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By J. J. Tietien, R. O. Clough

A technique previously used to prepare alloys of InAs1-xPx and GaAsl-x Px, miry: the gaseous hydrides arsine and phosphine, has been extended to grow single -crystalline GaAs 1-x Sb x by replacing the phos-phine with stibine. Procedures were developed for handling and storing stibine which now make this chemical useful for vapor phase growth. This represents the first time that this series of alloys has been grown from the vapor phase. Layers of P -type GaSb and GaSb-rich alloys have been grown with the carrier concentrations comparable to the lowest ever reported. In addition, a p-type alloy containing 4 pct GaSb exhibited a mobility of 400 sq cm per v-sec which is equivalent to the highest reported for GaAs. RECENTLY, interest has been shown in the preparation and properties of GaAs1-xSbx alloys, since it was predicted1 that for compositions in the range of 0.1 < x < 0.5, they might provide improved Gunn devices. However, preparation of these alloys presents fundamental difficulties. In the case of liquid phase growth, the large concentration difference between the liquidus and solidus in the phase diagram, at any given temperature, introduces constitutional supercooling problems. It is likely that, for this reason, virtually no description of the preparation of GaAs1-xSbx by this technique has been reported. In the case of vapor phase growth, problems are presented by the low vapor pressure of antimony, and the low melting point of GaSb and many of these alloys. In previous attempts1 at the vapor phase growth of these materials, using antimony pentachloride as the source of antimony vapor, alloy compositions were limited to those containing less than about 2 pct GaSb. This was in part due to the difficulty of avoiding condensation of antimony on introducing it to the growth zone. A growth technique has recently been described2 for the preparation of III-V compounds in which the hydrides of arsenic and phosphorous (AsH3 and pH3) are used as the source of the group V element. With this method, GaAs1-xPx and InAs1-xPx have been prepared2&apos;3 across both alloy series with very good electrical properties. Since the use of stibine (SbH3) affords the potential for effective introduction of antimony to the growth apparatus, in analogy with the other group V hydrides, this growth method has been explored for the preparation of GaAs1-xSbx alloys. In addition to GaSb, these alloys have now been prepared with values of x as high as 0.8. In the case of GaSb, undoped p-type layers were grown with carrier concentrations equivalent to the lowest reported in the literature. Thus it has been demonstrated that, with this growth technique, all of the alloys in this series can be prepared. EXPERIMENTAL PROCEDURE A) Growth Technique. The growth apparatus, shown schematically in Fig. 1, and procedure are virtually identical to that described2 for the growth of GaAs1-xPx alloys, with the exception that phosphine is replaced by stibine.* HCl is introduced over the gallium boat to *Purchased from Matheson Co., E. Rutherford,N+J. transport the gallium predominantly via its subchlo-ride to the reaction zone, where it reacts with arsenic and antimony on the substrate surface to form an alloy layer. The fundamental limiting factors to the growth of GaAs1-xSbx alloys from the vapor phase, especially GaSb-rich alloys, are the low melting point of GaSb (712°C) and the low vapor pressure of antimony at this temperature (<l mm). Thus, relatively low antimony pressures must be employed, which, however, imply low growth rates. To provide low antimony pressures, very dilute concentrations of arsine and stibine in a hydrogen carrier gas were used. Typical flow rates (referred to stp) were about 4 cm3 per min of HC1 (0.06 mole pct)+ from 0.1 to 1 cm3 per min of ASH, (0.002 to 0.02 mole pct), and from 1 to 10 cn13 per min of SbH3 (0.02 to 0.2 mole pct), with a total hydrogen carrier gas flow rate of about 6000 cm3 per min. Although no precise data on decomposition. kinetics exist, it is known4 that stibine decomposes extremely rapidly at elevated temperatures. However, the high linear velocities attendent with the high total flow rate (about 2000 cm per sec) delays cracking of the stibine until it reaches the reaction zone and prevents condensation of antimony in the system. To improve the growth rates of the GaSb-rich alloys, growth temperatures just below the alloy solidus are main-

Jan 1, 1970

By Horace Mann

A FEW years ago, it was generally thought that from 15 to 18 per, cent. of zinc oxide was the upper limit of a workable lead blast-furnace slag. With slags above this zinc-oxide content, the furnaces gave so much trouble because of hearth, wall, and crucible accretions that the campaign was very short. The time lost in cleaning out the frozen furnaces, for it was seldom possible to blow them out, and blowing in was so great that it was considered uneconomical to attempt the running of high-zinc slags, even if this were metallurgically possible. It is true that there are, references to one or two slags much higher in zinc than the foregoing,1 but the average smelterman regarded these, as freaks and not to be considered for regular furnace work. One or two plants, notably the plant of the United States Smelting Co, at Canyon City, Colo., ran charges, higher in zinc. At this plant, the zinc-oxide content of the charge was frequently 20 per cent. and higher but the slags from these furnace&apos;s seldom ran over 10 to 12 per. cent. zinc oxide. The furnaces were run with a large volume of air under a relatively low pressure, a low smelting column, and a very hot top; as a result, a large amount of zinc was volatilized. Even with the low smelting column and hot top, accretions caused much trouble and barring, down was a daily occurrence. At the time most of the theories on lead blast-furnace work were promulgated or worked out, it was necessary to run a furnace with a cold top in order to avoid an excessive loss due to fines and fume. At the same time, the smelting conditions had to be such that the lead and silver would be reduced and would enter the bullion. The slag had to be liquid but the charge must not give excessive accretions either in the hearth or on the walls of the furnace. This forced the operators to run the furnaces with a comparatively low blast, which, in turn, caused a small fuel consumption per unit of time with the accompanying result of a low working temperature.

Jan 8, 1925

By E. T. Dumble

Introduction..........914 I. Topography,........915 The Nueces Basin........915 The Coastal Slope...........918 Streams..........919 II. Geology..........921 Eocene..........923 Basal Beds .......923 Lignitic Stage........923 Atascosa Sections......924 International and Great Northern Sections .. . 928 Leona Sections.......929 Nueces Sections....929 Rio Grande Sections.....930 Lower Claiborne Stage......932 Marine Beds ........933 Atascosa Sections....... 933 International and Great Northern Sections .. . 934 Frio County Sections,.....935 Rio Grande Sections.....936 Yegua Clays........938 Atascosa Sections......938 Tilden Sections.......941 International and Great Northern Sections .. . 942 Rio Grande Sections.....942 Fayette Sands........945 Atascosa Sections......946 Tilden Sections......948 Rio Grande Sections.....950 Frio Clays........953 Atascosa-Frio Sections.....953 Tilden-San Diego Sections....955 Rio Grande Sections......955 Neocene ....966 Oakville Beds.......957 Lapara Beds,....... 987 Nueces Sections......958 Bartlett&apos;s Ford Sections.....959 Fort Merrill Section......963 Lapara Sections,.....964 Tilden-San Diego Section.....967 Lee Tiendas.......969

Jan 1, 1903

By R. W. Snyder, W. H. Guilinger, B. S. Gottfried

Two numerical methods are presented JOT solving the equations Jor one-dimensional, multiphase /low in porous media. The case oF variable physical properties is included in the Formulation, although gravity and capillarity are ignored. Both methods are analyzed mathematically, resulting in upper and lower bounds for the ratio of time step to mesh spacing. The methods are applied to two- and three-phase waterflooding problems in laboratory-size cores, and resulting saturation and pressure distributions and production histories are presented graphically. Results oJ the tuo-phase flow problem are in agreement with the predictions of the Buckley-Leuerett theory. Several three-phase flow problems are presented which consider variations in the water injection rate and changes in the initial oil-and ujater-saturation distributions. The results are different physically from the two- phase case; however, it is shown that the Buckley-Lez~erett theory can accurately predict fluid interlace velocities and displacing-fluid frontal snturations for three-phase flow, providing the correct assumptions are made. The above solutions are used as a basis JOT et~aluuting the numerical methods with respect to machine time requirements and allowable time step for a fixed mesh spacing. INTRODUCTION Considerable progress has been made in recent years in obtaining numerical solutions of the equations for two-phase flow in porous media. Douglas, Blair and Wagner2and McEwenll present different methods for solving the one-dimensional case for incompressible fluids with capillarity (the former using finite differences, the latter with an approach based upon characteristics). Fayers and Sheldon4 and Hovanesian and Fayers8 have extended these studies to include the effects of gravity. West, Garvin and Sheldon, l4 in a pioneer paper, treat linear and radial systems with both capillarity and gravity and they also include the effects of compressibility. Douglas, Peaceman and Rachford3 consider two-dimensional, two-phase, in compressible flow with gravity and capillarity and Blair and Peaceman1 have extended this method to allow for compressible fluids. No one, however, has examined the case of three-phase flow, even for the relatively simple case of one-dimensional flow of incompressible fluids in the absence of gravity and capillarity. In obtaining a numerical technique for simulating forward in situ combustion laboratory experiments, Gottfried5 has developed a method for solving the one-dimensional, compressible flow equations with any number of flowing phases. Gravity and capillarity are not included in the formulation. The method has been used successfully, however, for two- and three-phase problems in a variable-temperature field with sources and sinks. This paper examines the algorithm of Gottfried more critically. Two numerical methods are presented for solving the one-dimensional, multi-phase flow equations with variable physical properties. Both methods are analyzed mathematically, and are used to simulate two- and three-phase waterflooding problems. The numerical solutions are then taken as a basis for comparing the utility of the methods.

Jan 1, 1967

By P. D. Frost, H. A. Robinson, J. R. Doig, M. W. Mote

The mechanism of hardening in heat-treatable zirconium alloys was foUNd to be analogous to that for titanium alloys. Zirconium containing a relatively large addition of a ß -stabilizing element such as molybdenum or columbium can be hardened by the following transformation: Lean alloys, having insufficient alloy content to retain ß at room temperature are hardened by the following transformation: Application of these findings in Zr-Mo-Sn and Zr-Nb-Sn alloys produced strengths as high as 190,000 psi with reasonable ductility. PRIOR research on zirconium alloys has been concerned with development of greater strengths and creep resistance by solid-solution hardening or by dispersion hardening. Although solution and aging heat treatments had been applied earlier to zirconium alloys, quenching frequently produced low ductility. The possibility that the ß-to-w transformation, discovered earlier in titanium alloys,&apos; might also occur in zirconium alloys and cause low ductility was considered, and, indeed, was found as predicted2 to be the case. In the earliest experiments, the heat-treatment response of titanium, too, was disappointing. However, by avoiding the formation of the embrittling w phase, it became practical to obtain room-temperature strengths higher than 180,000 psi, with elongation values of 10 pct.3 Based on the present concept of titanium heat treatment, the principal requirement for a heat-treatable zirconium alloy is that it contains a certain minimum amount of one or more ß -stabilizing elements. Only molybdenum, columbium, and tantalum, when present in sufficient amounts, are known to stabilize ß zirconium to room temperature during rapid cooling from the ß field. Tantalum was undesirable because of its high thermal-neutron cross section. Aluminum and tin are effective a stabilizers, but aluminum has been shown to seriously decrease the corrosion resistance of simple zirconium alloys in hot water. Therefore, for the present study, tin was used as the stabilizer addition. The alloys selected for this evaluation are presented in Table 1 along with their analyses and ß-transus temperatures. The analyses indicated that intended compositions were usually realized. EXPERIMENTAL PROCEDURES All of the alloys were melted from sponge zirconium and fabricated to sheet for heat treatment

Jan 1, 1960

By Aureal T. Cross

THIS paper is a review of the published literature on research in coal geology, principally exclusive of resource studies, which appeared or became available during 1950 and the latter part of 1949. This report is not to be construed as being complete. The papers referred to in the bibliography are those among many more, which were read either in full or in abstract. Undoubtedly other papers were published which either escaped the author&apos;s notice or were not available to him. Those which were seen in abstract only (about one fourth of those listed) were not available in time for the inclusion of more than a notice. An outline of all papers listed in the bibliography has been arranged by subjects and reasonable subdivisions with some papers cited under more than one subject. Most papers are indexed according to the principal subject of discussion or research only as to an unusual or noteworthy section of the entire report. There will likely be some disagreement as to the quality or merit of some of the papers selected and the specialist may be supercritical of the outline or organization of papers in his field. It may be that attention has occasionally been drawn to papers reporting old information or conclusions of questionable value. Conferences and Meetings One of the best indications of the growing interest in coal geology problems in the United States is the increasing number of times this field has been the focus of attention at conferences and meetings. Notable among these are the joint meeting of the Society of Economic Geologists and the Geological Society of America at El Paso, November 1949, at which the principal thesis was concerned with low rank carbonaceous fuel deposits, especially of western United States. Among the papers given which are already available were those presented by Barghoorn,&apos;" Parry? Roe? and Parks."&apos; At the annual meeting of the Botanical Society of America in New York, December 1949, a joint meeting of the Paleobotanical and Microbiological Sections was held for which a symposium on Microbiology in Relation to the Geologic Accumulation of Organic Complexes was organized. Publication of the six papers presented by Ralph G. H. Siu, Elso S. Barghoorn, Irving Breger, Claude E. ZoBell, James M. Schopf, and A. C. Thayson is anticipated. At the regular meetings of the Paleobotanical Section at the same time, several other papers of interest reported on coal ball studies, partial coalification of petrified wood, and floras. In Chicago, April 1950, a symposium on Applied Paleobotany was held by the Society of Economic Paleontologists and Mineralogists in conjunction with the American Association of Petroleum Geologists. The five papers presented at this meeting dealt with the use of Paleozoic plant microfossils for stratigraphic work, J. M. Schopf, Devonian-Missis-sippian fossils of the black shales, Aureal T. Cross, Mesozoic plants of stratigraphic value, Th. Just, plant microfossils of the Tertiary, L. R. Wilson, and studies of the Brandon lignite, Elso S. Barghoorn. Early publication of these in the Journal of Paleontology is expected. The Nova Scotia Research Foundation and the Nova Scotia Dept. of Mines sponsored an excellent 3-day conference in June 1950, which dealt with several aspects of coal geology. Papers on coal classification, P. A. Hacquenbard, structure and sedimentation problems in Nova Scotia, T. B. Haites, new techniques of thermal analysis, W. L. White-head, geochemical investigations of Nova Scotia coals, Irving Breger, the role of fossil plant spores in coal correlation and the stratigraphy of the coal-bearing strata of the Appalachian Region, Aureal T. Cross, were given. Some discussions of these papers by those in attendance were recorded, and the entire proceedings is being prepared for publication. In September 1950, an unusual 3-day field conference was held by the Ohio and West Virginia Geological Surveys under the sponsorship of the Coal Geology Committee. This study of the stratigraphy, sedimentation, and nomenclature of the Upper Pennsylvanian and Permian coal-bearing strata of southeastern Ohio, southwestern Pennsylvania, and northern West Virginia was augmented by two discussions on associated rocks (clays and shales) and stratigraphic nomenclature at Wheeling and Morgantown, West Va. An extensive guidebook was prepared, and transcriptions of the Morgantown meeting were made. As a follow-up of the September field conference, a round-table discussion was held on this general topic at a special open meeting of the Coal Research Committee in conjunction with the November meeting of the Geological Society in Washington. Short prepared statements to invite discussion were given on each of several topics by L. M. Cline, Carl 0.

Jan 1, 1953

By V. M. Frey

IN 1936 the foreman at one of the oldest limestone quarries in northern Virginia discovered the remains of three old well-drill holes that contained dynamite. As consulting engineer for the property, I was then called upon to devise a method for removing the explosive. As no exact formula for the handling of unexploded dynamite exists, the proper steps for removing it must always be dictated by local conditions. A description of the procedure in this case may, therefore, be of interest to others faced with a similar problem.

Jan 1, 1939

By L. W. McKeehan, W. C. Elmore

The magnetic powder method, long used for roughly mapping magnetic fields, has recently been refined1, "or investigating the microscopic variations in the surface magnetization of ferromagnetic crystals. Bitter2 first discovered regular powder patterns connected with the crystal structure of such specimens. Several other investigators:&apos; have used Bitter&apos;s original technique, with slight modifications, to study the variation of the patterns with variations in the magnetizing field applied parallel to the surface, and their dependence upon the state of strain, of polish and of crystal cut. All of the explanations of these patterns on metallic ferromagnetics have been couched in general terms. In a preliminary report we have described an improvement ill the powder technique which led us to the discovery of a new effect throwing considerable light on the magnetic secondary structure of alpha iron4 and of nickel5 single crystals. We now report additional evidence confirming the existence and stability of a magnetic block secondary structure. Specimens The following list describes the specimens used in the present investigation. Designation Description A1 Silicon ferrite furnished to us by Dr. W. E. Ruder, of the General Electric Co., for which lie gave the following typical analysis: C, 0.05; P, 0.038; S, 0.026; Mn, 0.15; Si, 3.24. Disk, 0.60 cm. diameter, about 0.05 cm. thick. By X-ray analysis angles between disk normal and [100] 75o, [0101 76" [00l] 21o. A2 Same as A1 except: diameter 0.75 cm. A, Same as A1 except: diameter 0.68 cm.

Jan 1, 1936

By Paul Billingsley, Augustus Locke

Certain adequately developed mining districts give complete three-dimensional patterns of ore bodies as clusters rising from roots in basement rocks with details controlled by structure of cover rocks. Examples are Goodsprings, Tintic, Bisbee, Leadville, Hedley, Eureka, Ely and Goldfield. In these and others the controlling structures in both basement and cover rock are elements of the neighboring regional structure and have been produced by rock movements in harmony with continental adjustments, which are usually steep tear faults in basement and thrust crumples in cover. Invariably the structures and movements in the districts have long geologic history and result from intersecting or superimposed deformations of different ages. Salt Lake districts show intersecting Uinta and Cordilleran elements; Colorado districts show intersecting pre-Cambrian and Tertiary elements, and Bisbee shows Tertiary superimposed on fina1 Paleozoic folding. Thus the position of districts has been determined by the patterns of North American orogenic belts, which make crossroads in Rocky Mountains and blocks of superimposed deformation in Sierra Nevada, northwest Coastand Canadian Coast Ranges. Essential function of repeated deformation is to strengthen rock, as from shale to slate to schist to gneiss, and thus make it competent to carry channels to depth with or without addition of intrusives. The essence of a mining district is the presence of such competent rocks with long-lived, deep, penetrating breaks reopened to permit passage of heat and associated products from depths to surface. It is suggested that melts such as magmas; metamorphism up to and including granitization; alteration, such as orthoclase-quartz or quartz-sericite or garnet, and also mineralization, may all be by-products of such heat escape along channels made by tectonic forces at specific foci. Magnitudes of Districts (Fig. 1) Any synthesis of ore deposits must deal with comparable units. Ore deposits are innumerable, but great ore deposits, commercially important for a generation or more, are few. The bulk of metals has come from districts of the first and second magnitudes (over $1,000,000,000 and over $250,000,000, respectively), and of these the United States and adjacent provinces of Canada and Mexico contain only 28, of which 9 are first magnitude: Butte, Coeur d&apos;Alene, Bingham, Bisbee, Sierra Gold, in the West; Tri-State, Southeast Missouri, Michigan copper, Sud-bury, in the East. Another 28 or 30 districts are of third magnitude (over $50,000,000).

Jan 1, 1941

By Frank G. Miller

This report presents developments of fundamental equations for describing the flow and thermodynamic behavior of two-phase single-component fluids moving under steady conditions through porous media. Many of the theoretical considerations upon which these equations are premised have received little or no attention in oil-reservoir fluid-flow research. The significance of the underlying flow theory in oil-producing operations is indicated. In particular, the theoretical analysis pertains to the steady, adiabatic, macroscopically linear, two-phase flow of a single-component fluid through a horizontal column of porous medium. It is considered that the test fluid enters the upstream end of the column while entirely in the liquid state, moves downstream an appreciable distance, begins to vaporize, and then moves through the remainder of the column as a gas-liquid mixture. The problem posed is to find the total weight rate of flow and the pressure distribution along the column for a given inlet pressure and temperature, a given exit pres5ure or temperature and given characteristics of the test fluid and porous medium. In developing the theory, gas-liquid interfacial phenomena are treated. phase equilibrium is assumed and previous theoretical work of other investigators of the problem is modified. Laboratory experiments performed with specially designed apparatus. in which propane is used as the test fluid, substantiate the theory. The apparatus. materials and experimental procedure are described. Comparative experimental and theoretical results are presented and discussed. It is believed that the research findings contributed in this * paper should not only lead to a better understanding of oil-reservoir behavior, but also should be suggective in regard to future research in this field of study. INTRODUCTION In recent years much time and effort has been consumed in both theoretical and experimental studies of the static and . dvnamic behavior of oil-reservoir fluids in porous rocks. Although lack of sufficient basic oil-field data, principally concerning the properties and characteristics of reservoir rocks and fluids, largely precludes quantitative application of research results to oil-field problems, qualitative application has become common practice. In effect. oil-reservoir engineering research is serving as a firm foundation for oil-field development and production practices leading to increased economic recoveries of petroleum. This province of research. however, still poses many perplexing problems. The thermodynamic behavior of two-phase fluids moving through porous media constitutes one facet of reservoir-fluid-flow research that has not received the attention it deserves. This report embodies a theoretical discussion of this subject and a description of a series of related laboratory experiments. The significance of the problem to oil field operations is indicated but in articular the report centers around a theory and method for analyzing the steady. macroscopically linear, two-phase flow of a fluid (a single molecular species) through a horizontal column of porous medium. For simplicity in showing how the thermodynamic behavior of two-phase fluids moving through porous media affects oil-reservoir performance problems, attention is focused temporarily on a particular well producing petroleum from an idealized water-free solution-gas drive reservoir, the reservoir rock being a horizontal, thin, fairly homogeneous sandstone of large areal extent confined between two impermeable strata. The flowing hydrocarbon fluid is considered to exist entirely as a Iiquid at points in the reservoir remote from the well; however. the decline in fluid pressure in the direction of the well causes vaporization of the hydrocarbon to begin at a radial distance r from the well. Upstream from r the fluid moves entirely as a liquid and downstream from r it moves either entirely as a gas or as a gas-liquid mixture depending on the properties of the hydrocarbon and on the thermodynamic process it follows during flow. The distance r would be variable under transient flow conditions. but for purposes of analysis the flow is considered to l~e steady at the particular instant of observation during the flowing life of the well of interest. If the flow were isothermal and the hydrocarbon a pure substance, the fluid would be entirely gaseous downstream from r. Thus, this isothermal flow process for a pure substance would require that the heat of vaporization be supplied at r. over zero length of porous medium, at the precise rate necessary to maintain the constant temperature. This means that the solid matrix of the porous medium (reservoir rock) and the surroundings (impermeable strata confining the reservoir rock) would have to serve as infinite heat sources. Heat-transfer requirements would be somewhat less severe for the isothermal flow of a multicorn-ponent hydrocarbon as bubble and dew points at the same temperature correspond to different pressures. In this instance isothermal conditions would be sustained without complete vaporization of the fluid over zero length of porous medium. Nevertheless. as the flow is in the direction of decreasing

Jan 1, 1951

By A. H. Geisler, R. F. Mehl, C. S. Barrett

The mechanism by which the supersaturated solid solution of 20 per cent silver in aluminum decomposes has been reported in two previous publications.1&apos;2 The analysis of streaks in Laue photograms showed that thin platelike particles (the so-called Guinier-Preston aggregates) form upon matrix planes in the early state of decomposition.1 The size of these particles is larger, the higher the temperature at which they form in accordance with nucleation theory;³ at all temperatures they increase in size with aging.2 When they have grown thick enough to afford three-dimensional diffraction, powder X-ray photograms show that the structure is not that of the equilibrium precipitate but that of a transition lattice . Sincc this is also platelike in shape and also lies upon the (III) matrix planes with the [IIO] direction in the matrix parallel to the [II.O] direction in it seems likely that the original platelet particles are merely in an early stage of formation, and thus finely dispersed. The atomic spacing and pattern on the (00.1) plane in y&apos; are identical with those on the (111) matrix plane to which it lies parallel, and since comparable directions in the two planes are parallel, the lattices are thus coherent at the interface; an analogous coherence has been found in aluminum-copper alloys.3 The structures y&apos; and y are both close-packed hexagonal and are oriented alike; they differ only in interatomic distances. Consequently, y&apos; is regarded as y strained from its ordinary dimensions by the lattice coherency between it and the matrix.2 The lattice movements that transform the matrix to the equilibrium precipitate appear to be very simple.2 The mechanism of precipitation in this system is simpler and is more precisely known than that in any other system hence the system should be a profitable one for the difficult task of correlating property changes with structural alterations. The present report provides additional studies on powder X-ray diffraction from alloys of 10 per cent, 20 per cent and 30 per cent Ag, and presents the correlation of crystallographic changes with changes in microstructurc, Brinell hardness and electrical resistivity of the three alloys. Preparation of Samples and Experimental Procedure The preparation of the 20.2 per cent Ag alloy has been described2 Alloys containing 9.9 and 29.7 per cent Ag were prepared from 99.97 per cent A1 and 99.99+ per cent Ag using a similar procedure. Rolled

Jan 1, 1943

By Frederick Rhines

THE investigations of Wyman1 have demonstrated that copper deoxidized with several of the commonly used agents that confer immunity to ordinary hydrogen em-brittlement can still be embrittled if it is annealed alternately under oxidizing and reducing conditions. During the oxidizing cycle, oxygen diffuses into the copper and frequently deposits a subscale composed of the oxide of the residual deoxidizing agent. Upon subsequent reduction with hot hydro-gen, the copper becomes ruptured along the grain boundaries to a depth sharply limited by the previous penetration of oxy-gen as delineated by the inner boundary of the subscale. Obviously the sensitivity to this kind of hydrogen embrittlement is engendered by the introduction of oxygen during the oxi-dizing anneal, but beyond this the mecha-nism of the process, and hence the controlling factors, remain obscure. There are several possibilities: (I) oxygen dissolved in the copper matrix of the subscale may, upon cooling prior to the hydrogen anneal, precipitate as cuprous oxide which is subse-quently reduced by hydrogen as in the familiar case of hydrogen embrittlement; (2) oxygen in solid solution in copper may itself confer susceptibility to embrittlement by hydrogen; (3) the normally refractory oxides such as those of aluminum, silicon and titanium may themselves he reduced by hydrogen when in contact with copper; or (4) the precipitated oxides of the sub-scale may be complex compounds such, perhaps, as Si02-Cu20, which are partially reduced by hydrogen. These possibilities have been examined, and it has been con-cluded that the first three and possibly the fourth are operative collectively or indi-vidually under more or less predictable conditions.

Jan 1, 1940

By Arthur F. Taggart

The major portion of the work described in this paper was performed by R. W. Young, † a graduate student in the department of Mining and Metallurgy, Sheffield Scientific School, Yale University, working under a cooperative agreement between the Hardinge Conical Mill Co., the Sheffield Scientific School, and himself. Since this cooperative scheme is at present in effect in the case of a considerable number of other students in the department and since it is the hope of the school that the privilege thus extended may be utilized even more freely in the future by mining and manufacturing companies, it may not be amiss at this point to give a summary of the general plan. Briefly it is as follows: A graduate student, whose undergraduate work in this or other universities shows promise of ability to handle research work, is chosen by conference between the company and instructor involved. The aim of the company in the agreement then entered into is to obtain the solution of one or more of the technical problems with which it may be confronted, or, at the end of 1 or 2 years, to obtain as an employee a man especially trained in its work. As a means to accomplish one or both of these ends, the company furnishes the machine, apparatus, or material to be tested and pays the student during his graduate work a small salary, usually just sufficient to cover his living expenses, tuition and fees. The aim of the student is special training along a line in which he is particularly interested, the attainment of his advanced degree, and the chance to show to his future employer ability to handle such problems as may be presented to him. In return for the financial aid which he receives he agrees to devote at least half of his working time to the special problem submitted by his company. The other half is devoted to study of the collateral subjects required by the department for the granting of the degree which the student seeks. The student further agrees to enter the employ of the company in question at a wage not greater than that paid in like positions to recent graduates not specially trained and to remain with his employer at such wage for at east 1 year. If the student is to obtain a degree, the special work forming the basis of his investigation must be such as will involve real research and not mere routine manipulation. The subject is chosen by conference between the three parties to the agreement. The work is carried on under the direct supervision of the instructor involved. The school furnishes the general laboratory and library equipment essential to the pursuit of any extended investigation. In

Jan 1, 1918

By R. F. Mehl, C. S. Barrett, A. H. Geisler

The mechanism by which the supersaturated solid solution of 20 per cent silver in aluminum decomposes has been reported in two previous publications.1&apos;2 The analysis of streaks in Laue photograms showed that thin platelike particles (the so-called Guinier-Preston aggregates) form upon matrix planes in the early state of decomposition.1 The size of these particles is larger, the higher the temperature at which they form in accordance with nucleation theory;³ at all temperatures they increase in size with aging.2 When they have grown thick enough to afford three-dimensional diffraction, powder X-ray photograms show that the structure is not that of the equilibrium precipitate but that of a transition lattice . Sincc this is also platelike in shape and also lies upon the (III) matrix planes with the [IIO] direction in the matrix parallel to the [II.O] direction in it seems likely that the original platelet particles are merely in an early stage of formation, and thus finely dispersed. The atomic spacing and pattern on the (00.1) plane in y&apos; are identical with those on the (111) matrix plane to which it lies parallel, and since comparable directions in the two planes are parallel, the lattices are thus coherent at the interface; an analogous coherence has been found in aluminum-copper alloys.3 The structures y&apos; and y are both close-packed hexagonal and are oriented alike; they differ only in interatomic distances. Consequently, y&apos; is regarded as y strained from its ordinary dimensions by the lattice coherency between it and the matrix.2 The lattice movements that transform the matrix to the equilibrium precipitate appear to be very simple.2 The mechanism of precipitation in this system is simpler and is more precisely known than that in any other system hence the system should be a profitable one for the difficult task of correlating property changes with structural alterations. The present report provides additional studies on powder X-ray diffraction from alloys of 10 per cent, 20 per cent and 30 per cent Ag, and presents the correlation of crystallographic changes with changes in microstructurc, Brinell hardness and electrical resistivity of the three alloys. Preparation of Samples and Experimental Procedure The preparation of the 20.2 per cent Ag alloy has been described2 Alloys containing 9.9 and 29.7 per cent Ag were prepared from 99.97 per cent A1 and 99.99+ per cent Ag using a similar procedure. Rolled

Jan 1, 1943

By David J. Mack

The structures and properties of the copper-aluminum alloys have been the subject of much study since the classic investigation of Carpenter and Edwards1 focused attention on. the engineering utility of these alloys. It was recognized at an early date that the metallographic structures developed in the aluminum bronzes were similar to those developed in steels, both in the annealed and the rapidly cooled state. Most investigators have been concerned with the acicular, martensitic-like structure formed from the 0 solid solution upon rapid quenching; the transformation of the ß under equilibrium cooling to a lamellar eutectoid having been relatively neglected. With the introduction in 1930 by Davenport and Bain2 of the isothermal transformation technique for studying eutectoidal decompositions, a new field was opened. Although an enormous amount of work has since been done on the isothermal transformation of steel, study of structurally analogous systems has been almost totally overlooked. The outstanding exception was the prize-winning paper† of Smith and Lind1ief³ ho investigated the decomposition of the 0 phase in copper-aluminum alloys by isothermal methods. This was followed in 1934 by Wasserman&apos;s review&apos; of available information on analogous transformations in eutectoid alloys. Since that time no comprehensive study of isothermally transformed eutectoids analogous to steel has appeared, although many valuable contributions have been made to an understanding of the structures developed in such systems. Important papers have been published by Kurdjumow, Gridnew and co-workers, Obinata,18.&apos;9 Greninger,20.21 and Others. The work to be described in this paper was an outgrowth of preliminary studies on the isothermal transformation of a entectoid aluminum bronze, after it became apparent that the alloy under study was reacting somewhat differently than the similar alloy used by Smith and Lindlief. Preliminary Experiments The material used in this study was a high purity aluminum bronze especially prepared by Ampco Metal, Inc. It analyzed: Copper—88.07 pet, Aluminum—11.89 pct, Iron-—0.02 pet, Manganese—-.OI pct, Others—Balance. Although some disagreement exists on the exact composition of the eutectoid, this alloy was believed to be of essentially eutectoid composition even though some pro-eutectoid* delta particles existed in the microstructure of furnace cooled specimens. Specimens transformed isothermally at temperatures slightly below the eutectoid showed relatively large amounts of pre-eutectoid delta, but as will be shown later, this results

Jan 1, 1949

By J. H. Nead

The experiments herein described were undertaken with a view to investigating thoroughly the influence of carbon on the tensile and impact physical properties of carbon steel. The original comprehensive plan included investigation of a series of steels with varying carbon contents over a wide range of heat treatments. These were to be studied as to their static tensile qualities, and also their resistance to shock as measured by the Charpy impact bending test. A thorough metallographic examination was likewise included in the schedule. The Charpy tests and the metallographic examination have not been completed to date, and are accordingly withheld for another report. All heat treatments, however, have been made, and the static tensile tests have been completed. A description of the procedure of the experiment and the results thus far obtained are therefore reported herein. Conclusions No attempt is made to draw general conclusions from these experiments, but the curves and the data are submitted as being of general importance and wide applicability. Composition of Materials An attempt was made to secure steels increasing in carbon by increments of 0.1 per cent. from 0.1 per cent. up to 0.8 per cent., and from that composition to 1.6 per cent. by increments of 0.2 per cent. Actually, however, steels of the composition given in Table I were procured, and as the carbon contents were arranged sufficiently well so that satisfactory curves could be drawn showing the relation between carbon content and other properties, these steels were used in the experiments.

Jan 1, 1916

By H. M. Ziesemer

PRIOR to 1909 that mountain of porphyry, known as. Sacramento Hill, had remained hardly touched but had always aroused suspicions as to the presence of ore within.. During that year, exploratory work was started by underground methods; drifting and raising continued until 1913. It was proved that a mineralized zone existed, the limits of which had not been determined; so, because of the lower costs of exploratory work and the greater desirability of vertical sections, it was decided to prove the extent of the ore zone by churn drills. Drilling continued until the year 1917, when it seemed almost certain that the horizontal limits of the orebodies had been determined. Ore continued in depth in one direction beyond a point where it was economical to explore by churn drilling; this extension is still being developed by underground methods. The irregularities of the boundaries of the ore zones, together with the variable grades of ore encountered, made it necessary to drill on the corners of 100-ft. squares. Two ore zones were proved, known as the East and West Orebodies. The Sacramento Hill porphyry stock intruded into the Dividend fault. The fault ran roughly east and west with a dip to the south, having pre-Cambrian schists on the north against Paleozoic limestone on, the south. This intrusion was accompanied by a silica breccia on the south periphery, along the limestone contact side. The ore lay in the silica breccia and in the porphyry, some distance from the breccia. No ore was found in the heart of the porphyry mass on the north side, along the schist contact. The West Orebody is elliptic in shape, having a major axis of 1200 ft. (366 m.) and a minor axis of 800 ft. (244 m.); these diminish with depth until, at 300. ft., the axes are 500 ft. and 300 ft., respectively. The ore consists of chalcocite, some bornite, chalcopyrite, and considerable pyrite in a silicious gangue. About 30 per cent. of the copper is caused by

Jan 2, 1922

By R. J. Reynik

A semiempirial small flunctation theory of diff- sion in liquids is presented, which employs a fluctuation energy assumed quadratic for a small atomic or molecular displacement and Einstein&apos;s random-iralh model. The resulting diffusion equation is given by In these equations. D is the diffusivity, is the average liquid shite coordination number (at interatomic distance d. cm. T is the absolute temperature, xu. em, is (the diffusive displacement. K, is the quadratic fluctuation energy force constant, and rg, cm, are the radii oj diffusing atoms A and B, respectively. The quantities Xn and K are calculated from the computer-filled values of the slope and intercept. respectively. The radius of self-diffusing atom or radii and of diffusing atoms A and B are eta United and compared with values reported in the literature.. The predicted linear variation of diffusivity with. It tempera lure htm been observed in approximately thirty-iire metallic liquid systems, and in over seventy-fiee other liquid systems, including the organic .alcohols, liquified inert gases, and the molten salts, ALTHOUGH the average density within a macroscopic volume element of liquid is constant for fixed total number of atoms. pressure. and temperature, there exist microscopic: density fluctuations within the respective volume element. As such the microscopic volume available to an atom and its Z first nearest neighbors at any instant of time fluctuates above and below the average volume available to these atoms. If one assumes that liquid state atoms vibrate as in a solid. and further postulates that the mean position of any atom in the liquid state is not stationary. but shifts during every .vibration a distance 0 5 j 5 xo. then every atom in the liquid state continuously undergoes diffusive displacements which vary in the range 0 5 j 5 ro. Mathematically. for a binary liquid system consisting of atcrms A and B. the maximum diffusive displacement. .YO, is defined by the equation: where d is the average liquid state interatomic distance at specified liquid state coordination number Z. and v~ \ and vg are the effective radii of diffusing atoms A and B: respectively. For self-diffusion. r^ equals rg , and Eq. [I.] reduces to: It is interesting to note that Eq. [l] or [2] can be used to compute the radii of the diffusing atoms, provided one had an experimental evaluation of xo. As such. the computed radii could be compared with metallic or crystallographic ionic radii to ascerlain the electronic character of the diffusing atoms. Thus it is proposed that in the liquid state the n~otion of an atom relative to its original equilibrium position of oscillation represents the thermal vibration of any atom and its Z first nearest neighbors. while the small and variable displacements. 0 5 1 5 xc,. of the centers of oscillation represent the complex diffusive motions of the atoms at constant temperature and pressure. This is consistent with data obtained from slow neutron scattering by liquids1 &apos; and resembles an itinerant oscillator model of the liquid state.&apos;" It is further postulated that the atomic displacements characterizing the liquid state diffusion process are essentially a random-walk process. As such. it nlay be described by Einstein&apos;s equation:&apos; where D is the diffusivity. sq cm sec-&apos;. j2 is the mean square value of the diffusive displacement. and i> is the frequency of density fluctuations giving rise to diffusion. FORMULATION OF DIFFUSION EQUATION The effective spherical volume occupied by an atom, as a consequence of a microscopic density fluctuation which enlarges the volume available to any atom, exceeds its average liquid state atomic volume by an amount: where AV is the enlarged spherical volume, v is the radius of the diffusing atom. and j is the elementary displacement distance from the original center of oscillation of the vibrating atom to a new center of oscillation position. For small atomic displacements. where c is a constant whose value depends upon the assumed geometry of the enlarged volume. For a spherical increase in volume, c equals 4nr2. Following the treatment of Furthl&apos; and ~walin." assuming the enlarged volu~nes AL7 for the diffusing atoms are distributed in a continuunl. the probability of finding a fluctuation in the size range 0 5 j 5 xo defined by Where c includes the geometric constant cl and Eij) is the fluctuation energy causing the volume change. But the proposed model assumes all the Z first nearest-neighbor atoms are centers of oscillation. and hence the probability that any of these atoms is adjacent to a fluctuation of magnitude 05j5xo is unity. Thus:

Jan 1, 1970

By C. C. Martin, M. C. Fuerstenau, R. B. Bhappu

Experiments revealed that quartz could not be floated in conductivity water at any pH with a long-chained sulfonate as collector. Various cations, Fe+++, Al+++, Pb++, Mn++, Mg++, Ca++, are shown to function as activators when the pH is such that the cation hydrolyzes. As the solubility product of the various cation-sulfonates was exceeded at the concentrations involved, precipitated cation-hydroxy-sulfonates, e.g. Fe (RSO3)2OH must be functioning as the collector in these systems. A number of interesting and important phenomena were revealed during a study of the response of beryl to sulfonate flotation.&apos; Perhaps the most important observation is the effect of various cations on flotation response. Experiments showed that in the vicinity of pH 3.0, about three ppm Fe+++ increased recovery of leached beryl from about 60 pct to 100 pct, whereas about four ppm Ca+ + reduced the recovery from 60 pct to 2 pct. With the exception of ferric iron, all of the other cations investigated reduced flotation recoveries drastically at this pH. As postulated in the paper Sulfonate Flotation of Beryl,&apos; even with low concentrations of polyvalent cations and sulfonate (on the order of one ppm), cation-sulfonates are precipitated immediately in solution. That is, blueish-white clouds were noted to form after given additions of salts to known solutions of sulfonate. Furthermore, it was also shown that one-hundred-fold more ferric iron than necessary to form the precipitated cloud had to be added to effect complete flotation. In other words, some form of solid ferric sulfonate was found to function as the collector in these systems. The form of the compound was suggested to be Fe(RCO3)2OH and that bonding to the surface occurs through the hydrogen of the hy-droxyl. As the form of this compound was shown to be dependent on the extent of hydrolysis of ferric iron, it is to be expected that ferric iron will be unique in some pH region. Further, if the presence of hydroxyl in the neutral precipitated compound is of primary importance, then other cations should function similarly but at different values of pH, since they will hydrolyze at different concentrations of hydroxyl ion. To determine whether the premise of hydrolysis is correct, the study was extended to quartz systems in the presence of various cations at various values of pH. EXPERIMENTAL MATERIALS AND METHOD Sodium alkyl aryl sulfonate was chosen as the collector for the experimental work. The reagent, sup plied as a courtesy sample by the Shell Chemical Co., has the following physical properties: Physical form Solid — Finely ground Sulfonate content, pct wt 95 to 97 Molecular Weight 450 to 470 Number of carbon atoms in hydrocarbon chain 25 to 30 Melting Point, OF 250 to 260 Solubility Soluble in water with gel formation at concentrations higher than 25 pct by weight sulfonate This particular reagent was chosen because of its high active sulfonate content, long-chain length, and solid form. With the exception of the frother and sulfonate, all other chemicals were of reagent grade quality. Conductivity water was used in the experimental work. This water, made by passing distilled water through an ion exchange column, had an average measured conductivity of one micromho. Experiments were conducted at room temperature in a small glass flotation cell with the following procedure: 1) A redetermined amount of water and salt solution (e.g. CaC12 . 2H2O) were combined and the pH adjusted to a given value. 2) A given amount of sulfonate was added so that final solution volume was 130 cc. 3) One drop of Dow 250 frother was added. 4) Five g of quartz were added and the system conditioned for five minutes. 5) The pH of the system was measured (termed flotation pH).

Jan 1, 1963

By N. A. Stockett

SOUTHEAST Missouri is the largest and oldest lead-producing district in the United States. For the year 1941, the statistical picture of pig-lead production, stated in short tons (partly estimated by the Engineering and Mining Journal) is as follows. [Tons World production 2,000,000 United States production 460.000 Southeast Missouri production 242,000] The consumption of primary lead in the United States in 1941 was approximately 900,000 tons, or almost double the country&apos;s production. The largest previous year&apos;s consumption in the United States was 718,000 tons, in 1926. The largest quantities of lead are used for cable sheathing, storage batteries and white lead. During 1941 tetraethyl lead for auto and aviation gasoline consumed 50,000 tons of lead. The entire lead production of Southeast Missouri is now mined by the St. Joseph Lead Co., whose dominant position as the largest producer in the United States of lead directly from ores is best shown by the fact that in 1941 it produced approximately 31 per cent of the lead production of the United States from its mines in southeast Missouri, where 22,000 tons of ore, averag¬ing over 3.00 per cent lead, is mined per working day. It is known that lead was mined at Mine La Motte, Madison County, Missouri, by Renault in 1723. Other white men and Indians probably did some mining prior to that time. Since 1865, the recorded production to Jan. 1, 1942, shows that the St. Joseph Lead Co. and the various other companies that have operated in St. Francois County mined lead ore, which, after milling and smelting losses produced 5,00,000 short tons of pig lead. About 95 per cent of the present lead production of Southeast Missouri is mined in St. Francois County. The northern part of this area is 60 miles south of St. Louis. The remainder of the lead is obtained at Mine La Motte, about 25 miles southeast from the center of the producing area in St. Francois County. PROSPECTING In this district, most of the ore is discovered by surface and underground diamond drills and by prospect drilling underground with rock drills. Each 2-ft. length of the cuttings from these Jackhamer prospect holes is assayed for lead. These holes are marked and the records are entered on maps. It has been found that close drilling--100-ft. centers of holes, and sometimes less-is necessary in order to locate most of the smaller commercial ore bodies, many of which previously had been missed by drilling the areas with holes spaced 200-ft. centers or more.

Jan 1, 1943