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By W. H. Eardley

It is increasingly evident that the excellence of blast-furnace operation to a great extent depends upon the preparation of the products fed into the furnace. The preparation of these products is carried on largely in the roasting and sintering departments. Prior to the building of flotation plants in Utah and other western states for the treatment of lead-zinc ores, the gravity concentrates received at the Midvale smelter amounted to about 4000 tons per month, containing 24 per cent. lead and 10 or 11 per cent. zinc. This product was about 20 mesh—that is, 45 per cent. of it would be plus 20 mesh and the balance minus 20 mesh. About 1000 tons of pyrite per month, containing 5 per cent. lead and 10 per cent. zinc, was also received. These products were sent to the multiple-hearth roasters for calcining, after which they were sent to the Dwight-Lloyd machines for sintering with other ores. The sintering charge passed over the machines but once. The first flotation products received consisted of a wet, sticky, muddy mass, containing a large amount of moisture, up to 19 or 20 per cent., and it was almost impossible to feed them with any degree of regularity, if at all, through our standard feeders; but the amount of flotation product received during the first year or so was relatively small and it virtually lost its identity by being mixed with a large amount of jig and table concentrates. As the quantity of flotation products increased, more efficient filtering was accomplished and the moisture greatly reduced. Flotation Products Received At the present time the Midvale plant receives about 4300 tons per month of flotation product running 60 per cent, lead and 4.5 per cent. zinc, 85 per cent. of which is minus 200 mesh and contains about 8 per cent, moisture; and 4000 tons per month of pyrite of similar fineness, running about 2 per cent. lead and 3.5 per cent. zinc, containing about 10 per cent, moisture. The lower moisture greatly reduces the difficulties of handling, making it possible to run a 100 per cent. flotation feed on a multiple-hearth furnace without serious mechanical troubles. The calcine, however, would contain nodules and balls of unroast,ed concentrates, sulfur elimination

Jan 1, 1928

By Carville E. Sparks, Rollin Farmin

Edward Thomas (U.S. Bureau of Mines, Washington, D. C.)—This excellent article on an ingenious and successful installation of wooden rock bolts loses much of its effectiveness through an attempt by the authors to establish the general adaptability of this type of support. Possibly because they have only local experience as a guide, they imply erroneously in the first paragraph that the Bureau of Mines has been opposed to wooden bolting, although later in the article reference is made to a Bureau publication on the subject. In 1947 the Bureau of Mines decided to sponsor experiments in roof bolting in coal mines because the experience of the St. Joseph Lead Co. had indicated that this type of roof support appeared to be a roof-fall accident-prevention measure that might be adopted and also effect economies in operating cost. Justification for this belief has been borne out, particularly in coal mining. This program has been carried out under the following general program: 1—The Roof Control Section of the Bureau of Mines has advocated and initiated underground experiments under controlled conditions with many different ideas related to rock bolting since 1947. In no instance has cooperation in developing an idea been refused, no matter how ridiculous it may have seemed at first glance, if it has been requested by a mining company. 2—The Bureau of Mines has no police powers over the selection of roof-support devices and seeks none. 3—At the request of an operator, the Bureau of Mines will make comparative tests on various types of bolts underground and will submit resultant data for the operator's consideration. 4—Wherever possible, the Bureau publicizes successful installations, so that others may benefit from this experience; however, it is careful not to discriminate between manufacturers of bolts or bolt-installation equipment. Unsuccessful experiments probably should also be publicized, but from a practical standpoint it is usually not feasible. In other words, the role of the Roof Control Section of the Bureau is in line with the original purpose for which the Bureau was first organized: to serve industry through gathering, analyzing, and disseminating factual data. It would seem to be logical that the starting point for any experimentation on roof bolts in coal mines should be the time-proved practice of the

Jan 1, 1955

By Edwin Chance

DURING the last decade many conditions have been encountered that have materially increased the cost of the production of coal. As in most cases it has not been practicable to increase the selling price of such coal sufficiently to insure the necessary margin of profit, the mine management has been forced to avail itself of what might be termed unusual means that costs might be held at as low a figure as possible. The so-called efficiency engineer has been called upon, costly power plants have been built and machinery has been installed to replace manual labor wherever possible. Another aid used recently to secure economies through the more intelligent production of coal, is the chemist. As the coal industry, barring the production of byproduct coke, does not at once give evidence of its need of the services of the chemist, the writer will endeavor to point out a few of the services that this branch of the staff has been able to render. The preparation of coal in the past has been carried on entirely upon an empirical basis, that is, the criterion adopted has been an ocular inspection. Unfortunately, the appearance of a coal and especially of an anthracite, has but little relation to its fuel value, and as long as coal is purchased for the heat that 'can be obtained from it by its combustion, the quantity of such heat that is purchased must be one of the principal desiderata in selecting or preparing a coal. Were coals purchased for use as bric-a-brac or for exhibition in museums it might be both wise and just to purchase them upon their appearance. After 4 or 5 years of investigation the fact has been established that coals of very inferior appearance, and I now have special reference to anthracite, might and often did possess heating and burning properties superior to those possessed by, bright coals which in the past had commanded considerable and uniform premiums in the market. This being the case the question arose as to whether the trade could be convinced of this fact. While at first some difficulty was experienced in establishing the quality of such dull coals, still it was found that the real obstacle to the sale of these

Jan 4, 1916

By W. H. Eardley

IT IS increasingly evident that the excellence of blast-furnace operation to a great extent depends upon the preparation of the products fed into the furnace. The preparation of these products is carried on largely in the roasting and sintering departments. Prior to the building of flotation plants in Utah and other western states for the treatment of lead-zinc ores, the gravity concentrates received at the Midvale smelter amounted to about 4000 tons per month, containing 24 per cent. lead and 10 or 11 per cent. zinc. This product was about 20 mesh-that is, 45 per cent. of it would be plus 20 mesh and the balance minus 20 mesh. About 1000 tons of pyrite per month, containing 5 per cent. lead and 10 per cent. zinc, was also received. These products were sent to the multiple-hearth roasters for calcining, after which they were sent to the Dwight-Lloyd machines for sintering with other ores. The sintering charge passed over the machines but once. The first flotation products received consisted of a wet, sticky, muddy mass, containing a large amount of moisture, up to 19 or 20 per cent., and it was almost impossible to feed .them with any degree of regularity, if at all, through our standard feeders; but the amount of flotation product received during the first year or so was relatively small and it virtually lost its identity by being mixed with a large amount of jig and table concentrates. As the quantity of flotation products increased, more efficient filtering was accomplished and the moisture greatly reduced. FLOTATION PRODUCTS RECEIVED At the present time the Midvale plant receives about 4300 tons per month of flotation product running 60 per cent. lead and 4.5 per cent. zinc, 85 per cent. of which is minus 200 mesh and contains about 8 per cent. moisture; and 4000 tons per month of pyrite of similar fineness, running about 2 per cent. lead and 3.5 per cent. zinc, containing about 10 per cent. moisture. The lower moisture greatly reduces the difficulties of handling, making it possible to run a 100 per cent. flotation feed on a multiple-hearth furnace without serious mechanical troubles. The calcine, however, would contain-nodules and balls of unroasted concentrates, sulfur elimination

Jan 1, 1928

By Francis Donaldson

The direct injection of cement grout into water-bearing fissures as a means of checking or stopping the flow of water into shafts and tunnels has been experimented with for a decade or longer and seems to have been first attempted in Europe. The earliest application of which the writer has found a record was at a shaft sunk by the Mining Society of Lens; this is described by C. Dinoire in the Transactions of the Institution of Mining Engineers.1 It is only lately, however, that the process has been entirely successful. This success has been accomplished on the Catskill Aqueduct, now under construction by the city of New York. This aqueduct includes a number of deep pressure tunnels, reached by shafts for both waterway and construction purposes. In portions of these shafts and tunnels considerable underground water was met. The contract for the first of these deep pressure tunnels was let to the T. A. Gillespie Co.; this section is known as the Rondout Siphon. It leads under the Rondout valley at a depth of from 400 to 800 ft. and is about 5 miles long. The engineers expected that considerable water would be encountered, but fortunately this was not the case except at one shaft, known as No. 4, which penetrated the rock at a junction between limestone and conglomerate. Water-bearing fissures were encountered almost immediately. At a depth of about 200 ft. a flow of 1,500 gal. per minute was struck. The. shaft then contained as many pumps as could be used, and it seemed impossible to sink it further. After vain efforts had been made to proceed, John P. Hogan, a division engineer of the Board of Water Supply, suggested that cementation of the fissures be tried. The process was attempted for the first time in this country. Since the shaft was partly full of water it was necessary to drill grout holes with a diamond drill. Platforms were placed on the timbers at the water level, the diamond drill was installed and six 90-ft. holes were drilled in the bottom of the shaft. Several car loads of cement were pumped through these holes into the fissures, the drill casings being used for grout pipes. This largely cut off the flow of water from, the bottom and sinking could then

Jan 1, 1915

By Leslie Burris, J. C. Hesson

The diffusivity of uranium in liquid cadmium has been measured as a function of temperature by the capillary -bath technique. The diffusivity measurements were made at 4509 500°, 575º, and 650°C, over which temperature range the diffusivity of uranium varied from 1.3 to 2.3 x 10-5 sq cm per sec. The diffusivity of uranium in cadmium was less than that predicted by the Einstein-Stokes equation. VERY little information is available on the diffusivity of uranium in liquid metals. Bonillal has reported a single measurement of the diffusivity of uranium in bismuth. Measurement of the diffusivity of uranium in cadmium was undertaken, not only to supply data in an area in which a dearth of information exists, but also because of a need for this physical property measurement in connection with mass transfer studies now underway in the U-Cd system at Argonne National Laboratory. The capillary-bath method used in this work has been successfully used by other workers2"4 to obtain diffusivities in liquid metal systems. Although considerable experimental technique is required to obtain reliable diffusivity measurements, the basic information required is only that of temperature, capillary tube length, the initial and final compositions of the alloy in the capillary tube, and the composition of the bath into which the solute element is diffusing. From these measurements, diffusivities may be calculated using Fick's law. The diffusivity equations are presented in the Appendix. Equations which are often used to predict diffusivities in dilute solutions5 are the Einstein-Stokes equation: D= (kT)/(6pµr) and the Eyring equation: D = (?,kT/?y?zp), where D= diffusivity (sq cm per sec), k = Boltzman's constant, T= temperature ("K), p = viscosity (poises), r = radius of diffusing molecule or species (cm), and A,, Ay, and A, are the diameters of the diffusing molecule in the three axial directions. For round molecules, the Eyring equation gives values which are 37r times larger than the Einstein-Stokes equation. In this work, the experimental values were compared to the Einstein-Stokes equation. Experimental values of diffusivities in liquid metal systems usually lie between those predicted by the Einstein-Stokes and Eyring equations. The viscosity values for cadmium were obtained from the Liquid Metals Handbook.6 EXPERIMENTAL APPARATUS AND PROCEDURE The general procedure employed consisted of rapidly immersing in a molten cadmium bath containing a negligible amount of uranium a capillary

Jan 1, 1963

By W. A. Boyer

Edward Thomas (U.S. Bureau of Mines, Washington, D. C.)—This excellent article on an ingenious and successful installation of wooden rock bolts loses much of its effectiveness through an attempt by the authors to establish the general adaptability of this type of support. Possibly because they have only local experience as a guide, they imply erroneously in the first paragraph that the Bureau of Mines has been opposed to wooden bolting, although later in the article reference is made to a Bureau publication on the subject. In 1947 the Bureau of Mines decided to sponsor experiments in roof bolting in coal mines because the experience of the St. Joseph Lead Co. had indicated that this type of roof support appeared to be a roof-fall accident-prevention measure that might be adopted and also effect economies in operating cost. Justification for this belief has been borne out, particularly in coal mining. This program has been carried out under the following general program: 1—The Roof Control Section of the Bureau of Mines has advocated and initiated underground experiments under controlled conditions with many different ideas related to rock bolting since 1947. In no instance has cooperation in developing an idea been refused, no matter how ridiculous it may have seemed at first glance, if it has been requested by a mining company. 2—The Bureau of Mines has no police powers over the selection of roof-support devices and seeks none. 3—At the request of an operator, the Bureau of Mines will make comparative tests on various types of bolts underground and will submit resultant data for the operator's consideration. 4—Wherever possible, the Bureau publicizes successful installations, so that others may benefit from this experience; however, it is careful not to discriminate between manufacturers of bolts or bolt-installation equipment. Unsuccessful experiments probably should also be publicized, but from a practical standpoint it is usually not feasible. In other words, the role of the Roof Control Section of the Bureau is in line with the original purpose for which the Bureau was first organized: to serve industry through gathering, analyzing, and disseminating factual data. It would seem to be logical that the starting point for any experimentation on roof bolts in coal mines should be the time-proved practice of the

Jan 1, 1955

By P. Barnes

(Read at the Philadelphia Meeting, February, 1878.) IT may be of interest, and perhaps of importance, to the members of the Institute that specific mention should be made in detail of the great value of this method of copying or photographing all kinds of tracings.* Several samples are laid upon the table which may serve as illustrations of the results obtained. Some of these show slight imperfections, depending upon the character of the tracing, and upon the length of the exposure to the light, but it may be clearly seen that even a faint copy would be quite available for actual use. The process is believed to be of French origin, and has been used for many years. Special attention seems to have been directed to it recently, and its great value to engineers appears likely to be fully recognized. The manipulations required are of the simplest possible kind, and are entirely within the skill and comprehension of any office boy who can be trusted to copy a letter in an ordinary press. These particulars may be summarized somewhat thus 1. Provide a flat board as. large as the tracing which is to be copied. 2. Lay on this board two or three thicknesses of common blanket, or its equivalent, to give a slightly yielding backing for the paper. 3. Lay on the blanket the prepared paper with the sensitive side uppermost. 4. Lay on this paper the tracing, smoothing it out as perfectly as possible so as to insure a perfect contact with the paper. 5. Lay on the tracing a plate of clear glass, which should be heavy enough to press the tracing close down upon the paper. Ordinary plate-glass of ill thickness is quite sufficient. 6. Expose the whole to a clear sunlight, by pushing it out on a shelf from an ordinary window, or in any other convenient way, for six to ten minutes. If a clear skylight only can be had, the exposure must be continued for thirty or forty-five minutes, and under a cloudy sky, sixty to ninety minutes may be needed. * The introduction of this process into the United States is due principally to Mr. A. L. Holley, who first drew the attention of American engineers to its simplicity and convenience. Mention was also made of the process at the meeting of the Institute in New York, in February, 1877, by Mr. Ogden Haight.

Jan 1, 1878

By P. Crowther, G. J. Lamprecht

The solubilities of silver, zinc, and cerium in liquid sodium, in the temperature ranges 100 to 270°C, 190° to 550°C, and 120" to 460°C, respectively, have been determined. From the solubility data the heat the entropy the partial molal enthalpy of mixing the excess entropy and the partial molal free energy of solution for the systems Nu-Ag and Na-Zn have been calculated. For the system Na-Ce the observed negative is discussed in terms of the solubility of the oxide Ce2O3. In an earlier publication the results obtained in the study of the solubility of tin' in liquid sodium are presented, as well as the detailed analytical procedures used. 1) REAGENTS Spectroscopically pure metals as supplied by Johnson Matthey and Co, were used to produce the following tracers: 253-day Ag110, 245-day zn65, and 325-day ce141. The tracers were prepared by irradiation in a thermal neutron flux of 4 x 10 13 neutrons cm-2 sek-1. To obtain a uniform amount of the required specific activity, needed for each solubility experiment, the radioactive metal was diluted with the corresponding inactive metal, by melting them together in an inert atmosphere. The liquid sodium used contained 11 ±2 ppm of O,1 determined by the vacuum distillation method.' The oxygen was assumed to be present as the oxide NaD. 2) THE SYSTEMS: SODIUM-SILVER AND SODIUM-ZINC Plots were made of the log of the mole fraction of silver, Fig. 1, and of zinc, Fig. 2, dissolved in the liquid sodium vs reciprocal absolute temperature. The equations for the solubilities, based on the least-squares fit to each plot, are: where Xi is the mole fraction metal dissolved in sodium, T is the absolute temperature, and s is the standard deviation in the value of log Xi. The heats and the entropies lution were calculated from the solubility data by In neither of the two cases was any intermetallic compound formed between sodium and the solute metal as was the case for tin.' Thus, for the silver and zinc systems the pure metal was taken as the reference phase. Since the solids in equilibrium with the liquid sodium were the pure metals, one can calculate the partial molal enthalpy of mixing and

Jan 1, 1969

By H. I. Aaronson, H. A. Domian, A. D. Brailsford

A current study of the growth kinetics of k (hcp) plates in a Cu-Si (fcc)' has generated a requirement for data 02 the chemical interdiffusion coefficient in a (termed D,) as a function of temperature at the composition of the a/a + k pJase boundary. Rhines and Mehl 2 have determined D, as a function of composition at lower silicon contents by making Matano analyses of concentration-penetration curves. However, the accelerating increase in B, which they demonstrated as the phase boundary composition is approached at constant temperature and the rapidly diminishing accuracy of this analysis as the limiting compositions of a diffusion couple are approached (the silicon-rich component of their couples contained appreciably less silicon than is permitted by the solubility limit) indicate that the required information cannot be safely obtained by extrapolation of their data. Although the quite different method employed in this study is not exact, it will be shown that the approximations made are not serious ones, particularly from the viewpoint of the prgcipal application anticipated for these data. D, was determined from the migration kinetics of the a :k boundaries formed in sandwich-type diffusion couples produced by welding a block of high-purity copper to opposite sides of a cube (* in. on edge) of homogenized high-purity Cu-5.82 wt pct Si alloy. The alloy is pure k in the temperature range employed. The surfaces of the couple components which were normal to the diffusion direction were machined accurately flat and parallel, lightly polished, and carefully cleaned. Welding was then accomplished by means of the vacuum-encapsulated pressure jig technique previously employed.3 Welding was always conducted at the intended diffusion temperature; thus the welding anneal also served as the first diffusion anneal. Subsequent diffusion anneals were performed in evacuated Vycor capsules. Following the welding anneal, one of the surfaces parallel to the diffusion direction was machined, ground, and polished flat; additional material was removed from this surface after each diffusion anneal in order to avoid any effects of composition changes. After etching,4 the average distance between a : k boundaries was measured by means of a traveling microscope with an accuracy (per measurement) of better than 1 p. Satisfactory results were obtained at four temperatures in the range 775° to 655°C; attempts to obtain data at two lower temperatures were unsuccessful, evidently as the result of the interference of surface contamination during the welding process.

Jan 1, 1969

By R. C. Buehl, J. P. Morris

ACTIVITY values for sulphur dissolved in liquid iron and slags as functions of composition and temperature are needed in applying thermodynamics to sulphur-control problems in iron- and ' steel-making. The purpose of this investigation was to determine the effect of carbon on the activity of sulphur in the metal phase. The method employed was the same as that used in an earlier investigation' concerning the effect of silicon on sulphur activity in liquid iron. A study was made of the conditions of equilibrium in the reaction between hydrogen gas and sulphur dissolved in iron-carbon alloys. The chemical equation for this reaction can be written as follows: S (in liquid Fe-C alloy) + H2 (gas) = H2S (gas). It was found that the activity coefficient of sulphur in liquid iron increases as the carbon content increases. At 2.3 pct carbon and 1600 °C, the activity coefficient of sulphur is twice its value in carbon-free iron, and at carbon saturation it is more than six times as great. The effect of temperature on sulphur activity was found to be small. Previous work on the reaction between hydrogen gas and sulphur dissolved in liquid iron has been reported by several investigators2,³,4 but only recently have studies been made of the effect of alloying elements. Silicon1 is known to have a pronounced influence on the activity of sulphur in iron, its effect being similar to that shown by carbon as described in the present report. Kitchener, Bockris, and Liber-man5 recently have published a preliminary report of their work on the effect of carbon on sulphur activity in iron. Their experiments were made at 1570°C and carbon saturation in the melt. Under these conditions they found that the activity coefficient of sulphur was approximately doubled by the presence of carbon. This is a much smaller effect than that found in the present work. Experimental Method: The apparatus and procedure were essentially the same as those used in the earlier investigation of the effect of silicon on sulphur activity.' Briefly, the method was as follows: A molten iron-carbon alloy was brought to equilibrium at constant temperature with a mixture of H2 and H2S of constant composition by bubbling the gas through the metal. Samples of the melt were

Jan 1, 1951

By L. Sturkey

Quantitative X-ray diffraction studies of the precipitation of thorium in a Mg + 3.3 Th + 0.51 Zr alloy (HK31A) in both the as-cast and cold-worked states show that the precipitation may be described by f = 1 - e(t/T)1/2 over most of the aging period. The effects of cold work and temperature changes are determined. The precipitation of tile equilibrium Mg-Th compotund is Preceded by the formation of a transition phase of higher thorium content, with the cowposition Mg2Th and with a Laves-phase structure. Thorium-containing alloys of magnesium have assumed considerable commercial importance, especially for applications requiring exposures to temperatures greater than 500°F for appreciable lengths of time. The principal commercial wrought alloys in this system are HK31A, containing nominally 3 pet by weight thorium and about 0.7 pet by weight zirconium: and HM21A. containing 2 pet by weight thorium and 1 pet by weight manganese. These two alloys retain a high level of properties even after exposures of 100 hr at 600°F, while the more common alloys containing aluminum and zinc are badly overaged by these conditions. Therefore, in order to obtain some insight into the mechanism by which thorium produces high temperature stability in these wrought alloys, it seems desirable to investi- gate the effect of temperature and mechanical working on the precipitation processes involving thorium. Since the scattering power of a thorium atom for CuKa X-ray radiation is about ten times that for a magnesium atom, the magnesium alloys containing about 3 pet by weight thorium are ideal for quantitative measurements by X-ray diffraction of the amount of Mg-Th compound present at any time. Such quantitative measurements should be of theoretical importance in the study of the effects of time, temperature, and deformation on precipitation and precipitation hardening. Of the two commercial alloys, HM21A and HK31A, the latter is certainly the most suitable for study: In the Mg-Th-Zr2 system, only Mg-Th compounds need be considered, since no ternary compounds or binary Th-Zr3 and Mg-Zr4 compounds exist. The Zr is added to this alloy as a grain refining agent and probably plays a secondary role in precipitation. On the other hand. thorium and manganese form many

Jan 1, 1961

By B. J. Bayles, J. A. Ford, M. J. Salkind

Unidirecltonally sulidijied AL-A13Ni was found to exliibit excellent microstructural stability to 508°C. Above this temperature the transverse micvostructure coarsened in a manner analogous to "Ostwald Ripening", but the A13Ni whiskers did not spheroidize or foreshorlen. The coarsened whiskers reinforced the matrix as effectirely as the finer whiskevs and no reduction in room-temperature tensile strength mas noled after exposure for 90 hr at 96 pel 0-1 the absollite melling temperature of the eulectic. The slability was auribucted to the presence of low-index (and presurrlably lor-energy) cvystallographic interjaces between phases. The driving force for microstructural coursening was presumed to be the reduction of interfacial energy between the phases. Finer micvoslructures were found to coarsen more rapidly than those which weve imitally coarser. FIBER-reinforced metals have been shown to exhibit good short-time tensile properties at elevated temperatures.1-4 However, many elevated-temperature applications require long-time property retention which dictates the necessity for microstructural stability. Two types of instability are common to fiber composities. The first, chemical instability, is due to chemical reaction between the matrix and the relnforcing phase. Petrasek and weeton5 have shown that chemical reaction between tungsten wire and several copper alloy matrices resulted in degradation of the reinforcing phase and reduction in strength of the composite materials. Kreider and Leverant4 have noted similar behavior for boron-reinforced aluminum above 400°C. The second type of instability arises in systems in which the phases are essentially chemically stable with respect to each other and is characterized by spheroidization and/or agglomeration of the reinforcing phase. parratt6 has reported this type of degradation to occur relatively rapidly at moderate temperatures for nickel and cobalt alloys containing whiskers of silicon nitride, aluminum oxide, and silicon carbide and has identified it as "physicochemical" instability. Although both types of instability are the result of the differences in the chemical potential between the fibrous phase and the matrix, they may be differentiated by the fact that the second type, "physicochemi-call' instability, results in little or no net change in the composition or amount of each phase present. It does, however, result in a morphological change which profoundly affects the strengthening mechanism. Chemical interaction. on the other hand, results in a change in the composition and amount of one or more of the phases present, or the appearance of a new phase. In the latter case, the appearance of the mi-crostructure, that of a fibrous phase aligned in a matrix, may remain essentially unchanged, but the chemical degradation of the fiber results in markedly reduced composite strength. This investigation was initiated in an attempt to evaluate the microstructural and related mechanical property changes of a whisker-reinforced eutectic composite after elevated-temperature exposure. The composite system chosen for this study was the uni-directionally solidified A1-A13Ni eutectic which Lemkey. Hertzberg, and Ford7,8 demonstrated to behave as a whisker-reinforced composite. The microstructure of the unidirectionally solidified material consists of aligned needles of A13Ni in a matrix of aluminum. EXPERIMENTAL PROCEDURE Eutectic ingots having a nominal composition of 6.2 wt pct Ni were produced by melting 99.99+ pct A1 and 99.99 pct Ni in recrystallized alumina crucibles in an argon atmosphere. The analyses of the starting materials are listed in Table I. These master heats were cut up? melted by induction heating, and unidirectionally solidified vertically in 1/2 -in.-ID. 6-in.-long graphite crucibles, in a dynamic argon atmosphere. Therma1 gradients in the liquid were determined by measuring the temperature in the melt as a function of apparatus travel distance, as discussed by Kraft and Albright.9 The rate of solidification was assumed to be equal to the uniform rate at which the crucible assembly was withdrawn from the furnace. Ingots representative of nominal growth rates of 2, 5, and 11 cm per hr were produced and the solidification parameters are summarized in Table 11. Ingots used for met allographic analysis were pre-

Jan 1, 1968

By Dale A. Vaughan, Oliver M. Stewart, Charles M. Schwartz

Solid-solubility limits at 1500°, l000q and 500°C for carbon, nitrogen, and oxygen in high-purity tantalum were determined by X-ray lattice-parameter methods. For carbon, the solubility was found to be 0.17 at. pct at 1500°C, and less than 0.07 at. pct at 1000°C. A nitrogen solubility of 3.70 at. pct at 1500° C decreases linearly with temperature to 2.75 at. pct at 1000°C, and 1.8 at. pct at 500°C. In the case of oxygen, the solubility was found to be 3.65 at. pct at 1500°C, 2.95 at. pct at 1000°C, and 2.5 at. pct at 500°C. The phases Ta2C, the low-temperature modification of Ta205, and Ta,N of unknown composition but which has a superlattice structure based upon the original bcc tantalum lattice have been identified as the initial precipitates in the respective systems. Metallographic methods were employed to verify the X-ray analyses. The etching behavior of Ta is discussed in terms of lattice i?rzperfections and precipitate phases. The excellent fabricability, high melting point, and nuclear properties of tantalum are responsible for interest in this refractory metal. Data on the solid solubility of the interstitial elements (oxygen, nitrogen, and carbon) in tantalum and on the precipitate phases are somewhat limited. The significant contributions are discussed below. Because the purity of electron-beam melted tantalum (only recently available) is considerably higher than that used in previous studies, the present investigation was initiated. Gebhardt et all-3 have investigated the tantalum-oxygen and tantalum-nitrogen systems with particular reference to the changes in physical properties and to the rates of reaction between these gases and the metal. The solubility of oxygen in tantalum was reported2 to be 3.7 at. pet at 1500°, 2.3 at. pet at 100O°C, and 1.4 at. pct at 750°C. Schonberg4 reported that several oxide phases (Ta40, Ta,O, TaO and Ta,05) exist while X-ray studies by Gebhardtl showed only two oxides, Ta,05 and an unidentified phase which was associated with a platelet-type precipitate. La-gergren and Magneli,' however, questioned the existence of compounds other than the two allotropic modifications of Ta,05 for the tantalum-oxygen system. In the case of nitrogen, the solubility was estab- lished by Gebhardt3 to be of the order of 7 at. pct at 1800°c. The solubility was reported to decrease rapidly with temperature, and, although no limits were established, a precipitate phase was observed by Gebhardt except when the high-nitrogen specimens were cooled very rapidly from the reaction temperature of 1800c. He reported the initial precipitate phase to be a tetragonal distortion of the bcc tantalum lattice while Schonberg6 reported the phase lowest in nitrogen Jo be a cubic super-lattice with a cell size of 10.11 A. Two other nitride phases, Ta,N and TaN, were reported; these appear to be isomor-phous with the carbides of tantalum. The tantalum-carbon system was investigated by Ellinger7 and by Lesser and Braurer. Two compounds, Ta,C and TaC, were reported to exist, each with a range of composition. The solubility of carbon in tantalum was found to be practically nil at all temperatures. Thus, of the interstitial elements which are present in small amounts in high-purity tantalum, carbon might be expected to form precipitates. The present investigation was initiated to obtain additional data on the solid-solubility limits of these interstitials at 1500°, 1000°, and 500' with particular emphasis on the distribution and the identification of the precipitate phases. EXPERIMENTAL WORK AND RESULTS In the present investigations of the solid solubility and of the precipitate phases in the systems tantalum-nitrogen, -oxygen, and -carbon, high-purity tantalum was reacted with high-purity gases, homogenized at 1800°c, and annealed at and quenched from 1500°, 1000,

Jan 1, 1962

By J. P. Denny

The constitution of the Ga-In system was determined by thermal methods. An experimentally determined metastable equilibrium line (an extension of the indium-rich liquidus) was obtained. The various alloys were studied metallographically using polished samples obtained by a casting method. These low melting alloys required a special dry-ice assembly to maintain a suitable temperature. RECENT interest in alloys that are liquid at room temperature has led to rather extensive investigation of gallium-base alloys. Widely distributed over the earth, gallium could be produced in substantially larger quantities than at present, if a significant demand existed.' One study' has established its presence in 12 out of 14 zinc blends, in all of 15 aluminum ores, in 4 out of 12 manganese ores, in 35 out of 91 iron ores, and in all of 7 magnetite ores. It occurs as a rule in minute amounts, however, leading to high extraction costs. Recent quotations run from $2.50 to $7.50 per g. During the course of the present investigation, portions of the system Ga-In have been redeter-mined, and the results of this study are presented herein. Thermal and metallographic methods have been employed. Lecoq de Boisbaudran, the discoverer of gallium, conducted the first investigation" on Ga-In alloys in 1885. The temperatures of incipient melting, and of completion of melting, were determined at four alloy compositions. In 1936, Hansen' constructed a eutec-tic-type phase diagram for the system Ga-In, based on . work. The existence of a Ga-In compound was regarded as improbable by Hansen, and subsequent investigations are in agreement. French, Saunders, and Ingle3 conducted a more complete study of the system in 1938, using thermal methods. Their phase diagram is a eutectic type, containing a unique concave-upward liquidus. The solid-solution range of gallium in indium was reported as 9.5 pct by weight, and that of indium as less than 1 pct, at the eutectic temperature. The eutectic composition, determined as being bracketed by the compositions showing a true horizontal at the eutectic temperature (16°C), was reported as 76 5-0.5 pct Ga and 24 i 0.5 pct In. Experimental Procedure The preparation of Ga-In alloys is simplified by the low melting points involved. Various compositions were prepared by melting in pyrex tubes, using a cover of distilled water or parafin to prevent the alloys from wetting the glass wall. In all cases, the melts were homogenized. by stirring. Where possible, both cooling and melting curves were determined. The extensive undercooling of gallium was found to prohibit a satisfactory cooling-curve analysis of gallium-rich alloys, however, and transition points on the gallium side of the eutectic could be determined only by melting curves. The inverse rate method of thermal analysis proved to be most satisfactory and was used to a great extent. Various heating and cooling rates were used, ranging from 0.2" to 5.0°C per min. Low temperature melting analyses were conducted within a constant temperature bath, maintained at about 70 °C. The alloys were solidified (under water or paraffin) within a pyrex tube, using dry ice; the tube was then sealed within a cold Dewar flask, the unit transferred into the constant temperature bath, and periodic temperature readings taken. The high temperature melting-curve determinations and all cooling-curve determinations were made in a vertical tube furnace. At near-eutectic compositions, the furnace was placed within a refrigerated room held at —20°C. Accordingly, the furnace on cooling approached —20°C asymptotically and permitted the determination of those phase transitions occurring below room temperatures. Temperatures were measured with a 30-gage iron-constantan thermocouple, immersed directly in the alloy. To prevent contamination of the melt, the leads and junction were coated with Lucite, applied by painting with a solution of Lucite in ethylene dichloride. Electromotive force measurements were made with a Leeds and Northrup precision potentiometer, type 8662. The couples were calibrated against the boiling point. of water and, at lower temperatures, against a calorimeter thermometer having a Bureau of Standards certificate. The melting points of gallium and indium used in the present investigation were determined as 29.-77° and 156.1°C, in good agreement with previously reported values of 29.78°C° and 156.4"C.' The spec-

Jan 1, 1953

By W. O. Philbrook, R. S. Kaplan

Rates of oxidation were studied for levitation-melted samples of Fe-C, Fe-Si, Fe-C-Si, Fe-C-P, Fe-C-Mn, and Fe-C-S alloys oxidized by mixtures of either 5 or 10 pct O2, in helium at several temperatures in the range 1850o to 2050°C. The concentrations of the oxidized elements decreased linearly with time. Mass transport in the gas phase was found to be the rate-controlling step. Ilowever, a mulliple -film model was necessary to account for the flux of iron and manganese vapor counter to the oxygen flow. THE advent of the basic oxygen and spray-refining processes of steelmaking has generated considerable interest in the kinetics of reactions between oxygen-bearing gases and liquid iron alloys. The object of this research was the determination of the role of mass transport in the gas and metal phases and of surface chemical reactions in the overall oxidation process. Of the reactions for elimination of elements dissolved in liquid iron, the oxidation of carbon has been investigated most extensively. Studies by Fuji and Ura,1 Fuji,' and Gunji et a1.,3 done with pilot-scale basic oxygen furnaces, indicated that mass transport of gaseous oxygen was rate controlling when the metal carbon content was greater than 0.15 to 0.30 pct. When the carbon content was less than this critical amount, diffusion of carbon dissolved in the iron was thought to be rate limiting. L. A. Baker et a1.4,5 levitated samples of iron-carbon alloys and oxidized them in CO-CO2, CO-C02-He, and O2-He atmospheres at 1660°C. These investigators found that the metal carbon concentration decreased linearly with time and their samples exploded when the carbon content fell below about 0.8 pct. They concluded that the rate-limiting step was the transfer of oxidant to the gas-metal interface. A model based on this rate-limiting step predicted decarburization rates within a factor of two of those experimentally observed. The explosion of the samples was attributed to a shift in rate-controlling step from gas-phase mass transport to transport of carbon dissolved in the metal. L. A. Baker and R. G. ward6 and R. Baker7 used freely falling droplets to investigate oxidation kinetics. In both papers, the authors speculated that flame fronts may have been partially responsible for the lack of better agreement between experiment and theory. Swisher and Turkdogan8 oxidized liquid iron having an initial carbon content of 0.97 pct with CO-CO2 and CO-C02-Ar mixtures at 1580°C. They concluded that a surface reaction was the rate controlling step. Iron-silicon alloys have been oxidized by R. Baker7 and Filipov and Martynov.9 R. Baker 7 also studied iron-carbon-silicon alloys falling as liquid droplets through oxygen. He found that the rate of both carbon and silicon oxidation varied inversely with the drop radius. When the initial silicon concentration was greater than 6 pct, the samples cooled during their fall. Manganese oxidation has been studied by R. Baker,7 and by Filipov and Martynov.9 ward10 investigated the loss of manganese from liquid iron under vacuum. He found that mass transport of manganese vapor was rate limiting in argon atmospheres of 0.02 torr to 700 torr pressure. Iron-sulfur alloys were desulfurized with H2-He and H2-Ar mixtures by Peters et al.11 A model based on the transport of H2S from the gas-metal interface into the bulk gas gave fair agreement between the predictions of the model and the experimental results. EXPERIMENTAL TECHNIQUE Essentially, the technique consisted of using helium-oxygen gas mixtures to oxidize levitated samples of liquid binary and ternary iron-base alloys. The fused silica reaction tube is shown in Fig. 1. The coil design is similar to that of L. A. Baker et al.4'5 A Tef-lon-sheathed, ferritic stainless steel lifter (B) and an alumina pedestal (C) were used to support the sample in the coil prior to levitation and for the recovery of the sample. Samples were inserted into

Jan 1, 1970

By R. H. Tien

This paper presents an analytical solution of the problem of freezing of a semi-infinite slab with constant surface temperature; in this analysis accoz~nt is taken of the heat evolution during the solid-state transformations in the frozen skin. The regions where transformations occur are treated as plane isothermal heat sources; i.e., the rates of transformations are assumed to be infinite. In the model considered, three plane heat sources are assumed to be present in the frozen solid. The solution yields the temperature distribution in the solid, the rates of movement of the heat sources , and the rate of movement of the solidification front. It is shown that, although the sum of the heats of transformations in the solid is about 20 or 43 pct of the heat of fusion of iron or manganese, respectively, the effect of the heat evolution in solid-state transformations on the rate of solidification is insignzficant. IN several recent mathematical studies of solidification of liquid metals'-3 no account was taken of the heat evolution accompanying the solid-state transformations. In the case of, for example, steel, there are several phase transformations 6 -y, y -a, and the magnetic transformation. Whether or not a significant error is introduced into the mathematical simulation of solidification processes by the omission of the heat effects associated with these phase transformations is not known. The purpose of the present study is to investigate the effect of these phase transformations on the temperature distribution and the rate of solidification based solely on the heat transfer point of view. That is, for the sake of simplicity, freezing of a pure metal with solid-state transformations will be considered. The mathematical model which represents the present problem includes four moving heat sources representing freezing and phase transformations, 6— y — a — ferromagnetic. The thermal properties such as conductivity and specific heat, and so forth, are different from one phase to the other. But they are considered to be uniform over any particular phase. The usual Fourier heat flow law is employed. The concept of conservation of energy is applied at every heat source in order to estimate their rate of movement. The temperature distribution in the solid and the positions where transformations occur are expressed analytically in terms of error function solutions and four coefficients which are determined from four nonlinear algebraic equations. These coefficients can be calculated either by trial and error or by any numerical method. MATHEMATICAL ANALYSIS Fig. 1 is a schematic diagram showing the zones of different phases 1, 2, 3, and 4 in the solidified portion of a semi-infinite pure liquid metal. The heat is subtracted from the system at x = 0 which is maintained

Jan 1, 1968

By R. F. Mehl, B. Lustman

THE formation of intermediate phase layers in cementation processes has been subjected to extensive qualitative investigation though to relatively little quantitative study; this work has recently been fully summarized by F. N. Rhines.1 It is necessary here only to enumerate the general conclusions drawn concerning the kinetic laws governing the growth of intermediate layers and to state what is known concerning the structural changes accompanying the generation of phase layers. I. When the intermediate phase is protective in type-i.e., when its density is less than that of the base metal, so that a continuous coating is formed and maintained the isothermal growth of the phase follows a simple parabolic equation: X2 = kt [I] where X is the thickness of the alloy layer, k the reaction rate constant, and t the time. The applicability of this equation to diffusion processes is tested by plotting the square of the thickness versus time, or by plotting the thickness versus the square root of time; the resultant achievement of a straight line in such. a plot has been con¬sidered sufficient proof of the validity of this equation. Exceptions have been found where liquid phases are involved in the reaction, where the diffusion layer is cracked,2 and where thin semimetallic oxide and sulphide coatings are formed on metals.3 In the first two cases the thickness increases linearly with time, and in the latter it is a logarithmic function of time. 2. The rate of thickening varies with temperature according to the Arrhenius equation k = Ae-Q/RT [2] where k is the parabolic rate constant of Eq. I, or some other rate-descriptive function, A is the action constant, e the base of natural logarithms, Q the heat of activation, R the gas constant, and T absolute temperature. This equation has been found to be generally valid except when transformations occur during reaction in either the base metal or in the reaction layer; in such instances Eq. 2 is still applicable with different values for the constants A and Q above and below the transformation temperature. 3. All phases that are stable at the temperature at which diffusion occurs will appear in the interdiffusion of two components. In some cases certain of the phases may be too thin to be observed and identified easily. Nonequilibrium phases have never been noted in thick reaction layers; i.e., layers of a thickness that may be discerned microscopically. The relative, thickness of each phase in a diffusion layer is proportional to the concentration gradient and to the rate of diffusion in that phase .4 The reaction layers tend to have a

Jan 1, 1942

By W. A. Hockings, M. E. Volin, A. L. Mular

Batch grinding tests at short times were made in a laboratory rod mill with 10 x 14 mesh quartzite in corn syrup-water mixtures of varying viscosity. The weight fraction broken and size modulus were found to be independent of viscosity up to 20 cp, but at higher viscosities breakage of the feed decreased while the size modulus increased. The mechanisms of the effect of viscosity are discussed on the basis of particle dynamics. The effect of viscosity of the suspending medium on grinding has not been accorded much attention, although both wet and dry grinding are used in bene-ficiation processes and the viscosities of water and air differ greatly. schweyerl investigated the rates of grinding of quartzite in a pebble mill with air, water and glycerol as the suspending media and found the rate in terms of new surface developed per thousand revolutions of the mill to be constant and dependent on viscosity up to 20,000 rev, but to decrease and become independent of viscosity for longer grinding times. Based on considerations of the drag forces exerted on suspended particles and on the grinding media under turbulent and laminar flow conditions, viscosity can be expected to inhibit the rate of grinding in a given system as it changes the flow conditions from turbulent to laminar. The objective of this study was to determine the effect of viscosity of the suspending fluid in the batch grinding of a homogeneous feed of uniform size for short residence times, a region of more practical interest than the long times investigated by Schweyer. In actual grinding operations, the viscosity of the fluid does not change, but the consistency (apparent viscosity) of the pulp increases with additions of fines. In this study the consistency of the pulp was not measured because it was thought that the grinding times were too short to alter the apparent viscosity appreciably.* *Minus 200 mesh quartz at 65% solids has an apparent viscosity of about 25 cp as measured by a simple consistometer. Personal communication from D. F. Kelsall to A. L. Mular. For the purposes of this study, the effect of viscosity on grinding can be shown sufficiently well on the basis of the cumulative weight fraction finer than the feed size at any time, and the size modulus, ku, of the finer than feed sizes. The parameter, ku, is obtained from a form of the Gaudin-Schuhmann equation. METHOD AND MATERIAL The grinding tests were accomplished in a laboratory rod mill 10-1/2 in. long and 8 in. bore with a 20-lb rod charge consisting of two 1-in., eight 3/4-in., eight 1/2-in., and eight 1/4-in. diam rods. The mill speed was 43.2 rpm. Charges of 400 g 10 x 14 mesh Wisconsin quartzite** were ground for times of 60, **Courtesy of Minnesota Mining and Mfg. Co. 120, 180 and 240 sec in 500 cc of fluid made up of corn syrup and water in measured proportions. The temperature of the pulp was measured immediately upon completion of grinding, and the size distribution of the quartzite was determined by a wash-wet-dry screening technique. Corn syrup was chosen because of its high viscosity and ideal viscous behavior, and also because its density is not greatly different from that of water. The viscosity of each fluid mixture was measured with an Ostwald viscometer at 25 C. and a correction was made for the temperature of the pulp according to tabulated values for sucrose solutions. The density differences were so small that they probably did not significantly affect breakage. RESULTS AND DISCUSSION The conditions of the grinding tests, computed viscosities, weight fractions finer than the feed size and values of a and ku are listed in Table I. The values of a and ku were taken from the linear portions of the log-log plots of cumulative weight fraction finer vs size for the various grinding times. The plots for tests in fluids of average viscosity 8.6 cp are shown in Fig. 1. In general all of the sets of curves were linear throughout most of the size

Jan 1, 1965

By M. T. Worley

This paper reports investigative work conducted to develop a method of estimating the groundwater influx from a homogeneous permeable formation into a vertical mine shaft during sinking. A method of analysis was developed using data obtained from pumping tests and a modification of the Theis non-equilibrium interpretation technique. Excess influx of groundwater into mine shafts has long been one of the more important problems encountered in the development of a mining property. Much work has been done on methods of preventing such influx and on pumping schemes to control inflow if preventive measures fail. The fundamental aspects of the problem, on the other hand, seem to have been neglected. The purpose of this paper is to review the fundamentals of groundwater flow and to propose a rapid method of analyzing hydrologic data in order to estimate influx from a homogeneous permeable formation into a mine shaft. Such an estimate of the quantity of water to be encountered is of value in planning grouting, pumping and other programs designed to control that influx. It is emphasized that the proposed method of analysis should be regarded only as a tool to be used in evaluating the problem before investing the capital necessary to begin development of a property. FUNDAMENTALS OF GROUNDWATER FLOW In order to effectively approach the problem of estimating influx into a mine shaft, a knowledge of the fundamentals of fluid flow through a porous medium is necessary. Darcy, in 1856, developed an empirical relationship to explain the flow of water through sand filters. This relationship V = k (dh/dl), is the basis for all other flow formulae. It has been shown that Darcy's relation is a solution of the Laplace equation and thus is analagous to other natural phenomena such as heat flow. Theis, using the analogy of heat flow by conduction, developed an expression for determining the transient or time-dependent groundwater flow through a homogeneous, isotropic medium. The resulting equation Was also derived by Jacob using hydrologic considerations alone.' The individual terms in the equation are described in Table I. It is important to understand the assumptions upon which this equation is based. 1) The medium through which the fluid flows is infinite in areal extent, homogeneous and isotropic. 2) The well into which the fluid discharges completely penetrates the medium. 3) The characteristics of the medium remain constant at all times. 4) The initial pressure surface is horizontal. 5) The confining media are impervious and horizontal. 6) Fluid is removed from storage instantaneously by a decline in pressure. 7) The diameter of the discharge well is infinitesimal with respect to the drainage radius of the medium.

Jan 1, 1962