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By Robert C. Mackenzie

EXAMINATION by the differential thermal analysis technique of a large number of samples of soil and other clays from various parts of the world has demonstrated that the occurrence of cold-precipitated hydrated ferric oxide (the identification of which in soil clays has previously been reported5) is not confined to any limited locality; e.g., it has been found in varying amounts in clays from Britain, France, South Africa, and Mexico. The conditions necessary for its formation have not yet been elucidated in spite of the number of samples examined, and, since this mineral is so easily prepared in the laboratory, it has been considered that a study of its constitu¬tion and of the conditions under which it could be prepared might. lead to a better understanding of the factors involved. These experiments form the subject of this short paper, and while they do not supply a definite answer to the mode of formation of this mineral in nature, they may, it is hoped, add something to our knowledge in this direction. EXPERIMENTAL WORK Materials Employed The a-Fe2O3.H2O (goethite) and B-Fe2O3.H2O (Weiser and Milligan") were obtained from the Department of Geology, University of Aberdeen, and Rothamsted Experimental Station, respectively. The beta material had been prepared by the method described by Fernelius.1 y-Fe2O3.H2O (lepidocrocite) was prepared at the Macaulay Institute for Soil Research by the method of van Schuylenborgh.6 The method employed for preparation of the cold-precipitated hydrated ferric oxide* was as follows: 1: 1 NH4OH was added (moderately fast with rapid stirring) to a solution of 5 grams FeC13.6H2O in 250 ml distilled water at room temperature (ca. 15°C) until red litmus turned blue, and then 2 to 3 drops in excess. The resultant precipitate was filtered off on a Buchner funnel and washed free from Cl- with distilled water. Previous experiments having shown that drying over P2O5 at room temperature or drying at 105°C in the oven did not significantly affect the thermogram,5 samples were nor-

Jan 1, 1952

By M. C. Leverett

THE dynamic behavior of a multiple fluid system is completely describable in terms of driving forces and resistances to flow. The latter are proportional to the vis-cosity of the fluid under consideration and inversely proportional to a property of the system termed the " effective permeability" to that fluid, a property therefore defined by this relation. Since three phases are usually present in oil reservoirs, it is essential to know the effective permeabilities to the several fluid phases, and the relationship between the composition of the fluid in the pore space and that of the flowing stream, in order to handle satisfactorily certain problems of oil production. In this regard, there are many unknown factors and parameters, and many that can be evaluated only indi-rectly. However, it is expected that work along lines similar to this present under-taking will help materially in solving these problems. Previous workers in this field have inves-tigated the two-phase systems, water-gas,1 water-oil2 in unconsolidated sands, and water-gas3 in consolidated sands. The ex-tension of the study of the flow of hetero-geneous fluid systems from two to three phases involved only slight changes in technique. The apparatus used in the present work, except for slight changes to be described, was that used by Leverett in his water-oil experiments.2 Correlation and interpretation of data were made by methods analogous to those used in two-phase work. The relative permeability to a phase-the effective permeability divided by the permeability of the system to a homogeneous fluid-was employed through-out in correlating the rate of flow of that phase with the composition of the pore space. Quantitative measurements of two inde-pendent physical properties of the system were required to determine the composition of the pore space. As in the two-phase work, the fraction of water was determined electrically. The gas fraction was deter-mined by measuring changes in volume accompanying measured pressure changes. Suitable account was taken of the solubility of the gas in the liquid phases, and of the vapor pressure of the water phase. Since this work was exploratory in nature, no attempt was made to obtain highly accu-rate numerical results. Reasonable precision and reproducibility were sought.

Jan 1, 1940

By Richard Akerman

At the International Sessions of the Iron and Steel Institute of Great Britain, the American Institute of Mining Engineers and the Verein Deutscher EisenhUttenleute, held in Allegheny City, Pa., in October, 1890, Sir James Kitson, then President of the Iron and Steel Institute, presented an account by Sir Henry Bessemer of the origin of the process which bears his name.? The paper graplhically told how, after the first successes immediately following the first reports given at Cheltenham of the new process, there rapidly succceded such obstacles and difficulties in its practical application, that the whole matter was nearly abandoned in 1858. Suddenly, however, the situation changed, so that at length it became possible

Jan 1, 1894

By Henry Lloyd Smyth, J. Ralph Finlay

The most important area of the so-called Keewatin rocks of northern Minnesota is that which runs westerly from Lake Saganaga, near the national boundary, and finally disappears beneath the drift (or has not been farther traced), in the neighborhood of Vermilion Lake. With this belt we have a general acquaintance, extending back some four years. During the past year we have had the opportunity of studying in considerable detail a small part of it, embracing an area of about 12 square miles on the south and east shores of Vermilion Lake. In this paper we desire to record our observations and conclusions, which seem to us important. II.—Literature. Outside the Minnesota Geological Survey, the list of the investigators who have studied the geology of the Vermilion Lake area is not long. Whittlesey, in 1876,* mentioned the occurrence, in the area about Vermilion Lake, of rocks resembling the Canadian Laurentian. Chester,? in 1884, described the iron-ore at Vermilion Lake as occurring in connection with jasper and quartzite, intimately bedded with the country-rock, chiefly sericite schist, and standing in a nearly vertical attitude. The Vermilion iron-bearing rocks, and those of the Mesabi range, he says, are of the same age.

Jan 1, 1896

By Persifor Frazer

At a time when all those interested in the iron trade are carefully scanning the horizon for new sources of the raw material, a few words concerning a field, which though not new, has not been hitherto fruitful of statistical information, may be deemed appropriate at this meeting. The district alluded to is the belt of the Middle James River, or in other words, that portion of the ferriferous belts of Virginia lying between Josua Falls and the little settlement of Norwood, in the counties of Amherst and Nelson, and on the left bank of the James River. This region shows unmistakable signs of developing a very considerable market for iron ores and for iron in the future, as well as a tempting appearance of possible productiveness in the former. It, is extremely hazardous to deal in generalizations as to the productiveness or non-productiveness of these measures without a more thorough development than has yet been attained. It is true that they probably constitute an horizon whence comes a part of the marvellous mineral wealth of the northern peninsula of Michigan. But

Jan 1, 1883

By C. W. MacGregor

THE observation of the flow layers, or Lüders' lines, produced in mild steel when it is stressed into the plastic range often provides considerable useful information for the study of the fundamental mechanism of the plastic flow of metals. It is a commonly observed fact that as soon as the upper yield point in a mild-steel tensile-test bar is passed, an unstable condition develops in the equilibrium, the load on the testing machine drops and if the surface of the bar contains a thin mill scale, the latter begins to flake off rapidly along certain "lines." These "lines" are in reality traces of wedge-shaped flow layers and are formed by the intersection of the surface of slip and the surface of the bar. The average plane of the flow layer itself has been found by various experimenters to be inclined at an angle of approximately 45° to the axis of the test bar. In a body of more complicated shape stressed in possibly a different man-ner, the tangent planes to the flow layers at each point seem in many cases to be inclined at an angle of about 45° to the principal stress direc-tions at the point. As examples of the latter may be mentioned the logarithmic spirals obtained when a rivet hole is punched in a thin plate, or when a tube is subjected to internal pressure only, etc. Hence if the flow layers are observed from an experiment, the shear-stress trajectories -the curves indicating the directions of the maximum shearing stresses in the body-may then be approximately determined. Since the latter curves form an orthogonal family inclined at 45° to the principal stress directions, the family of principal stress trajectories, or the curves indicating the directions of the principal stresses, may be thus obtained. Although the discontinuous type of stress-strain curve at the yield point is commonly observed with test bars of mild steel, more recent experiments have shown that this is by no means the only material exhibiting this interesting phenomenon. A similar effect has been observed in zinc and cadmium crystals, by Becker and Orowan;1 in duralumin and other aluminum alloys, by Dawidenkow,2 Elam,3 Fell, and others; in copper and copper-alloy crystals, by Elam;5 in brass by Elam;5 in brass wires by deForest;6 in higher carbon steels, tungsten steel, and

Jan 1, 1939

By T. L. McCall

THE late Walter Herd1 in 1929 gave a full description of past and present conditions in No. 2 mine, Springhill, Nova Scotia, developed theories regarding the cause of these bumps and made certain suggestions regarding possible methods of future development. Recapitulating briefly from Mr. Herd's paper, the seam is bituminous coal, averages 9 ft. in thickness and has a well defined parting containing fusain about 14 in. from the roof. This roof coal is somewhat stronger than the rest of the seam and has a tendency to cling to the roof. The pitch of the seam where it is now being worked is about 20°. The first manifestations of bumps began when the room and pillar workings had reached a depth of cover of 1900 ft. and under continuously increasing depth of cover these bumps increased to such an extent, both in number and severity, that in the year 1924 it became apparent that some change in the system of extraction was necessary. After closely studying all the factors involved and benefiting largely by valuable out-side advice obtained by the Provincial Department of Mines of Nova Scotia,2 the system of working was changed from room and pillar to longwall retreating. Mr. Herd's paper described in detail three remarkable bumps in the year 1928 in April, July and October that affected the 5700-ft. and 5900-ft. East levels, the last bump being so severe both in intensity and in extent of damage done that this district was abandoned. The longwall workings to the west of the slope had been stopped in the year 1926 owing to an inbreak of water, coming from the flooded waste of No. 3 seam lying some 400 ft. vertically overhead. This inflow was not excessive, but a large quantity of water being impounded in the old workings it was considered advisable to take the prudent course and not incur the risk of possibly increasing the flow by further working. This district has remained idle ever since.

Jan 1, 1934

By C. B. Alcock, M. G. Hocking

The kinetics of the growth of sulfate layers on blocks of Cu20 has been studied between 688" and 800°C. At 788c the over-all weight increases followed the parabolic rate law, with k = 216 30 sq mg per cm4 min, using a 1:1 entering gas mixture of SO2:02. At 757 after an initial linear period the parabolic rate law was followed, with k = 57.8 10 sq mg per cm4 min. The gas mixture required a platinum catalyst to produce the maximum SOs pressure. The sulfation rate at 757' and 788c was high until all the CUZO had changed into a core of CuO, when it became very much lower. At 757°C marker experiments showed that the sulfates (CuO. CuS04 and CuSO4) grow outwards from the oxide surface, but CuO. CuS04 mixed with CuO was found beneath the markers. At 688 markers were found at the CuO. CuS04/CuS04 interface. Visual observations at 757 showed a liquid eutectic moving beneath the sulfate surface. causing very rapid sulfation and extruding to solidify as thick 'needles" up to 8 mm long. Marker experiments have shown conclusi.cely that CuO grows on Cu20 in air by the outward migration of copper. ThermODYNAMIC measurements on the sulfate and basic sulfate of copper, reported recently,' are followed here by measurements of the rates of formation of these sulfates on cuprous oxide, in order to provide a background for the understanding of roasting processes. peretti2 and McCabe and Morgan3 have shown that the phase Cu20 lies next to Cu2S when the sulfide is roasted under conditions where sulfates will be formed. Since this would present too complex a system for kinetic study, the present work4 has been based on the kinetics of sulfation of the oxide phase. The results of a study of the kinetics and mechanism of the sulfation of cobaltous oxide have recently been reported.4,5 Results on the sulfation of cuprous oxide have also appeared,6 but are at variance with those to be reported here. This seems to be because the previous workers6 did not obtain constant SO3 pressures from the SO2/O2 sulfating gas mixtures used, as will be discussed later. Wadsworth, Leiter, Porter, and Lewis found that the sulfates produced when SO2/O2 mixtures are passed over Cu20 at red heats are CuS04 and the basic sulfate CuO.CuSO4. When the decomposition of CuS04 was followed' by differential thermal analysis, a stage corresponding to CuO .CuS04 was reached before decomposition into the oxide occurred. APPARATUS The vertical furnace used for quantitative studies was a conventional resistance-heated and propor- tionately controlled furnace with an even zone (1 deg) which was 4 cm long. The gas mixtures of SO2 and 02 were made by mixing measured flows from capillary flowmeters and drying over phosphorous pentoxide before passing them into the Pyrex top-piece of the furnace assembly. A mullite tube of bore 2% cm was used as reaction vessel and at the bottom of this tube was a trap for SO3, which condensed as a colorless liquid. The residual gas was led into a fume cupboard for ventilation to the atmosphere. The furnace used for visual observations of needle growth and other phenomena consisted of a transparent silica reaction tube of bore 3 cm, having an optically flat silica window sealed into its wall. The reaction tube was clamped vertically, inside a mullite tube of bore 4 cm and length 42 cm which was heated by Kanthal windings. The window in the silica reaction tube was arranged opposite a hole 3 cm wide and 2 cm tall which had been cut in the wall of the mullite winding tube 19 cm from its top end. A binocular microscope was used to look through the window, illumination being provided by a focusing microscope-lamp offset sideways and downwards. The oxide block to be sulfated was suspended from the removable Pyrex top-piece to the reaction tube, by means of which it was inserted at the start of the experiment, and through which entered the S02/02 gas mixture. The variation of the temperature inside the reaction tube with horizontal and vertical displacement from the window was investigated, and, while it can be said that the temperature was constant 1 deg, its value at a given position was known only to 12 deg. In both furnaces, the oxide block to be sulfated was suspended from a small silica hook immediately downstream from a platinum thimble used as catalyst, which was held on a long silica rod from a Pyrex spring attached to the removable Pyrex top-piece of the furnace. The spring was only included in the quantitative sulfating furnace; its sensitivity was 1.4 cm per g and it was found to be free from creep in a 16-hr test when carrying the working load. The extensions were followed by a cathetometer which could be read to 0.001 cm, corresponding to i0.7 mg. Extensions of the spring were measured on adding weights between 5 and 500 mg to the working load (thimble + oxide block), and Hooke's law was closely obeyed. SAMPLES Cuprous oxide blocks were prepared by oxidizing Johnson Matthey "Specpure" copper sheet of 1 mm thickness (impurities: iron at 3 ppm, silver at 2 ppm, lead, nickel, sodium, and silicon each at 1 ppm, calcium, chromium, magnesium, and manganese each at less than 1 ppm) for 6 days in air at 1000°C in a re-crystallized alumina boat. It has been reported7 that when Cu20 is prepared by heating copper sheet for 1 day the central plane of the blocks produced consists

Jan 1, 1967

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 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 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 rakes' 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 station¬ary 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 breaker' 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 John D. Ridge

For mining geologists, the most important trends during 1962 have been the increased concentration of the exploratory activities of American mining companies in the United States and Canada and the greater use of the combined techniques of geology, geophysics and geochemistry in searches over larger areas for wider varieties of metals and minerals. The principal reasons for these changes in approach have been the deterioration of the political-economic climate in many areas of the globe of equal or greater geologic promise and the realization that modern exploration is most efficiently and economically conducted through the use of all available means of detecting ores in areas sufficiently large to raise to a maximum the chances of success. The attitude of certain major U.S. metal-producing companies can be shown by the officially ex- pressed positions of their principal officers. Early in 1962, Clyde E. Weed, Chairman of the Board of Anaconda, remarked that "because of unsettled conditions and disruptive influences in many of the copper-producing areas of the world, it is imperative that domestic copper-producing capacity be improved and made as efficient as possible in order to meet consumer demands at reasonably stable prices." In November, Robert G. Page, President of Phelps Dodge, pointed out that his company is not only concentrating most of its exploratory effort on this continent but is also increasing the number of metals for which it is searching. Frank R. Milliken, President of Kennecott, recently said that "most of our exploration money is going into the northern part of the Western Hemisphere."

Jan 2, 1963

By J. P. Carson

THE Croton water-shed furnishes the source and storage of watersupply to both the old and the new aqueduct. The Croton river rises in the southern part of Dutchess county, about 68 miles from the lower end of New York city. Its three main branches, called the East, Middle and West branches, flow southward across Putnam county, joining, near its southern boundary, to form the Croton, which continues thence in a general southwest direction across Westchester county to the Hudson river at Croton Point, about 35 miles north of the city. The water-shed above the proposed site of the Quaker Bridge dam extends about 33 miles north and south, with an average width of 11 miles, making in all about 362 square miles, from which, by complete storage, an average daily supply of 250,000,000 gallons may be collected—sufficient for the needs of the city, probably, for the next fifteen years. The water-shed above the Croton dam is 23 square miles smaller, and furnishes the present daily supply of 100,000,000 gallons. By referring to the map it will be seen that the shortest approximately straight line between the proposed site of Quaker Bridge

Jan 1, 1891

By H. C. Howard

Reaction of oxygen and bituminous coal starts as soon as the coal bed is exposed to air and, with some coals, proceeds with significant velocity even at normal temperatures and at normal oxygen partial pressures of one-fifth of an atmosphere. At higher temperatures, the reaction is greatly accelerated and ultimately a condition is reached where the process is very rapid and we then speak of combustion. It is the purpose of the present paper to discuss the reactions of oxygen and coal at temperatures below those of active combustion. It is these low temperature oxidation reactions which are responsible for heating in storage and for marked changes in agglutinating proper-ties. These reactions may also be employed for the preparation of organic acids, which are of direct interest to the chemical industry. For convenience in discussion, the low temperature reactions of oxygen and bituminous coal can be roughly divided into three stages though there is, of course, overlapping. Stage I is a surface oxidation stage, characterized by the addition of oxygen, with the formation of oxygen containing groups some of which have acidic properties. Carbon dioxide, carbon monoxide and water may be formed con-comitantly and are always liberated at higher temperatures, and in cases where the oxidation is prolonged. Superficially, the coal is little affected by this primary stage of oxidation and usually only minor changes in ultimate composition result. There may be definite changes in coking and coking properties, and heat of combustion susceptibility to further oxidation. The presence of acidic groups can be demonstrated by specific reactions. These groups may show cation exchange properties like the mineral zeolites. The formation of oxalic acid has been reported. If the oxidation is continued, a large fraction of the organic material of the coal is converted ultimately into alkali soluble, acid insoluble products, which have been given the name "regenerated humic acids" and which are the characteristic products of Stage 2. These humic acids, in the solid stage, do not differ greatly in appearance from the original coal, but show large differences in chemical composition and chemical and physical properties. Along with the humic acids, carbon dioxide and some of the water soluble types of Stage 3, are also formed. If the oxidation is carried still further, the humic acids may be degraded completely to the simpler, lower molecular weight acids of Stage 3 which are characterized by solubility in acid as well as in alkaline media, and by their orange, yellow or white colors. Additional carbon dioxide is formed in the transformation from Stage 2 to Stage 3 and, for a number of American coals, a maximum yield of the water soluble types of acids is reached when about 50 pct of the carbon of the coal is converted to carbon dioxide. Primary Oxidation The initial step in the reaction of gaseous oxygen on coal, like that on carbon,

Jan 1, 1949

By Harrison Everett Ashley

Slimes are usually defined as all material passing a certain sized sieve, which is invariably the finest sieve employed by each metallurgist in his tests; 100-mesh and 200-mesh have been taken as the limits by different writers in recent volumes of the Transactions; 150-mesh is common practice. The reader of the first two volumes of Richards' is impressed by the inflexibility with which all grinding-arrangements are praised or condemned according as they make little or much slime. Until recently, one of the principal aims of the mill-man was to keep down the slimes. He was obliged to have separate apparatus for sand- and slime-treatment. The latter was sometimes puzzling and erratic. Often it was found most economical to omit treatment of the slimes entirely, or to store them in immense basins or heaps, waiting for possible future improvements in methods of treatment. Recently, improved processes of agitation and filtration have made possible the successful extraction of values from many slimes. The tendency, when the metal is exceedingly finely disseminated, is to cut out all sand-treatment and to slime everything. These processes have been almost entirely mechanical in their conception, and it is the object of the present paper to show that certain chemical considerations may greatly hinder or assist their successful operation. It has long been a source of dissatisfaction to chemists that their analyses fail to be of much help to the clay-worker; that it is a matter of common occurrence for clays of closely identical ultimate chemjcal constitution to show the widest possible divergence in physical properties.

Jan 1, 1911

By James Douglas

This sketch of the history, geography and topography of the American transcontinental railways is based upon a paper read many years ago by the author before the American Geographical Society, and now re-cast, with numerous modifications and additions required to bring it up to date. It was intended primarily for the information of members and guests of the Institute from the East attending the California meeting; and, with that purpose in view, the Secretary of the Institute compiled;

Jan 1, 1900

By W. Bradley, R. G. Hall

This paper will attempt to show how a metallurgical problem at one California quicksilver mine was solved, and how the solution was applied successfully at another mine. The pronouns "we" and "our," as used below, refer '0 the Bradley 'lining Co. of San Francisco. The term "concurrent firing" for the purpose of this paper can be defined as feeding and firing a a kiln at the same end—that is, of course, the upper end' This is as opposed to "countercurrent firing," the orthodox method, in which a kiln is fed at the upper and fired at the lower end. The terms "quicksilver" and "mercury" are used interchangeably. Early References The earliest work on nonferrous metallurgy, we believe, was The Pirotechnia of Vannocio Biringuccio,l its first edition having been printed in Italy in 1540. Quoting from its chapter entitled "Concerning Quicksilver and Its Ore": Quicksilver ... is one of the gods and has divine strength in itself, and also, to the annoyance of the alchemists, it is winged. Hence, when it sees that it is in gravest danger, it loosens itself from . . . every bond . . . and fies away into the heavens, escaping from the hands of those who crucify it. Almost laughing, it leaves all its adversaries mocked and scorned, with their phials and filters empty . . . How thorough a job, under certain conditions, it can do of mocking its adversaries and leaving their phials and filters empty, was found out four centuries later at the Sulphur Bank mine, on the east shore of Clear Lake, in Lake county, California, The other mine mentioned in the title is the Reed, in Yolo County, California, 35 miles by road southeast of Sulphur Bank, Reed and Sulphur Bank ranked respectively Nth and seventh in U. S. production in 1943. The earliest direct reference we can find to furnacing troubles at these mines was by Thomas Egleston in 1890.2 Speaking of Sulphur Bank, Egleston says: of there is more sulphur than cinnabar in the ore, which is a detriment to both . . . making the sulphur impure, and rendering the cinnabar difficult to work on account of the soot. In some of the early . . . furnaces the accumulation of soot from the excess of sulphur has been known to penetrate as far as the fan blower at the end of the . . . condensers, and completely prevent its revolution. In order to get rid of the inconvenience of this accumulation . . . , as well as to get a commercial value from the sulphur, it (the sulphur) is now separated by steam and sold. It is claimed that the sulphur alone pays all the expenses of ... the mine. The mine was first worked for sulphur, and the cinnabar it contained was considered to be an inconvenience, and was carefully picked out and thrown away, as its richness and value were not

Jan 1, 1949

By M. S. Smani, P. Blazy, J. M. Cases

Investigations on the beneficiation of sedimentary Moroccan phosphate ores are reported in four separate parts. The first discusses electrochemical phenomena at the solid-aqueous solution interface for minerals of the apatite group. In the second part, the electrochemical properties of the calcareous gangue associated with the phosphate ore are investigated. The flotation of calcite and phosphate oölites, using both anionic and cationic collectors, is discussed in the third part. It is shown that selective recovery could be obtained for precise concentrations of collectors and pH ranges. Results of work aimed at optimizing depression of phosphate oölites during inverse flotation of the carbonate gangue with sodium oleate are reported in Part 4.

Jan 1, 1976

Jan 1, 1969

PRESIDENTS DAVID THOMAS 1871 R W RAYMOND 1872-1874 A L HOLLEY1875 ABRAM S HEWITT 1876 T STERRY HUNT 1877 ECKLEY B COXE 1878 - 1879 WILLIAM P SHINN 1880 WILLIAM METCALF 1881 RICHARD P ROTHWELL 1882 ROBERY W HUNT 1883 JAMES C, BAYLES 1884-1885 ROBERT H RICHARDS 1886 THOMAS EGLESTON 1887 WILLIAM B POTTER 1888 RICHARD PEARCE 1889 ADAM S HEWITT 1890 JOHN BIRKINBINE 1891-1892 H M HOWE 1893 JOHN FRITZ 1894 J D WEEKD 1895

Jan 1, 1923

By B. Habermann

Artificially consolidated sand models, representing one-quarter of a five-spot, have been developed and used to study factors aflecting misciblt. displacrmenr. Sweep efficiency at breakthrough, size of the mixing zone between two miscible liquids and per cent area contacted by drive after breakthrough were determined tor the high mobility ratios encountered in actual resvrvoirs. Quantitative relationships between the degree of viscous fingering and mobility ratio were obtained by measuring the length of the fluid interface. Scaled miscible-slug experiments, supported by field evidence reported in the literature, have shown that when the slug is followed by dry gas the process is less efficient than expected. In addition to low areal sweep efficiencies encountered for high mobility ratio displacements, the effectiveness of a miscible slug is greatly reduced. This is caused by an accelerated growth of the mixing zone between the driving and the displacing fluids. INTRODUCTION Considerable interest in miscible displacement as a secondary recovery process has been shown by the oil industry in recent years. In addition to extensive laboratory investigations, numerous field operations have been initiated so that 39 miscible displacement projects had been reported' in the United States by early 1959. By far the most popular approach in these projects is the use of an LPG slug followed by dry gas. Laboratory tests have indicated that with a small miscible slug, amounting to several per cent of the hydrocarbon pore volume, practically 100 per cent recovery of the oil in place can be achieved and that all of the slug material can be recovered by a subsequellt gas drive. However, these experiments were conducted on small-diameter long cores that can be considered as essentially uni-dimensional reservoirs that do not represent actual field conditions. It soon became apparent that the inherently adverse mobility ratios existing in the reservoir cannot be ignored in any miscible displacement field project. When a less viscous fiuid such as an LPG slug drives a more viscous reservoir oil, fingers develop that reduce the areal sweep efficiency. The slze of the miscible slug to be used is a subject of some controversy. It has been proposed that the size of siug needed be calculated by setting lengths of the mixing zone proportional to the square root of the distance traveled. This proposal is based on experimental evidence' and theoretical considerations"' in which fingering was not a factor. A prerequisite for successful application of the miscible displacement process to field operations is a better understanding of the following factors. L What is the effect of mobility ratio on the rate of deterioration of a miscible slug? 2. How large a slug should be used for given reservoir conditions? 3. What is the sweep efficiency? The purpose of this investigation was to provide some additional laboratory data that should help to answer these questions. More specifically, it was intended to study more quantitatively the effect of viscous fiinger-ing, mobility ratio and slug size on the efficiency of this relatively new secondary recovery process by means of experiments on thin, horizontal, porous medium models.

By J. M. Woodall

GuAs crystals which have been grown in quartz boats by the horizontal Bridgman method in the pvesence of Ga20 vapov have beetz found to have carrier and donor distributions which do not correspound to those expected from simple dopant seg-vegation during directional freezing; Instead, the carrier distribution is determined by the heat-trentnzent history of the crystal, while the donor distribution, zohiclz is principally due to silicon, is fixed by the pozuth rate, the geo)tlet.ry of the crystal growth vessel, and tlze initial Ga20 pressure. WHEN semiconducting materials are made into doped crystals by the normal freezing method,&apos; they usually exhibit doping variations along the growth axis. If a) there is no dopant diffusion in the solid, b) the dopant is distributed uniformly in the melt, and c) the distribution coefficient, k, does not vary with composition, then the doping variation along the growth axis is represented by the equation: where C is the doping level in the solid at a point where a fraction g of the original liquid has frozen, and Co is the mean concentration. When the dopant is either a singly ionized shallow donor or shallow acceptor, C also represents the carrier concentration. Even though this equation accurately describes the dcping profiles of a large number of normal freeze systems, there are several special systems for which Eq. [I] does not apply. One such system is the horizontal Bridgman method for preparing oxygen-grown GaAs crystals using quartz vessels. Several workers2"* have shown that GaAs crystals grown by the horizontal Bridglnan method using quartz vessels are generally contaminated with silicon in concentrations in excess of 5 < 10lG atoms per cu cm. This contamination is ascribed to a reaction: occurring at the walls of the crystal-growth vessel which liberates silicon into the melt and Ga2O vapor. It has been shown4 that this reaction, and, hence, the silicon contamination, can be suppressed by the addition of oxygen to the crystal-growth apparatus. It is the purpose of this paper to describe a special apparatus capable of yielding single crystals of GaAs grown in the presence of oxygen and to describe both the kinetics of silicon suppression in this system and the relationship between the carrier concentration profile and the silicon concentration profile. EXPERIMENTAL-CRYSTAL GROWTH A schematic diagram of the apparatus used in the oxygen addition experiments is shown in Fig. 1. The most important features of this apparatus are: a) the use of a sand blasted quartz boat, h) a quartz rod of length 1, with a hole of cross section A, that is placed near the boat to limit the free space volume V, over the melt during the growth, and c) the temperature gradient at and near the solid-liquid interface. Sand blasting the boat is necessary to prevent wetting of the melt. The quartz rod retards the diffusion of the GazO vapor away from the melt to the colder portions of the ampoule. A crystal is prepared by first loading a 5.5-in. boat, which has been cleaned in aqua regia, with 40 g of 99.9999 pct Ga along with 1 to 8 mg of Ga203 powder. GazO3 is a convenient source of oxygen since it reacts with gallium at the melt temperature to form Ga20 vapor, the species which apparently controls the suppression of silicon contamination. The loaded boat, the quartz rod, and the 99.9999 pct As are placed in the ampoule as shown in Fig. 1. Generally, GaAs seeds were not used since most of the unseeded growths resulted in monocrys-tals. The ampoule is evacuated to 10-5 Torr and sealed off. The GaAs melt is synthesized by placing the ampoule into a two-zone horizontal Bridgman furnace. The two zones are separated by several sandwiched layers of -in. Fibre-Fax board drilled with holes slightly larger than the OD of the ampoule. This causes a very large temperature gradient between the two zones, which is necessary for single-crystal growth. The two-zone furnace is mounted on a stand fitted with a roller bearing which allows uniform motion of the furnace in a horizontal direction. A uniform velocity of the stand is achieved by the use of a windlass device which winds up a wire attached to the stand. Movement of the solid-liquid interface is accomplished by fixing the position of the ampoule and moving the stand. Growth rates investigated in this experiment were between 0.4 and 1.2 in. per hr. The composition of the melt is fixed by maintaining an arsenic reservoir at 618°C. The stand is moved away

Jan 1, 1968