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By F. G. McCutcheon

UNTIL about 1930, the universal practice of horizontal-retort zinc smelters in the United States, as far as the writers are aware, was to operate the retort furnaces on a 24-hr cycle; that is, the retorts were charged in the early morning of one day, and in the early morning of the following day the residues were cleaned out, the retorts recharged, and a new cycle started. During the business depression of the early thirties, zinc production fell off to the extent that zinc smelters had idle retort capacity. Rather than continue to run some of the retort furnaces on a 24-hr cycle and shut down the remainder, a few companies decided to try out a longer cycle. Although the output of zinc per retort per day is lower, the longer cycle permits a larger charge per retort and improved zinc recovery. Advantages of the longer cycle were soon evident, and the practice spread rapidly. Various lengths of cycle were used, typical examples being 28-hr, 32-hr, 36-hr, and 48-hr. The 48-hr cycle fits in best with the standard routine of smelter practice that was built up on the basis of the 24-hr cycle; that is, the retort furnace "maneuver" always comes at the same time of day, and can be performed in the cool hours of the early morning. Under some conditions, particularly in some of the older plants, where the retorts are smaller than in newer plants, a 48-hr cycle is longer than necessary, and some intermediate length of cycle may theoretically be most economical. Use of an intermediate cycle, however, means that the maneuver comes at different times on consecutive days, and that sometimes it comes during the hottest part of the day. The work on the retort furnaces is extremely hot and arduous at best, and it is much worse, of course, if it is done during the heat of a summer day. When labor was plentiful and tractable, many plants were able to operate on cycles of intermediate length, but the workmen did not like the working hours. Under present labor conditions, it is hardly practicable to operate with a cycle of intermediate length, so the choice has narrowed down to the alternatives of 24-hr or 48-hr cycles. In any discussion of economics, too comprehensive generalization is not warranted, because local conditions affecting economics vary greatly. The best economic practice at one plant at any given time may be uneconomical at another plant, or even at the same plant at another time. To determine the length of cycle that is the better practice at a given plant at a given time requires a weighing of the advantages and disadvantages of each cycle, taking into consideration all the local conditions. Some of the factors that must be considered in making the comparison are discussed briefly in the following paragraphs.

Jan 1, 1947

By T. S. Washburn

Deoxidation is one of the most complex metallurgical operations in the basic open-hearth process. The necessity for deoxidation arises from the fact that the refining operations that precede it require the oxidation of the steel bath. when the refining is completed and the desired composition of the bath has been obtained with respect to the elements subject to control by 'oxidation. there is usually an excess of oxygen present in the bath from the standpoint of the amount desired in the finished steel. The objectives of deoxidation are to control the amount and type of oxides and, although not directly ilnp1it.d by the term or always considered as a Part of the process, to control the amounts of gases such as hydrogen or nitrogen that will be present in the finished steel. There are other aspects to be consideretl in connection with deoxidizing procedures. In addition to the primary objectives of oxide and gas control. the composition of the steel is affected by the elements introduced during the deoxidizing process. Factors in furnace operations are likewise involved, such as slag composition, temperature control. arid heat time. .ill of these should be considered in establishing the most satisfactory deoxidizing procedure for each grade of steel. The purpose of this paper is to outline the objectives of deoxidation as related to steel characteristics, and to summarize the factors in furnace practice and the economic aspects to be considered in connection with deoxidation procedures. Objectives of Deoxidation The primary objectives of deoxidation are the formation and elimination of oxides. The amount of oxygen present in the bath prior to deoxidation is an important factor, since it is the basis of any deoxidation procedure. The oxygen content of the bath is primarily a function of the carbon content, although it is affected also by the temperature, the oxidation of the slag, and transient conditions within the furnace. The relation of oxygen to carbon in the bath is shown in Table I. Table I shows that under actual operating conditions, the amount of oxygen present in the bath is higher than the theoretical amount. This relation would be expected, since the bath is in a state of metastablc equilibrium during the period that the carbon is being eliminated. The most important feature demonstrated by this table, however, is the rapid increase

Jan 1, 1945

By John A. Putnam, Morrough P. O’Brien

DATA on the physical and thermodynamic properties of hydrocarbons have been made available in recent years but the formal method of applying these data to flow in porous media appears not to have been fully developed. By making usual thermodynamic assumptions and employing existing data on permeability to two-phase flow, Darcy's law may be applied to obtain the flow characteristics for representative combinations of flowing medium and geometry. The numerical examples presented herein are based on hydrocarbons for which complete physical and thermodynamic data are available under equilibrium conditions. INTRODUCTION Thermodynamic data are obtained in the laboratory under equilibrium conditions and their application requires the assumption that equilibrium also exists during flow. This assumption is at least usual in engineering analyses, though not easily justified in many instances, and will be followed here. In regard to hydrocarbons, laboratory experience in determining the pressure-volume-temperature relationships indicates that gas-liquid mixtures must often be stirred vigorously for periods of 15 to 20 min. before reaching equilibrium. On the other hand, boiling and condensation are known to occur on solid surfaces and the large surface exposed to the flowing substance by a porous medium may bring about rapid approach to equilibrium. For the purpose of providing at least a guide to experimentation and a standard for later comparison with experimental results, it will be assumed that the phases present in cross sections perpendicular to the direction of flow are in thermodynamic equilibrium. Another assumption usually made in the solution of problems of flow in porous media is that the fluid remains at a constant temperature; i.e., isothermal flow. This assumption is arrived at by considering the porous medium and surroundings to be an infinite heat source and the rate of heat flow to be infinite at a boiling front. Its validity depends in large measure upon the character of flow, the number of components, and the physical and thermodynamic properties of the fluid. However, the assumption of isothermal flow represents a limiting case. The other limit can be represented by the assumption that the fluid is thermally isolated; i.e., irreversible adiabatic. The thermodynamic process characterizing the actual flow of a given fluid system probably lies somewhere between these two limiting cases and might be thought of as a flow system in which the confining walls are maintained at a constant temperature. For isothermal flow the solid material of the porous media is considered as the infinite heat source capable, without loss in temperature, of giving up heat to the fluid as the latter tends to cool by expansion. For the thermally isolated system, the solid material is considered to give up no heat to the fluid. In the intermediate case the impervious walls confining the porous media are at constant temperature from which heat is transferred along various paths, solid and fluid, throughout the porous media. It would appear that an actual petroleum-

Jan 1, 1941

By AIME

To be born in the East, reared and educated in the West, to do graduate work in Germany, leading to the doctorate in metallurgy, and to wind up-for the time being at least-in the Middle West as head of one of the outstanding mining and engineering schools of the country, is a unique career. Curtis Laws Wilson, dean (and in most respects, president) of Missouri School of Mines and Metallurgy at Rolla, is a native of Baltimore. He came to Anaconda in 1918 and in due course was graduated from Montana School of Mines, with an exceptional record. In 1921, after experience in metallurgical research at Anaconda, he became instructor in metallurgy at his alma mater. Because of his ability as a teacher, he rose rapidly to head of the department after special work at Columbia in 1923-24. In 1927, Wilson was granted leave of absence to study physical metallurgy under the great Tammen at Goettingen, and returned with his doctorate to his work at Montana School of Mines. His major metallurgical interest was then in age-hardening of copper alloys. Also after his return to Montana Mines, Wilson started

Jan 1, 1948

By M. G. Corson

UNTIL recently, the characteristics of cast copper have seldom been studied and such study as has been made has been inadequate. The prevailing idea seems to be that since pure copper is infrequently used in the cast state, there is no reason for trying to establish precise data regard-ing the properties of the metal in that condition. On the other hand, wrought copper either in the shape of sheets or wire rarely fails in service, except as a result of the action of reducing gases at the annealing tempera-tures, so there is little incentive to study the properties of the cast shapes -cakes, bars, ingots and billets-for-the sake of tracing the causes of failures of the wrought metal to the cast stock. However, about a decade ago, wirebars of American origin often cracked badly while being hot-rolled in mills in Germany. This led to four investigations: by E. Seidl and E. Schiebold,1 by P. Siebe,2 by O. Bauer and G. Sachs,3 and by G. Welter.4 These authors came to the conclusion that failures in hot-rolling were due essentially to the presence .of a wide zone of columnar crystals between the thin layer of fine crystals near the surfaces of the bars and the large but more nearly equiaxed grains of the central core. This macrostructural defect was explained in turn by the probable upward deviation in the temperature of the metal while it was being poured into the molds of the casting machine. More recently, cast shapes of copper were investigated by N. P. Allen5 and by C. Blazey.6 Allen examined vertically cast wirebars and hori-zontally cast wedge cakes of electrolytic tough-pitch copper, but only for the distribution of densities; i.e., porosity. Blazey was interested mainly in the mechanism of the variations in electrical conductivity clue to cold-work and anneal, but gave introductively an account of the composi-tion and average densities of the tough-pitch horizontally cast wirebars used. As far as the present writer can tell, no investigation was under-taken for the sake of presenting a picture of the distribution of mechanical characteristics in the wirebars of copper, tough-pitch or otherwise.

Jan 1, 1938

By D. G. Westlake, D. T. Peterson

The saturation solubility of thorium dihydride in thorium was studied by saturation of samples and subsequent analysis. The solubility increased from about 1 at. pct at 300°C to above 20 at. pct at 800 °C. Over this temperature range the log of the solubility was a linear function of the reciprocal absolute temperature for thorium of good purity. The heat of solution of thorium dihydride was found to be 7.9 kcal per atom of hydrogen in crystal bar thorium and 6.6 kcal per atom of hydrogen in Ames thorium, The important effect of hydrogen on the physical and mechanical properties of many metals is receiving increasing recognition. The basic physical and chemical data necessary to help explain the observed effects of hydrogen on the mechanical proper ties of metals are all too often not available. The solubility of hydrogen in thorium metal was determined to provide a portion of this basic data for the thorium-hydrogen system. The absorption of hydrogen by thorium metal and the formation of thorium hydrides was studied by several investigators, beginning in 1891, and their work is summarized in Gmelin's Handbuch.1 No effort was made to determine the extent of solid solubility in the metal in these early investigations and the impure metal available made interpretation of the results uncertain. Nottorf2 reported the results of a careful study of pressure-composition isotherms for the thorium-hydrogen system. The principal interest in this work was in the composition and dissociation pressures of the thorium hydrides. Mallett and campbel13 reported the pressure-composition isotherms for the thorium-hydrogen system up to the composition of thorium dihydride. The saturation solubility of thorium dihydride in thorium was reported to be 13 at. pct at 650°C and 23 at. pct at about 900° C. Mallett and Campbell used thorium metal which had been prepared by the calcium reduction of thorium tetra-fluoride or thorium oxide. The results obtained with thorium of these two types agreed within the experimental error. PROCEDURE AND MATERIALS Procedure—The method used to determine the solubility was to saturate a sample of thorium with hydrogen and analyze a portion of the saturated sample. This method was chosen rather than a determination of pressure-composition isotherms since it was much less time consuming and could be applied at temperatures at which the equilibrium hydrogen pressure was too low to measure. The

Jan 1, 1960

By J. S. Bryner

In the study of metallographic specimens in the electron microscope, there is need for a method of locating the same field in both the light microscope and the electron microscope. This need arises chiefly from the fact that in the electron microscope the magnification and degree of resolution are so much higher, and the field so much smaller than in the light rnicroscope that it is often difficult, if not impossible, to identify positively what is being observed. The difficulty is increased by the fact that, because a transparent film replica of the metal surface must be used in the electron microscope, micro-constituents can be identified not by their color but only by their texture and contours. For these reasons it is desirable to obtain a series of photographs showing the same field in both microscopes in order that the appearance of common microstructures and micro-constituents in the electron microscope may be identified and catalogued for future reference. The need for a method of locating the same field in both microscopes arises also when it becomes desirable to enlarge in the electron microscope for more detailed study a particular interesting structure observed in the light microscope. Using the standard polystyrene-silicalJ replica technique, in which the silica film replica is fished from the ethyl bromide on a 1/8 in. diam zoo-mesh specimen screen, the possibilities of locating a particular area on the film in the electron microscope are rather remote. The desired structure may be obscured by the wires of the specimen screen or unrecognizable at the high magnification. A solution to the problem would be provided if a specially designed specimen screen, containing an opening which could be absolutely identified and quickly located in the electron microscope, could be fastened to the silica film replica in such a position that the desired field on the specimen would be located at the identifiable opening in the specimen screen. The design for such a specimen screen, a method for producing it, and a technique for fastening it to the silica film replica are described below. Description OF Method The Specimen Screen A simple design for a specimen screen containing an opening easy to identify and locate in the electron microscope is one with two lines of openings at right angles in the form of a cross. Such a screen is shown in Fig I. The opening at the center of the cross is identified easily and can be located quickly in the light microscope and in the objective image of the electron microscope. The specially designed specimen screens for this work were produced in quantity by electroforming. On both sides of a polished strip of copper I X 3 X 1/8 in., twenty patterns of the cross of openings were punched with a diamond point micro-hardness tester, using a load of magnitude

Jan 1, 1949

By M. H. Pilkuhn, H. Rupprecht

p layers on n-type substrates of GaAs were prepared by difhsion of zinc into these substrates. Experimental details about the diffusion technique will be presented. It will be shown that inhomogeneity in the substrate doping level and crystal shucture defects cause nonplanarity in the junction plane. These nonplanarities give rise to high threshold current densities. From incremental sheet-conductivity measurements the zinc profile is derived. Data about surface concentration and gradient of the zinc concentration at the junction are presented. Finally, some results of laser diodes, which were made of wafers with extremely planar diffusion fronts, are discussed. ThE investigations reported here are part of a program concerned with the materials aspect in the fabrication of GaAs laser diodes. This includes studies of the influence of crystal defects introduced both during the growth of the crystal and as a consequence of subsequent diffusion. Compared with the progress made in the investigation of structure defects, for instance by X-ray microscopy in materials like silicon, no similar results are known so far for the case of GaAs. The further progress in laser diodes will depend very much upon our knowledge of these structure defects and subsequently upon our ability to avoid them. Laser diodes of GaAs had been made mostly by diffusing an acceptor impurity, normally zinc, into an n-type substrate. This procedure was found more convenient than the inverse one for various technical reasons. We will follow this line and restrict ourselves to zinc diffusion only in this paper. DIFFUSION TECHNIQUES AND EXPERIMENTAL DETAIL In order to set a refgrence for our experiments, we used a standard procedure for the diffusion runs. The diffusions were carried out in a sealed quartz tube for 2-1/2 hr at 850°C. One milligram zinc arsenide (ZnAsz) per cu cm of the tube volume served as zinc source. Under these conditions the junction depth was between 25 and 30 p. It is assumed, according to the investigations of the zinc arsenide system by V. Lyons and V. ilvestri,' that ZnAs2 dissociates completely at 850°C into ZnsAsz and Asg. Since there is a condensed phase of ZnsAs2 in the tube at 850°C, the partial pressure of zinc is controlled by the pressure of the arsenic formed by the dissociation of ZnAs2. Due to the fact that the zinc partial pressure resulting from the dissociation of ZnsAsz is only a weak function of the partial pressure of arsenic, the amount of the initial ZnAs2 is not very critical. Experimentally, we found that the junction depth, as well as the surface concentration, was practically the same, if the ingots of ZnAs2 varied between 0.2 and 5.0 mg per cu cm. The wafers were oriented with the main faces in (100). Surface damage due to cutting and lapping was removed by a chemical-etch treatment in a rotating beaker (etch solution: HzSOr, H202, and HzO in a ratio 3:l:l). The GaAs substrate material was n type and doped with tellurium, selenium, silicon, or germanium. It was grown by means of horizontal or Czochralski techniques. After the diffusion process, junction depth and planarity were checked either by grooving with a

Jan 1, 1964

By Michael J. Messel

THE critical shortage of asbestos fiber in the world today brings to the foreground the question of locating and developing new deposits. The object of this paper is to discuss some of the more important factors which should be considered in the examination and valuation of a new asbestos enterprise. Some of the more important uses of asbestos fiber are for textiles, heat insulators, building materials, filters and a series of other uses. The properties of this mineral, such as fibrous structure, color, strength, silkiness and flexibility, coupled with resistance to fire, certain chemical action and decay make its application unique for certain industrial uses which consume over 500,000 tons annually. These same unique properties which make this mineral so valuable also make a deposit one of the most difficult to appraise accurately, because of the many undeterminable and varying factors which must be considered before a deposit can properly be termed commercial. The majority of the asbestos fiber today, having the above mentioned properties, is sold by grades which are based on fiber length. Present day fiber prices vary over a wide range from $800 to $225 for crude fibers and $300 to $20.00 per ton for milled grades. For valuation purposes a careful study should be made of existing fiber prices and markets. EXAMINATION OF DEPOSITS In carrying out prospecting and examination of a deposit, considerable caution is required to get the necessary information in the form that will have the most value for the final determination. There are two main classes of asbestos fibers, chrysotile and the amphiboles, the chrysotile being, by far, the most important both in abundance and uses. This paper will stress mainly chrysotile deposits, however, the amphiboles have many important uses, especially amosite and crocidalite. Their valuation presents special problems as other factors may be involved, especially as they are not graded according to any well defined and adopted standard but usually according to the use for which they are being supplied. Most chrysotile deposits occur in two main types of rock, (I) mainly in basic igneous, such as dunite and peridotite, (2) to a lesser extent in sedimentary rocks, such as dolomite and limestone. All of these require a certain degree of metamorphism to be favorable to asbestos formation. Approximately 90 pct of the asbestos deposits are derived from serpentinization of dunite or peridotite, whereby the magnesiumsilicate olivine was altered to hydrous magnesium-silicate serpentine. Under certain favorable geological conditions, this serpentine takes a fibrous form having a definite crystal structure, probably due to molecular rearrangement, and is known as chrysotile. The fiber veins are usually ir-

Jan 1, 1947

By A. A. Bauer, H. A. Saller, F. A. Rough, J. R. Doig

among uranium alloy systems are the U-Zr, U-Ti,and U-Mo binary systems, in that an intermediate phase, of limited solubility range, exists in each system. These intermediate phase alloys offer a promising field of investigation, both as binary alloys and as ternary alloy combinations. While a limited amount of work has been done on the binary alloys, none has been done on ternary combinations of these alloys. As a possible prelude to more intensive investigation of these systems, a study of the phase relationships between the 6 phases of the U-Zr and U-Ti systems was undertaken. The solid-state portions of the binary constitutional diagrams for the U-Ti,1 Zr-Ti,2 and U-Zr3 systems are shown in Fig. 1. The solid to liquid transformations are not shown, as these transformations were not studied in the ternary system. The phase designations employed are based upon those shown in the uranium constitutional diagrams. The crystal structures of the various phases are given in Table I. Experimental Materials and Methods The ternary section presented is based upon the results of thermal, metallographic, and X-ray analyses of a series of alloys ranging in composition between the phases of the U-Zr and U-Ti systems (U-74 atomic pct Zr to U-35 atomic pct Ti). After preparation of the alloys, thermal data were obtained. On the basis of these data, specimens were heat treated and examined metallographically. Specimens were then selected from those heat treated for X-ray determination of the phases present in what were considered critical phase regions. Alloy and Specimen Preparation—Alloys for this investigation were prepared from selected as-reduced uranium and crystal-bar zirconium and titanium. For nominal compositions, see Table 11. Charges were arc melted from five to seven times under a helium atmosphere, finally being cast into wire-bar form for fabrication. A zirconium getter button was used to clean the furnace atmosphere prior to melting. The alloys were homogenized 20 hr at 900 °C and furnace cooled. A portion of each bar was then removed for thermal analysis; the remainder was saved for fabrication. Alloys 8 through 14 were placed in steel tubes along with zirconium getter chips and, after flushing with argon, the tubes were welded shut and rolled at 1500 °F to a 50 pct reduction in diam. The remaining alloys were annealed 24 hr at ll00°F to insure transformation of the ? phase to the 8-U2Ti phase and were then hot rolled from a salt bath. Attempts to roll alloys 6 and 7 at 1100 °F were unsuccessful. Following this, attempts were made to roll pieces of alloys 1 through 5, which had cracked rather severely during casting, at 1200 °F, but these efforts were also unsuccessful. These alloys were, therefore, further treated in their cast and homogenized condition. All alloys were pickled to remove oxide formed during rolling. Thermal data were obtained on these alloys by conventional differential thermal analysis at a heating rate of 30C per min, and by a high-speed heating method at rates of approximately 10°C per sec. For the latter method of analysis, a 36-gage Chromel-Alumel thermocouple is spot welded between two slivers of alloy, the sandwich being en-

Jan 1, 1958

By J. Gurland

The strength variation ofWC-Co alloys with composition and particle spacing falls into two ranges. 1) Above a critical value of the mean free path, the strength follows a dispersion hardening relation; it is proportional to the volume fraction of WC and in-versely proportional to the particle size. 2) Below a critical value of the mean free path, the strength variation is based upon the Griffith criterion of fracture and is controlled by the case of crack propagation. The maximum strength is attained when the structure and load just satisfy the critical conditions for spontaneous crack propagation. THE relation between the strength and the structure of cemented carbides is of interest not only for its own sake but also for its contribution to the understanding of composite materials in general. The cemented carbides are essentially aggregates of a brittle carbide constituent and a ductile binder phase and, at certain structures of intermediate composition, the composite alloys attain strengths far higher than those of the separate constituents in bulk. It is this variation of strength with structure which will be discussed. The experimental procedures of sample preparation, mechanical testing, and quantitative metallo-graphic analysis have been described in Ref. 1. The reported strengths are the maximum fiber-stresses in bending calculated on the basis of completely elastic behavior. The plastic contribution to the over-all deformation is small and was neglected in the calculations (the elongation at fracture of the most ductile alloy, 50 pct WC-50 pct Co, is less than 0.5 pct).2 The pertinent structural parameters are: f, the volume fraction of tungsten carbide; p, the mean free path through the binder phase; the contiguity C, defined as the average fraction of surface area shared by a particle of wc with all neighboring particles of the same phase; and d, the average equivalent spherical diameter of the WC particles. The strength variation of WC-Co alloys with composition and particle spacing is shown in Fig. 1 and Table I, which are based partly on previously published data' and partly on new experimental work which extends the range to higher values of the mean free path. Each data point represents the average of five samples. For a given composition, the transverse rupture strength reaches a maximum

Jan 1, 1963

By R. V. Lundquist

Leaching manganese-bearing materials with NaOH to remove caustic-soluble silica has been demonstrated as a method for upgrading manganese. Those materials containing opaline varieties of silica respond most readily. Spent leach liquors are regenerated by treatment with lime to precipitate calcium silicate and to reactivate the NaOH for leaching. ALL of our larger domestic deposits of manganese are very low grade, but estimated tonnages in these deposits are large enough to constitute a potential strategic reserve of manganese for emergency periods, provided these ores can be upgraded sufficiently to meet industrial specifications. Many types of processes have been suggested for upgrading these ores, several have been studied in pilot plants, and a few have attained limited commercial production for special purposes. The hydrometallurgical process to be described below proposes a leaching operation for removing caustic-soluble silica and other gangue minerals and consequently upgrading a manganese ore or flotation concentrate to a commercially acceptable moduct. It is known that some forms of silica and some silicate minerals are soluble in NaOH solutions under suitable conditions. This new process proposes to use NaOH for removing the soluble materials from manganese ores or concentrates and, as a result, upgrade the manganese content. Since spent leach liquors are not efficient leaching agents the liquor must be treated with lime to precipitate calcium silicate and reactivate the NaOH. Experimental Procedure Manganese-ore samples ground to —35 mesh were leached in iron containers into which the ore sample and appropriate NaOH solutions were placed. Flotation concentrates were already ground to —200 mesh. The slurries were then placed on a hot plate or into a pressure digester and stirred continuously during the period of digestion. Where the- digestion was performed at atmospheric pressures, water lost by evaporation was replaced at regular intervals to maintain approximately a constant volume of slurry. In the pressure digester, volume changes were not controlled. After digestion, the slurry was allowed to cool enough for easy handling, but it was filtered hot, 50" to 70°C, on a Buechner filter. Filtration under these conditions was satisfactory. The resulting filter cake was washed and dried. In most instances, a single leach would not produce maximum extraction of silica from the ore sample; consequently, the dried tailing was treated again in the same manner with a fresh solution of NaOH to obtain an additional extraction of silica. This procedure was repeated a number of times to get the maximum extraction of silica. Usually three or at most four stages of leaching were adequate for this purpose. This leaching procedure was used for obtaining the data reported in this paper on the effects of NaOH concentration, pulp dilution, temperature, and time of digestion on the efficiency of extraction of silica from the ore sample. The experimental procedure does not match industrial methods. consequently tests for counter-current leaching were set up. Data from these tests are not yet complete, but in a qualitative way they indicate that thickeners between stages of leaching will be satisfactory and that the quantity of silica in a leach liquor moving forward to a new solid has only a minor effect on the quantity of silica extracted from the new solid. A pilot plant is now being designed for operation in the near future to test and evaluate the merits of this process.

Jan 1, 1954

By R. E. Miner, J. K. Jackson, T. L. Wilson

THE nature of the decomposition reactions producing hardening in aluminum-rich A1-Ag alloys is now fairly well understood. The silver is not uniformly dispersed even at temperatures above the solvus line: rather, it is clustered into zones and associated with dislocations.' During quenching, nearly all of the silver segregates into zones' and some is attracted to dislocations, producing stacking faults. Growth of these faults produces the semicoherent y precipitate.1 During aging, the larger zones and the y precipitates grow at the expense of the smaller zones. The large zones persist up to about 350°C; where they redissolve in favor of the y' and y precipitates.' The equilibrium hcp y precipitate occurs both by a cellular reaction at the grain boundaries1 and by growth of the Y' plates to a critical size where incoherency results. Damask and Nowick 4 observed an internal friction peak in an A1-6 at. pct Ag alloy at about 140°C (0.25 cps). The peak was found to exhibit a systematic instability. After aging at successively higher temperatures between 155' and 23Z°C, the peak first migrated to higher temperatures while increasing in height, then returned to lower temperatures and decreased in height. After aging at temperatures above about 200°C, the peak position remained constant while the height decreased very slowly. In quenched specimens, elastic after-effect measurements inhcated a rapid initial transient in peak position from low temperatures up to 155°C. The authors concluded that a stress induced growth and resolution of the clusters and the 7' was the most reasonable mechanism to account for the behavior. It would seem, however, very unlikely that both the clusters and the y' precipitate would provide damping contributions whose relaxation time and activation energies were identical, which is required for them to produce the same internal friction peak. The present investigation was motivated by this apparent anomaly and the development of a very low thermal inertia torsion pendulum5 capable of monitoring transient behavior. Low frequency internal friction measurements were made on four binary A1-Ag alloys nominally containing 5, 10: 15, and 20 at. pct Ag. The results of measurements made on a 10 at. pct Ag alloy in the quenched condition are shown in Fig. 1. There are two peaks apparent in the spectrum, one centered at about 160°C, the second at about 210°C. The two peak spectrum was observed in each alloy, but it was best resolved in the 10 pct Ag specimens. Because of the instability in the internal friction, 4 it seemed possible that the second peak was not a peak at all, but simply a manifestation of a single, sharply transient, peak. This effect has been observed in Au-Ni alloys.6 The existence of the higher tempera-

Jan 1, 1970

By B. H. Kear

All the possible ways of forming simple two-dislocation boundaries in multiple slip orientations are deduced. It is shown that the principal differences in work hardening behavior of crystals plastically deformed in these orientations can he accounted for in terms of the likelihood of formation of diffuse boundaries, or deformation bands, consisting of the products of dislocation reactions of the Lomer type. Also, it is pointed out that the break-up of boundaries under the applied stress is more likely to yield interstitial jogs than vacancy jogs, whereas glide dislocations cutting throuqh dislocations trapped in particularly stable boundam'es can acquire both types of jogs. USING Frank's' grain boundary formula, Ball and Hirsch2 determined the parameters of all the possible boundaries that can be built from two sets of glide dislocations in the fee structure. This paper deduces the geometrical possibilities for the formation of these two-dislocation boundaries in the different multiple slip orientations, and discusses the role of boundaries in work hardening and in jog formation. Formation of Two-Dislocation Boundaries in Mutiple Slip Orientations. The parameters of the possible two-dislocation boundaries for any crystal orientation can be deduced most conveniently using the boundary formulae due to Amelinckx,3 in conjunction with the stereographic projection shown in Fig. 1. Suppose that slip occurs in a-BC and ß-CA. According to Amelinckx, when the two systems of glide dislocations are parallel, the rotation axis, u, of the boundary is parallel to (a x ß) and the unit normal, u, defining the boundary plane is parallel to (a x ß) x (BC x CA). On the other hand, when the glide dislocations form a crossed grid, u is parallel to (BC x CA) and u is parallel to (a x CA) x (ß x BC). In Fig. 1, (a x ß) is the pole of the great circle passing through a and ß, so that u is parallel to DC, i.e., parallel to [110]. Furthermore, (a x ß) x (BC x CA) is the pole of the great circle passing through DC and 6, so that u is parallel to [110]. Hence, when all the glide dislocations are parallel, the boundary is pure tilt with parameters u = [110], v = [ 110]. Similarly, it may be shown that the corresponding crossed grid of dislocations is a mixed boundary with u = [111], u = [111]. Consider the case of a crystal compressed in the [001] orientation. In this orientation, according to Fig. 1, there are eight available slip systems. In what follows, the different types of two-dislocation boundaries that are possible in this orientation will be examined by taking different combinations of two slip systems out of the available eight, with a-BC always one of the systems. Case (i)—Slip Systems a-BC and d-CB. The formation of a tilt boundary in (101), which consists of a crossed grid of edge dislocations with vectors BC andCB, is illustrated in Fig. 2(a). As the figure shows, slip is required in the system a-BC in one part of the crystal and in d-CB in the other part, with both sets of dislocations entering the boundary from opposite sides. The rotation axis of the boundary lies in (101), depending on the relative densities of the two sets of edge dislocations in the boundary. Case (ii)-Slip Systems a-BC and ß-CA. The two possible boundaries are shown in Figs. 2(b) and (c); boundary (b) is tilt with u = [110], u = [110], and

Jan 1, 1962

By A. M. Gaudin, D. W. Fuerstenau

IN concentration of certain ores by soap flotation, prevention of quartz flotation is desired; the contrary is true in treatment of some oxide iron ores. Experimental study of the flotation of quartz goes back at least a quarter of a century.' Clean quartz does not float with fatty acids or soaps but does float when activated by one of many metallic salts. Control of pH is important. Broadly speaking the problem of quartz flotation has been approached from the empirical side, as was the related topic of flocculation or dispersion of quartz suspensions? Empirical studies indicated the existence of critical relationships between the additions of collector and activator. These additions were not stoichiometric for the formation of soaps of the activator cation. For example, Gaudin and Rizo-Patrona found optimum quartz flotation at pH 10.6 using barium activation and oleate collection when the molar ratio of oleate to barium was 1 to 1 instead of 2 to 1, as would be called for formation of Ba(OL),. Cooke and Digre" ' found that if calcium is the activator, a minimum quantity of that agent is required for effective flotation when the pH is 11.5. In other words, if the concentration of Na' exceeds 10 -2.5 mols per liter or if the concentration of H exceeds 10-11 mols per liter, the concentration of Ca++ in solution required for quartz activation is increased. This suggests that H+ is much more effective than Na+ on 10-2.5 quartz, perhaps in the ratio ofp or 108. Schuh- mann and Prakash6 studied anew the activation of quartz by barium, calcium, aluminum, and ferric iron. Salts of these metals are activators provided they are in stoichiometric excess over the collector used with them. Alkaline-earth salts are effective only in alkaline circuits. Important as they are in giving data on the effect of various agents on quartz, all these studies fail to give information on the detailed structure of the quartz-solution interface. A beginning in this direction was made by Gaudin and Chang,? who measured the adsorption of radioactively marked barium and laurate ions at quartz surfaces, and by Gaudin. Spedden, and Laxen,8 ho measured the adsorption of radioactively marked sodium at quartz surfaces. Work has also been done by Bell0 n measurement of the adsorption of sodium ion and chloride ion at quartz-solution interfaces. In all these experimental measurements of adsorption, the solid was centrifuged or filtered from the bulk of the liquor with which it had been associated; and the composition of the solid surface was ascertained by analysis, after allowance was made for the ionic composition of the liquor included with the centrifuged solids on the assumption that it is identical to the bulk liquid. Adsorption measurements give only the total amount of collector adsorbed at the quartz-solution interface; they give no indication of the distribution of these adsorbed ions at the interfacial layer. It is the ionic structure of the solid-solution interface and its importance to flotation that is the subject of this paper. The structure of this interfacial layer can be investigated by means of electrokinetic methods so that by combining electrokinetic studies with adsorption measurements, a more complete picture of the quartz surface may be obtained. The following studies were made to ascertain how electrolytes used in the soap flotation

Jan 1, 1956

By B. F. Oliver

A levitation zone melter is described which has the necessary characteristics for processing metals of controlled purity. No crucible is required; control of the solidification variables is stable; the environment of the charge is chenzically controlled. Rotation of the solidifying interface and mixing in the liquid by the magnetohydrodynamic stirring produce an eight-fold increase in freezing velocity over former melting units with better resulting solute redistributions. The smooth appearance of processed specimens, resistivity ratios as a hnction of position, as well as a segregation curve, are presented as evidence of smooth continuous solute fransport over distances in excess of ten zone lengths. THE difficulties of the floating zone-purification of higher density metals in large quantities under conditions of lowered surface tension are well known and have hindered fundamental research programs for some time. The inordinate amount of time required to obtain a small reproducible yield of high-quality metal has excluded the use of such material for many important material research programs. However, with the use of controllable induction levitation forces' to accomplish stable liquid zones with nearly flat solidifying interfaces, and with good physical and chemical control of the processes involved, these difficulties can be overcome. A zone melter that is to be used for both high-purity and controlled composition work in metal systems must have the following three characteristics: 1) The process must avoid the use of containers. 2) Physical control of the solid-liquid interface and of the mixing within the liquid phase must be stable. 3) The chemical environment of the melt chamber must be controllable. A description of an apparatus that accomplishes these objectives follows.* APPARATUS One of the basic features that is necessary for good process control of large sections is that the charge, the coil, and the motion mechanisms be within the same chamber. This arrangement permits a close coupling between the work coil and the load, which then provides a good flexibility for adjustments of coil dimensions, for controlling the amount of levitation needed for stable operation at a given power level. An overall view of the melter is shown, with the melt-chamber door open, in Fig. 1. The radiation shields surrounding the single-turn induction coil are of water-cooled copper. The chamber is stainless steel, as are most of the components within the chamber. The control panel for the scanner is located at the immediate lower right of the melt chamber. This panel controls the operation of the scanner. The operations controlled are the interface rotation rate, the stretch-squeeze or diameter control, the up and down scanning speeds, and the induction power. All of the drive motors are constant-torque variable-speed motors. The scanning speeds are set with precision helipots and continuously observed with the voltmeter on the control panel and checked with a mechanical indicator within the melt chamber. The rotation rate is also set with a precision helipot. The up-scanning speeds are 2 to 300 in. per hr.

Jan 1, 1963

Jan 1, 1915

By C. Edward Capes

Fine particles in liquid suspension can be agglomerated by a number of mechanisms. Well-known methods include the addition of electrolyte to reduce the zeta potential and allow mutual adhesion arid the use of polymeric flocculants to bridge between the particles. A more recent technique, "spherical Agglomeration", is the subject of this paper. The process involves the addition of a second liquid which is immiscible with the suspending liquid and preferentially wets the particles to cause particle adhesion by capillary liquid bridges. Progress in the application of spherical agglomeration to a number of distinct technological fields is reviewed in this paper. The areas of interest include the formation of dense, highly spherical agglomerates, the separation of solids from suspension and the fractionation of complex, multi-component solids mixtures, such as ores. Some of the more interesting recent applications in the energy and environmental fields, such as the beneficiation of' coal and tar sands, are highlighted.

Jan 1, 1977

By William D. Klopp, Joseph R. Stephens

ThE phenomenon of high ductility associated with a phase transformation, termed super plasticity, has been reported for a number of alloy systems. Abnormally high ductility has been observed during tensile testing of cast eutectic alloys of Pb-Sn and Mg-cu.1 Brasses of Cu-37 at. pct Zn and Cu-40 at. pct Zn elongate up to 180 pct when tested near their transformation temperature.' Enhanced ductility was also observed in Cu-47 at. pct Zn tested near the order-disorder transformation temperature. The most remarkable super-plastic effect reported to date is for the eutectoid alloy A1-60 at. pct Zn, where elongations up to 1000 pct have been reported.3 underwood4 has recently summarized the conditions that normally accompany the superplastic effect which are: 1) a phase transformation or allotropic change or order-disorder transformation; 2) an externally applied stress; 3) presence of an interface between two phases; and 4) a metastable structural condition. In addition, higher ductility is observed when the specimen is tested at slow deformation rates rather than under impact. The purpose of this note is to present evidence of the superplastic effect in a Cr-30 at. pct Co alloy. In addition, low-temperature bend ductility data are given for the alloy in the quenched, metastable, single-phased condition and in the slow-cooled, two-phased, near-equilibrium condition. Sixty-gram alloy ingots were prepared by noncon-sumable arc melting of iodide chromium and electron-beam-melted cobalt. These were cast into rectangular ingots and fabricated to 0.035-in. sheet by rolling at 2300°F. Attempts to roll at slightly lower temperatures invariably resulted in severe cracking, apparently due to presence of the brittle a phase below the transformation temperature of 2230°F. Tensile specimens with a 0.25 by 1.0 in. reduced section were cut from the sheet by electrical discharge machining. The specimens were heated at 2400°F for 1/2 hr to obtain a recrystallized, bcc, single-phased structure. Temperature of the specimens was subsequently raised or lowered to the desired test temperature and held for 10 min prior to testing at a crosshead speed of 0.01 in. per min. Fig. 1 shows the chromium-rich side of the Cr-Co phase diagram.6 The alloy composition investigated is near the point of maximum solubility of cobalt in chromium, and the alloy is two-phased when in equilibrium at temperatures below 2230°F. The results of tensile tests conducted at temperatures indicated by X's in Fig. 1 are summarized in Figs. 2, 3, and 4. Tensile elongations shown in Fig. 2 increase from 11 pct at 1900°F to a maximum of 160 pct at 2250°F. The elongation then decreases to 44 pct as the test temperature is further increased to 2600°F. The proximity of the temperature of highest elongation and the solvus temperature suggests that a superplastic effect is present in Cr + 30 at. pct Co similar to that observed for other alloys that show anomalous ductility. The variation of upper yield stress with temperature is shown in Fig. 3. A small peak in yield stress occurs at 2250"F, coincident with the maximum in

Jan 1, 1967

By Warren J. Jackson, John L. P. Campbell

Automatic recording of the radioactivity of the earth's formations provides a log of relative intensities that, if properly interpreted, can be applied to oil-field engineering. Production, engineering, and geological departments regard the radioactivity log as a forward step in the securing of more conclusive information for successful well completions. Explanations of the technique, together with some of the problems to which radioactivity logging have been applied, are presented in this paper. Introduction Those responsible for the completion of new oil and gas wells, or with planning workover operations on old wells, have followed closely the development of radioactivity well logging because they are interested in reducing the number of unknowns that usually are present in such work. Many operators have made use of the log, or are acquainted with at least one of the applications, but it is unlikely that any one operator is familiar with all of the many applications that are possible. The purpose of this paper is to present a representative example of each of the many applications, wherever the information has been released by an operator, and to illustrate by hypothetical examples other applications, releases for which have not been given. In this way, it is hoped that a better understanding of the scope of this new engineering tool may be obtained. Athough the literature contains many references that describe in detail the theory, development, and application of radioactivity well logging, a brief discussion of the technique may be helpful to those who are investigating the subject for the first time, All rocks contain radioactive material in varying concentrations. In general, shales contain relatively more radioactive material than sandstones or limestones. These radioactive materials disintegrate with time into other materials of lower atomic weight, and in that process of disintegration the rocks are emitting many rays, the most penetrating of which is the gamma ray. The intensity of emission of the gamma ray is proportional to the quantities of radioactive materials present. A higher rate of emission would be observed, therefore, opposite a shale than opposite a sandstone or limestone. Since measurable intensities of gamma rays are capable of penetrating as many as five concentric strings of casing, and as the gamma-ray intensity is relative to the formations, the measurements of variations in gamma-ray intensities offer a means of identifying cased-off formations in their proper stratigraphic sequence. TEe Gamma-ray Curve The measurement of gamma-ray intensi ties is accomplished by means of an ioniza-tion chamber that consists of a heavy cylinder, about 3 ft. long, that contains two insulated electrodes and is Med with an inert gas under high pressure. Under normal conditions no current will flow through the gas when an electrical potential is set up between the electrodes, but when

Jan 1, 1946