations. Two- and three-phase relative permeabilities have been determined on Boise sandstone using the NMR technique of saturation measurement. Three-phase relative permeability to water was found to depend only on the water saturation, whereas three-phase permeability to oil depended on both the water and oil saturations. Relative permeability to gas in three-phase flow was found to depend only on the total liquid saturation. INTRODUCTION Three-phase relative permeabilities are extremely useful in calculating field performance for reservoirs being produced by simultaneous water and gas drives. Three-phase relative permeability data are also needed for analyzing solution gas-drive reservoirs which are partially depleted and are being produced by water drive. Some thermal recovery processes involve three-phase flow which require three-phase relative permeability data for predicting reservoir behavior. Unfortunately, three-phase relative permeability measurements have rarely been made. Also, because of the scarcity of three-phase data, it has not been possible to date to relate other measured rock characteristics to the relative permeabilities with a great certainty. Leverett and Lewis,l Reid2 and Snell3 have reported three-phase relative permeability data on unconsolidated sands. Leverett and Lewis used ring electrodes spaced along the length of the sand sample to measure the resistivity of the sample which was assumed to be monotonically related to brine saturation. Gas saturation was determined from pressure-volume measurements. Oil saturation was obtained by material balance on the cell containing the sand sample. This method is involved and time consuming. Another difficulty arises from the fact that the resistivity of the sand is a function not only of saturation of brine but also of the distribution and saturation history of the brine in the pore spaces. Reid2 used a gamma ray absorption technique for measuring liquid saturation. This method has the disadvantage that total liquid saturation rather than oil or brine saturation is all that can be measured and still another method is required to determine the saturations of individual components. snel13 used a neutron bombardment method which also required a separate determination of the individual component saturations. Caudle et al.4 measured three-phase relative permeability on consolidated sandstones using vacuum distillation for determining fluid saturations. Distillation after each reading makes this technique very lengthy and time consuming. Corey et a1. 5 and Naar and Wygal 6 measured three-phase relative permeability on sandstones by the capillary-pressure method. Semipermeable diaphragm assemblies were used at each end of the core specimen to keep the water phase in the core. Gravimetric methods were used to determine fluid saturations. Sarem7 recently reported an unsteady-state method for measuring three-phase relative permeability on sandstones. This method is an extension of Welge's method8 for measuring two-phase relative permeability. Although Sarem's method is simple and comparatively fast, the assumptions involved may oversimplify the problem. Sarem's assumption, that in all rocks relative permeability to each fluid will depend only on the saturation of that fluid, seems to be rather unrealistic. Neglecting capillary effects at the end of the core is also a weak assumption. Donaldson and dean9 measured three-phase relative permeability using a method similar to Sarem's.

By M. E. Straumanis, J. -P. Krumme

In basic ([KOH + KCl] with a total polarity of 2) or acidic (2N H2SO4) electrolytes and at anodic current densities of more thun 2 to 4 ma per sq cnz, n-type GaAs single crystals of lozo resistivity preferentially dissol~je forming etch tunnels with triangular or civc~ilay cross sections and of a width between 0.5 arid 5 p. These etch tunnels are oriented along any one of the four possible (111) directions of GaAs. However, their growth occurs only in one direction of a given (111) whick apparently is determined by the atomic sequence Ga —As (and not the rezlerse) in respect to an individual valence bridge in the crystal. It is concluded from comparison with the cubic lattice structure of GaAs that the etch tunnels represent macroscopic evidence for the tetrahedral bonds and their polar properties. If the anodic current density is increased the tunnel fomation results in the development of a fibrous surface layer consisting of GaAs. The latter separates frorn the substrate (in an anodic s~irface disintegration process) by the growth pressure of an As,0, filnz forming in the interior of the fibrous layer, 100 to 200 µ under the surface, at more than about 50 ma per sq cni. The fibrous GaAs film has the same crystallographic orientation as the substvate and represents a skeleton of the original crystal. Since the etch-tunnel density in a separated GaAs layer is about 108 c?n-', and the etch tunnels develop only along (111) in a given polar direction, it is assurraed tlmt the dislocations have no influence on the growth of these tunnels. ElECTROLYTIC treatment of smooth surfaces of poly- and single-crystalline GaAs at high anodic current densities causes the formation of porous surface layers.' This phenomenon suggests comparison with effects being observed with magnesium,' indium,, gallium,4 and aluminum5 and known as "anodic disintegration". The purpose of the present paper is to explore and to explain the reasons for the formation of such surface layers on GaAs and, in particular, to investigate the influence of the lattice polarity of this III-V compound semiconductor in the (111) direction on the anodic dissolution behavior. GaAs SINGLE CRYSTALS For the experiments described below GaAs single crystals from the Monsanto Co., St. Louis, Mo., were used. Their impurity levels were below 1 ppm and their dopant levels between 1 and 100 ppm. They were grown in (111) using the Czochralski or the gradient-freeze technique. The crystals had n-type conductivity and electric resistivities between 1 and 5 ohm-cm. EXPERIMENTAL The GaAs single-crystal rods were cut perpendicularly to (111) into wafers of about 1 mm thickness using a wire-blade crystal slicer and an aqueous slurry of Sic or a diamond saw. The orientation of the faces of these wafers were checked by Laue back-reflection patterns. If there was a deviation from (111) the faces were abraded under a certain angle using grinding paper and distilled water. The damaged surface layer was removed from each crystal by chemical etching with a mixture of 1HF:1HNO3: 1H20 or 2HF:1HNO3:2HAc (glacial). {110) faces were obtained by mechanical cleavage, producing surfaces which did not require a further treatment. The GaAs wafers were mounted using "alligator" clamps instead of soldered electrical contacts.' Only the bare crystal surfaces were dipped into the electrolyte. The clamps were coated with insulating wax to prevent any contact with the electrolyte. The experiments were carried out in aqueous 2 N H2so4,' or in an aqueous solution of KOH and KCl1 (1 mole KOH + 1 mole KCl in 1000 cu cm solution). Anodic current densities up to several hundred ma per sq cm were applied for periods between 30 sec and 2 hr. For the purpose of investigating the initial steps of disintegration the anodic current density applied never exceeded 20 ma per sq cm. The films which partially separated from the anodic surfaces under high-field conditions were treated with KOH to further their detachment by dissolving the As2O3 formed. The washed and dried films were pasted to strips of filter paper, and Laue pictures were made. The back-reflection patterns obtained were compared with those of the original anode surface before and after anodic dissolution. Furthermore, space reciprocal lattices7 were constructed from asymmetric rotation crystal patternsa which permitted the determination of the crystallographic orientation of the detached films of the corrugated anodic surfaces. The disintegration products were identified from assymmetric powder patterns.8 The polarity of the {111) faces was determined by chemical etching with mixtures of 1HF:1H2O2(30 pct): 2H2O or 1HNO3:2H2O. Different patterns on each of two inverse (111) sides appeared.'-l8 The correlation of these patterns to the Ga{111) or the As(111) side has already been established by the use of light figures,18-20 by X-ray diffraction near the absorption edges of gallium and arsenic,'lmZ4 and by LEED measurements.25 The geometric structure of these surfaces and the interior of the anodically attacked crystals were observed and photographed with a high-power microscope using oil immersion objectives up to magnification of X1720.

Jan 1, 1968

Jan 1, 1898

By Frank H. Riddle, Wilfrid R. Foster

GENERAL treatment of the various minerals of importance in refractories appears in the chapter entitled "Refractories" elsewhere in this volume. The present chapter is restricted to a discussion of minerals of the sillimanite group and brings up to date the excellent information contributed by Prof. Paul F. Kerr to the first edition (1937). Since the appearance of that edition, the status of the group has changed some- what. Kyanite remains the preferred source material for mullite refractories but total consumption of kyanite has increased considerably.85 The exigencies of World War II forced an increased dependence on domestic sources and led to an intensification of the search for higher-grade deposits of kyanite and allied minerals. The first discovery of massive kyanite similar to that of India has been reported from Georgia.37 British East Africa has joined India as a substantial supplier of our imported kyanite, but that from India continues to hold preference.85 During World War II, prices of both domestic and foreign grades reached peaks unparalleled since the earliest years of the use of kyanite and as yet have shown no tendency to return to prewar levels. Topaz, by virtue of the deposit outlined in South Carolina, merits inclusion in the group.20,36,95 Large andalusite deposits, which threaten to rival our one large domestic occurrence, have been found in Russia.69,88 Sillimanite has not yet attained an important position among these useful minerals because of the lack of accessible deposits of high-quality material in adequate supply.37,50,58 Tests by the Bureau of Mines have indicated the possibilities of economically beneficiating low-grade sillimanite and kyanite.105.106,140 Government, university, and industrial

Jan 1, 1949