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The Third Theory Of ComminutionBy Fred C. Bond
MOST investigators are aware of the present unsatisfactory state of information concerning the fundamentals of crushing and grinding. Considerable scattered empirical data exist, which are useful for predicting machine performance and give, acceptable accuracy when the installations and materials compared are quite similar. However, there is no widely accepted unifying principle or theory that can explain satisfactorily the actual energy input necessary in commercial installations, or can greatly extend the range of empirical comparisons. Two mutually contradictory theories have long existed' in the literature, the Rittinger and Kick. They were derived from different viewpoints and logically lead to different results. The Rittinger theory is the older and more widely accepted. In its first form, as stated by P. R. Rittinger, it postulates that the useful work done in crushing and grinding is directly proportional to the new surface area produced and hence inversely proportional to the product diameter. In its second form it has been amplified and enlarged to include .the concept of surface energy; in this form it was precisely stated by A. M. Gaudin2 as follows: "The efficiency of a comminution operation is the ratio of the surface energy produced to the kinetic energy expended. According to the theory in its second form, measurements of the surface areas of the feed and product and determinations of the surface energy per unit of new surface area produced give the useful work accomplished. Computations using the best values of surface energy obtainable indicate that perhaps, 99 pct of the work input in crushing and grinding is wasted. However, no method of comminution has yet been devised which results in a reasonably high mechanical efficiency under this definition. Laboratory tests have been reported' that support the theory in its first form by indicating that the new surface produced in. different grinds is proportional to the work input. However, most of these tests employ an unnatural feed consisting either of screened particles of one sieve size or a scalped feed which has had the fines removed. In these cases the proportion of work" done on. the finer product particles is greatly increased and distorted beyond that to be expected with a normal feed containing the natural fines. Tests on pure crystallized quartz are likely to be misleading since it does not follow the regular breakage pattern of most materials but is relatively harder to grind at the finer sizes, as will be shown later. This theory appears to be indefensible mathematically, since work is the product of force multiplied by distance, and the distance factor (particle deformation before breakage) is ignored. The Kick theory' is based primarily upon the stress-strain diagram of cubes under compression, or the deformation factor. It states that the work required is proportional to the reduction in volume of the particles concerned. Where F represents the diameter of the feed particles and P is the diameter of the product particles, the reduction ratio Rr is F/P, and according to Kick the work input required for reduction to different sizes is proportional to log Rr/log 2.5 The Kick theory is mathematically more tenable than the Rittinger when cubes under compression are considered, but it obviously fails to assign a sufficient proportion of the total work in. reduction to the production of fine particles. According to the Rittinger theory as demonstrated by the theoretical breakage of cubes the new surface produced, and consequently the useful work input, is proportional to Rr-1.5 If a given reduction takes place in two or more stages, the overall reduction ratio is the product of the Rr values for each stage, and the sum of the work accomplished in all stages is proportional to the sum of each Rr-1 value multiplied by the relative surface area before each reduction stage. It appears that neither the Rittinger theory, which is concerned only with surface, nor the Kick theory, which is concerned only with volume, can be completely correct. Crushing and grinding are concerned both with surface and volume; the absorption of evenly applied stresses is proportional to the volume concerned, but breakage starts with a crack tip, usually on the surface, and the concentration of stresses on the surface motivates the formation of the crack tips. The evaluation of grinding results in terms of surface tons per kw-hr, based upon screen analysis, involves an assumption of the surface area of the subsieve product, which may cause important errors. The'evaluation in terms of kw-hr per net ton of 200 mesh produced often leads to erroneous results when grinds of appreciably different fineness are compared, since the amount of -200 mesh material produced varies with the size distribution characteristics of the feed. This paper is concerned primarily with the development, proof, and application of a new Third Theory, which should eliminate the objections to the two old theories and serve as a practical unifying principle for comminution in all size ranges. Both of the old theories have been remarkably barren of practical results when applied to actual crushing and grinding installations. The need for a new satisfactory theory is more acute than those not directly concerned, with crushing and grinding calculations can realize. In developing a new theory it is first necessary to re-examine critically the assumptions underlying
Jan 1, 1952
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Drilling Technology - Drilling Fluid Filter Loss at High Temperatures and PressuresBy F. W. Schremp, V. L. Johnson
This paper discusses the results obtained from high temperature, high pressure filter loss studies in which field samples of clay-water, emulsion, and oil base fluids were used. High temperature, high pressure tests of some premium priced emrilsion and oil base drilling fluids show filter loss peculiarities that are not predicted by standard API tests. It is recommended that high temperature, high pressure filter loss tests be used to evaluate the performance of such fluids. Apparatus is described which proved to be satisfactory for evaluating filter loss behavior over a wide range of temperatures and pressures. INTRODUCTION The petroleum industry spends large sums of money each year on chemical treating agents for lowering filter loss and on premium-priced low filter loss drilling fluids. While it is an accepted fact that low filter loss is advantageous during drilling operations, it is questionable whether the present standard method of determining filter loss gives a reliable indication of the loss to he expected under bottom hole conditions. The purpose of this paper is to show that high temperature. high pressure filter loss tests Should be used to evaluate filter loss behavior of fluids for deep drilling. Concern over possible effects of filter loss on oil well drilling and well productivity dates back to the early 1920's. During the years 1922 to 1924, filtration studies were reported by Knapp,' Anderson2 and Kirwan." These studies were the first to be reported in the literature on this subject. No further information was published on the subject until 1932 when Rubel' presented a paper in which he discussed the effect of drilling fluids on oil well productivity. In 1935. .Jones and Babson constructed the first laboratory tester designed to study the effects of temperature and pressure on the filter loss behavior of clay-water drilling fluids. In a discussion of their investigations, Jones and Babsons stated, "Performance characteristics of a mud can he evaluated with considerable reliability by a single test at 2,000 psi and 200°F. Exact correlation between the results of performance test5 made under these conditions and the behavior of muds in actual drilling operations is of course impossible." Jones arid Babson apparently were well aware that at best laboratory tests can give only qualitative answers to the question of what is the actual behavior of a drilling fluid when subjected to deep drilling conditions. Jones' presented a paper in 1937 in which he described a static filter loss tester to be used for routine filter loss tests. This instrument subsequently was adopted as the standard APl filter loss tester. In 1938, Larsen7 developed a relationship between filtrate volume and filtrate time that is in general acceptance today. Larsen was cognizant of the danger of estimating bottom hole behavior from filter loss measurements at room temperature. He tried to predict the effect of temperature on filter loss by relating temperature effects through the temperature dependence of filtrate viscosity. This was undoubtedly an over-sirriplification of the temperature dependence of drilling fluid filter loss. In 1940, Byck" published a summary of experimental results of filter loss tests made on six representative California clsy-water drilling fluids. He concluded that "no existing method will permit even an approximate determination of the filtration rate at high temperature from data at room temperature. It is necessary to measure filtration at the temperature actually anticipated in the well, or to make a sufficient number of tests at various lower temperatures so that a small extrapolation of these data to the anticipated well temperature may be applied." Byck's findings were presuma1)ly well accepted and recognized by drilling Fluid technologists, and yet, they did not lead to wide adoption of high temperature drilling fluid filtration equipment. This is evidenced by the fact that no addition information has appeared in print on the subject since 194). Study of Byck's data shows that there was a useful consistency in them. The fluids did not show predictable losses at high temperatures, but they did line up at high temperatures in approximately the same order that they lined up at low temperatures. That is, if a fluid appeared to be a good fluid with relatively low loss at low temperatures, it would also be a good fluid with relatively low loss at high temperatures. In the last decade. the above situation has changed. The drilling fluid art is markedly different from what it was. The outstanding change, as far as the present discussion is concerned, has been the adoption of wholly new types of drilling fluids. Oil base and emulsion drilling fluids have come in to wide use. It is, therefore, necessary- to re-examine previously satisfactory generalizations to see if they are still valid. It turns out. as might have been expected. that Byck's explicit generalization. already quoted, is still true. Filter losses at high temperatures cannot be predicted from filter losses at low temperatures. However, no further generalizations are valid now. Fluids of different chemical types show different general behaviors. No longer do the fluids line up approximately the same at high temperatures as they do at low temperatures. They may line up entirely differently. Special fluids exhibiting very low loss at low temperatures may have losses as high as those of ordinary clay-water fluids at high temperatures. This fact is highly significant, because premium prices are being paid for the special fluids.
Jan 1, 1952
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Part XII – December 1969 – Papers - Zinc Extrusion as a Thermally Activated ProcessBy J. J. Jonas, G. Gagnon
SHG zinc was extruded in the temperature range 110" to 350°C and the strain rate range 0.05 to 5 sec-1 The strain rate/flow stress/temperature results were analyzed using a power sinh stress relationship. When temperature changes due to the heat of deformation and to heat losses are neglected, the exponent of the sinh function of the stress is 5.6, and the apparent activation energy of deformation is 28 kcal per mole. When these changes are taken into account, the exponent decreases to 4.7 and the activation energy to 23 + 2 kcal per mole. The corrected stress exponent and activation energy are in very good agreement with published values obtained from creep experiments, and suggest that the hot extrusion of zinc is controlled by a mechanism involving self-diffusion. When the extrusion and creep data are compared using a Zener-Hollomon parameter and either a sinh or an exponential stress term, an appreciable offset is observed, which may be due to the difference in impurity content. For a given set of extrusion conditions the ram speed, maximum pressure, and initial temperature can also be correlated using a Zener-Hollomon parameter and a sinh pressure term. THE deformation of metals at temperatures over about one-half the absolute melting temperature has been extensively studied at creep strain rates. By contrast, relatively little work has been carried out on the behavior of metals at hot working strain rates. Most of the latter investigations have been performed using simulative methods, such as hot torsion and hot compression, in which the friction conditions and temperature rise during deformation may differ appreciably from those existing under industrial conditions. Recently, however, Wong and Jonas1 used a scaled-down industrial process to determine the stress and temperature dependence of the strain rate during the extrusion of aluminum. In such tests, the effects of friction and adiabatic heating are closer to those produced in industrial operations. Also, with regard to the testing of materials of limited ductility such as zinc, hot compression and hot torsion do not permit the attainment of true strains as large as the deformations usually applied commercially. The present study was undertaken to investigate the extrusion behavior of Special High Grade (SHG) zinc. The detailed objectives were: 1) to establish the stress and temperature dependence of the strain rate with and without a consideration of adiabatic heating, 2) to study the pressure and temperature dependence of the ram speed, and 3) to investigate the microstruc- tural changes occurring during the deformation. The last aspect of the investigation will be covered in a separate paper. The treatment described below differs from that of Wong and Jonas in that the adiabatic temperature rise during deformation is taken into account, and the calculation of the mean equivalent strain rate is based on the redundant as well as on the homogeneous work. EXPERIMENTAL PROCEDURE Rods from two shipments of continuously cast SHG zinc* were used in the investigation. The composition *Supplied by courtesy of Cominco Ltd. range of the impurities present, as given by the supplier, was: Pb: 0.0013 to 0.0023 pct, Fe: 0.001 pct max Cd: 0.0001 to 0.0006 pct, Cu: 0.0002 to 0.0005 pct, Ti: 0.0001 pct max; thus, by balance, zinc valued from 99.9963 to 99.9966 pct. The as-received rods were machined into billets having a nominal diameter of 1.56 in. and a nominal length of 1½ in.; longer billets up to 4 in. in length, were also used to investigate special aspects. The as-machined rods were annealed at 400°C for 24 hr and slowly cooled. This treatment produced a columnar grain structure, with a grain size of about $ by 2½ cm which was appreciably larger than the as-cast one. A 150-ton, direct extrusion, vertical press was used. Ram displacement and force were recorded continuously against time. A constant flow control valve permitted the maintenance of a range of preselected ram speeds up to in. per sec. The selected speed was held constant, irrespective of the required force, as long as the load developed was below the maximum available. Strain gages were used to determine the force; the gages were calibrated before and after each testing period with a 200,000-lb capacity load cell. Further details of the experimental equipment can be found in Ref. 2. The billets were preheated for 90 min in the extrusion container, which was well insulated so as to minimize temperature gradients. This period was sufficient for the billet to reach a uniform temperature at all temperatures between 110" and 350°C. A square-shoulder die having a 0.290-in. diam central hole was used. The extrusion ratio was 30 to 1. This is equivalent to a reduction in area of 96.7 pct, an elongation of 2900 pct, and a true strain of 3.4. The ram speed was varied over two orders of magnitude from 0.0027 to 0.26 in. per sec. The ram was water-cooled during most of the tests, although some experiments were conducted with a preheated, uncooled ram. All extrusions were run without lubricant, which resulted in conditions of sticking friction. EXPERIMENTAL RESULTS Stress Dependence of the Strain Rate Neglecting Adiabatic Heating. The maximum force required to extrude is given in Table 1 for each of the five initial
Jan 1, 1970
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PART XI – November 1967 - Papers - Slag-Metal Equilibria in the Pb-PbO-As2O3 SystemBy A. D. Zunkel, A. H. Larson
Equilibrium arsenic contents of Pb-As alloys in contact with PbO-As2O3 slags containing less than 30 mol pct As2O3, were determined at 650°, 700: and 750 C in an inert at?rzosphere. In this temperature range, the arsenic content of the alloy increased with increasing temperature in the single-phase liquid slag region and decreased with increasing temperature in the two-phase slag region and the single-phase solid-solution slag region. The PbO-As2O3 phase diagram below 22 mol pct As2O3 was determined by thertrzal analysis and by application of a log ?As2O3/?PbO vS log XAs2o3 /x3pbO plot determined from the equilibrium actiuity data. The resulting phase diagram was not well-defined since the eutectic temperature was not detected in the thermal analysis experiments, although a region of terminal solid solubility of As2O3 was found. Results from the phase diagram determination are compared with an existing diagram in the literature. THIS experimental investigation is an extension of a study by the authors1 on the slag-metal equilibria in the systems concerned with commercial lead refining processes such as softening and dross fuming. The first part of this investigation was a study of the slag-metal equilibria in the Pb-PbO-Sb2O3 system. The only experimental work previously done on the Pb-PbO-As2O3 system was by Pelzel2,3 in which the phase diagram for the PbO-As2O3 system was determined below 50 wt pct As2O3 and the equilibrium constant for the reaction 3Pb + As2O3 + 3PbO + 2As was determined as a function of temperature. No slag-metal equilibrium data have been determined. It is due to the scarcity of information regarding the Pb-PbO-As203 system that this work was undertaken. This paper describes the determination of the slag-metal equilibria in the Pb-PbO-As203 system by equilibrating Pb-As alloys with PbO-As2O3 slags in an inert atmosphere, the effect of 1 wt pct additions of bismuth and copper on the slag-metal equilibria, and the PbO-As2O3 phase diagram both by thermal analysis and the use of the slag-metal equilibria data. EXPERIMENTAL Materials. The materials used in this investigation were analytical reagent-grade and assayed as follows: 1) 99.8 pct PbO (0.014 pct insoluble in CHJCOOH, 0.02 pct not precipitated by H2S, 0.1 pct CaO, and 0.08 pct SiO2); 2) 99.95 pct As2O3; 3) 99.99 pct Pb; 4) 99.0 pct As; 5) 99.99 pct Cu; and 6) 99.97 pct Bi. Room-temperature X-ray patterns revealed no detectable impurities in any of these materials. Apparatus for Equilibrium and Thermal-Analysis Determinations. The resistance-heated crucible furnace used in this investigation employed nichrome elements and was mounted so that it could be raised to surround the reaction tube during each experiment and, subsequently, lowered. A schematic diagram of the apparatus is shown in Fig. 1. Each charge was heated in a 3+-in.-OD by 31/2-in.-high 416 stainless-steel crucible placed in a 41/4-in.-1D by 18-in.-long fused-silica reaction tube which was closed at one end. On a shoulder around the crucible was placed a 3: -in.-OD by 12-in.-long open-end fused-silica condenser tube. The open end of the reaction tube was covered by a water-cooled brass cap with ports for 1) admitting an inert atmosphere to the system through a stopcock, 2) introducing a stainless-steel, motor-driven, paddle stirrer into the crucible, 3) evacuating the system with a mechanical vacuum pump, and 4) sampling the melt with Vycor sampling tubes. The brass cap was fitted to the open end of the reaction tube with a silicone gasket and collar clamp. The furnace temperature was controlled by a Barber-Coleman Capacitrol controller and a chromel-alumel thermocouple. Due to the corrosiveness of the melt, the controlling thermocouple also served as the measuring thermocouple. The temperature of the melt was calibrated against the controller temperature and was checked periodically during each test with a Vycor-enclosed calibrated chromel-alumel thermocouple. The temperature measurement and control can be considered accurate to ±3°C. Procedure. The charge placed in the crucible for each experiment consisted of 1000 g of Pb-As alloy and 300 g of PbO-As2O3 slag. The crucible was then placed in the reaction tube, the condenser tube was placed on the shoulder of the crucible, the silicone gasket and brass cap were fitted on the open end of the reaction tube, and the entire system was evacuated and filled with argon ten times. After the last flushing, a positive argon pressure of 1 psig was impressed on the system. The furnace was then raised to sur-
Jan 1, 1968
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Part VII – July 1968 - Papers - Cellular Precipitation in Fe-Zn AlloysBy G. R. Speich
The interlarnmelm spacing, growth rate, and degree of segregation that accompany cellular precipitation in four Fe-Zn alloys containing 9.7, 15.2, 23.5, and 30.5 at. pct Zn have been determined in the temperature range 400" to 600°C. The chemical free-energy change for the reaction was calculated from the available thermodynamic data and the known compositions of the phases. The fraction of the chemical free-energy change for equilibrium segregation that is converted into interfacial free energy decreases from 0.43 to 0.08 as the magnitude of this free-energy change increases from 35 to 270 cal per mole. At constant temperature the cellular growth rate is proportional to the cube of the dissipated free energy. At 600°C newly 100 pct of the equilibrium segregation is achieved during cellulm precipitation whereas at 400°C only 85 pct of the equilibrium segregation is attained. During cellular growth, mass transport of zinc occurs by grain boundary diffusion; excess zinc remaining in the a! phase after the completion of growth is removed slowly by volume diffusion. A modified Cahn theory of cellular precipitation predicts the observed interlamellar spacing within a factor of two. In cellular precipitation reactions such as pearlite formation or discontinuous precipitation, the basic problem is to predict the variation of growth rate G, interlamellar spacing S, and degree of segregation P with composition and temperature. To accomplish this we need three independent equations relating these quantities. One of these equations comes from the diffusion solution. To obtain two additional independent equations, some assumptions must be made. cahnl has suggested recently that two plausible assumptions are 1) that growth rate is proportional to the dissipated free energy and 2) that the spacing which occurs is that which maximizes the dissipated free energy. According to the first assumption, this spacing also maximizes the growth rate and the rate of decrease of free energy per unit area of cell boundary. The present work was undertaken to test these assumptions. To test the first assumption it is necessary to study a cellular reaction over a wide range of supersatura-tions to establish a relationship between G and the dissipated free energy at constant temperature. This is possible only in discontinuous precipitation reactions since in pearlite reactions constituents other than pearlite form if the composition of the parent phase deviates even slightly from the eutectoid composition. The Fe-Zn system was chosen for study because 1) discontinuous precipitation proceeds to completion over a wide temperature and concentration range, 2) the degree of segregation within the cell can be measured by lattice parameter measurements,2 and 3) the thermodynamics of this system have recently been determined by Wriedt.3 In this system the cells consisting d alternate lamellae of a and r phases form from supercooled iron-rich a phase. The a phase within the cells is bcc as is the original a phase, cia, but has a different orientation and a slightly lower zinc content than the original a phase. The r phase has a zinc content of about 70 at. pct and a crystal structure isomor-phous with T brass. EXPERIMENTAL PROCEDURE Four Fe-Zn alloys with 9.7, 15.2, 23.5, and 30.5 at. pct Zn were prepared from carbonyl-iron powder (400 mesh, 99.8 wt pct Fe) and zinc powder (200 mesh, 99.99 wt pct Zn). The powders were ball-milled together and cold-pressed under 60,000 psi to discs $ in. thick by $ in. diam. The cold-pressed discs of the alloys with 9.7 and 15.2 at. pct Zn were sealed in evacuated silica capsules and heated slowly to 1100°C over a period of 1 week (3 days at 600°C, then 3 days at 80O°C, then 1 day at 1100°C). The alloys with 23.5 and 30.5 at. pct Zn were treated similarly except that the final homogenization temperatures were 1000" and 85O°C, respectively, to prevent melting. The alloys were quenched in iced brine from the final homogenization temperature. Specimens of each alloy were subsequently aged in salt pots at temperatures of 400°, 450°, 500°, 550°, 600°, and 650°C for times that varied from a few minutes to several hundred hours. At a late stage of this work, an alloy containing 11.2 at. pct Zn was prepared by vapor-impregnation of iron foil with zinc vapor at 890°C. This alloy proved useful for electron microscope studies because it was free of porosity. The homogenization and aging conditions were based on the recent Fe-Zn phase diagram of Stadelmaier and Bridgers4 rather than the earlier diagram of ansen.5 They consist of a homogenization heat treatment in the homogeneous a field followed by an aging treatment in the two-phase a + r field. The aged specimens were metallographically polished and etched in 2 pct nital and the radius of the largest cell in the microstructure determined. This radius plotted vs time gave a straight line whose slope is the boundary migration rate or growth rate G of the cell. To determine the interlamellar spacing, specimens were examined by surface-replica and thin-section electron microscope techniques. Because of the irregular nature of the lamellae within the cell, the average interlamellar spacing S .of the cell was measured by the method of Cahn and Hagel,6 where S is defined by:
Jan 1, 1969
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Coal - The Graphite of the Passau Area, BavariaBy R. G. Wayland
SINCE the installation at Kropfmuehl, Bavaria, of a modern flotation concentrator in 1938, the flake and fine graphite from the Passau area can now be delivered in about any normal specified carbon content of any size range up to a flake averaging about 0.7 mm. The graphite finds a wide German and export market for crucible manufacture, pencil leads, dry cells and other uses. A controversy over the origin of the graphite deposits is being resolved in favor of syngenesis rather than epigenesis. The syngenetic theory is newly supported by the yet unpublished work of Hartmann of the Bavarian Geological Survey. Development work and exploration for graphite in the area may be changed in direction as the syngenetic theory is accepted. Crystalline graphite is produced in the area east of Passau near the junction of Germany, Austria and Czechoslovakia, as shown in Fig. 1. This is the only graphite area of importance in Germany, and Gra-phitwerk Kropfmuehl AG is the only operating firm in the area. The plant and mine are located at Kropfmuehl near Hauzenberg, Kreis Wegscheid, about 10 miles east of Passau. A narrow gage railway from the mine connects with the German Railway at Schaibing Bahnhof. The Pfaffenreuth mines date from about 1730. Until the early 20th century mining operations were carried out in a haphazard fashion. During World War I graphite mining and milling was increased, since it had to cover almost all of the crucible needs of the Central Powers. Between the wars some 11 mines were operated by two large and several small companies, but under the Nazis these were consolidated by 1938 into the Kropfmuehl enterprise. Kropfmuehl built a modern flotation mill to treat its own ores and small amounts of custom ores and tailings from the area. Since Graphitwerk Kropfmuehl AG was an I.G. Farbenindustry subsidiary, it has been under Military Government Property Control and probably will be sold to private German capital. Geology The country rock of the graphite area is part of the "kristallines Grundgebirge," the series of old gneissic and schistose rocks that constitutes the bed rock of most of the Bohemian basin and rims the Sudeten-land. The gneissic rocks of the graphite area are considered to have been metamorphosed during the Carboniferous period. They are bordered on the north by granite stocks and penetrated by numerous smaller granite and pegmatitic intrusive rocks, as shown in Fig. 1. The gneiss is classed as a micaceous, coarse-grained cordierite gneiss by most investigators. It is much metamorphosed by the granite, particularly in the north near the larger granite bodies. Interbedded in the gneiss are the graphite seams and lenses, and also beds and lenses of crystalline limestone containing disseminated graphite in noncommercial quantities. The gneiss, together with the included graphite and limestone seams and lenses, is cut and displaced by a number of granite sills of medium to fine grain and by a large number of diorite lamprophyre dikes and a few syenite-pegmatite dikes. The lamprophyre dikes are of various mineral compositions and textures, but many are banded and richly impregnated with pyrite; while the syenite-pegmatite dikes are coarse-grained with good crystals of titanite, pyroxene, uralite and other green amphiboles. Most investigators and the miners speak only of diorite and granite dikes cutting the graphite seams. The diorite dikes are later than the granite and some of the faulting, as is evident from Figs. 1 and 2. Individual graphite seams and lenses may be mined for thicknesses of several feet up to several scores of feet, and for distances of several hundred feet. The aggregate thickness of a series of some 20 seams of graphite, limestone and interbedded gneiss at Kropfmuehl is stratigraphically about 450 ft. Laterally, the graphite in a seam may pinch out or grade into crystalline limestone. Graphite crystals also are found disseminated in the gneiss itself, although in unmineable concentrations. The faults that cut the graphite seams carry graphite for some feet or tens of feet away from the seams, apparently mechanically. Similarily, the graphite lenses themselves often contain mechanically introduced inclusions of wall rock, probably from flowage during folding. Graphite crystals make up 10 to 30 pct of the fresh, mineable graphite lenses at Kropfmuehl, averaging about 20 to 25 pct after hand-sorting by the miners. In weathered lenses, the graphite concentration is said to be as high as 50 pct. The associated primary and hydrothermal minerals are dom-inantly feldspar and calcite, plus quartz, pyrrhotite, pyrite, biotite and occasional garnet, hornblende, sphalerite and galena. Associated secondary minerals include kaolin, nontronite, mangano-oxide-silicates (mog), adularia and chlorite. The superimposed suite of siliceous cementation minerals present consist largely of opal, chloropal, chalcedony, jasper, and hyalite. The kaolin is of special interest since it too was mined as early as 1730 and was used in the well-known Nymphenburg porcelain from 1756 on. The kaolin is derived from the gneiss and the syenite pegmatites. The crystals of graphite vary in size within a given seam, but in seams more than a mile away from the granite on the north the average crystal-linity is less coarse, lowering the commercial value. The lenses in the Kropfmuehl-Pfaffenreuth area are the most developed, and are the only ones with deep workings now accessible. Other similar crystalline graphite lenses are known from older workings at Habersdorf, Oberoetzdorf, Ficht, Diendorf, and
Jan 1, 1952
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Mineral Beneficiation - The Third Theory of ComminutionBy Fred C. Bond
MOST investigators are aware of the present unsatisfactory investigatorsstate of information concerning the fundamentals of crushing and grinding. Considerable scattered empirical data exist, which andare useful for predicting machine performance and give acceptable accuracy when the installations and materials compared are quite similar. However, there is no widely accepted unifying principle or theory that can explain satisfactorily the actual energy input necessary canexplain commercial installations, or can greatly extend the range of empirical comparisons. Two mutually contradictory theories have long existed in the literature, the Rittinger and Kick. They were derived from different viewpoints and logically lead to different results. The Rittinger theory is the older and more widely accepted.'TheRittinger In its first form, as stated by P. R. Ritted.'tinger, it postulates that the useful work done in crushing and grinding is directly proportional to the new surface area produced and hence inversely proportional to the product diameter. In its second form it has been amplified and enlarged to include the concept of surface energy; in this form it was precisely stated by A. M. Gaudin' as follows: "The efficiency of a comminution operation is the ratio of the surface energy produced to the kinetic energy expended." According to the theory in its second form, measurements of the surface areas of the feed and product and determinations of the surface energy per unit of new surface area produced give the useful work accomplished. Computations using the best values of surface energy obtainable indicate that perhaps 99 pct of the work input in crushing and grinding is wasted. However, no method of comminution has yet been devised which results in a reasonably high mechanical efficiency under this definition. Laboratory tests have been reported- hat support the theory in its first form by indicating that the new surface produced in different grinds is proportional to the work input. However, most of these tests employ an unnatural feed consisting either of screened particles of one sieve size or a scalped feed which has had the fines removed. In these cases the proportion of work done on the finer product particles is greatly increased and distorted beyond that to be expected with a normal feed containing the natural fines. Tests on pure crystallized quartz are likely to be misleading, since it does not follow the regular breakage pattern of most materials but is regularrelativelybreakage harder to grind patternat the finer sizes, as will be shown later. This theory appears to be indefensible mathematically, since work is the product of force multiplied by distance, and the distance factor (particle deformation before breakage) is ignored. The Kick theory4 is based primarily upon the stress-strain diagram of cubes under compression, or the deformation factor. It states that the work required is proportional to the reduction in volume of the particles concerned. Where F represents the diameter of the feed particles and P is the diameter of the product particles, the reduction ratio Rr is F/P, and according to Kick the work input required for reduction to different sizes is proportional to log Rr /log 2." The Kick theory is mathematically more tenable than the Rittinger when cubes under compression are considered, but it obviously fails to assign a sufficient proportion of the total work in reduction to the production of fine particles. According to the Rittinger theory as demonstrated by the theoretical breakage of cubes the new surface produced, and consequently the useful work input, is proportional to Rr-l.V f a given reduction takes place in two or more stages, the overall reduction ratio is the product of the Rr values for each stage, and the sum of the work accomplished in all stages is proportional to the sum of each Rr-1 value multiplied by the relative surface area before each reduction stage. It appears that neither the Rittinger theory, which is concerned only with surface, nor the Kick theory, which is concerned only with volume, can be completely correct. Crushing and grinding are concerned both with surface and volume; the absorption of evenly applied stresses is proportional to the volume concerned, but breakage starts with a crack tip, usually on the surface, and the concentration of stresses on the surface motivates the formation of the crack tips. The evaluation of grinding results in terms of surface tons per kw-hr, based upon screen analysis, involves an assumption of the surface area of the subsieve product, which may cause important errors. The evaluation in terms of kw-hr per net ton of —200 mesh produced often leads to erroneous results when grinds of appreciably different fineness are compared, since the amount of —200 mesh material produced varies with the size distribution characteristics of the feed. This paper is concerned primarily with the development, proof, and application of a new Third Theory, which should eliminate the objections to the two old theories and serve as a practical unifying principle for comminution in all size ranges. Both of the old theories have been remarkably barren of practical results when applied to actual crushing and grinding installations. The need for a new satisfactory theory is more acute than those not directly concerned with crushing and grinding calculations can realize. In developing a new theory it is first necessary to re-examine critically the assumptions underlying
Jan 1, 1953
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Institute of Metals Division - Measurement of Particle Sizes in Opaque BodiesBy R. L. Fullman
IN the investigation of metallurgical transformations and the relationships between microstructure and properties of metals, it frequently is desirable to obtain a measurement of the relative amounts of the various phases present and of the mean size of particles into which each phase is dispersed. The relative amounts of the phases can be measured by the classical methods of area, lineal, and point analysis,1-5 in accordance with the principle that the volume fraction of a phase, the fraction of a polished cross section occupied by the phase, the fraction of a random line occupied by the phase, and the fraction of randomly arrayed points occupied by the phase are all equal. The validity of this relationship depends only on the attainment of a truly random sample of area, length, or points, and not on the size, shape, or distribution of the particles constituting the phase. Smith and Guttman8 have derived a relationship between the interface area per unit volume S, and the measurable quantities L., the interface length per unit area on a cross section, and NL, the number of interfaces per unit length intersected by a random line. Their equation, Sv = — L8 = 2NL is also valid regardless of the distribution of particle sizes and shapes. In contrast to the situation concerning measurement of relative fractions of phases and of interface area, the measurement of particle sizes in opaque samples has not been subjected to a complete analysis. It has been common to measure some lineal or area dimension of particles on a polished cross section and to use the mean value as a qualitative measure of particle size. In the present paper, quantitative relationships are established among the various mean dimensions on a polished cross section and the actual dimensions of the particles present. Particles of Uniform Size Spheres: If a metal sample contains particles of a phase a dispersed in the form of spheres of uniform size, a polished cross section through the sample will reveal circular areas of phase a with radii from 0 to ?, the radius of the spheres. Consider a cube of unit dimensions to be cut from the sample. If a cross section parallel to one of the cube faces is examined, the average number of particles per unit area (N,) equals the number of particles per unit volume (Nv) times the probability p1 that the plane would intersect a single sphere positioned at random within the unit cube. Since, of the various possible positions for the cross-sectional plane over the unit length from top to bottom of the cube, only those positions existing over the length 2r would lead to the plane intersecting the sphere, the probability of intersecting a single sphere is just 2r. N8= Nvp1 = Nd-2r [1] Applying the equality of area and volume fractions, the relationship is found between sphere size and average area s of uniform spheres intersected by a random cross section, 4 - f = NV V = Nr . — pra = N s = Nd . 2rs S = —pr2 [2] A similar analysis reveals the average traverse length across spheres of uniform size when random lines are passed through the sample. If a randomly oriented unit cube is cut from the sample and a randomly positioned line is passed through the cube parallel to a cube edge, the number of spheres intersected by the line (Nl) equals the number of spheres per unit volume times the probability p1 of the line hitting a single randomly placed sphere in the cube. Since possible positions of the line occupy unit area, and possible positions for which it will pass through the sphere occupy an area of pr2, the probability of the line hitting a randomly placed single sphere is pr2. NL = Nv p1 = Nvpr2 [3] Combining this relationship with the equality of volume and lineal fraction, the desired relationship is obtained between radius and mean lineal traverse length -i, for spheres of uniform size. 4 - - 3 l=4/3r [4] Circular Plates: Consider a sample containing particles of a phase a in the form of circular plates of uniform radius r and thickness t, where r >> t. If the plates are randomly oriented, as in a sufficiently large sample of a fine grained polycrystalline material, area and lineal analysis may be carried out with parallel cross-sectional planes and lineal traverses. If the plates are not randomly oriented, it is necessary to randomize the orientation of the cross-sectional planes and traverse directions. Let a unit cube be cut from the sample, and a cross-section plane be passed through the cube parallel to one of the cube faces. The number of plates cut by the cross-sectional plane per unit area is equal to the number of plates per unit volume times the probability of a plate intersecting a single randomly positioned and randomly oriented plate in the cube. If J is the component of the plate diameter in the direction normal to the cross-sectional planes, the probability of a plane cutting a single randomly oriented plate is equal to J, the mean value of J for all possible orientations of the plate. Let 4 be the dihedral angle between a plate and the cross-sectional plane, and let p?, d? be the probability that a plate makes an angle between 4 and ? + d? with the cross-sectional plane. Then for ran-
Jan 1, 1954
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Producing-Equipment, Methods and Materials - Sand Movement in Horizontal FracturesBy H. A. Wahl, J. M. Campbell
This study extends our information on solid-liquid slurries to the flow of sand in horizontal fractures. Inasmuch as this is basically an unsteady-state process, a comprehensive photographic study was undertaken in a 10-ft windowed cell to determine if the basic flow regimes described for steady-state flow in pipes applied to the subject process. Since the number of potential variables far exceeds the capacity of a single study, emphasis has been placed on the effects of sand concentration, oil viscosity and oil flow rate. The extensive photographic evidence obtained has proven very valuable in gaining an insight into the basic flow mechanisms. Being able to follow visually the flow characteristics that accompany the quantitative data is valuable in the application of the results. Although the use of dimensionless parameters was carefully investigated. it was found that the data obtained could be more easily, and as accurately, correlated by judicious use of the dimensional variables investigated. However, a study into the feasibility of scaling slurry flow was made in the event this technique is justified in future investigations. The data presented show that the pressure behavior observed in solids transport in pipes basically applies to slurry flow in horizontal fractures. The roles of the parameters are altered but a basic equivalence exists. The most significant correlating parameter was the oil viscosity (µo) and the bulk velocity of the slurry (vn), expressed as ''µv" product. The most significant correlation expresses the rate of advance of the sand as a function of the variables investigated. There are many practical ramifications of this phase of the investigation that should aid in better treatment design. Evaluation of sand advance rates provides a means of estimating sand placement efficiencies during a treatment and the resulting sand distribution in the fracture. The results show that sand placement efficiencies are low under typical treatment conditions. A brief description of the effects of overflushing is also included. INTRODUCTION The flow of sand-oil slurries in fractures is an area in which little basic knowledge is available. This stems to some degree from the fact that it is impossible to duplicate fractures at the surface. They occur in various shapes and sizes with an infinite combination of irregularities. Unfortunately, we can never "see" these fractures except in cores and by indirect means of measurement. In spite of this inherent difficulty, it is desirable to develop some basic concepts that will provide a better understanding of the sand transport mechanism. An insight into the problem is provided by investigations of fluid flow in rectangular conduits. Several studies on the flow of liquids in non-circular conduits1,13 show that a Reynolds number-Fanning friction factor relationship can be written if the hydraulic diameter is substituted for the regular diameter in a circular pipe. This hydraulic, or equivalent, diameter is taken as four times the cross-sectional area occupied by the flowing fluid divided by the wetted perimeter. Eq. 1 expresses an extension of this same work when applied to infinite parallel planes b distance apart.' Eq. 1 is a theoretical equation expressing the friction factor as a function of the Reynolds number for laminar single-phase fluid flow. This expression has been verified experimentally. The equivalent expression for a smooth circular conduit differs only in that the value of the constant is 16 instead of 24. Numerous studies have related friction losses to Reynolds number in both circular and non-circular conduits. These results are widely used and are not reviewed here. Huitt' investigated the effect of surface roughness on fluid flow in simulated fractures. He concluded that fluid flow in fractures may be treated similarly to fluid flow in circular conduits. This work, together with that of Nikuradse,' shows that surface roughness has no appreciative effect upon the resistance to flow in the viscous flow region. In the region of turbulent flow, surface roughness is a prominent factor. Hydraulic conveyance literature is another important source of information. Durand3 has attempted to organize systematically the variables involved in hydraulic-solid transport in pipes. He has classified the modes of flow into three types according to the size of the particles in the mixture— homogeneous mixtures, intermediary mixtures and heterogeneous mixtures. With the usual concentrations and flow rates used in hydraulic transportation, particles with diameters of less than 20 or 30 microns form eszentially homogeneous mixtures with water. The data show, however, that even small materials will tend to settle out under laminar flow conditions. Mixtures containing solids over 50 microns in diameter do not achieve total homogeneity even under turbulent flow conditions. Particles from 50 microns to 0.2 mm in diameter may be transported in fully suspended flow at normal transport velocities although the concentration in the vertical plane is not uniform. Above 2 mm in diameter solid materials are transported along the bottom of the conduit at a velocity substantially less than that of the liquid itself. Between 0.2 and 2 mm in diameter, the particles tend to be in a transition zone between heterogeneous suspended flow and deposit flow at normal hydraulic transport velocities. The sand sizes used in fracturing usually fall in this size range. It is interesting to note that the grain size range designated by Durand for this transition zone corresponds closely to the transition zone between
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Institute of Metals Division - Solid State Physics in Electronics and in Metallurgy (Institute of Metals Division Lecture, 1952)By W. Shockley
THIS lecture can best begin with a statement of the chief conclusion: The metallurgical industry will find profit in supporting fundamental research on dislocations. This support should be done both in their own laboratories and in universities. My lecture consists of an exposition of the basis for this conclusion. The experience on which I base it is drawn largely from two fields in solid state physics—one field is transistor electronics and the other is dislocation theory. At present the relationship of solid state physics to technology is different in these two fields. In electronics without question, the physics has led the technology. In metallurgy, on the other hand, the technology in the form of metallurgical art is far ahead of the fundamental science. In transistor electronics, physics has suggested and can still suggest previously unachieved combinations of matter that will have new and useful properties; that is, the physicist can make specific predictions. The physicist can also have some confidence that the predicted devices will actually come into existence in a matter of months or years and that they will live up to the predictions. In metallurgy, the physicist cannot to a comparable degree make predictions and have the same hope that they will lead to something new and valuable. There are a number of reasons for this difference. The first is simply historical. Transistor physics is young. It may be regarded as dating from the announcement of the transistor, in which case it is about four years old, or from the first real control of semiconductors as materials (this was accomplished largely by metallurgists, by the way) in which case it is about ten years old. Metallurgical art, on the other hand, is thousands of years old. There is no doubt that the advance of this art has been and will be hastened by a good fundamental understanding of the quantum theory of atomic phenomena. It, is too much to expect, however, that theory will soon catch up with the lead that practice has gained in a thousand years, and that theory will then point out specific pathways to better materials. It seems more probable that modern atomic theory will serve to interpret and organize information much as thermodynamics has done through phase diagrams. In this lecture, I shall emphasize an important feature common to both solid state electronics and to metallurgy. This common feature is the harmonizing principle that justifies discussing electronics and metallurgy as related topics in solid state physics. In both cases the important properties of the materials arise from imperfections. By imper- fections I mean deviations of the materials from perfect single crystals. The imperfections may be of many forms. From the point of view of utility they may be either good or bad, and a given type may be good or bad depending on circumstances. The technical material of my lecture will be divided into two parts. The first will be chiefly concerned with four types of imperfections in germanium crystals. The control of these imperfections makes possible the fabrication of useful electronic devices. A good example of such control is the junction transistor, which I shall discuss from this viewpoint later. The junction transistor, as some of you may have heard, can be used as an amplifier of electrical signals and in a number of respects surpasses what has hitherto been achieved with vacuum tubes. The second part of my technical material will be concerned with dislocations. For about fifteen years the theoretical physicist has had dislocations in mind as the most important kind of imperfection in metals. He has, however, until recently had experimental material of a highly speculative nature to back up his assertions. I am fortunate in the timing of this lecture to be able to describe some recent results that put dislocations on a far more definite basis than has been the case in the past. In fact there are now some experiments which reveal the characteristic properties of dislocations almost as clearly as experiments in transistor physics reveal the properties of holes and electrons, properties that I shall soon describe. It is this advance in the status of dislocations that emboldened me to make my initial assertion that the metallurgical industry will profit from supporting fundamental research on dislocations. Transistor Electronics In order to discuss imperfections in semiconductors, it is necessary to visualize a reference condition that may be regarded as perfect. In the cases of silicon and germanium, which find application in transistor electronics,' the perfect structure is the diamond structure shown in Fig. I. In this structure, each atom is surrounded by four neighbors with which it forms four covalent or electron-pair bonds. These bonds use all of the four valence electrons possessed by each of the silicon or germanium atoms. The electronic structure of the crystal is thus complete and perfect. A crystal of silicon or germanium with a perfect electron-pair bond structure would be an insulator, In order for electrical conduction to occur, it is necessary for imperfections to arise in the electronic structure. In this lecture, I shall discuss four possible imperfections whose symbols and relationships are indicated in Table I. We shall consider first, as an example, a crystal of silicon containing an arsenic atom as an impurity.
Jan 1, 1953
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Iron and Steel Division - Topochemical Aspects of Iron Ore ReductionBy T. L. Joseph, G. Bitsianes
The gaseous reduction of dense iron ore is a topochemical process in which reduction takes place at distinct interfaces between solid phases or layers. Under normal conditions, these interfaces remain parallel to the exterior surface of the ore body as they move inward. Certain conditions, such as cracking, high porosity, impurities, entrapped residual oxides, may cause departures from normal topochemical behavior. THE gaseous reduction of dense iron ore proceeds at interfaces between several solid phases or layers.',' Under normal conditions, these interfaces progress inward and remain parallel to the exterior surface of the ore body. This topochemical behavior is clearly illustrated in Fig. 1 which shows partially reduced specimens of natural and synthetic hematite. Using a coordinated sequence of macro, micro, and X-ray examinations, the authors1-'2 found that the number of interfaces and participating phases was in agreement with the Fe-0 system. Above 570°C, reduction of the ore involved a maximum of three common boundaries between four solid phases: iron, wiistite (Fe,O), magnetite (Fe,O,), and hematite (Fe,O,). Below 570°C, reduction proceeded through two interfaces between three phases: iron, magnetite (Fe,O,), and hematite (Fe,O,). The decrease in the number of phases below 570°C was due to the instability of wiistite below this temperature. The sequence of phases was also consistent with the equilibrium requirements. For example, the layers of iron oxides that were formed in topochemical fashion were always orientated in the order of increasing oxygen content. Thus, in Fig. 1 an outer layer of metallic iron is followed in turn by a thick intermediate band of black wiistite, by a thin layer of light magnetite, and finally by a relatively large core of hematite. This arrangement of the oxide layers was due to restrictions in reducing conditions which were imposed by the physical structure of the solid. The highly reducing gas on the outside of the particle gradually lost its reducing power as it penetrated into the specimen. On a macro scale, the layers of the various oxides appeared to be sharply defined and uniform in composition. Microexamination of the sections, however, revealed that the interfaces did possess measurable widths which varied with the porosity and chemical activity of the oxide phase undergoing reduction. For example, Fig. 2 shows three interfaces in a dense hematitic ore which was partially reduced at 850°C. At the iron-wiistite interface where the greatest porosity developed, the reaction proceeded over a zone 25 to 30 microns in width. Toward the interior, the interfaces became progressively narrower until at the magnetite-hematite boundary the reaction zone was about 1 micron wide. In this region the structure was exceedingly dense; the hematite possessing a porosity on the order of 3 pct. A careful micro study across polished layers of the various oxides revealed generally homogenous and single-phase structures. As reported in a previous paper,' the wiistite layer was characterized by an increase in oxygen content with depth of penetration. The topochemical behavior of reduction was studied in six types of ore of different origin, composition, and physical structure. In most cases, reduction proceeded at the boundaries of well defined layers or phases, and this behavior may be regarded as normal for most dense fine grained ores. Deviations from Ideal Topochemical Behavior A number of deviations from the normal topochemical behavior were noted. In these cases, the continuity of the reduction interfaces was disrupted in one of four ways: 1—Cracking of the specimen interrupted the geometric configuration, and the interfacial advance was no longer parallel to the exterior surface. 2—As a result of high porosity, the interfaces were spread over an appreciable distance and all but obliterated. 3—Impurities in the ore promoted a variety of deviations, including cracking. 4—A residual oxide phase was entrapped in the reaction product and left behind the advancing macro interface. Results from Cracking: A crack leading into the interior of an ore specimen presents a path of least resistance for the counter-flow of reducing gases and gaseous reduction products. Higher reducing conditions can be maintained along such cracks and reduction accordingly will propagate well ahead of the normally advancing reduction interfaces. Cracking was caused by a number of factors, one of which was the thermal spalling of impurities in the massive form. A more general type of cracking was due to reduction and was found in all dense varieties of natural and synthetic hematite, particularly in the temperature range of 500" to 700°C. The effect is shown clearly in Fig. 3. In this case, a dense sphere of pure hematite was partially reduced at 650°C for 100 min. The macrosection shows that one large reduction crack had penetrated the specimen and disrupted the normal topochemical advance of the interfaces. The outer layer of iron was only slightly affected but the thin dark layer of wiistite, adjacent to the ferrite, had widened perceptibly as it progressed along the crack. Farther inward, the magnetite layer was greatly disrupted and had penetrated irregularly to form islands of unaltered white hematite. A great deal of internal cracking is evident in the magnetite phase. From a practical point of view, the cracking of dense ores in the blast furnace could lead to desirable as well as undesirable effects. The general result
Jan 1, 1956
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Part V – May 1969 - Papers - Dissolution of Alumina in Carbon-Saturated Liquid IronBy Kun Li, Alex Simkovich
The rate of dissolution of alumina in carbon-saturated liquid iron has been studied experimentally in a system where alumina was in the form of a cylindrical rod immersed in an iron bath contained in a graphite crucible. Data obtained consisted of the concentrations of aluminum in the melt as a function of time. In the case of static experiments, the data are shown to agree with theoretical prdictions based on the diffusion of aluminum.. The rate of dissolution was greatly increased by the rotation of the alumina rod. It is concluded that the diffusion of aluminum from the alumina/metal interface is the rate-controlling step. In the past, thermodynamic investigations of systems encountered in ferrous process metallurgy have received widespread attention. More recently, considerable work has been devoted to the study of kinetics associated with these systems in an effort to determine their rate controlling mechanisms. The alumina-iron system is of great importance in ferrous metallurgy. Yet information concerning kinetics of reaction in this system is seriously limited. The present study was made in order to establish the rate-controlling step for dissolution of solid alumina in liquid iron. LITERATURE REVIEW A number of papers concerning dissolution of solid metals in liquid metals have been reported in the literat~re. Generally, for these simple systems, dissolution is controlled by mass transfer of the dissolving species. Complex systems involving dissolution of solid metal carbides and oxides in liquid metals and slags have been studied to a much lesser extent. Skolnick5,6 reported on the reaction between liquid cobalt and poly-crystalline cylinders of tungsten carbide, in which the cylinders were dissolved while being rotated about their longitudinal axes at various speeds and temperatures. As a result of unexpected preferential grain boundary attack by the liquid cobalt, large errors in the measured dissolution rates occurred because of loss of tungsten carbide grains to the liquid cobalt. Nevertheless, it was possible to establish that the liquid Co-W carbide reaction was not controlled by mass transfer. In a similar approach, cooper7 was able to show that artificial sapphire rods, (alumina single crystals) dissolving in lime-alumina-silica slags obeyed a mechanism of mass transfer control. Here, again, the rods were rotated at various speeds and temperatures, and the process was followed as a function of these variables. Forster and Knacke8 took a practical approach to reaction between slags and refractories. By blowing argon through refractory cylinders of silica, silli-manite, or dolomite and directing the gas to rise along the slag-refractory interface, it was possible to increase the rate of mass transfer. Although the method was admittedly crude, it nevertheless permitted an evaluation of the relative stabilities of refractories with respect to slag attack. Data were interpreted on the basis of mass transfer control. EXPERIMENTAL TECHNIQUE Apparatus. An illustration of the apparatus used in this study is shown in Fig. 1. The furnace consisted of a Morganite recrystallized alumina tube wound with a molybdenum coil. A secondary molybdenum heater was mounted around the upper half of the primary coil to aid in controlling the thermal gradient within the furnace. The primary heater tube was 3 in. in ID and 30 in. long. A reducing mixture of 95 pct N and 5 pct H was maintained around the heating elements. Thermal insulation was provided by alumina powder. The chamber within the primary combustion tube contained a boron nitride block near the top to assist in controlling the thermal gradient to the furnace and also to provide a bearing surface for the rotating graphite shaft. The outside diameter of the graphite shaft was $ in. A separate threaded graphite specimen holder was screwed into the end of the shaft. The holder contained a tapered hole drilled into the end to guide the oxide specimens as they were pressed into it for mounting. Additional guidance for the rotating graphite shaft was furnished by a water-cooled bronze bushing attached to the top of the furnace. A steel clamp was fastened to the upper end of the graphite shaft and rested on a thrust bearing; the shaft and clamp were driven by a dc motor through a set of gears. Two O-rings located immediately above the bronze bushing maintained a gas-tight seal about the graphite shaft. The lower half of the alumina tube housed the crucible and charge, which were placed on a 3/4-in. diam movable alumina support tube. With this arrangement, charges could be inserted into or removed from the furnace while the hot zone was maintained at or above 1000°C. To control the temperature of the furnace, the thermocouple was mounted inside the support tube and in contact with the crucible bottom. Stray electric fields in the furnace were of sufficient intensity to cause erratic indications by the thermocouple. By enclosing the thermocouple protection tube in a molybdenum sheath and grounding this shield, the problem was eliminated. Output of the thermocouple went to an automatic continuous balance controller. Procedure. A typical run was as follows. First, electrolytic iron was premelted in graphite crucibles and cast into graphite molds with the same configura-
Jan 1, 1970
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Minerals Beneficiation - Effect of pH on the Adsorption of Dodecylamine at the Mercury-Solution InterfaceBy S. Usui, I. Iwasaki
The effect of pH on the adsorption of dodecylamine at the mercury-aqueous solution interface was investigated by differential capacity and electrocapillary measurements. With dodecylammonium acetate, the differential capacity curves showed two desorption peaks in the cathodic branch with their relative intensities varying with the solution pH. With dodecyltrimethylammonium chloride, only one cathodic de-sorption peak was observed in the same pH range. Through thermodynamic analysis of the electrocapillary curves, the adsorption density of undissociated amine was evaluated separately from that of aminium ion. The adsorption densities of the un-dissociated amine and of the total amine increased with increasing pH. The ratio at the interface of undissociated amine to aminium ion was several orders of magnitude greater than the ratio in the solution and increased with increasing pH. The potential at the closest distance of approach of counter ions to the mercury surface was compared with values of zeta potential on quartz previously reported. The most important variable in the flotation separation of minerals is probably the pH of the pulp, and a number of theories have been proposed to explain its effect on the condition of the mineral surfaces, on the dissociation of collectors and of inorganic and organic species (accidentally present or intentionally added) in the pulp, and on the mineral-collector interaction. In the development of a theoretical background for oxide flotation systems, an experimental approach based on electrokinetic measurements has been of much value, although the effect of pH becomes confounded since it governs both the electrochemical conditions of the oxide surface and the dissociation of the collector. For investigation of the adsorption behavior of long-chain collectors on oxide minerals, however, electrokinetic potential measurements are the most widely used technique. Hydrogen and hydroxyl ions are found to be the potential determining species, thereby governing the interfacial electrical conditions. The electrostatic interaction between the charged mineral surfaces and ionized collectors is regarded as the driving force for the adsorption of the collectors. An association of alkylamine collectors adsorbed on quartz surfaces has been postulated from streaming potential measurements, and a term "hemi-micelles" has been proposed.' The possibilities of coad-sorption of undissociated amine along with aminium ion has been inferred from contact angle measurements? and from adsorption studies.~ Electrochemical titration as applied to silver sulfide provides a more quantitative approach to the analysis of the electrical double layer at an ionic solid-solution interfaceqG and the electrochemical evidence for the adsorption of amine at pH 4.7 indicates a specific affinity of dodecylammonium ion towards silver sulfide surfaces, whereas at pH 9.2 the adsorbed species might be free arnine." A combination of differential capacity and electrocapillary measurements on a dropping mercury electrode was reported to be a sensitive method of provid- ing reliable information on the adsorption behavior of dodecylammonium acetate (DAA) at a natural (near neutral) pH.? It was also shown that there were striking similarities in the properties of the double layer and in the adsorption behavior of the amine on mercury and on such ionic solids as quartz, silver sulfide, and silver iodide. The effect of pH on the differential capacity curves at a mercury-sodium fluoride solution interface has been investigated by Austin and Parsonss who reported that between pH 7 and pH 11 there was very little effect. In the present paper, the adsorption behavior of DAA was investigated as a function of pH through differential capacity and electrocapillary measurements and the information gathered was correlated with that available in literature on quartz and silver sulfide. Experimental The apparatus and the method used for determining the differential capacity and the electrocapillary curves were identical to those described previously.' The ionic strength of the supporting electrolyte was fixed at 0.1 M with potassium fluoride, and the pH of the solution with potassium hydroxide. Only the neutral to alkaline range was covered in order to avoid the dissolution of the glass vessel with hydrofluoric acid. Results In Fig. 1 the differential capacity has been plotted against the applied potential at a DAA concentration of 10-' M at three different pH values. The curves are characterized by one capacity peak in the anodic branch, by two capacity peaks in the cathodic branch, and by a marked depression in capacity between the peaks. The depression indicates an adsorption of the arnine in this potential range. One of the cathodic peaks appears at pH 7.3 near -1.4 v and decreases with increasing pH. The other appears at pH 8.9 near —1.2 v and increases with increasing pH. At pH 9.6 only the latter peak is observed. Beyond the cathodic peaks, all the curves tend to converge with the curve in the absence of DAA, implying that two different species are being desorbed in this potential region. The anodic peak near 0.0 v increases markedly with increasing pH. The well-defined anodic peaks at pH 8.9 and 9.6 were accompanied by an appreciable increase in the current flow (in excess of O.luA), and, therefore, is a "pseudo-capacity"'" due to a
Jan 1, 1971
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Part II – February 1969 - Papers - Tensile Properties of Unidirectionally Solidified AI-Cu AI2 Eutectic CompositesBy A. S. Yue, A. E. Vidoz, F. W. Crossman
Tensile specimens were prepared from a single grain of an epitaxially grown Al-CuAl2 eutectic ingot. The eutectic lanzellae were oriented parallel and perpendicular to the tensile axis of the specimens. Since the composite was of the eutectic composition, the aluminum-rich matrix could dissolve up lo 5. 7 wt pct Cu in solid solution and, therefore, was amenable to strengthening by precipitation hardening. The tensile properties of the eutectic single crystals were determined at room temperature as functions of interlamel-lar spacing, platelet orientation, and thermornechanical trealment. The obserced variations in composite stress and modulus with respect to the level of' composite strain are discussed in terms of premature fracture of CuAlz platelets, a distribution function for the strength of the lamellae, and unequal strains due to localized fracture of' platelets. The discontinuous fiber composite model of Kelly and Tyson is modgied to account for a changing distribution of fiber lengths during composite loading. The tensile properties at elevated temperatures were determined for the direc-tionally solidified eutectic oriented with platelets parallel to the tensile axis. The observed properties are attributed to the onset of plasticity of the CuAL2 phase above 150°C. DURING the investigation of whisker- and fiber-reinforced metallic matrix composites in recent years, two major problem areas have developed: 1) The fabrication of the composite involves tedious handling techniques in order to obtain a unidirection-ally aligned and uniformly spaced set of whiskers in the metal matrix. 2) Due to weak interfacial bond strengths or because of the formation of additional embrittling phases at the metal-fiber interface during long-time exposure or fabrication at elevated temperatures, many composite systems have exhibited considerably lower strengths than those predicted by a law of mixtures analysis.' These problems have been bypassed by the technique of growing whiskers and plates of high-strength materials in a ductile metal matrix by controlled unidirectional eutectic solidification.2 The tensile properties of directionally solidified A1-CuA12 eutectic are presented here. This alloy consists of a ductile aluminum matrix, containing up to 5.7 wt pct Cu in solid solution, which is amenable to precipitation hardening by heat treatment and a reinforcing high modulus CuAlz intermetallic phase. The two phases are present in the form of alternating platelets or lamellae. The microstructural stability of this unidirectionally solidified alloy at elevated temperatures has been studied extensively.3.4 and preliminary tensile and bend tests have been reported. 5-7In the present investigation the tensile properties of the A1-CuA1, eutectic have been studied as a function of several ther-momechanical variables: solidification rate. heat treatment. rolling at elevated temperatures. and lamellar orientation. It was felt that the uniformity of structure and excellent interfacial bonding would give tensile properties concomitant with the metal matrix composite theory of strengthening proposed by Kelly and coson. 8-9 The tensile properties that were obtained point to a wide distribution of strengths for the CuAlZ platelets, which leads to large deviations from the predicted mechanical behavior for this composite. EXPERIMENTAL PROCEDURE Epitaxial Growth of Eutectic Alloy. The A1-CuA1, eutectic alloy was prepared by an epitaxial growth process. Sections of a master alloy ingot (total impurity content <0.008 pct) were placed in an alundum boat, melted. and directionally solidified to obtain a multigrained plate 12 by 2 by 4 in. This plate was tapered at one end to mate with a seed crystal 1; in. long and 4 by $ in. square. Then the seed-plate combination was placed in an alundum boat which sat in a quartz tube passing through the center of a horizontal resistance wound tube furnace. A dried argon atmosphere was maintained. The temperature gradient in the furnace was such that the liquid-solid interface of the eutectic alloy was located near the end of the furnace and could be observed through the quartz tube. Single-crystal plates were formed by melting the material back to the midpoint of the seed crystal of the desired platelet orientation and then epitaxially growing the plate from the seed by withdrawing the alundum boat from the furnace at a constant rate. This technique was used to produce aluminum and CuA12 lamellae parallel and perpendicular to the transverse direction on the plate. Metallographic examination showed that both phases were continuous across the original liquid-solid interface. It was also possible to grow a plate from two seeds placed side by side: and, although the lamellae of one seed were oriented at 90 deg to those of the second seed, the interface between the two grains remained parallel to the growth direction along the entire ingot length. Maintenance of a straight intergranular boundary during the solidification process was possible as long as both seeds were oriented with their original growth direction parallel to the solidification direction of the plate. Eutectic plates were directionally solidified at rates of 0.2, 1.0. and 4.7 cm per hr and sectioned transversely to the solidification direction to determine the apparent inter lamellar spacing of the lamellae. Metallographic examination was also employed
Jan 1, 1970
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Part III - Papers - Anodic Behavior of GaAs Single Crystals at Increased Current Densities in Alkaline and Acidic SolutionsBy M. E. Straumanis, J. -P. Krumme
In basic ([KOH + KCl] with a total polarity of 2) or acidic (2N H2SO4) electrolytes and at anodic current densities of more thun 2 to 4 ma per sq cnz, n-type GaAs single crystals of lozo resistivity preferentially dissol~je forming etch tunnels with triangular or civc~ilay cross sections and of a width between 0.5 arid 5 p. These etch tunnels are oriented along any one of the four possible (111) directions of GaAs. However, their growth occurs only in one direction of a given (111) whick apparently is determined by the atomic sequence Ga —As (and not the rezlerse) in respect to an individual valence bridge in the crystal. It is concluded from comparison with the cubic lattice structure of GaAs that the etch tunnels represent macroscopic evidence for the tetrahedral bonds and their polar properties. If the anodic current density is increased the tunnel fomation results in the development of a fibrous surface layer consisting of GaAs. The latter separates frorn the substrate (in an anodic s~irface disintegration process) by the growth pressure of an As,0, filnz forming in the interior of the fibrous layer, 100 to 200 µ under the surface, at more than about 50 ma per sq cni. The fibrous GaAs film has the same crystallographic orientation as the substvate and represents a skeleton of the original crystal. Since the etch-tunnel density in a separated GaAs layer is about 108 c?n-', and the etch tunnels develop only along (111) in a given polar direction, it is assurraed tlmt the dislocations have no influence on the growth of these tunnels. ElECTROLYTIC treatment of smooth surfaces of poly- and single-crystalline GaAs at high anodic current densities causes the formation of porous surface layers.' This phenomenon suggests comparison with effects being observed with magnesium,' indium,, gallium,4 and aluminum5 and known as "anodic disintegration". The purpose of the present paper is to explore and to explain the reasons for the formation of such surface layers on GaAs and, in particular, to investigate the influence of the lattice polarity of this III-V compound semiconductor in the (111) direction on the anodic dissolution behavior. GaAs SINGLE CRYSTALS For the experiments described below GaAs single crystals from the Monsanto Co., St. Louis, Mo., were used. Their impurity levels were below 1 ppm and their dopant levels between 1 and 100 ppm. They were grown in (111) using the Czochralski or the gradient-freeze technique. The crystals had n-type conductivity and electric resistivities between 1 and 5 ohm-cm. EXPERIMENTAL The GaAs single-crystal rods were cut perpendicularly to (111) into wafers of about 1 mm thickness using a wire-blade crystal slicer and an aqueous slurry of Sic or a diamond saw. The orientation of the faces of these wafers were checked by Laue back-reflection patterns. If there was a deviation from (111) the faces were abraded under a certain angle using grinding paper and distilled water. The damaged surface layer was removed from each crystal by chemical etching with a mixture of 1HF:1HNO3: 1H20 or 2HF:1HNO3:2HAc (glacial). {110) faces were obtained by mechanical cleavage, producing surfaces which did not require a further treatment. The GaAs wafers were mounted using "alligator" clamps instead of soldered electrical contacts.' Only the bare crystal surfaces were dipped into the electrolyte. The clamps were coated with insulating wax to prevent any contact with the electrolyte. The experiments were carried out in aqueous 2 N H2so4,' or in an aqueous solution of KOH and KCl1 (1 mole KOH + 1 mole KCl in 1000 cu cm solution). Anodic current densities up to several hundred ma per sq cm were applied for periods between 30 sec and 2 hr. For the purpose of investigating the initial steps of disintegration the anodic current density applied never exceeded 20 ma per sq cm. The films which partially separated from the anodic surfaces under high-field conditions were treated with KOH to further their detachment by dissolving the As2O3 formed. The washed and dried films were pasted to strips of filter paper, and Laue pictures were made. The back-reflection patterns obtained were compared with those of the original anode surface before and after anodic dissolution. Furthermore, space reciprocal lattices7 were constructed from asymmetric rotation crystal patternsa which permitted the determination of the crystallographic orientation of the detached films of the corrugated anodic surfaces. The disintegration products were identified from assymmetric powder patterns.8 The polarity of the {111) faces was determined by chemical etching with mixtures of 1HF:1H2O2(30 pct): 2H2O or 1HNO3:2H2O. Different patterns on each of two inverse (111) sides appeared.'-l8 The correlation of these patterns to the Ga{111) or the As(111) side has already been established by the use of light figures,18-20 by X-ray diffraction near the absorption edges of gallium and arsenic,'lmZ4 and by LEED measurements.25 The geometric structure of these surfaces and the interior of the anodically attacked crystals were observed and photographed with a high-power microscope using oil immersion objectives up to magnification of X1720.
Jan 1, 1968
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Part III – March 1968 - Papers - Evaluation of Bulk and Epitaxial GaAs by Means of X-Ray TopographyBy Eugene S. Meieran
The effects of methods of crystal growing, wafer sawing, polishing, routine handling, diffusion, and epitaxial growth on the defects in GaAs are reviewed and studied using reflection and transmission X-ray topographic techniques. In general, it was found that boat-grown crystals exhibited fewer defects than Czochralski crystals, although all crystals showed large numbers of precipitates visible when examined in the electron microscope. Mechanical surface treatments such as sawing and mechanical polishing introduce damage to a depth of about 5 µ, most of which can be removed by suitable chemical or chem-mechanical polishing. In addition, defects can be introduced through routine handling of wafers, for example with metallic tweezers. These defects can be quite severe, and have been observed 20 µ below the wafer surface. Defects can also be introduced through diffusion and epitaxial growth. These defects, which include precipitates, growth pyramids, stacking faults, dislocations, and so forth, can be detrimental to device fabrication. It is shown that wafers or films which appear defect-free optically can contain defects visible in the X-ray topographs. WHILE the use of GaAs in the semiconductor industry has increased very rapidly in the last few years, due mainly to the recent development of many important GaAs devices,1,2 the major limit to the production of commercial quantities of many GaAs devices remains a severe lack of suitable materials technology. This lack is apparent in two critical areas. First, production quantities of high-quality GaAs crystals, reproducibly doped and precipitate-free, simply are not available commercially, although some reasonable quality material is available on a limited first-come, first-serve basis. Second, in comparison to silicon technology, little is known about the effects of processing variables on the defects either present in as-grown GaAs or introduced through processing and handling of wafers. These areas are now receiving some attention from semiconductor device manufacturers, who are studying defects in GaAs in order to better understand how either to prevent their occurrence or to cope with their existence. Most investigations of the defects in GaAs have been made by optical microscopy3-5 or transmission electron microscopy techniques.'-' Recently, however, the imaging techniques of X-ray topography, electron mi-croprobe analysis, and scanning electron microscopy are being applied to the study of GaAs.9-14 In the case of X-ray topography, a one-to-one image is obtained that must be photographically enlarged. In compensa- tion, the defects within entire wafers may be imaged by simple scanning (Lang technique15) if the wafer is reasonably perfect, or by using the scan oscillation technique developed by Schwuttke16 if the wafer is warped or distorted. The purpose of this paper is to both review and extend the general application of X-ray topographic techniques to GaAs. Emphasis will be placed on the effects of growth and process variables on the quality and perfection of both bulk and epitaxial GaAs. Reference to optical or electron microscopy results will be made when useful. Since the effects on defects of a wide variety of processing variables such as crystal growing, sawing, polishing, diffusion, and epitaxial growth will be somewhat superficially reviewed, a fairly extensive bibliography of the most important recent results in these areas is included. However, for completeness, important defects will be illustrated here, although such defects have been previously shown by others. While this paper is concerned with defects rather than with the physics of X-ray scattering, the mechanisms of contrast formation in the topographs will of necessity be briefly mentioned. EXPERIMENTAL GaAs crystals, both boat-grown18 and Czochralski-grown,'8 containing a variety of dopants of various concentrations, were purchased from outside vendors. Wafers were sliced from the crystals using a Hamco ID saw and were mechanically polished using 1 µ diamond paste. Chem-mechanical polishing was done in bromine-methanol as described by Sullivan and Kolb.18 Chemical polishing was done using a modified sulfuric-peroxide solution, 11 parts H2SO4, 1 part 30 pct H2O2, 1 part DI water.5 Zinc diffusion was carried out in a closed tube, using a 10 pct Zn-In source at 825°C for 1 hr. Oxide masking techniques were used to select the area to be diffused. Epitaxial wafers were either purchased or prepared here. All epitaxial runs prepared here were carried out using a Ga-GaAs-AsC13 source in a closed tube at a substrate temperature of 750°C. Wafers were chem-mechanically polished and gas-etched prior to deposition. The X-ray topographs were taken on a Krystallos Lang camera, operating in the transmission scanning geometry (Lang technique15) or in the reflection scanning geometry (modified Berg-Barrett technique20,21). MoKa, radiation was used for all transmission topographs using a Jarrell-Ash 100-µ spot focus. CuKal radiation was used for all reflection topographs using a General Electric CA-7 1-mm spot focus X- ray tube. Topographs were printed from an intermediate contrast inversion film, so the contrast shown in all figures here is the same as that of the original 50-µ-thick emulsion L4 Iiford nuclear plate used to record the topograph.
Jan 1, 1969
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Iron and Steel Division - The Mechanism of Sulphur Transfer between Carbon-Saturated Iron and CaO-SiO2-Al2O3 Slags - DiscussionBy W. O. Philbrook, K. M. Goldman, G. Derge
T. Rosenqvist—The most interesting point in this paper is the observed transfer of iron into the slag in the initial stage of the desulphurization process, after which the iron again is reduced to the metallic state. The authors interpret this observation as showing that the sulphur enters the slag as an iron-sulphur compound which subsequently is decomposed by the slag. The present writer has previously suggested the following equation for the desulphurization process: S + O2- ? S2- + O For equilibrium in the blast furnace the oxygen potential is defined by equilibrium with graphite and CO of 1 atm pressure: C + O ? CO [2] During the desulphurization process the reactions proceed in the direction of the arrows. If one assumes eq 2 to be significantly slower than eq 1, the transfer of sulphur into the slag, in accordance with eq 1, will build up a local oxygen potential at the metal-slag interface very much higher than that corresponding to the value defined by eq 2. This is possible because the equilibrium oxygen potential in eq 1 is high as long as the sulphur content in the slag is low. This oxygen potential will again be able to oxidize some iron: Fe + O ? Fe2+ + O2- and an increase in the iron content of the slag will be observed. Adding up eqs 1 and 3 one obtains: S + Fe ? S2- + Fe2+ The net effect is thus in harmony with the experimental observation but is obtained without assuming any close ties between the sulphur and iron atoms during the process. Furthermore, it follows from eqs 1 and 2 that when the sulphur content in the slag increases, and equilibrium with C and CO is finally approached, the local oxygen potential at the metal-slag interface will decrease, and the iron in the slag will be reduced back into its metallic state. C. E. Sims-—The data and conclusions presented in this paper are thoroughly convincing in establishing the mechanism of sulphur transfer from iron to slag as in a blast furnace. The evolution of gaseous CO in step 3 of the reactions given on p. 1112 makes the process virtually irreversible. Assuming that the process is similar in slag-metal systems other than in the blast furnace, it is readily seen why free CaO and re-ducing conditions so greatly favor desulphurization. On the other hand, the very effective desulphurization obtained in oxidizing slags when strongly basic, must be attributed to the relatively high stability of CaS as compared to FeS. The ease and simplicity with which the reactions of classic chemistry agree with the experimental data and explain the mechanism is noteworthy. The concept of molecules of FeS, soluble in both phases (metallic iron is not soluble in the slag), migrating from the iron to the slag and there reacting with CaO, which is soluble only in the slag phase, is clear and uncomplicated. This is likewise true for step 3. Those who would deny the existence of molecules or molecular-type combinations in liquid iron, must strain to provide a mechanism so lucid. In the absence of molecules, the Fe and S exhibit a remarkable collusion. L. S. Darken—The investigation and interpretation of rate phenomena in the range of steelmaking temperatures is a difficult task. Most of the laboratory investigations of steelmaking reactions have been concerned with equilibrium. Having determined the equilibrium, our attention naturally focuses next on the mechanism and rate of approach to equilibrium. The authors seem to have contributed substantially to our understanding of these factors for the case of sulphur transfer. I should like to ask the authors whether they consider that the sulphur transfer reaction is diffusion controlled as many high-temperature reactions seem to be. If so, it would seem reasonable to suppose that the slow diffusion step of the process is the transfer across a pseudo-static layer or film similar to that considered in heat flow problems. As the diffusivity and fluidity are smaller for the slag than for the metal, it may tentatively be assumed that the sulphur gradient exists in a thin layer in the slag adjacent to the slag-metal interface and that the metal and the main mass of slag are each maintained uniform by convection. On this basis the amount of sulphur transferred across unit area per unit time is D p (?S%)/100 ?1, where D is the diffusivity, p the density, (?S%) the difference in percent sulphur on the two sides of the layer, and ?l is the layer thickness. At the beginning of the experiment the main body of the slag and hence one side of the layer contains no sulphur; therefore (?S%) may be replaced by (S%), the sulphur content of the slag at the slag-metal interface, which in turn is equal to L[S%] where [S%] is the sulphur content of the metal and L is the distribution coefficient. The rate of transfer thus becomes DpL[S%]/100 ?l, which the authors designate K[S%]. Equating these two quantities and setting D = 10-6 cm2 per sec, p = 3 g per cm3, L = 40, and K = lo-+ g cm-2 sec-1, it is found that ?l, the film thickness, is about 0.01 cm—a value of the order of magnitude of that found in heat transfer problems in liquids. The uncertainty of the numerical values used leaves much to be desired, but at least it can be said that this calculation tends to support the proposed model involving diffusion through a film. Although this does not seem to affect the general argument, I should like to call attention to the fact that the diffusivity3 of sulphur in hot metal is found (on conversion of units) to be about 10-4 cm2 per sec rather than 104 cm2 per sec as stated by the authors. The three equations written by the authors to express the steps in the overall process of sulphur transfer may alternatively be written ionically as only two Fe + S = Fe++ + S-- Fe++ + O-- + C (graphite or metal) = CO (gas) + Fe where the underscore is used to designate the metallic phase; ionic species are slag constituents. After the authors have so neatly demonstrated that iron and sulphur transfer together (at least initially), this fact seems almost self evident; from eq 4 it is seen that if sulphur acquires a negative charge during transfer
Jan 1, 1951
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Corrosive And Erosive Wear In Magnetic Taconite Grinding ( May 1984 Minerals And Metallurgical Processing )By K. A. Natarajan, S. C. Riemer, I. Iwasaki
The relative significance of corrosive and erosive wear in magnetic taconite grinding is examined. The influence of different types of aeration (nitrogen, air, and oxygen) on ball wear was established for mild steel and high carbon low alloy steel balls. Ball wear data from dry and wet grinding tests are compared with those obtained in the presence of an organic solvent that does not promote electrochemical corrosion. Marked ball grinding tests and electrochemical measurements involving ball material and magnetite electrodes indicate that contribution from oxygen toward wear (corrosive wear) is relatively small, and abrasive wear appears to be significant. Rheological properties of the slurry appear to have an important bearing on the abrasive wear of grinding balls.
Jan 1, 1985
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Cheap Bonneville Power Should Attract ElectrometallurgicaI IndustriesBy Walter W. R. May
FOR more than 25 years a few business men who represent virile private enterprise in the Pacific Northwest have been trying to awaken the community to the potential benefits of an open Columbia River. No threat of government com- petition then hung over the industry, which was adjusted to state regulation. Numerous sites were engineered and the findings were laid before the operators of heavy industry in the East, Middle West, and South -even of Europe. These engineering data became, if not the basis, the inspiration upon which the U. S. Army Engineers eventually were to "build the Columbia River Bible" - their great document known as House Document 103, the report on the Columbia River and minor tributaries.
Jan 1, 1940
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Practical and Legal Aspects of Mine FinancingBy Philip S. Mathews
THE tremendous stimulus given to the mining industry by the gold and silver policy of the present administration has found the capital market for mines ill prepared to afford practical means of financing. Particularly has this been true of the host of abandoned high-cost producers and prospects which increased gold and silver prices have made potentially profitable. In a comparatively short time, experience has demonstrated abundantly that valuable properties have frequently failed to secure capital, while questionable properties have drawn to themselves and their promoters more of the public moneys than their prospects justify. Singularly enough the fault is usually attributable to faulty financing. Discussion and study of this problem are vital to the industry.
Jan 1, 1936