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By V. Leroy, A. G. Guy

Serious disagreements are often found between experimentally determined intrinsic diffusion coefficients and those calculated employing the usual form of the vacancy theory. In the new theory it is proposed that the total intrinsic flux, Ji, of component i, is the sum of a part, f, due to the usual random exclzanges of component i with the vacancies, and a second part, Ji, due to exchanges with the uacancies composing the net vacancy flux. The present treatment, while less powerful than that of Manning, has the advantage of easy uisualization and of facilitating the application of the vacancy-flux effect to complex systems. IT is becoming increasingly evident that there are serious deficiencies in the version of the vacancy theory of diffusion that has been widely used for the past 20 years. One type of evidence is the frequent lack of agreement between intrinsic diffusion coefficients and tracer diffusion coefficients, even taking account of the thermodynamic factor. A second kind of evidence is the observation of a Kirkendall shift larger than theoretically possible, that is, larger than can be accounted for without assigning a negative value to one of the two intrinsic diffusion coefficient.'- The thermodynamic factor could conceivably make both coefficients negative, but not just one. It is clear that a cause of these anomalies, apart from any inadequacy of the usual vacancy theory, might lie in an oversimplified treatment of the data. Adequate experimental techniques, including the use of moderate pressure during the diffusion anneal, are now available to insure that porosity, lateral expansion, and so forth, can be kept negligibly small in most cases. The effect of differences in atomic volume can be of major importance, and it is essential that one of the available methods4 be used to account for this factor. In the present treatment this is accomplished by the consistent use of moles per cubic centimeter as the unit of concentration. Of the various possible inadequacies of the vacancy theory, attention will be given here only to effects of the net vacancy flux. annin' has previously considered this question, beginning with an analysis of atomic jumping of tracer atoms. When he added the effect of a concentration gradient, new terms arose that could be associated with the flow of vacancies. The present treatment uses quite a different approach. The usual vacancy flux, J,, is introduced explicitly, and a simple analysis predicts major changes in the intrinsic diffusion coefficients from this cause. The usual assumptions are made that only a vacancy mechanism is operative, that the formation of voids can be neglected, and that changes in the partial molal volumes, vl and v2, are negligible. The significant diffusion coefficients for the present topic are Dl and D,, the intrinsic coefficients, which enter in the equations, where the flux Ji, moles per sq cm per sec, is that crossing the Kirkendall interface. The concentration, ci, is in units of moles per cu cm, and the concentration gradient, aci/ax, is evaluated at the Kirkendall interface. It will be recalled' that the calculation of Dl and D2 involves the measurement of areas on the diffusion curve with respect to the positions of the Kirkendall and Matano interfaces. In the case of the anomalies mentioned earlier, the Kirkendall shift is too large to be accounted for by the diiferetzce in fluxes (J2 -J1), given by Eqs. [I] and [2]. The logical inference is that the flux of the solvent atoms, J1, is actually in the same direction as the flux of the solute atoms, Jz. In terms of Eq. [I] this requires that Dl have a negative value. However, it would be somewhat misleading to state that the solvent atoms are diffusing up their own concentration gradient. The explanation that will be advanced here pictures competing processes producing the net flux of solvent atoms: 1) diffusion of the solvent atoms down their own gradient by random exchanges with vacancies; and 2) diffusion of solvent atoms in the opposite direction by exchanges with the net vacancy flux. ACTION OF THE NET VACANCY FLUX Theories of vacancy diffusion can be formulated with varying degrees of refinement, and the present theory has purposely been kept as simple as appeared adequate to explain the phenomenon in question. In particular the following aspects have been neglected: 1) the gradient of vacancy concentration in comparison to the gradient of the atomic species; 2) departure of vacancy concentration from the local equilibrium value; 3) variation of the jump frequency, LO, with the specific surroundings of the atom-vacancy pair being considered; 4) correlation effects. These and other refinements can be considered once the essential mechanism has been established. The essential idea of the present analysis is to calculate the total intrinsic flux, Ji, of component i as the sum, JlJ?±j{ [3] where J; is attributable to the usual random atomic jumping, and J{ is a contribution arising from the net vacancy flux, J,. The latter quantity, of course,

Jan 1, 1967

By D. H. Thompson, A. W. Tracy

Season-cracking is a type of failure of brass that results from the simultaneous effect of stress and certain corrodants. The object of this paper is to present data that will aid in a more complete understanding of the mechanism of season-cracking and related phenomena. Results presented show that certain high copper alloys are susceptible to season-cracking or stress-corrosion cracking, and possible explanations are discussed. Starting at least as far back as 1906, many papers have been devoted to this subject but the symposium1 held in Philadelphia in 1944 is the richest source of information. In order to study season-cracking, several of the many variables were held constant so as to learn the effects of others. Season-cracking is generally understood to refer to the corrosion cracking of brass having internal stresses;²,³ it is a special case of the general stress-corrosion cracking. Inasmuch as applied stresses are more readily produced and controlled, they were used exclusively in this research and the resulting phenomenon must he called stress-corrosion cracking.²,³ Only constant tensile stresses were used. The agents believed to be most frequently responsible for season-cracking are ammonia. amines and compounds containing then]. Both moisture and oxygen also appear to he necessary. Therefore, an atmosphere containing ammonia, water-vapor and air was selected for these tests. Briefly, the work consisted of exposing sheet metal specimens, having a reduced section ¼ by 0.050 in., of copper-base alloys to the effect of static tensile stresses between 5,000 and 20,000 psi and simultaneous contact with a. continuously renewed atmosphere containing 80 pct air, 16 pct ammonia and 4 pct water vapor at 35°C. The gas mixture and the speci- mens were maintained above the dew-point. The time-to-failure in minutes was the primary measure of results. In order to limit the experiment to finite time, it was considered that a specimen which had neither failed nor undergone microscopically detectable cracking in 40,000 min. (4 weeks) while under a stress of 10,000 psi or more could be considered immune to cracking. This is merely a convenient limit and is not to be considered proof of immunity. Supplementary tests in the absence of stress using weight loss or microscopical appearance as measures of attack were made. Apparatus The apparatus used in this research is shown in Fig 1. To facilitate the description it may conveniently be divided into six parts: stress-producing units, test chamber, gas train, electrical controls, timers and gas analysis device. A stress-producing unit is shown in an exploded view at the left in Fig 2. At the right is an assembled unit with a specimen in place in the lower portion; it is this part that remains in the ammonia atmosphere during a test. The upper part contains a spring, a central threaded rod, a large nut and necessary washers, pins, and so forth. Stress is produced in the specimen by screwing down the top nut against the spring, thus putting a tensile load on the central rod and so on the specimen. The wrench that turns the nut by extending through the upper cap, is seen at the upper right of the figure. The magnitude of the load is gauged by measuring from the pin that extends through the side of the tube, to a fixed point on the large flange. Measurement is made with a vernier beam caliper, shown at the right of the figure. The necessary spring compression to give a desired stress is calculated from the calibration curve of the spring and the dimensions of the specimen. The test chamber, center Fig 1, consists of a thermally insulated steel box 32 in. long by 10 in. high by 7 in. wide. A horizontal baffle reaching nearly to each end divides the chamber equally. Below this baffle are inlets for air and ammonia, a heating coil and a fan. Thus the gases are warmed and mixed in the lower level and flow past the specimens in the upper level. A thermo-regulator and thermometer project into the upper space. The top is pierced by 12 ports flanked by 3/8 in. threaded studs. A test starts when a port is opened and a unit containing a stressed specimen is thrust through it and bolted down against a neoprene gasket. The test chamber is held at 35°C. The gas train, right rear Fig 1, carries ammonia and air continuously to the test chamber. Tank ammonia passes through two reducing valves, a needle valve, a flow meter and into the test chamber. The air from either the plant compressor or a small laboratory compressor passes through wool towers and flow controls to the flow-meter. It then bubbles through water at 34°C and through a heated line to the test chamber. Electrical controls, left rear, Fig 1, provide rectifiers and mercury relays for the test-chamber and humidifier-heating-control circuits and outlets for

Jan 1, 1950

By W. A. Anderson

IN the pressure die-casting of zinc alloys it is customary to force the molten alloy under high pressure into a permanent steel die by means of a plunger moving in a bushing that has a clearance on the diameter of the order of 0.002 in. Successful operation of the plunger type of machine requires the presence in the zinc alloy of certain percentages of aluminum. Without these aluminum additions, the normal reaction of molten zinc on ferrous materials causes sticking of the plunger and a complete shutdown of the equipment. All of the zinc alloys used for pressure die-casting today contain approximately 4 per cent of aluminum, which is more than sufficient to make plunger operation feasible. The clearance between the plunger and its bushing is an important matter. As the space becomes larger, there is a loss in effective metal pressure. Ordinary gray cast iron served fairly well and is still used in some machines. However, the rate at which the plunger clearance increases with this material is considered by many to be far too great. There is, therefore, a serious interest in finding new materials more capable of retaining the desired clearance during long periods of use. Today many die casters are using special materials for plungers and bushings selected by the somewhat expensive and time-consuming test of actual experience. An analysis of the problem reveals two possible end points of plunger operation: (1) the building up of zinc-alloy plunger-material reaction products in sufficient bulk to cause sticking and (2) rapid solution, wear or erosion, all of which will increase the clearance to an undesirable extent. If neither of these takes place, the plunger will operate for a long time, of course. The authors have developed a laboratory apparatus in which the action of a plunger moving in a bushing immersed in molten zinc alloy could be simulated closely. Such a machine made possible a more rapid and less expensive survey of the available construction materials and an analysis of the specific alloying reactions taking place in the clear-ance area.

Jan 1, 1939

By Charles Clayton

CAST-STEEL runners, while not interesting from a commercial standpoint, furnish valuable material for microscopic study. Foley1 found not only the usual ingot structure, but zones of Widmannstattian structure, which he explains as due to differential crystallization. The writer, in examining nickel-steel runners, found a type of pro-eutectoid ferrite that is unusual and most probably new. The runner in question was 8.75 cm. (3.5 in.) in diameter and analyzed at its center 2.69 per cent, nickel and 0.350 per cent. carbon and at its edge 2.62 per cent. nickel and 0.359 per cent. carbon. The macrostructure, which is the usual type, is shown in Figs. 1 and 2, which are a cross-section and the longitudinal surface, respectively. Slight segregation of ferrite can be seen near the center of the segment and at other points near the edges of polyhedral grains. Stead's reagent brings out the dendritic structure within the grains as shown in Figs. 3 and 4. This texture is what would be expected of such a steel. Figs. 5 to 10 show the peculiar swirls of pro-eutectoid ferrite, the finding of which prompted this paper. These swirls, or eddies, if such a term can be applied, occur in all parts of- the runner and in all parts of the individual grains. I he tipper left-hand figure shows this ferrite at a grain boundary; the middle left-hand figure shows the inner portion of a grain; and the lower left-hand figure shows these swirls at the edge of a grain which is also the outer edge of the runner. Straight-lined ferrite associated with swirls is found in the areas of Figs. 11 and 12. The texture of the carbon-bearing constituent of the runner is shown to- some extent in Fig. 12, the pearlite being very fine or sorbitic. Higher magnification does not bring out any new features either in the peculiar ferrite or in the pearlite. Figs. 13 and 14, at 240 diameters, show the curved and straight-lined ferrite.

Jan 3, 1920

By Wilson T. Lundy

The history of the production of sulfur from salt domes in Louisiana and Texas originated with the operations of the Union Sulphur CO. at Sulphur, La., followed by the Freeport Sulphur Co. at Bryanmound, Tex. Including the present development of Grande Ecaille by the Free-port Sulphur Co., which constitutes the tenth dome to be equipped for the production of sulfur in the Gulf Coast, less than 10 per cent of all the known domes have proved to contain sulfur in commercial quantities. The Grande Ecaille salt dome is in the tidal marsh of the Mississippi River delta in Plaquemines Parish, Louisiana. It is 10 miles southwest of the right descending bank of the river approximately 45 miles below the city of New Orleans and is within 4 miles of the shore line of the Gulf of Mexico. Terrain Characteristic of the delta region, the terrain consists of a low, flat, uninhabited area of marsh land intersected by many shallow lakes and bayous. With the exception of salt grasses, the region is devoid of vegetation and presents, in all directions, an unobstructed path to the vagaries of the winds. The general character of this area can be best visualized from the mechanism of its formation.' Offshore bars formed enclosing long narrow lagoons between the bar and the inner shore line, the lagoons communicating with the sea by means of tidal inlets. The water in the lagoons, being comparatively quiet, favored the deposition of fine debris composed of sand carried into the lagoons by action of the waves, tides and river-borne sediments from the land surface. As this material accumulated the bottoms of the lagoons were built up and eventually salt grasses obtained a foothold. The successions of growth and decay of these grasses formed a brown fibrous mat varying in depth from a few inches to several feet. This mat of vegetation virtually floats on an ooze that is several feet thick and is composed of alluvial sediments and very fine sand, and the whole is underlain by an unctuous clay. The decayed vegetation from the upper layer when dried has a peaty appearance.

Jan 1, 1934

By W. A. Anderson

Recrystallization of cold-worked metals has long been known to proceed by a process of nucleation and growth.' When a cold-worked metal is heated to a temperature at which recrystallization will ensue, nuclei of new grains, essentially strain-free, appear and grow. As the process proceeds, nuclei continue to appear and to grow, until the cold-worked matrix has been entirely consumed and recrystallization has been completed (Fig. I). Conducted isothermally, a measurement of the fraction of the matrix recrystallized plotted against time, yields an isothermal recrystallization curve, showing the time course of the recrystallization process (Fig. 2).2 Evidently, then, the rate of recrystallization is determined by the rate at which nuclei form and the rate at which they grow. The rate of nucleation N is the number of nuclei that form in unit time in unit volume of the unrecrystallized matrix, and the rate of growth G is the increase in radius of the recrystallized grain per unit time. In recent years attempts have been made to determine N and G as these vary with the well-recognized variables affecting recrystallization: time, temperature, degree of deformation, etc.1 Such studies yield information that is more fundamental than that conveyed by the conventional recrystallization diagram,' since the rate of recrvstallization is thus analyzed into its two component rates3 Methods are now available by which N and G can be measured, and analytical expressions have been developed for the interrelationships among N, G, the isothermal recrystallization curve, and the final grain size, which greatly facilitate analysis.2-4 The application of these methods has been demonstrated recently for the recrystallization of silicon ferrite.2 Data on N and G in dependence upon the recognized recrystallization variables are, however, very fragmentary;" values of N and G have been determined for some metals, but the effect of temperature, which would yield the fundamentally important activation energies, has been too little studied. Thus far there has been no detailed study of the recrystallization of any one metal in terms of X and G ovcr appreciable ranges of the variables time, temperature, degree of deformation, and original grain size. It is the purpose of the present paper to provide such a study, employing aluminum.

Jan 1, 1945

By Robert Parker

Measurements of the latent heat of transformation from a to 0 titanium were made using a pulse-heating technique. Rapid heating was accomplished electrically by discharging a low-inductance capci-tor hank through a thin-strip specimen. Both high-purity titanium and titanium containing 2700 ppm of 0 were studied. An electrical-resistivity technique and a plot of energy input us temperature rise were used to monitor the phase change. It was concluded that: 1) the latent heat of transformation is 800 i 48 cal per mole; 2) phase change occurred in less than 200 sec; and 3) the percentage phase change that occurs is linearly a function of the energy available for phase change. In addition, this experiment provides a simple and inexpensive method for determining specific heat of electrical conductors over large temperature ranges. The chief advantages of this technique over past pulse-heating experiments are: 1) static measurements of capacitor-bank voltage capacitance and specimen resistance can be made quickly and accurately to determine the energy supplied to the specimen; 2) the specimen is heated so rapidly (10 µ sec) that there is no appreciable heat loss during the heating. THE purpose of this paper is to illustrate the use of the capacitor bank as a tool for basic experimental investigations and to determine the rapid phase-change kinetics of titanium. The capacitor provides a number of unique properties: 1) rapid heating rates in the order of l09oC per sec can be obtained; heating rates as slow as l04oC per sec are available by merely adding a given amount of inductance to the circuit; 2) the energy input can be precisely determined and can be varied from several joules to millions of joules, depending on the bank capacitance and voltage; 3) the specimen can be heated uniformly through the thickness and length or non-uniformly, as desired; 4) the apparatus is simple and inexpensive and can be easily altered; 5) the form of the specimen can be wires, sheets, foils, rods, and cylinders; 6) there is great precision in the timing of events; 7) this technique may be readily used in conjunction with rapid cooling.

Jan 1, 1965

By M. Takeda, H. Majima

Pyrite has been subjected to xanthate adsorption experiments in order to determine the nature of adsorption. The identification of adsorbed species by means of IR spectroscopy, as well as UV, shows that the dixanthogen adsorption is undoubtedly predominant on pyrite surface. The rest potential measured in a xanthate solution coincides with the redox potential of the xanthate-dixanthogen couple. Considering all the factors together, the adsorption mechanism of dixanthogen on pyrite has been proposed as This mechanism is consistent with the "passive" character of pyrite. From the measurement of the redox potential of the xanthate-dixanthogen couple in the homologous series, a rule similar to that for surface tensions proposed by Traube is also applicable. The polarization experiments were conducted on pyrite in a solution containing xanthate. In the anodic polarization, xanthate is observed to oxidize to dix- anthogen, which depresses oxygen evolution on py rite at higher potential levels. In spite of the importance of the presence of pyrite in the flotation of sulfide minerals, not many studies have been made on the xanthate-pyrite system in the absence of an activator or a depressant. In an early study by Gaudin and Wilkinson,' it was pointed out that no ferric xanthate was formed on a pyrite surface, while in another study Gaudin and his collaborators2 proved the formation of a very small amount of ferric xanthate. Afterwards, Gaudin et al.3 studied the pyrite-xanthate system with a radiometric technique and found indications of the presence of adsorbed dixanthogen on pyrite surfaces. Mamiya4 studied the flotation behavior of the pyrite-xanthate system and also suggested the possibility of dixanthogen. Recently, Fuerstenau and his coworkers at The Colorado School of Mines5 studied the role of dixanthogen in the xanthate flotation of pyrite and discussed the problem in terms of such properties as oxidation potential, zeta potential, flotation recovery, pH of solution, etc. However, the mechanism of dixanthogen adsorption at the pyrite-water interface is not yet understood. This paper is concerned with an electrochemical in-vestigation through which the mechanism of dixanthogen adsorption on pyrite is interpreted. EXPERIMENTAL MATERIALS AND TECHNIQUES Pure potassium xanthates were synthesized by an

Jan 1, 1969

By E. A. Anderson, C. W. Siller, Gerald Edmunds

In the pressurc die-casting of zinc alloys it is customary to force the molten alloy under high pressure into a permanent steel die by means of a plunger moving in a bushing that has a clearance on the diameter of the order of 0.002 in. Successful operation of the plunger type of machine requires the presence in the zinc alloy of certain percentages of aluminum. Without these aluminum additions, the normal reaction of molten zinc on ferrous materials causes sticking of the plunger arid a complcte shutdown of the equipment. All of the zinc alloys used for pressure dir-rnsting today contain approximately 4 per cent of aLUminum, which is more than suffieient to make plunger opcration feasible. The clearancc bet,ween the plunger and its bushing is an important matter. As the space bccomes larger, there is a loss in effective metal pressure. Ordinary gray cast iron served fairly well and is still uscd in some machines. However, the rate at which the plunger c1earance. increases with this material is considered by many to be far too great. There is, therefore, a serious interest in finding new matcrinls more: capable of retaining the desired clearance during long periods of use. Today marly die casters are using special materials for plungers and bushings selected by the somewhat expensive and time-consuming test of actual experience. An analysis of the problem reveals two possible end points of plunger. operation: (1) the building up of zinc-alloy plunger-material reaction products in sufficient bulk to cause sticking and (2) rapid solution, wear or erosion, all of which will increase the clearance to an undesirable extent. If neither of these takes place, the pluriger will operatc for a long time, of course.. The authors have developed a laboratory apparat,us in which the action of a plunger moving in a bushing immersed in molten zinc alloy could be simulated closely. Such a machine made possible a more rapid and less expensive survey of the available construction materials and an analysis of the specific alloying reactions taking place in the clearance area.

Jan 1, 1940

By Gerald Edmunds, C. W. Siller, E. A. Anderson

In the pressurc die-casting of zinc alloys it is customary to force the molten alloy under high pressure into a permanent steel die by means of a plunger moving in a bushing that has a clearance on the diameter of the order of 0.002 in. Successful operation of the plunger type of machine requires the presence in the zinc alloy of certain percentages of aluminum. Without these aluminum additions, the normal reaction of molten zinc on ferrous materials causes sticking of the plunger arid a complcte shutdown of the equipment. All of the zinc alloys used for pressure dir-rnsting today contain approximately 4 per cent of aLUminum, which is more than suffieient to make plunger opcration feasible. The clearancc bet,ween the plunger and its bushing is an important matter. As the space bccomes larger, there is a loss in effective metal pressure. Ordinary gray cast iron served fairly well and is still uscd in some machines. However, the rate at which the plunger c1earance. increases with this material is considered by many to be far too great. There is, therefore, a serious interest in finding new matcrinls more: capable of retaining the desired clearance during long periods of use. Today marly die casters are using special materials for plungers and bushings selected by the somewhat expensive and time-consuming test of actual experience. An analysis of the problem reveals two possible end points of plunger. operation: (1) the building up of zinc-alloy plunger-material reaction products in sufficient bulk to cause sticking and (2) rapid solution, wear or erosion, all of which will increase the clearance to an undesirable extent. If neither of these takes place, the pluriger will operatc for a long time, of course.. The authors have developed a laboratory apparat,us in which the action of a plunger moving in a bushing immersed in molten zinc alloy could be simulated closely. Such a machine made possible a more rapid and less expensive survey of the available construction materials and an analysis of the specific alloying reactions taking place in the clearance area.

Jan 1, 1940

By M. R. Todd, J. Szekely

THE mechanism of carbon oxidation in steelmaking processes has attracted considerable attention in recent years. The generally accepted model postulates that the reaction between carbon and oxygen occurs at the surface of CO bubbles that originate at the suitable nucleation points and subsequently rise through the metal bath.1-4 Although this model describes adequately the behavior of open-hearth type operations, it is not a satisfactory representation of carbon oxidation in oxygen steelmaking processes since it cannot account for either: i) the very high rate of oxidation per unit bath area,or ii) the commonly reported shapes of the curves showing the dependenie of the oxidation rate on the carbon concentration. The very high decarburization rates commonly encountered in oxygen steelmaking processes need no further elaboration; some typical plots of the rate of carbon removal against carbon concentration, taken from a publication by Li, Dukelow, and smith,' are reproduced in Fig. 1. It is seen from the curves that the decarburization tends to decrease from a peak or a plateau once the carbon concentration falls below a certain value; in the experiments reported, this critical value ranged from 1.2 to 0.2 wt pct C. The apparent dependence of the decarburization rate on the carbon concentration indicates that within this region phenomena associated with the transfer of car- bon must play an important if not predominant role. Since the concentration of oxygen in molten iron at steelmaking temperatures (removed from the immediate impact zone) is only about 0.1 wt pct,6 it is clear that simple simultaneous diffusion of carbon and oxygen to the surface of CO bubbles could not account for the rate of carbon transfer being the controlling step at carbon concentrations as high as 1.0 wt pct. The purpose of this communication is to present an alternative model which may explain at least qualitatively the apparent anomalies mentioned and may stimulate further experimental work. The Physical Model. It is suggested that the principal mechanism of decarburization is the reaction between CO bubbles and an emulsion consisting of molten iron and molten iron oxide particles in the vicinity of the "slag-metal interface9'.* This mech-

Jan 1, 1968

By W. A. Anderson, R. F. Mehl

RECRYSTALLIZATION of cold-worked metals has long been known to proceed by a process of nucleation and growth.1 When a cold-worked metal is heated to a temperature at which recrystallization will ensue, nuclei of new grains, essentially strain-free, appear and grow. As the process proceeds, nuclei continue to appear and to grow, until the cold-worked matrix has been entirely consumed and recrystallization has been completed (Fig. I). Conducted isothermally, a measurement of the fraction of the matrix recrystallized plotted against time, yields an isothermal recrystallization curve, showing the time course of the recrystallization process (Fig. 2).2 Evidently, then, the rate of recrystallization is determined by the rate at which nuclei form and the rate at which they grow. The rate of nucleation N is the number of nuclei that form in unit time in unit volume of the unrecrystallized matrix, and the rate of growth G is the increase in radius of the recrystallized grain per unit time. In recent years attempts have been made to determine N and G as these vary with the well-recognized variables affecting recrystallization: time, temperature, degree of deformation, etc.' Such studies yield information that is more fundamental than that conveyed by the conventional recrystallization diagram,' since the rate of recrystallization is thus analyzed into its two component rates.2 Methods are now available by which N and G can be measured, and analytical expressions have been developed for the interrelationships among N, G, the isothermal recrystallization curve, and the final grain size, which greatly facilitate analysis.2-4 The application of these methods has been demonstrated recently for the recrystallization of silicon ferrite.2 Data on N and G in dependence upon the recognized recrystallization variables are, however, very fragmentary;* values of N and G have been determined for some metals, but the effect of temperature, which would yield the fundamentally important activation energies, has been too little studied. Thus far there has been no detailed study of the recrystallization of any one metal in terms of N and G over appreciable ranges of the variables time, temperature, degree of deformation, and original grain size. It is the purpose of the present paper to provide such a study, employing aluminum.

Jan 1, 1945

By J. O. Whiteley, C. Dietz

It is difficult to give a refining outline that may be followed for any and all combinations of the platinum metals; different combinations require different methods of attack. This paper does not pretend to go into all of the reactions of the metals of the platinum group, but will outline the commercial refining of platinum scrap. Typical Platinum Scrap As a concrete case, let us take 100 oz. of miscellaneous scrap, made up of jewelry scrap, dental scrap and laboratory ware. This lot will contain some platinum, palladium, iridium, ruthenium, rhodium, gold, silver and copper. The first problem is to get all of the metals in solution. If the scrap is principally platinum, palladium and gold, a treatment with aqua regia is the course to pursue; but if the scrap contains alloys high in iridium or ruthenium, aqua regia will act too slowly. In the case in hand, we are going to presume that we have scrap high in iridium and ruthenium, and proceed accordingly. Obtaining Residue A Place the scrap, together with six times its weight of granulated test lead, in a solid carbon crucible. This crucible may be placed inside a clay graphite crucible packed with charcoal, to prevent the excessive oxidation of the carbon crucible by the furnace blast. Place a tight cover on the carbon crucible; heat gradually to a good red heat and allow it to soak in the heat for 4 or 5 hr. After the leaded mass is cool, dissolve in dilute nitric acid (1-6) on a steam plate or sand bath. This dissolves practically all of the lead and most of the palladium, silver and copper, together with seme of the platinum and rhodium, and leaves the iridium, ruthenium, gold, and most of the rhodium and platinum as a finely divided residue. Siphon off the clear solution and treat the residue with another portion of dilute nitric acid to insure the solution of the lead and copper. The second nitric acid solution is added to the first, and the residue is filtered on suction and washed thoroughly with hot

Jan 1, 1928

By J. E. Sandor, P. F. Schmidt

A general review of the present knowledge of the semiconductor/oxide interface is given, with emphasis on silicon and germanium. The electrical properties of clean surfaces and the changes that occur upon oxidation are described. A brief disczcssion of the methods and mechanisms of oxidation of silicon is given, and the interaction between the semiconductor substrate and the oxide phase is considered. Physical properties of the oxide film, charge storage effects due to the dielectric, and some device applications of oxide films on semiconductors are discussed. THIS paper will be heavily preoccupied with the elemental semiconductors germanium and silicon. Undoubtedly some injustice is done thereby to other semiconductor-oxide systems, but it is not readily possible to cover all aspects of so vast a field in the present review. In considering the semiconductor/oxide interface, we may start out by discussing briefly an idealized clean semiconductor surface, and may then follow the changes brought about by oxidation, as the oxide is allowed to grow progressively thicker. The references given are not a complete list, but are to be taken as guides to the literature. Tamml suggested in 1933, based upon the study of a one-dimensional asymmetrical potential model, that localized surface states may appear at the surface of a crystalline lattice; it was pointed out by Fowler that these states should occur in pairs. shockley3 examined the origin of such surface states on the basis of a more general one-dimensional model and found that surface states may appear in the forbidden region between the highest filled and the lowest vacant band. This happens when the two bands overlap, as, for instance, the "s" and ('p" bands of the diamond structure. In a three-dimensional model these levels would produce a surface band which is half-filled for diamond, and the number of surface states should be approximately equal to the number of surface atoms. This picture of the surface has been refined by more recent theoretical work, like Handler's4 and Koutecky and Tomasek's~ without introducing essential modifications. When these concepts were applied to semiconduc-

Jan 1, 1965

By Clarence Thom

This chapter presents, in summarized form, standard procedures for making separations of minerals from their ores by the froth flotation process to produce marketable concentrates. These are typical mineral separations which are being made commercially with the reagents and conditions generally used in the mining industry. Typical separations are presented for 17 metallic and 11 nonmetallic ores. The review of each includes a brief description of the mineral and the particular problem presented, general market specifications for its concentrates, an outline of treatment method, and kinds and quantities of reagents usually employed. This chapter does not include de- tails about ore preparation (crushing, grinding, and classification), elements of ore and pulp transportation (conveying and pumping), or concentrate preparation for market (thickening, filtering, and drying). In each presentation it is assumed, if not detailed further, that the ore is ground to the economical point of liberation of the minerals to be separated. Specific information, such as ratio of concentration and recovery, that depends upon the grade of ore being treated is considered beyond the scope of this chapter. Effective flotation separations that produce marketable concentrates may produce widely varying results in terms of percent recovery and still be economically profitable operations. Details of plant practice on specific ores are presented in Chapters 16 and 17. In this chapter the chemical names of the reagents are given. The extent to which different reagents are used in flotation plants in the U. S. is presented in Chapter 4. A compilation of the various flotation reagents, their trade names, manufacturers, and use has been prepared by H. T. Spedden. ANTIMONY The principal ore mineral of antimony, stibnite (Sb2 S3), is generally found in the U. S. in ore bodies in association with other valuable minerals such as galena (Pbs), sphalerite (ZnS), chalcopyrite (CuFeS2), or tetrahedrite (3Cu2 S – Sb2 S3), The sulfo-salt minerals of antimony, such as tetrahedrite or pyrargyrite, are often associated with high silver values, so that the presence of antimony may indicate economic importance even though the actual antimony content is low. Antimony is also significant to the mineral economy because of its occurrence in some ores where lead, gold, and silver are the

Jan 1, 1962

By Eugene Guccione

Evidence that the United States is gradually converting to the metric system of measurement can be perceived today even by housewives in a supermarket. The question is no longer whether but when the country will have completed the conversion. To the extent that any bickering about metrication still exists, the debate now centers on such issues as finding agreement on details of implementation, and whether federal legislation should speed up the metric-conversion process or allow it to proceed along its present evolutionary and voluntary course. Apparently, the voluntary or "make-haste-slowly" approach is gaining widespread support. According to The Research Institute of America, Inc., if and when federal legislation is enacted it will likely include the following national ground rules: (1) A National Metric Conversion Board will develop and submit to the President and Congress a comprehensive plan to achieve a coordinated, minimum-cost changeover. (2) The change- over will be completed 8 to 10 years after the board's plan goes into effect, and by that time the US will be predominantly, though not exclusively, metric. (3) Costs will "lie where they fall"; subsidies, special tax concessions, and antitrust exemptions will not be authorized by the legislation. (4) The changeover will be voluntary because of the recognition that while some firms can "go metric" in a matter of weeks, others may require 15 years or more, and a few might never convert. (5) In determining whether or not to convert, on an individual company basis, adherence will be to the "rule of reason-that is, ". . . do not convert unless the engineering, economic, or other benefits outweigh any metric-related disadvantages. No one is talking about rip- ping up our railroad tracks or rewiring our homes just to conform to the practice of metric nations in Europe." (6) Government is to be part of the solution, not part of the problem; in effect, says The Research Institute of America, the leverage of federal procurement will not be exerted to force-feed the metric changeover but will be coordinated with the sector-by-sector conversion of the economy.*

Jan 12, 1975

By Geoffrey Purcell

For anyone contemplating flotation research with only a very limited amount of mineral available for testing, the choice of suitable experimental equipment is by no means obvious. Hallimond's original and delightfully simple cell1 has been modified by subsequent investigators2to give quantitative and reproducible results on small samples. However, the modifications have necessarily compromised its simplicity, and the services of a skilled glass blower are required to duplicate the cell. Vacuum flotation tests3 at best qualitative and may, under certain conditions4, be quite impracticable. A hundred years ago, Thoreau observed that "our life is frittered away by detail," and his advice was to "simplify, simplify," The success of the simple cell described below, which was developed by the author and differs somewhat from Hallimond's original, suggests that Thoreau's advice still has merit a century later. CELL CONSTRUCTION The cell [Fig. 1 (a) and 1 (b)] consists essentially of a 25-ml pipet from which has been cut the con- stricted top. The length cut off is not critical since this merely determines the final volume of the cell. Cell volume may be varied in this way from 20 to 50 cc. A pyrex extension tube, equal in diameter and approximately half the length of the cut pipet, is attached to the top of the pipet by means of 2 ½ in. of close-fitting tygon tubing. When assembled, the two pyrex tubes should be spaced about ½ in. apart. Another length of tygon tubing is added to the extension piece for sealing purposes. A ¾ -in. disc of porous material (teflon cloth is ideal), secured in place over the pipet tip with another piece of shaped tygon tubing, completes the cell assembly. Tygon tubing may be shaped by pushing it over the pipet tip or some similar form and heating carefully over a low flame. For flotation [Fig. 1 (c) 1, the pyrex extension tube is rotated approximately 70º from the vertical and held in position by a wire hook and eye. Floated material, after reaching the free surface, falls and rests on this inclined plane. The barrier formed by the bent tygon tubing ensures that floated material does not slide back and return to the vertical portion of the cell.

Jan 11, 1965

By AIME AIME

CHARLES A. CHASE, manager of the Shenandoah-Dives Syndicate, operating the Shenandoah Mines in southwestern Colorado, reviewed the current work at that property at a recent meeting of the Colorado Section, in Denver. This operation is a new one, having been in effect only two years, but the properties that were consolidated by Mr. Chase had had certain production in earlier years, since when they had: been inactive. These properties are located. in the high mountains of the San Juan section in Colorado, and although they had had a substantial production of ores of good grade in the upper levels, the project as a whole involved the bold undertaking of driving through the mountain, starting on the Mayflower claim on the Arrastre Gulch side and passing through the Mayflower, Slide, Terrible, North Star, Dives and Shenandoah No. 3 claims. This is a distance of over 8,000 ft. which is known to be mineralized, and the main operating tunnel was started at an elevation of approximately 11,000 ft. The main exploration work has already extended in nearly 4,200 ft. and the present mining production of nearly 550 tons daily is being secured while the main exploration work is being continued. The main heading is now within the North Star claim and the plan of operations involves continuing ahead for a few hundred feet and then starting an upraise which will he 2,200 ft. high and which will connect with the old workings of the North Star mine. The plan of ruining then will he to drive levels along the vein in both, directions to daylight and retreat downward, taking out all the ore and abandoning, the workings after the ore is removed. In this way one level after another progressing downward will be abandoned. The raise will be of two compartments, one of which will carry the 8-ton skip and the other the counterweight and manway. So far the ore has been broken over an average width of more than 11 ft., with an output of 39 tons per machine shift.

Jan 1, 1932

By Albert Hayes

FOUR mines at Wabana, on Bell Island in Concep-tion Bay, Newfoundland, produced 1,209,777 tons of ore in 1927, and it is expected that the produc-tion will be larger in 1928. The ore is a stratified oolitic hematite of sedimentary origin. Three workable beds and many thin beds occur in a thickness of 400 ft. of interbedded sandstones and shales. It is not profitable under present conditions to mine extensively in ore beds less than 4 ft. thick. The iron ore beds outcrop on the small island and are inclined northward more steeply, than the slope of the ocean bottom. The mine work-ings follow the bedded ore below the sea bottom, No. 3 Mine extending about 2 miles north of the island. At this point there is a cover of 1500 ft. of rock and 600 ft. of ocean water. It is impracticable to operate drills in the ocean to prove the extent of the submarine orebody in advance, and diamond drilling from the mine workings is the only method of exploration. Bell Island has been settled for a long time and a monument at Cupids, near Brigus at the head of Conception Bay, commemor-ates the tercentenary of a settlement there in 1611 by Captain Guy of England. was one of the chief ports of Newfoundland for deep sea fishing and doubtless many a captain wondered about the red rocks as he sailed past. The famous geologist, J. B. Jukes, records seeing a bright red sandstone 8 ft. thick on the northwest side of Bell Island during a visit in 1842, but he evident ly did not try to land on that rocky coast to get a sample. The iron ore is plainly visible in the high cliffs along the coast of the island, as bright brown layers interbedded with gray and white sandstones and dark shales. The heavy red rock was used by the fisher-men as anchor weights for fish nets and small boats, but its real value, so the story goes, was discovered by a merchant in Saint John,

Jan 8, 1928

By A. Poll, J. E. Stantan, L. J. Jolley

THE basic problem in the generation of water gas from carbonaceous fuels and steam is the supply of the heat of reaction, and in general the source of this heat is the combustion of a further quantity of carbon with oxygen. Existing and proposed processes for complete gasification differ in the methods employed for transferring this heat to the fuel, and involve one or other of the following alternatives: 1. Use of a steam-oxygen mixture as the gasifying medium, so that the combustion and gasification reactions are combined. 2. Alternate passage of air and steam through a fixed bed, as in conventional water-gas production. 3. Cyclic passage of fluidized fuel through combustion and gasification zones. 4. Intense preheating of steam and of a portion of the gas made, and recirculation of this mixture through the fuel bed. 5. Supply of heat to the fuel bed through an externally heated wall. Except for the conventional water-gas process using large coke or low- volatile coal, only processes in the first group, operating with steam and oxygen, have proved practicable with fuels other than brown coals and lignites. A possible exception, which has not so far reached a commercial scale, is the moving-burden process developed by Imperial Chemical Indus- tries, Ltd. The cost of industrial oxygen is so high that its use can probably be justified only if it is attended by substantial savings in other directions; for instance, the use of cheap fuel. In the United Kingdom, no very cheap solid fuels are available, and it is unlikely that an oxygen-gasification process could compete economically with conventional production of blue water gas from coke. Hence particular interest attaches to all possibilities of making water gas without using oxygen, if any possible saving in fuel or other costs is involved. The cheapest and most abundant coals in the United Kingdom are the low-rank noncaking bituminous coals in small and ungraded sizes, typically those from the East Midlands coal field, and-fines of high ash content produced in coal-cleaning operations. A process capable of gasifying

Jan 1, 1953