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By D. F. Kelsall

The hydraulic cyclone, in simple or modified form, is finding increasing application in metallurgical processing. In this article, the author considers several aspects of conventional applications, less conventional applications and some potential uses of modified cyclones. Information concerning the mechanism of separation within a cyclone and the effect of the major variables is summarized. During the past twenty years, and especially in the last decade, hydraulic cyclones have found increasing application in metallurgical processing as classifiers and, under special circumstances, as thickeners. To a more limited extent cyclones have been used to extend heavy, or dense, medium separation into the finer size ranges, and several attempts have been made to separate dispersions of immiscible liquids with a view to use in the field of liquid-liquid extraction. A large proportion of published work reports incomplete data, applicable only to particular systems. The more useful papers, covering data of relatively wide significance, have been reviewed recently in considerable detail1,2 and no attempt will be made to cover the same material in the present paper. However, before considering several aspects of conventional application, less conventional applications and some potential uses of modified cyclones, it is considered pertinent to summarize information relating to the mechanism of separation within a cyclone and the effect of the major variables. LIQUID FLOW PATTERNS At any point within a simple cyclone the liquid velocity may be resolved into three components, i.e., the tangential or swirling velocity (v), the vertical velocity (w), and the radial velocity (u). The relative values of these components at selected positions within a typical cyclone have been established for water. 3 The extent to which similar flow patterns exist in systems of considerably higher viscosity, or apparent viscosity, operating under conditions of reasonable pressure drop, is not known with precision, but indirect evidence indicates that up to approximately five centipoise there is no marked change. Beneath the bottom of the vortex finder, envelopes of constant tangential velocity are cylinders coaxial with the cyclone, and, at any horizontal level, starting from near the conical wall, this component of velocity increases with decrease in radius (r) according to the relationship vrn = constant (where 0 < n < 1) This holds to regions near the center of the cyclone where v reaches a maximum value at a radius somewhat smaller than that of the inside wall of the vortex finder. At this point, the centrifugal acceleration, v2/r reaches a maximum value. As the radius is further decreased the tangential velocity decreases so that v = r. Above the bottom of the vortex finder there is a tendency for the first relationship to persist to near the outside wall of the vortex finder, until v reaches a maximum and then decreases rapidly as the wall is approached. The two most significant features of the vertical velocity distribution are an approximately conical Table I. List of Symbols v = liquid tangential velocity at any point in the cyclone w = liquid vertical velocity at any point in the cyclone u = liquid radial velocity at any point in the cyclone r = radius from cyclone axis to any point ? = half angle of conical portion of the cyclone ?= fluid viscosity d = particle diameter s = liquid specific gravity p = particle specific gravity d50 = the particle diameter which distributes 5090 to overflow, 50% to underflow e = overflow diameter, in. b = feed diameter, in. G = gpm of feed slurry

Jan 1, 1963

By Francis A. Thomson

IN reviewing mineral industry education a year ago, occasion was taken to congratulate the Institute in general and to felicitate the Education Di- vision in particular on "the most gratifying growth which is taking place in Institute consciousness in regard to its responsibility for the recruitment and adequate training of student personnel and for the successful bridging of the difficult gap between graduation and achievement of professional status." Continuation of this growth of interest throughout 1939 is a recognition of the validity of the splendid statement of George Otis Smith that the mining students of today are the ore reserve of the Institute for the future. In this connection one recalls the equally apt expression of another distinguished geologist, George M. Fowler, who, speaking of exploration for ore deposits, says, "The place to look for elephants is where elephants have been found."

Jan 1, 1940

By Gerald Edmunds

CASTINGS of pure metals and many alloys usually have a coarse-grained structure characterized by long columnar grains throughout the main body of the casting. Frequently, the surface exhibits finer, some-times nearly equiaxed grains, and such grains may also compose other parts of the casting. This paper deals primarily with determinations of the grain-orientation textures of the columnar and surface grains of polycrystalline zinc castings. It includes some results upon a cadmium casting and a magnesium casting. A hypothesis is devel-oped to account for the observations on columnar grains and to use as a basis for predicting orientations in other cast metals. A general description of the position of the columnar grains in castings is that their long axes are approximately parallel to the direction of the thermal gradient during crystallization. Thus, in cylindrical castings the columnar grain axes tend to be radial, and in large flat castings where most of the cooling is through one or both of the large mold surfaces they tend to be perpendicular to the mold surfaces. At the edges and corners the direction of heat flow and there-fore the position of the grains is more com-plex. Actually observation shows that even in castings made in flat molds the cooling seems to be somewhat irregular, since columnar grains tend to emanate from certain areas of the cooling surface, indicat-ing that thermal contact was better there than in neighboring areas.

Jan 1, 1940

By Leo H. Duriez, James V. Neuman

THE Bayard property of the united States Smelting Refining and Mining Company is in south central Grant County in southwestern New Mexico about fifteen miles east of Silver City and one mile west of Santa Rita. The present holdings cover a belt roughly one mile wide by ten miles long, lying west of, and adjacent to, the holdings of the American Smelting and Refining Co., Kennecott Copper Corp., Empire Zinc Co., and Peru Mining Co. The area extends from the village of Bayard on the south to a point three miles northeast of Fierro. The property is a part of the well-known Central mining district which has been New Mexico&apos;s leading copper-zinc producer for many years. The property is segregated into three sections, the Bullfrog, Hanover Bessemer, and the Shingle Canyon sections. Of these, the Bullfrog section covers the area between the towns of Bayard and Hanover and includes the Bullfrog No. 1, Bullfrog No. 2, Slate, Hobo,

Jan 1, 1948

By R. T. Hukki

The purpose of this paper is to present an analysis of the unit operation of grinding and the circulating load, of the unit operation of classification and the circulating load, and of the two superimposed into one operation to clarify the overall trend of events relating the circulating load to the capacity of the closed circuit grinding system, to the specific surface area of the final fine product, and to the energy consumption in the closed circuit grinding process. The capacity of the closed circuit is frequently, if not always, determined by the classifier, not by the mill." With these words a startling idea was expressed in 1934 by Dorr and Anable.1 Today, some 30 years later, grinding in closed circuit is universally accepted. The basic curve presenting the capacity factor versus circulating load by Dorr and Anable has obviously been so convincing that not a single authoritative investigation regarding its validity seems to have been conducted. The only major subject of discussion appears to have been the relative merits of the &apos;high&apos; and &apos;low&apos; circulating loads. It seems to be universally agreed that much still remains to be hoped for regarding sharpness of classification. BASIC CURVES FOR CONSTANT MILL LOADING Fig. 1 presents a series of basic curves for constant mill loadings in function of new feed rate and circulating load. The mill loading indicated by each curve is the sum of hourly tonnages of new feed and circulating load. For example, at point 0 where the new feed rate is 100 t/h and the circulating load 300%, or 300 t/h, the mill loading is 400 t/h. In closed circuit grinding, the new feed rate corresponds to the rate of finished classified material produced. Although at this stage the effect of classification is excluded in construction of the basic curves, the trend indicated by these curves is strongly in favor of closed circuit operation under relatively small circulating loads. A study of the curves reveals that, e.g., a mill operating under a load of 200 t/h at point P where the new feed rate is 50 t/h and the circulating load 300% will also operate under the same total load at point Q where the new feed rate is 100 t/h and the circulating load 100%. In other words, a reduction of circulating load from 300% to 100% would lead to doubling of the new feed rate and doubling of the rate of production of finished material, without a change in the total mill loading. The obvious question is, is it also possible by a reduction of the circulating load in a closed industrial grinding circuit to increase the production of finished classified material and, if so, how and to what extent? GRINDING TESTS BY DORR AND ANABLE In a series of open circuit grinding tests reported by Dorr and Anable1 limestone was ground at various feed rates in a 3-ft ball mill. The original data are reproduced in Table I. It can be seen that with the increased feed rate production of -65-mesh material increased and the energy consumption per unit weight of the -65-mesh product decreased in the reverse ratio. The data shown in Table I have been reproduced for our purposes in Table II for a scale corresponding to grinding in a large industrial mill. This reproduction

Jan 1, 1968

By R. L., Fullman

During the past year there have been a number of significant investigations that have furnished evidence on the driving forces governing grain growth and on the role played by boundary impurities. Thus Burke has shown that in high purity alpha brass the rate of grain growth in the earliest stages is approximately inversely proportional to the existing grain size. This relation agrees with one derived by Zener assuming that surface energy was the driving force in grain growth. Also in confirmation of the surface energy hypothesis, Burke found that growth virtually stopped when the grain boundaries or even only the grain corners were melted.

Jan 1, 1949

By Oliver Bowles

DELICATE PLANTS are now put to bed for the winter under glass-wool or rock-wool blankets. Thus arise new and unexpected uses for non-metallic materials and rocks and, at the same time, certain unique uses are fading out; for instance, the Italians have taken steps to bar the use of salt for money in Ethiopia. Novel sources of supply find a place in the record of recent achievements as exemplified in the migration of the frontiers of industrial mineral exploitation beyond the land area of the earth to include the ocean. Salt, of course, has been recovered from the sea for years but the treatment of enormous quantities of sea water for bromine has lately added to the importance of the ocean as a reservoir of mineral wealth. Increased use of non-metallic minerals in the commercial and economic life of the country is reflected in the wide scope and activity of the Industrial Minerals Division of the Institute. The outstanding recent achievement of the Division is the publication of a 955-page volume on industrial minerals and rocks, comprising 48 commodity chapters each written by an authority on the subject.

Jan 1, 1938

By V. Koump, T. F. Perzak, R. G. Olsson

The vate of dissolutioz of carbon in molten Fe-C alloys urns studied by votating- cylindrical g-vaphite sairlples in a stationary crucible containing the melt. The rate of dissolltion was determdined from the change in the bnth co)npositiorz. Alccss-tvansfev coeffi&apos;cients, calcilated with the assurlption that the inte)yacial liquid ulas saturated with carbon, were found to be in agreement with an existing Correlation fov mass transfer jroni votating cylinders. It is corzcllrded tlat, itz the wnge of- Reynolds&apos; numbers itzvestigated (790 to 18,000), the vate of dissolutio of carborz in Fe-C alloys is controlled by tile rate of carbon difirsion from the interface. The dissolution of carbon in molten Fe-C alloys has been the subject of a number of investigations. Most of these investigations have been inconclusive because of poorly defined experimental variables. Two of the more sophisticated studies are summarized below. Dahlke and Knacke&apos; studied the phenomenon by, in part, immersing graphite rods into 0.5 pct carbon-steel for different lengths of time. Since the experiments were conducted in air or in CO atmospheres, the melt was strongly agitated by gas evolution. It was concluded that the change in bath composition as a function of immersion time was in agreement with the assumption that the dissolution process was transport-controlled. The hydrodynamic conditions in these experiments, however, were not well-defined and gave no indication of the nature of the dissolution process at higher fluid velocities. In a recent study Shurygin and ruk investigated the dissolution of carbon in molten Fe-C, Fe-Si, Fe-P, and Fe-Ni alloys. Small graphite disks were rotated in a crucible containing molten alloys under such conditions that only the lower face of the disk was exposed to the melt. The results of this investigation indicate that, over the range of velocities (100 to 1000 rpm) and bulk liquid concentrations (0.7 to 4.5 wt pct C) considered, the dissolution of carbon in the iron alloys is limited by the diffusion of carbon from the interface to the bulk liquid (a transport mechanism). For the particular geometry used by these authors, exact analytical solutions of hydrodynamic and diffusion problems are aailable. Hence the experimental results obtained by Shurygin and Kryuk permit the evaluation of diffusion coefficients of carbon in the four systems investigated. In the present investigation a series of experiments were conducted in which the rate of dissolution of carbon in Fe-C alloys was measured under conditions which permitted wide variation of the fluid velocity and the carbon concentration of the bulk liquid. Graphite cylinders were rotated at different speeds in a stationary concentric crucible containing various molten Fe-C alloys. THEORETICAL DEVELOPMENT In general, the resistance to mass transfer from a solid interface to a turbulent liquid is assumed to reside in a laminar boundary layer adjacent to the interface. If it is also assumed that the diffusion coefficient is independent of concentration, the steady-state rate of dissolution for the case of arbitrary liquid and solid densities can be obtained from the integration of the equations of continuity. The derivation is similar to that used by Lommel and chalmers4 for the case of pl = ps. The solution, expressed in terms where N = rate of diffusion of the solute from the interface. Exact analytical solutions of the hydrodynamic equation for the boundary layer thickness are available for only a limited number of geometries. Consequently, a mass-transfer coefficient, k, is usually

Jan 1, 1967

By N. T. Cotman, C. H. Pickering, P. B. Crawford

A beat-conduction model has been developed to study the flow of fluids in a stratified oil reservoir which is being subjected to unsteady-state depletion. To simulate stratification, plates of different metals were joined together so that cross flow could occur between strata. A description of the model, plate construction and necessary instruments is included. The data indicate that stratified oil reservoirs experiencing cross flow may be treated as a single, homogeneous, producing sand having properties intermediate between those of the layers making up the system. A technique for averaging core-analysis data to arrive at the proper average value of rock permeability and porosity is presented INTRODUCTION Although oil has been produced from reservoirs for 100 years and reservoir injection processes have been undertaken for 40 years, the industry is still inadequately informed on the problem of reservoir inhomogeneities. Stratification is perhaps the best-known type of reservoir heterogeneity. Urenl discussed the possible significance of this nonuniformity in his 1927 paper on the theoretical aspects of water flooding. Since this time the problem of vertical permeability variations has been the subject of much discussion and numerous papers. Levorsen2 simply describes the origin of layered beds in his Geology of Petroleum. Some beds are field-wide and may be traced from well to well, while others apparently pinch-out and become discontinuous. In addition, the physical characteristics of a layer may vary from place to place. For these reasons, a stratified system is not easily defined. In calculations involving oil reservoirs in which permeabi1ities vary, methods presently used contain many simplifying assumptions. The reservoir frequently is considered as consisting of permeable layers, each of uniform vertical and lateral permeability and each behaving as if separated from adjacent layers by thin impermeable layers. Other assumptions frequently made in reservoir calculations are steady-state flow conditions, unit mobility ratio, linear geometry, average or homogeneous porosity, and negligible capillary-pressure and gravity effects. Muskat3 has. developed solutions to the stratification problem for mobility ratios other than unity for both linear and exponential permeability distributions. He assumes lateral uniformity and continuity of all productive strata and does not consider porosity. This study will take into account transient effects, cross flow and varying porosity, as well as the variations in permeability, by means of a heat analogy. Muskat5 has shown the similarity of the equations which describe the flow of fluids in a porous medium to the flow of heat through a solid. Landrum, et al,6 made an analogy between the flow of fluid in an unsymmetrical reservoir and the conduction of heat in a similarly shaped metal plate. This analogy is summarized briefly as follows. If fluid is produced from an oil reservoir above the bubble point, the resulting pressure distribution will be identical to the temperature which would result in a metal or heat-conducting plate if heat were similarly removed. This means that a study of heat flow in stratified thermal models will behave like fluid flow in stratified oil reservoirs. For mathematical correspondencies, set- Ref. 6. The fluid mobility k/p is proportional to the thermal conductivity, and the porosity-times-compressibility product is proportional to the density times specific heat of the thermal plate. EXPERIMENTAL EQUIPMENT AND PROCEDURE The stratified reservoir model used in this study is illustrated schematically in Fig. 1. A Leeds and Northrup Speedomax Type G temperature recorder

By F. B. Plummer

THE physical properties of oil-producing sands, such as grain size, porosity, and permeability, are becoming more and more important in petroleum production engineering as oil fields are being repressured and rejuvenated. A number of excellent papers have been published recently on all three of these properties. Faucher, Lewis and Barnes1 give a com-plete survey of the work done through 1932 and contribute also much information on sands that they themselves have examined. Muskat and Botset,2 Wykoff, Botset, Muskat and Reed,3 Hurst,4 and Muskat5 have contributed a great deal to the theory and actual measurement of flow of liquids and gases through porous media. Muskat and Botset have measured the permeabilities of different sands with gases and liquids. They find that the radial is always slightly under the linear permeability. However, in most of the previous experiments small samples of the sand were used, and the method of production of fluid or gas through the sands has not been very close to actual oil-field conditions. In addition, so far as the authors are aware, no measurements of linear and radial permeabilities have been made simultaneously under exactly the same conditions. The multiple permeability apparatus described here is a part of the equipment being acquired by this laboratory for thorough investigation of the physical properties of producing sands. It possesses certain advantages for comparative studies of liquid flow. Additional data and descriptions of other instruments will follow in papers to be written later on. The essential features of the permeability apparatus are as follows:

Jan 1, 1934

By Frank L. Nason

During the months of June and July of the present year, the writer made a special geological survey of the mining property of Messrs. Cooper and Hewitt, at Ringwood, New Jersey. Some of the results of this survey are presented to the society through the courtesy of Hon. Abram 8. Hewitt.

Jan 1, 1895

By J. J. Lillie

Sublevel stoping was first developed in the Michigan iron mines many years ago. Since that time this method, and modifications with long hole drilling, have been used in a number of non-ferrous mines and have been described in various papers and articles. With a few exceptions, the operations where sublevel methods have been applied are producers of large daily tonnages from ore bodies of considerable size. In selecting mining methods for small properties or relatively small detached ore bodies, sublevel methods often have been overlooked. The method has been used success- fully in relatively small operations at Copper Canyon, Nevada, and, more recently, in mining small ore bodies at Darwin, Calif. As a result of this experience, we believe that a review of the general procedure, the advantages noted, and the results obtained will be of interest to many operators of relatively small mines.

Jan 1, 1949

By George H. Deike

DURING the past year a survey was conducted by the Committee on the Promotion of Student Interest in Coal Mining to determine whether the program as laid down in past years was operating effectively. It is a source of satisfaction and pleasure to be able to report considerable headway among operating companies in putting cooperative scholarship plans into operation. In previous committee reports the pioneer work along this line by Eugene McAuliffe, president of the Union Pacific Coal Co., has been cited. That Company now has in its employ, in responsible positions, three men who received their education under such scholarship plans. One student under a similar plan is now studying at the Colorado School of Mines.

Jan 1, 1942

By John P. Huger

me phase diagram for the system Ag-Si has been established by thermal analysis. The diagram is a simple eutectic type with a eutectic at 3.0 pct Si and 840°C. From the liquidus curve and with the aid of regular solution theory, the thermodynamic properties of the liquid Ag-Si system at 1420 °C have been determined. Silicon exhibits positive deviations from Raoultain behavior at all compositions, while silver exhibits both positive and negative deviations. MEASUREMENTS of silicon activities in liquid iron alloys by means of distribution studies between the immiscible liquids silver and iron have been reported by Chipman, Fulton, Gokcen, and caskey.&apos; The applicability of this technique is dependent, however, on the accuracy of the silicon activity values in the Ag-Si alloys, particularly in the dilute silicon region. Darken and Gurry2 have shown that log ?si/(1-xSi)2 is approximately linear with composition, but uncertainty exists in the extrapolation to dilute solutions. Their calculations are based on the old Ag-Si phase diagram of Arrivaut3 and any variation in the position of the liquidus curves will strongly influence the extrapolation. The purpose of this study is to redetermine the Ag-Si phase diagram and calculate the associated thermodynamic properties. EXPERIMENTAL The Ag-Si phase diagram was determined by thermal analysis of liquid alloys. The alloys were contained in a 35 mm alumina crucible under a protective stream of purified argon. The crucible was placed inside a 64 mm alumina tube fitted with a gas-tight, water-cooled, copper head. The tube and assembly were heated in a manually controlled globar furnace. The temperature was measured with a Pt, Pt + 10 pct Rh thermocouple in a high-temperature porcelain protection tube. The thermocouple calibration4 was checked against the melting point of pure silver at the start and during the course of the experiments, and against both gold and silver at the completion of the experiments. The alloys were prepared from granular silver analyzing 99.95 pct Ag and powdered silicon analyzing 99.88 pct Si and 0.026 pct Fe. Approximately 150 g of alloy were used for each run. The composition of the alloy was determined by withdrawing samples of the liquid alloy with a vycor tube-aspirator bulb device. Analysis of solidified samples agreed, for alloys containing less than 23 pct Si, within ±0.3 pct Si of the calculated composition. Duplicate samples showed a variance within 50.05 pct Si of the mean analysis. The alloy was heated to 100&apos; to 20pC above the estimated liquidus temperature and then the furnace was adjusted to give an average cooling rate of 2" to 7°C per min. A cooling curve was obtained by taking potentiometer readings at 15-sec intervals. Several analyses were made by recording the thermocouple output on a high-speed, Stip-chart recorder, with the exception of run NO. 11, a minimum of two thermal analyses were made for each alloy and the cooling curves then obtained duplicated the liquidus and eutectic temperatures to about 1°C. RESULTS The results of the thermal analysis are given in Table 1, and are represented as the Ag-Si phase dlagram, Fig. 1. The eutectic composition was found

Jan 1, 1963

By Jacques B. Wertz

Detailed structural studies in southeast Arizona have successively revealed (1) the local attitudes of individual fractures (with lateral and/or vertical displacements), (2) the patterns exhibited by groups of fractures, and (3) the trends and directions shown by fracture groups or zones on a regional scale. The results of the studies have been twofold: First, domes were locally determined from these fracture arrangements, even where other criteria failed; and, second, fundamental breaks brought out the breadth of the Texas lineament in southeast Arizona as well as major northwest- and northeast-trending fracture zones. Coincidence of one or several domes with the major intersections of fundamental breaks can be centers of important mineralization, as in the instances of Bisbee, Ajo and Morenci. THE OVER-ALL STRUCTURE OF ARIZONA A northwest-southeast trending anticlinorium has been suggested as the structural setting of Arizona. Starting in Triassic and culminating in late Cretaceous times, this deformation resulted from stresses of considerable magnitude with varying ratios of com pres sional and uplifting forces. However, the series of parallel flexures could just as well have been caused by isostatic movements involving dilation under tension with only incidental compression, as later emphasized by dike filling and block faulting (Fig. 1). The anticlinorial deformation, which is also suggested by the fact that the Pre-cambrian rocks to the southwest are all concealed by sediments, could be somewhat reminiscent of the conditions that affected the classical swarm of parallel dikes of wager.&apos; ANALYSlS OF DATA As a first step in this analysis, all structural information obtained on such features as fractures and their relative displacements, faults, dikes, anticlines, synclines, and Precambrian and Laramide-Tertiary intrusives were plotted on maps along with structural trends inferred from aerial photographic mosaics. Next, the faults in southwest Arizona were classified according to time of occurrence and relative importance. The fault assemblages were then examined as to geometric or spatial arrangement and correlated with the occurrences of domes and existing Finally, the conjunction of fracture intersections and domes was analyzed and compared with locations of known ore deposits. Differentiation of Faults According to Time and Relative Importance: The faults encountered were grouped as follows: (1) Basin and Range faults, latest in time; (2) secondary faults; (3) primary faults; and (4) lineaments, earliest in time by inference. BASIN AND RANGE FAULTS- Generally concealed by alluvium, the Basin and Range faults are normal

Jan 1, 1969

By M. C. Flemings, P. J. Ahearn

Dendvite morphology of unidirectionally solidified Sn-12 pct Bi alloy was determined with the aid of X-ray and macroetch techniques. Columnar growth direction (growth direction of primary arms) in this alloy is [110]; secondary arms grow in the [lii], [111), and [112] directions. Interstices between [112] dendrite arms fill in during early stages of solidification so that well-defined (110) planes are seen in the final structure (parallel to the heat-flozo direction). Similarly, interslices betweex the [111] secondary arrlls fill in to form (112) planes, and interstices between [1111 ] arms fill in to form (112) planes. DENDRITE morphology in alloys is conveniently studied in unidirectionally solidified castings. In this type of solidification, heat is extracted from a single chill surface of the casting while other surfaces are insulated. Solidification progresses from the chill and results in cast grains that are columnar with the long axis of the grain perpendicular to the chill. Dendrite morphology is conveniently studied by examination of etched surfaces parallel and perpendicular to the chill, as previously described.&apos;" Experimental studies on the growth direction for tin are in general agreement. The major growth direction is [110]:-&apos; although this is altered somewhat by supercooling. In one study, tin dendrites pulled from a supercooled melt had a growth orientation 12 deg away from the [110] direction toward the [002] direction.&apos; This orientation could be changed back to the [110] or close to the [110] direction by changing the tempera- ture gradient in the melt. In a study using autoradio-graphic techniques, (111) directions were shown to be directions of preferred growth in addition to the [110) direction.7 PROCEDURE The samples employed in this study were cut from 12 pct Bi-88 pct Sn castings, 1.5 in. in diam and 3.5 in. tall. The casting procedure consisted of heating the charge to 390°C and then pouring the molten alloy directly into a gypsum sleeve mounted on a massive copper chill. Specimens were cut from the ingot, mounted, polished, and etched with Taffs reagent [FeC13 .6H2O, 2 g; HC1, 5 cu cm;H20, 30 cu cm; CzHaOH (95 pct), 60 cu cm].&apos; The dendritic pattern was clearly visible after etching. Photomicrographs at about 8 and 35 times were taken on surfaces parallel and perpendicular to the chill. Laue back-reflection patterns were obtained from three different columnar grains in a singIe polished face 2 in. from the chill. The cut face was polished and positioned in the beam of a Laue camera, so that diffraction occurred from a single dendritic grain. The resulting diffraction pattern was interpreted to determine crystal log raphic orientation in relation to the heat-flow direction and in relation to microstruc-ture of the given grain. RESULTS Fig. 1 shows a horizontal and vertical section of the columnar structure, at low magnification. Light regions are rich in tin, and darker regions tin-poor; the primary phase is tin-rich a phase. The two sections shown were taken orthogonally from the same metallographic specimen. It is readily seen from Fig. 1 that the dendrites have

Jan 1, 1968

By W. S. Stahmann, F. W. Bowdish

Previously published experimental data showing that both collectable and non-collectable sulfide films may be formed on chrysocolla were analysed, and chemical mechanisms were proposed for the formation of the films. A special technique was developed by which the quantity of sulfur adsorbed was determined for samples sulfidized under different conditions of pH and soluble sulfide concentration. The data on sulfur adsorption were used together with the expression for the equilibrium constant for the proposed reaction to indicate the validity of the chemical mechanism theory. A recent paper 1 about contact angle studies on chrysocolla reported the effects of pH value and sodium sulfide concentration during sulfidization upon the character of the surfaces produced. In each experiment the surface of a specimen of chrysocolla was prepared by grinding it with fine abrasive and washing it in tap water. The specimen was then placed in the sulfidizing solution for 10 min, rinsed in tap water, treated for 15 min in a solution containing 30 mg of potassium amyl xanthate per liter, rinsed in distilled water, and tested for air adhesion in a contact angle apparatus. The results, when plotted as in Fig. 1, showed an island representing conditions giving air adherent or collectable surfaces surrounded by conditions giving non-collectable surfaces. Particular interest may be attached to the region of non-collectability to the right of and above the island in Fig. 1, and to the boundry curve separating these two regions. It is apparent that at any pH from 4.0 to 6.0, where a collectable surface may be produced, a sufficient increase in the sulfide concentration results in a non-collectable surface. Thus it appears that too much soluble sulfide has a depressing effect upon the mineral, just as it has in sulfide flotation. This paper presents some speculations regarding the chemical mechanisms by which the collectable and non-collectable sulfide films may be formed and reports on a physical-chemical study intended to support these speculations. THEORETICAL CONSIDERATIONS The experimental results presented in the previous paper were analysed in several ways in an attempt to understand better the chemical mechanisms involved. For several points on the boundary to the right of the region of contact in Fig. 1, molar concentrations of H+, OH-, HS-, and S= ions, as well as various ion concentration products, were calculated. Following the reasoning of Wark and Cox, 2,3 no single kind of ions may be credited with causing depression of the surface because none of them have a constant con-

Jan 1, 1968

By S. C. Sircar, D. R. Wiles

The rate has been studied of the hydrogen reduction of nickel ions in acetate -buffered solutions, using a nickel catalyst. At temperatures between 130°and 160°C, the rate is found to be proportional to the catalyst area, the nickel ion concentration, and the hydrogen pressure. The effect of hydrogen ions is to reduce the observed rate, likely by causing the reverse reaction (dissolution) to proceed. The experimental activation energy was found to be 25 kcal per mole. THE precipitation of metals and lower oxides from solution by hydrogen reduction has been quite actively investigated during the past few years.1 In the case of nickel, the kinetics of the precipitation have been studied in ammonia solution2 but extension of this study to acid solutions has not attracted much interest, largely because of the unfavorable thermodynamics at all but the lowest acidities. For example, Schaufelberger foundg that only 10 pct reduction of nickel could be effected in sulphate solutions. One kinetic study of the reduction of Ni++ has been reported by Knacke, Pawlek, and Sussmuth,4 in which the order of the reaction was found to be one in nickel ion and one-half in hydrogen pressure. No mention was made as to the part played by the nickel catalyst, or by the pH of the solution. Moreover, the activation energy reported (4 .12 kcal per mole) is so low as to lead to some question as to whether diffusion might be playing a major role in determining the kinetics. We have recently completed a study5 of the kinetics of the hydrogen precipitation of nickel from acetate-buffered acidic solutions whose results confirm and amplify those of Knacke et al. EXPERIMENTAL PROCEDURES The work was done in a high-pressure autoclavee by the usual technique of removing small samples of the solution for analysis. Nickel analysis was done colorimetrically by the dimethylglyoxime method.&apos; The catalyst used was carbonyl nickel powder (Standard A powder of the Mond Nickel Co., Ltd.) which was found to be composed of spheres of less than 350 mesh. The surface area of the powder was determined in this laboratory by the B. E. T. method to be 1.85 sq m (m2) per g. The catalyst was added to the solution only after the proper temperature and pressure had been reached. Agitation of the baffled system was by a turbine-type impeller, rotated at speeds between 400 and 750 rpm. The reduction rate was found to be independent of the stirring rate, so it was assumed that diffusion in the liquid does not limit the rate. In typical experiments, the nickel concentration was unchanged during an induction period of variable length. The concentration then decreased sharply, and gradually levelled off to approach the final equilibrium value. In some cases, notably at high stirring rates, the nickel concentration was found to increase considerably during the induction period, and then to decrease. In all cases, the rate was determined from the slope of the tangent to the rate curve as the concentration first decreased below the initial value. This is seen in Fig. 1. The rate measurements were found to be reproducible to within about 5 and to be quite independent of the nature or duration of the induction period. The range of conditions used is given in Table I.

Jan 1, 1961

By W. A. Backofen, G. Mayer

Single crystals of iron, copper, and a Cu-7 wt pct A1 alloy were pulled through conical dies to simulate the constraint in a polycrystalline aggregate undergoing axisymmetric reduction. With Taylor-type hardening, dependence of the drawing stress, od, on the Taylor orientation factor, M, is predictable from the polycrystal stress-strain curve; in particular, for a power-law relationship, it should follow that d log od/d log M = (1 + n). A first-order agreement with analysis was found in the data from iron. For copper, the implied n from the observed d log od/d l°g M was -0, while for Cu-7Al it was negative. The trend was in the direction of random polycrystal behavior. Thus the idea of hardening only in response to the amount of prior slip loses validity as stacking fault energy (SFE) is lowered. Two possible explanations have been suggested: as stacking fault ribbons are widened, barriers from dislocation reactions become increasingly effective in dispersing slip and reducing the orientation dependence of the total glide strain dm that appears in alternatively, or conjointly, the polyslip shear stress, 7, acquires an orientation dependence of a kind which has the same leveling effect on M. The problem of relating the strain hardening of polycrystalline material to that of an isolated single crystal is still largely unsolved. In a new experimental approach from recent work, single crystals of different orientations have been deformed under the constraints found in an aggregate while measuring their deformation resistance. Procedures have involved drawing cylindrical crystals through conical dies1 and compressing slab-shaped crystals in plane strain.2&apos;3 Predictions for the outcome of such experiments were made first by Taylor~ and later, in more general form, by Bishop and Hill.5&apos;6 Taylor&apos;s example was the axisymmetric extension of an fcc crystal slipping on the usual {111}(110) systems or, equivalently, a bcc crystal undergoing &apos;kestricted" slip on {110}(111). In his solution, the deformation work supplied was equated to that dissipated internally in slip on all active systems. With o the single applied tensile stress, dc the resulting axial strain, and dyT the total glide strain on systems operating at resolved shear stress, 7: The orientation dependence of M was found by minimizing dyT for each orientation while activating five independent systems, Fig. l(a).? The Bishop and Hill analysis, based on a principle of maximum work, leads to essentially the same conclusion; the need for at least five active systems is recognized in the finding that either six or eight are actually brought into operation. The mean value from the entire stereo-graphic triangle in either case is M - 3.06. More recently, Hutchinson8 made a Taylor-type analysis for pencil glide in a bcc structure, from which piehlerg prepared Fig. l(b) as the counterpart in Fig. l(a); here M = 2.75. The obvious weakness in such analyses is the indifference to slip-system interactions. A condition of what might be termed "independent"

Jan 1, 1969

By Sylvan Z. Beer

Aluminum phosphide was synthesized and grown in solution of excess aluminum using a modified two-temperature technique. An inversion in the density difference between ALP and molten aluminum takes place at about 1100°. Dispersed nuclei can act as sources for further crystal growth in a manner resembling ripening. Advantage was taken of this phenomenon by introducing a stirring motion into the molten liquid. This was done with a split-phase 10-kH2 rotating magnetic field produced by four horizontal coils placed symmetrically about the furnace at the level of the molten metal. The method also prevents the formation of a surface film which would impede the reaction. By this technique vastly improved yields were obtained and flat crystals 5 by 5 by 0.5 mm were grown at lower temperatures and at greater rates than heretofore. THE family of III-V intermetallic compounds has received much attention since the prediction of their semiconducting properties in the early 1950s. Of the family, A1P has perhaps the highest band gap of those compounds normally possessing the zinc-blende structure. But it has been least studied because it is difficult to handle and grow. The handling difficulties have been dealt with elsewhere and it is sufficient to say here that, by various techniques, many of the difficulties can be overcome.&apos; The difficulties encountered in crystal growth can be related to the refractory nature of A1P and in turn to its high band gap. Because of the anticipated high melting point of the material and the accompanying high phosphorus vapor pressure, the reported work on synthesis and growth was done by epitaxial synthesis-growth via chlorine2 and iodine3 transport and from solution of excess aluminum by the two-temperature technique.4&apos;5 The transport-grown crystals take on the dimensions of the substrate but do not grow easily in thickness. In the usual two-temperature technique as applied on the synthesis of Alp, the temperature of the molten aluminum is kept at 1000° to 1250°C while the phosphorus is maintained at 1 to 20 atm. A thin film of aluminum phosphide and oxide form immediately, impeding the reaction and affecting the yield. Attempts to grow the Alp from such solutions by the methods used to grow Gap and InP from excess gallium and indium have not been successful. As discussed in the preceding paper,5 the yield can be greatly increased

Jan 1, 1969