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There were two official representatives of Foreign Governments as guests at the Chicago Meeting. One was Frederick Goransson, managing director of the Saudvikens Steel Works, who represented the Jernkonteret, the Iron and Steel In-stitute of Sweden, and who came to this country especially for our meeting. The other distinguished guest was Commander Toublet, who repre-sented the French Embassy. Commander Toublet delivered a most polished address at the Banquet, dealing with the felicitous relations existing between this country and France for the last 150 years. Com-mander Toublet was accompanied by Mrs. Toublet, who won the hearts of all the ladies present, whose guest she was.

Jan 11, 1919

By E. N. Pennebaker

A PRESENT, a comprehensive account of the geology and ore deposits of the Robinson mining district, in eastern Nevada, is not warranted. Though several years' work has been done, the district is so large that it will be some time before the investigation nears completion. In this paper I purpose merely to discuss methods of study and the application of geologic data to the search for ore. In the first place, the purpose of a geological depart¬ment in a mining organization is to collect and correlate all geologic and engineering data likely to be useful. In an extensive and well developed mining camp this involves a detailed study of the structure and stratigraphy of the district as a whole, as well as careful analysis of the orebodies exposed. The problem then is to find continuations or similar ore environments in other parts of the district in which like phenomena have been active, and to explore these for new orebodies. Experience gained in other similar mining districts is useful but one must always remember that a great many mining districts are unique and that exploration rules and procedure applying to one cannot always be transferred to another of apparently similar character and be made to work. One also has to be careful in moving from one to another part of the same district. The geologist must first examine the region critically to determine its individual characteristics. .

Jan 1, 1932

By R. S. Busk

Niels Engel (University of Alabama, University, Ala.)— In this paper it was pointed out that the electron-gas and energy-band theory accounts for the fact that the lattice parameters exhibit a sudden change when the electron concentration (number of bonding electrons per atom) exceeds a certain number around two. This statement is said to support and prove the electron-gas theory. But this theory is not able to account for a series of experimental data. Also several expectations, deduced from this theory, are not found to exist. In Figs. 6 and 7 the energy bands of the second and third periods are given as they must be assumed in order to account for the electrical properties of the elements in these periods. In Figs. 6 and 7 the electron-gas and energy-band theory is compared with the electron-oscillator hypothesis in accounting for the properties of the elements in the second and third periods. Fig. 6 shows the second period, The energy-bands are overlapping and separated to be in agreement with the electrical conductivity of the elements. The oscillator hypothesis explains conductivity due to electron vacancies. In graphite there is a closed s-shell in every other atom and two vacancies in the others. Conductivity is therefore only maintained by migration of s-electrons in graphite. In boron there are no s-electrons. The diatomic molecules of nitrogen and oxygen and the paramagnetism of oxygen can be accounted for by a similar behavior as the s-electrons of the bonding electrons. But this explanation will deviate too much for the purpose of this discussion. Fig. 7 shows the third period. In the energy-band picture about two s-electrons are assumed in magnesium and aluminum, but only one s-electron is assumed in silicon. The diamond lattice is assumed to be controlled by a sp3 hybrid. However the electron distribution develops ideally according to the oscillator hypothesis. Only sodium, magnesium, and aluminum exhibit electron vacancies and conductivity. To account for the insulator properties in Si, P, and S in the third period it must be assumed that the four last added p-electrons must be taken up in bands containing only one electron per band.' (Compare the electron band picture in Hume-Rothery.' Hume-Rothery does not consider the insulator properties of the nonmetals.) In the second period already the first p-electron must have entered a single electron band. Based on the energy-band picture in Figs. 6 and 7, the following questions must be asked: 1—Is it consistent with the energy-band idea that electrons of the same kind (p-electrons) can be divided into separated bands? 2—Is it consistent with the energy band idea that single electron bands can exist? 3—Why are the first two p-electrons (in boron and diamond) separated into two single electron bands in the second period, but overlapping in the third period (aluminum)? 4—Why are s-electrons and d-electrons taken up in continuous overlapping bands, while p-electrons are divided into single electron bands? 5—Why do the peaks and valleys (y and w and further x and z) of the energy band below four electrons per atom not show up in the electrical conductivity of alloys? For example consider the Li-Mg system or the alloys between Mg and three electron metals where the mentioned discontinuity in the lattice parameter is found. 6—Why does the beginning of the p-electron band (x) not show up in the lattice constants similar to the filling up of the s-electron band (z) ? In magnesium alloys the electron-gas theory postulates the first Brillouin zone to be filled at about two electrons per atom. This is claimed to explain the sudden change in lattice spacing and c/a values of several magnesium alloys when the electron concentration exceeds a few percentage points over two electrans per atom. This was emphasized in the paper by Busk. If the electron-gas energy-band theory is correct a sudden change in electrical conductivity and possibly other properties .should be expected when the same electron-concentration or temperature is exceeded. A sudden change in lattice spacing or other properties should also be expected when the filling degree is such that p-electrons are introduced into the p-band, for example at x in Figs. 6 and 7. Such phenomena are at found by experiment. and If the number of electrons should vary with the energy level depending on the average number of bonding electrons per atom, the electrical conductivity should be expected to vary in accordance with the energy band layout (Figs. 6 and 7) caused by different numbers of conducting electrons at different filling up degrees. Nothing indicating such a behavior is observed. In addition to these discrepancies between the electron-gas and energy-band theory and measured data, the theory violates the principles developed along with the Bohr theory of atomic structure. According to these principles a filled shell is saturated and therefore unable to form bonds. Therefore two S-electrons per atom should form a closed or saturated shell, which has been pointed out as accounting for the inability of helium to form bonds. Beryllium, magnesium, or calcium atoms with two s-electrons should be expected to form inert atoms with properties almost like the helium atoms. Several other inconsistencies and disagreements with measured data of the energy-band theory can be mentioned. Some of these are discussed with reference to other papers. 8 Because the electron-gas and energy-band theory seems to fail on several points, I have developed another theory which can account for all the phenomena the electron-gas theory is able to account for. This new theory is further able to account for things which are impossible to explain by the electron-gas theory at the present state.

Jan 1, 1953

By Arthur Coffinberry

EVE have studied the gold-aluminum system by X-ray diffraction and by the microscope over the entire range of composition for temperatures between 300° and 500° C. Results obtained are shown in Fig. 1, com-bined with the work of Heycock and Neville1 at higher temperatures. The diagram differs in important details from that given by Hansen2 in his critical compilation of the literature of binary alloy systems. This work was, undertaken both because of the intrinsic value of a knowledge of the phase diagram of this system and because of the need of theoretical metallurgy for precise and accurate data, particularly X-ray diffraction data. Systematic studies of equilibrium diagrams, particularly by Hume-Rothery,3 have shown regularities that yield a certain insight into the nature of alloying forces. It has been shown, for example, that solid solubility depends on the concentration of free electrons in the alloy, on the relative radii of solvent and solute atones, on the forces of attraction between atoms, and on the relative stability of intermediate phases. The well-known Hume-Rothery rule states that the crystal structures and compositions of many intermediate phases depend on the electron-to-atom ratio. This has been confirmed and extended by wave mechanical calculations.4 A knowledge of the forces between atoms in alloys, even an imperfectly developed empirical one, should be a valuable guide in the preparation of technological alloys of desirable properties. Furthermore, such informa-tion is basic in such problems as rate of diffusion, age-hardening, phase transformations, and others. The most valuable data for this purpose are furnished by X-ray diffraction studies. Unfortunately, work has been

Jan 1, 1938

By T. O. King, Y. P. Gupta

The self-diffusion of sodium in two sodium silicate liquids was measured in the temperature range 850" to 1500°C by the capillary-reservoir technique. Radioactive Na 22 was used as the tracer. The total count and autoradiographic methods were used for determination of the total Na 22 depletion and diffusion profiles of the dqy-used specimens. The diffusion coefficients obtained by the autoradiographic technique are slightly smaller than those obtained by a total count method. Error analysis of the two methods suggests that more confidence be placed in the results of the total count method. The experimental results were analyzed in terms of the existing activated rate process theory. The activation energy for diffusion was shown to decrease markedly as the temperature increased. This was attributed to a variation in the heat of activation with temperature, probably related to a change in the distribution of anions associated wilh the cation. In terms of a model, suggested for diffusion in liquid silicates, differences in the aclivation energies for diffusion and electrical conduction may arise from the effect of the electric field applied in conduction measurements. It is generally accepted that liquid silicates consist of cations and an equilibrium distribution of complex anions determined by temperature and composition. Transport properties in molten silicates are of interest, not merely because of their relevance to the kinetics of pyrometallurgical reactions and glassmak-ing processes, but also because they are useful to development of the theory of such ionic liquids. Self-diffusion is one such transport process that may, if studied for liquid silicates of widely varying compositions, indicate structural changes through changes in the activation energy for diffusion. The self-diffusion of calcium, silicon,' sulfur: aluminum, 4 and oxygenS in lime-alumina-silica melts and of iron6 in molten iron silicates have been measured. Unfortunately, the errors in some of the reported activation energies for diffusion are too large to allow firm conclusions concerning structure and the mechanism of the diffusion process to be drawn. The research reported here was a study of the self-diffusion of sodium in liquid sodium silicates. The soda-silica system was chosen since: i) a reasonable composition range can be covered in the binary system at moderate temperatures; ii) suitable isotopes of sodium (radioactive Na 22 and NaZ4) can be obtained; iii) data on the electrical conductivity and viscosity of sodium silicate liquids are available. However, the range of composition actually used in diffusion experiments was limited, to 20 to 35 wt pct soda, by the relatively high viscosity of silica-rich compositions and by evaporation of soda from basic melts. EXPERIMENTAL PROCEDURE The capillary-reservoir technique was used, wherein a radioactive tracer, Na 22, incorporated in the capillary melt, was allowed to diffuse out of the platinum capillary tube into a large reservoir of silicate liquid containing a chemically identical melt, but without radioactive tracer. After a specific diffusion time, both the total depletion in the tracer concentration and concentration-distance profiles of the diffused samples were measured by procedures to be described later. The diffusion cell assembly was similar to that used by Koros and King.' The temperature of the diffusion cell was measured with a calibrated Pt, Pt-10 pct Rh thermocouple located at the center of the liquid reservoir. The same thermocouple was used to obtain the temperature profile in the reservoir. The temperature at the top of the reservoir was slightly higher (2°C) than that at the bottom, to minimize convection in the capillary tubes, which were placed, open end up, in the reservoir. Convection was not expected to be a problem since the length-to-diameter ratio of the tubes was about 12:1 and the maximum capillary diameter was 1 mm. The diffusion cell was heated in a molybdenum-wire resistance furnace, previously used by Koros and King, but somewhat modified. A Pt, Pt-10 pct Rh thermocouple enclosed in an alumina tube and located near the furnace winding was used in conjunction with a preamplifier and Micromax proportional controller for temperature control, within 4°C, at temperatures near 1500°C. Before starting a diffusion run, the furnace was heated to the desired temperature and an alumina guide assembly for the capillaries was slowly lowered to within 2 cm of the liquid reservoir. The capillaries were thus heated to about the temperature of the bath. The run was started by lowering the assembly till the open ends of the capillaries were about 1 cm below the surface of the liquid. The run was ended by raising the assembly to about 15 cm above the liquid bath. Later, the sample assembly was slowly withdrawn from the furnace. Six diffusion samples were usually run at the same time. Three runs made with the open ends of the capillaries down were discarded because in the majority of these samples air bubbles trapped at the open end were observed. Some glass adhered to the outside of the capillary on withdrawal. This was carefully removed and used to check that the Na 22 activity in the sink remained at a low level. Materials. Nonradioactive sodium silicates were prepared by melting, in a platinum crucible, weighed quantities of sodium carbonate and powdered silica. To prepare radioactive sodium silicates, Na2 obtained in HC1 solution, was first checked for radioactive impurities by obtaining a y-ray energy spectrum, then the chloride ions were removed by anion-ex-

Jan 1, 1968

By E. W. Johnson, M. L. Hill

Equilibrium concentrations of hydrogen in iron were measured at H2 pressures up to 136 atm and temperatures down to 145°C. Residual hydrogen was prominent near 600°C in air-melted but not in vacuum-melted iron. The diffusible hydrogen solubility is abnormally high below 390°C, confirming the hypothesis of hydrogen trapping.' It appears that the traps for hydrogen in iron form suddenly on cooling. The estimated H2 pressure in equilibrium with 5 ppm hydrogen in steel at room temperature is less than 1000 atm. It was shown previously1 that the diffusivity of hydrogen in a-Fe below 200°C is anomalously low, a behavior attributed to the presence in the metal structure of hydrogen "traps." The energy of the trapped hydrogen was computed as 4.8 kcal Per g-atom below that of the interstitially dissolved hydrogen. The strongest confirmation of the trap hypothesis should be obtainable from measurements of the hydrogen solubility at low temperatures. such measurements have been performed and are reported in this paper. The "residual hydrogen" effect1'' must be carefully controlled if valid measurements of the solubility are to be obtained, and such an effort was made in the present work. Previous data for the solubility of hydrogen in iron have been summarized by Geller and Sun.3 Their equation for the most probable solubility at 1 atm in a-Fe above 400°C is

Jan 1, 1962

By L. M. Pidgeon, W. Curlock

FREE energies of formation of zinc sulfide and magnesium sulfide had previously been estimated to an accuracy of ± 5.0 kcal per g mol. In the present work, these values were determined experimentally. As the determinations of the free energies of formation of zinc sulfide and magnesium sulfide presented different problems, separate experimental procedures were employed for each. ZINC SULFIDE It is difficult to measure the free energy of formation of either zinc sulfide or magnesium sulfide by measuring their decomposition pressures directly, as they are very stable compounds. An attempt was made by Jellinek and zakowski3 to study the equilibrium. zns(s) + H2(g) = Zn(g) + H2S(g) [I] They passed hydrogen over zinc sulfide and analyzed the gases leaving the reaction zone for H2S. They were unable to determine the true partial pressures of the H2S by this method, as some of the H2S on being cooled from the reaction temperature, reacted with the zinc in the gas to produce ZnS. Consequently, they were unable to establish any true equilibrium data for reaction [I]. More recently,' the equilibria ZnS(sphaledte) + Fe (s) — FeS(s) + Zn(g) [2] and ZnS(sphalerite) + 2Cu(s) — Cu2S(S) + Zn (g) [3] were studied. As the standard free energy of formation of Cu2S is known to * 3.0 kcal, and of FeS to ± 1.0 kcal, it should be possible upon performing equilibrium studies on reactions [2] and [3] to deduce the standard free energy of formation of ZnS (sphalerite). However, as both of these equilibria involve 2 solid sulfides, and as it is possible for these sulfides to dissolve in one another, it is necessary first to ascertain the activities of the various sulfides in these solid phases.

Jan 1, 1959

By G. N. Goldberg, Robert A. Rapp

The steady-state kinetics and microstructures of simultaneous internal oxidation and external scale formation were investigated for the oxidation of Cb-Zr and Ch-Zr-Re alloys in pure oxygen at 1000°C. For each binary alloy, a constant rate of scale formation was observed at steady state; the internal oxidatton zone reached a steady-state, time-independent thickness. The dependence of the scaling rate on zirconium content exhibited a maximum at a low zirconium colttent; more concentrated alloys oxidized at a slower rate than pure columbium. This composition dependence of the scaling rate may be partially attributed to the effect of the internal oxidation process as an intenla1 sink for oxygen, with the formation of voluminous, and relatively impermeable ZrO2 precipitates. However, the morphologies of the ZrO2 internal oxide precipitates also affected the scaling rate. The internal oxide precipitates were distributed uniformly in the external scale. The steady-state thicknesses of the internal oxidation zones were not in agreement with those predicted theoretically from an idealized simple model. However, in this particular alloy systen1 the ideal model is not satisfied experitmentally. For ternary Cb- Zr - Re alloys with Nr10e = 0.02 or 0.05, the steady-state thicknesses of the internal oxidation zones were less than those for the corresponding binary Cb-Zr alloys. For ternary alloys with NRe(0) - 0.05, a more adherent and much less porous external scale was formed, and a reduction in the kinetics of scale formation was observed. A number of authors'-7 have reported linear oxidation kinetics for the reaction of pure columbium at 1000°C in air or in oxygen of about 1 atm pressure. A thin and tightly adherent oxide layer is found at the metal/oxide interface beneath a porous external layer of scale. Although the suboxides CbO and CbO2 represent thermodynamically stable phases at 100O°C, generally only Cb2O5* is identified as a reaction product in quenched specimens. Studies at 1000°C at lower oxygen pressures8,10 (Po2 - 10-4 Torr) show that both CbO and CbO2 do form and that CbO2 is a protective oxide. The growth of CbO2 results in parabolic kinetics until Cb2O5 is nucleated and grows. Apparently because of the large volume change associated with its formation, Cb2O5 is porous and does not serve as a diffusion barrier; linear kinetics prevail after the surface is covered with Cb2o5. On the basis of these observations, several authors5,9,10 have suggested that the linear oxidation of pure columbium at 1000°C in air or oxygen of 1 atm is limited by a Loriers-type mechanism,11 whereby the total rate or reaction is controlled by ionic diffusion through a thin layer of CbO2 which is maintained at a constant thickness throughout the linear oxidation. However, the concept of a Loriers model for a three-phase CbOlCbO2 Cb2O5 scale, with the only oxygen activity gradient across the NbO2 phase, is not self-consistent. Further, the suboxides CbO and CbO2 were not observed in the high-temperature X-ray diffraction study of columbium oxidation by Goldschmidt.8 From investigations in which the large PO2, dependence of the linear scaling rate was demonstrated, the importance of an oxygen adsorption or dissolution step has been suggested.4,5,7,10,12 Thus the mechanism for the linear oxidation of pure columbium remains quite controversial. Since further insight into the oxidation mechanism of pure columbium is not provided by this investigation, the authors wish to emphasize at the outset that their experimental results are not interpreted in terms of a particular rate controlling step for the oxidation of pure columbium. Previous investigations13-18 of the oxidation of Cb-Zr solid-solution alloys in air or oxygen at 1000°C suggest a remarkable dependence upon zirconium content. For an alloy of bulk zirconium mole fraction, N2r(0) equal to 0.05 or 0.10, the oxygen uptake is reported to be as high as four times greater than that for pure columbium;13,14 for alloys with NZr(0) 0.05 or 0.10 the oxygen uptake is reported to decrease with increasing NZr(0); to a minimum uptake of about one quarter that for pure columbium at NZr(0): = 0.50.13-15Since zirconium forms a more stable oxide (ZrO2) than the lowest columbium oxide (CbO), and since columbium exhibits a high solubility19,20 and diffusivity21,23 for oxygen, the internal oxidation of the zirconium component to ZrO2 is expected at a reaction front ahead of the advancing metal/scale interface. The external scale is then formed at the metal/scale interface by the inward migration of oxygen through the scale, probably through a series combination of molecular and ionic diffusion. Internal oxidation in conjunction with external scale formation has been investigated by Maak24 for the oxidation of dilute Cu-Be alloys in pure oxygen at 850°C. For cu-Be and many other binary alloys,24-27 very small, essentially uniaxial internal oxide particles are formed in the most dilute compositions; for somewhat more concentrated alloys. the internal oxide particles precipitate as platelets or needles. From pertinent solutions to the diffusion equation, Maak28

Jan 1, 1967

By F. D. Wright

Production of a coal preparation plant is governed by many restrictions, such as the tonnage of different products and blends that can be sold within a given period, capacities and output proportions of the cleaning and sizing units, blending proportions, quality specifications, and costs and prices for the various products. Determination of the tonnage of each product and blend that should be made in order to obtain the maximum profit can be difficult unless a systematic method such as linear programming is used. In this paper the basic method of linear programming is described briefly. The Old Ben No. 9 preparation plant is used as an example to illustrate in detail how eqwations can be written to form a linear programming model of a coal preparation plant. Three sample problems, each requiring 56 or more equations and 63 structural variables, were solved with an IBM 650 computer. Linear programming is one of several mathematical tools used for operations research. It has been applied to many fields and has been used by a number of industries either to maximize the profits of certain operations or to minimize costs. P. B. Nalle and L. W. weeks' have described the use of the method by the Riverside Cement Co. to minimize the cost of blending raw materials to make portland cement. Their problem is to obtain at minimum cost a mix with certain specifications from a number of possible materials which have various costs and various amounts of CaO, SiO2, Fe2O3, and other constituents. In a paper on the use of linear programming by the National Coal Board in England, K. B. Williams and K. B. Halley2 describe how the transportation method, a variation of linear programming, is used to minimize the cost of sending 37 grades of coal from 28 mines to seven central washing plants which produce coal for furnace coke and foundry coke. The various coals have different percentages of volatile matter, moisture, sulfur, ash, and phosphorous, so there is considerable choice in how they can be blended to meet the specifications of the two products. The purpose of this paper is to show how linear programming can be used to maximize the profits of a coal washing plant which produces individual final products as well as blends. The Old Ben Corp. furnished assumed sample data from their Old Ben Mine No. 9 preparation plant for this investigation. However, the data that have been used are entirely the author's responsibility. METHOD OF LINEAR PROGRAMMING Numerous articles and books have been written on the theory and applications of linear programming.3-5 However, since the method has not been widely applied by the mining industry, a brief, nontheo-retical discussion of its basic method seems to be in order. Linear programming (Table I) is used to determine the best possible solution to a number of interdependent activities. It is essentially a method for making systematic selections from a number of possible solutions to determine positively the optimum solution. There may be other equally good solutions but no better ones. Each activity must have linear coefficients and there must be a criterion to judge how good the solution actually is. Linear programming is different from the solution

Jan 1, 1961

By B. M. Larsen

Attempting to review the fundamental aspects of segregation in steel ingots of all types in a paper of reasonable length, we encounter two difficulties: (I) the fact that a large number of different physical and chemical effects are involved, and (2) rather incomplete and confusing evidence on certain aspects of detail and mechanism in the freezing process in which the segregation effect is involved. The best solution seemed to be to link together most of the underlying factors into a simplified theoretical picture that appears to the writer to explain most of the observed data, in the hope that this will serve as a reasonably good target for discussion and criticism. Segregation effects, especially in steel ingots or castings, are often divided into " microscopic" and "macroscopic," depending on whether the variations in concentration of solutes or dissolved elements in the iron occur as: (I) a periodic variation over the small distances between the nuclei and the surfaces of the primary grains, or (2) as a larger scale effect involving concentration gradients over distances of the order of several inches, more or less. The reason for this somewhat artificial division is, of course, that it is only the macroscopic scale effect that has much practical importance. About the only effect of practical importance that results from microscopic segregation is the banded structure often left in rolled sections, and even this is relatively harmless in most cases. However, the causes of microscopic segregation also untlerly the larger scale effect, so we must first consider matters such as the formation and growth of crystal nuclei, selective freezing and diffusion, and others that are fundamental to all sepregation effects. Undercooling and Nuclei Formation It is probable that although the degree of undercooling is small in iron, as in metals in general, a certain amount of it takes place, and also that the number of crystal nuclei increases very rapidly with increased undercooling below the liquidus temperature. In practical terms this means that the nuclei number illcreases very rapidly with increased cooling or freezing rate, thus being dependent on the rate of heat flow out from the zone of crystallization. Temperature Gradients and Heat Dissipation during Freezing Each pound of steel evolves about 100 B.t.u. when freezing. In addition to this, the temperature gradient in the solidified portion (required to dissipate the heat as freezing progresses into the axis) necessitates a loss of heat required to cool the solid metal below its freezing range, which is equivalent to an amount of not so much less in magnitude. In a 5-ton ingot, the total would include about one million B.t.u. for freezing alone and about 0.4 to 0.5 million B.t.u. for the gradient, up to the end of the freezing period. Thus the rate of freezing depends primarily on the rate of heat dissipation. In the ordinary ingot shapes, the axial rate of growth of the solid

Jan 1, 1945

By H. C. Brassfield, R. E. Fryxell, E. C. Duderstadt, E. A. Aitken, P. K. Conn

Permeation rates of hydrogen through are-cast tungsten were measured at temperatures from 1300" to 2600°C with hydrogen pressure differentials of 1 and 0.1 atm across isothermal membranes. Rates were nearly Proportional to square root of pressure, were inversely ProPortional to membrane thickness, and were temperature-dependent according to the equation: p = permeation coefficient in cu cm (stp)-mm per sq cm-min-atmlr2, R = gas constant in cal per mole-OK, T = absolute temperature in OK. Permeation rates of oxygen through tungsten were deternlined in the range 1965" to 2300°C and at calculated oxygen (02) pressures of 3.3 x 10-4 to 2.2 x at?n using sealed capsules containing Kmown quantities of tungsten oxide. Permeation coefficients obtained in this manner had a temperature dependency in the range of 40 to 45 kcal per mole of permeating species. Permeation coefficients for oxygen were higher than those for hydrogen in the temperature range studied. This is probably the result of oxygen solubility being much greater than hydrogen solubility at these temperatures at a gzven pressure. The purpose of this investigation was to determine experimentally the permeabilities of hydrogen and oxygen through polycrystalline tungsten at temperatures ranging from 1300° to 2600°C. Permeation rates of hydrogen through tungsten have been measured at temperatures up to 925°C,but no previous measurements have been reported for the temperature range covered in this investigation. Some diffusion measurements3&apos;&apos; and solubility measurements3 have been made for hydrogen at temperatures below 2200°C. No previous permeability studies of oxygen through tungsten are known to the authors; however, efforts have been made to determine diffusion rates5-&apos; and solubilities PERMEATION THEQRY Permeation has been defined by ortton" as the overall steady-state flow process from the gas phase on one side of a membrane or wall to the gas phase on the other side and includes the steps of adsorption, solution, diffusion, exsolution, and desorption; in a given temperature range, any of these processes may be rate-controlling. For diatomic gases, which dissociate prior to diffusion, the quantity of gas which permeates through a membrane or wall at a given temperature is directly proportional to the surface area of the membrane, the length of time of permeation, and the difference between the square roots of the pressures on each side of the membrane, and it is inversely proportional to the thickness of the membrane when diffusion-controlled, thus: q = total amount of gas permeating a membrane, p = temperature-de pendent permeation coefficient, A = area of membrane exposed, / = time, p i = gas pressure of high-pressure side, p2 = gas pressure of low-pressure side, d = thickness of membrane. When the surface reactions are not rate-controlling steps and the solution of the gas in the metal follows Henry&apos;s law, the permeation coefficient, P, is equal to the product of diffusivity and solubility. The permeation coefficient is also temperature-dependent according to the equation: Po = permeation constant, Q = activation energy, R = gas constant, T = absolute temperature. MATERIALS The tungsten materials used in this investigation were greater than 99.9 pct pure. The interstitial impurities ranged from < 1 to 50 pprn C, 7 to 35 ppm O, less than 15 pprn N, and undetectable quantities of hydrogen. Previous high-temperature studies of are-cast tungsten have shown that thermal treatment similar to that which the hydrogen permeation cells experienced reduces the carbon content from starting levels of 50 to 60 ppm to about 30 ppm. Metallic impurities were in the low (1 to 50) ppm range. The argon gas used in this investigation contained about 8 ppm N. None of the following gases were

Jan 1, 1968

By S. E. Maddigan, B. R. Zimmerman

MOST metallurgists are well acquainted with the contributions already made to the study of metals by the use of X-rays. On the one hand, the radiographic method is constantly becoming of increasing importance as a nondestructive testing procedure, while on the other hand the techniques of X-ray diffraction have made important contributions to the fundamental knowledge in studies of phase diagrams, stress conditions, and so forth. A new, and as yet insufficiently appreciated, tool exists in the application of microradiography to alloy structures. This new procedure in many respects bears the same relation to microscopic investigations as does macroradiography to the gross inspection of metal surfaces. However, where macroradiography is used ordinarily to determine the soundness of the metal structure, this new method can be used not only to investigate micro-un- soundness but also to examine the distribution of the constituent elements within the body of the alloy. When combined with the normal procedures of microscopy, this offers a technique of great potential power. It is intended in this paper to present a few examples of copper-base alloys demonstrating the additional knowledge obtained from the microradiographic method. The detection of micro-unsoundness is demonstrated in Fig. I for a sample of cartridge brass as cast. The sample appeared quite sound when viewed under the microscope, but in reality was thickly populated with minute voids. This application of the method conforms in every way to conventional large-scale radiography and has been used to facilitate production of metal for vacuum devices.1 The true potentialities of the technique are revealed by comparison of Figs. 2a and 2b, which are respectively a- photomicrograph and a microradiograph of a cast alloy of 80 per cent Cu, 10 per cent Sn, 10 per cent Pb. The remarkable difference in appearance provides some concept of the additional information this method may yield when used as an auxiliary to microscopic studies. Fig. 2a shows two phases of the copper-tin system plus segregated lumps of lead. Fig. ab, on the other hand, shows with exceptional clarity the actual dendritic growth of the metal crystals during solidification. The practice of microradiography depends upon the laws of absorption of X-rays. This subject has been reviewed thoroughly in recent papers,1,2,3 but for clarity a brief resumé will be given here. As is well known, when a beam of X-rays is transmitted through a layer of homogeneous material, the intensity is reduced according to the relation:[ ]

Jan 1, 1944

By H. H. Rachford

Numerical solutions of immiscible flow problems in which dispersive effects of capillarity are dominated by convection require excessively fine grid spacing with attendant high computing costs. The use of coarser spacing reduces cost but often produces oscillation or undue dispersion associated with displacement fronts, A numerical formulation is proposed here which should be applicable to two-dimensional flow problems. it is in part analogous to an approach previously tested for miscible systems. The convective transport is approximated using a change of variables to yield a coordinate system moving approximately with the local characteristic velocity. The capillarity-induced dispersive terms in the differential system describing the process are approximated with respect to a fixed coordinate system by the usual implicit formulation. One-dimensional tests of the procedure yielded results in which the saturation profiles tended smoothly to the zero-capillary pressure solution as the ratio of viscous to capillary forces was successively increased in a sequence of calculations. This contrasted favorably with solutions by other numerical procedures which would require attendant grid refinements to approach the zero capillary pressure results. INTRODUCTION Numerical solution of displacement problems has until recently relied on applying methods developed primarily for transient heat-flow problems. Such problems are classified as parabolic in type, and where the heat transport is purely by diffusion their solutions are characterized by a high degree of smoothness. It is not surprising, therefore, that for approximating these solutions available finite difference methods are quite adequate. In flow problems the transport is partly by diffusion, partly by convection or flow. Although the problem remains of parabolic type because the dispersive effects of capillary forces or diffusion play some role in every displacement, at high flow rates the problem is dominated by convection, and solutions tend toward those of equations of the hyperbolic type. Solutions of hyperbolic problems are characterized by the translation of fronts, or discontinuities, that may progressively increase in sharpness. Numerical methods for treating parabolic problems become less and less satisfactory as displacement rates increase and the role of dispersion due to concentration or capillary pressure gradients becomes small relative to transport due to flow. In computation the difficulty manifests itself as an error associated with the grid size chosen. 1-6 In summary, if the heat-flow type approximations are to include the terms arising due to convection, one of several choices may be made: (1) an upstream (to the direction of flow) approximation for the convection terms may be used; (2) a centered-in-distance (CID) approximation may be used; or (3) a recently developed approximation based on the theory of oscillation matrices may be chosen.6 The last appears to have significant promise for one-dimensional flow problems; its extendibility to two or three dimensions is an open question. In either of the first two approaches, a suitably small ratio of v&/D must be maintained, where v is the velocity, & is the grid spacing and D the effective dispersivity in the direction of flow. In the first choice, the approximation of the convective part is only first-order correct and errors introduced appear as a numerically induced dispersivity of magnitude proportional to v?x. In the CID choice, the approximation can be second-order correct, but the difference formulation fails to satisfy the maximum principle unless a condition on v?x/D is met. Practically, this means that for high flow rates oscillatory solutions may result in the neighborhood of a front unless exceedingly small grid intervals are taken. While the procedure proposed by Stone and Brian4 permits a less severe limitation to be placed on this ratio, ultimately the flow rates increase relative to the dispersivity the oscillation obtains. Further, extensions of their approach to higher dimensional systems may be attended by considerable

Jan 1, 1967

By W. R. Hansen, F. W. Boulger

Twenty-nine laboratory steels were studied to determine the effects of composition and ferrite grain size on drop-weight and Charpy V-notch transition temperatures. The experimental steels covered the following ranges in composition.. 0.10 to 0.32 pct C, 0.30 to 1.31 pct Mn, 0.02 to 0.43 pct Si, md nil to 0.136 pct acid-soluble Al. Although most of the data were obtained on hot-rolled samples, some plates were heat-treated in order to cover a wider range in ferrite grain size. The experimental data were used for a multiple-correlation analysis conducted with the aid of an electronic computer. The study showed that carbon raises and that manganese, silicon, aluminum, and finer ferrite grains lower both drop-weight and Charpy transition temperatures. Quantitatively, variations in composition and grain size have a more marked effect on V15 Charpy transition temperatures than on the drop-weight transition temperature. Useful correlations were found between transition temperatures in drop-weight tests and those defined by seven different criteria for Charpy tests. Evidence was accumulated that the conditions ordinarily used for drop-weight tests are more severe for 1-1/4-in. -thick plate than for 5/8- to 1-in. -thickplate. PROJECT SR-151, to study quantitatively the effects of metallurgical variables on performance in the drop-weight test, was established by the Ship Structure Committee late in 1958 on recommendation of the National Academy of Sciences, National Research Council. This project was initiated as a result of the increasing use of the drop-weight (nil-ductility) test in predicting the ductile-to-brittle behavior of steel. Qualitative data indicated the drop-weight was not as sensitive to metallurgical variables as the Charpy V-notch test. Furthermore, the available information indicated that the drop-weight test did not show the superiority of killed steels over semikilled steels reflected by Charpy tests. This difference in sensitivity to brittle fracture is considered important because the drop-weight transition temperature has been reported1 to correlate better with service-temperature failures than the V-notch test does at a constant energy level. Therefore, this project was concerned with establishing quantitatively the effects of metallurgical variables in the drop-weight test. For comparison, Charpy V-notch data were obtained for the steels investigated. This paper summarizes the results of the investigation. Most of the steels used for the study were made and processed in the laboratory. However, some tests were also made on commercial killed steels available from Project SR-139 (SSC-141). During the course of the investigation, data were obtained on the effects of carbon, silicon, manganese, and aluminum on transition temperatures of drop-weight and Charpy specimens. In addition, the effects of heat treatment which changed the ferrite grain size and the transition temperatures were also investigated. Finally a few exploratory studies were made on commercial killed steels to evaluate the effects of plate thickness, grain size, and heat treatment on the performance of drop-weight specimens. EXPERIMENTAL PROCEDURES Preparation of Materials. A total of twenty-nine 500-lb induction-furnace heats were made and processed in the laboratory for the investigation. Carbon, manganese, silicon, and aluminum contents were systematically varied. Melting and rolling techniques proven satisfactory in a previous project2 were used as a guide for the current investigation. Composition. The composition of the twenty-nine laboratory heats made for this project are given in Table I. The steels are divided into three groups. The first group consists of ten aluminum-killed steels similar in composition to Class C ship-plate steel. The second group consists of ten semikilled or Class B type steels. In both of these groups the carbon and manganese contents were intentionally varied over a wide range. This wide range in composition was helpful in obtaining quantitative data from a limited number of steels. The primary purposes of these two groups of steels was to determine the effects of carbon, manganese, and deoxidation practice. In addition, one steel in each group (Steels 2-2 and 9-2) were made about 1 year after the start of the program in order to check consistency of melting practice. The third group of nine steels listed in Table I was intended for studies on the effects of silicon and aluminum. In eight of these steels carbon and manganese were held relatively constant at levels of about 0.2 and 0.8 pct, respectively, while silicon and

Jan 1, 1963

By James Gayley

The development of blast-furnace practice in America in the direction of large yields is mainly the history of our working since the year 1880, as the advancement that has been made in the last decade is greater than that in the third of a century previous. A new era in the manufactnre of pig-iron began in 1880 with the putting in blast of the Edgar Thomson furnaces. These furnaces at once leaped to the front as pig-iron producers, and have maintained that position—with but one brief interruption—ever since. I shall, therefore, confine myself mainly to a description of these works, showing the changes in design and practice by which these results have been achieved. In order to show more clearly the progress that has been made since 1880, I shall refer briefly to the best work that was done in the ten years previous to that time. The Struthers furnace, in Ohio, was one of the first to attract attention in the matter of large outputs. This furnace was 55 feet high, 16 feet in diameter of bosh, 9 feet in the hearth, and about 8 feet 6 inches at the stock-line. The fuel was raw coal. This furnace, in December, 1871, made 1602

Jan 1, 1891

By C. Baldwin Sawyer

During the last half century, much time has been devoted to investigations of the effect of nitrogen on the physical properties of steel, but in all discussions of results there is considerable doubt as to the accuracy and interpretation of analyses. No conclusions concerning the effects of nitrogen on the physical properties of steel can be more reliable than the methods used for determining the quantities of nitrogen present. The work described in this paper endeavors to establish some additional conditions required by the customary distillation method for reliable and nccurate determinations. Results by a combustion method of analysis for total nitrogen content are presented; these indicate that all of the nitrogen in steel, exclusive of that contained in blowholes, may be determined by the distillation method. Based on these more sound and more reliable analyses, results havc been obtained that bear on the following divisions of the general subject, nitrogen in steel: Nitrification of steel by melting in nitrogen, nitrification of steel by heating in ammonia, decomposition of nitrified steel by heating, and thermal analysis of nitrified steel. Consideration of Two Methods of Analysis and Some Results The details of the distillation and combustion methods are chemical in character and of little interest to most readers. They are therefore described in an appendix. The distillation method is essentially that described by Hurum and Fay1 and was generally used throughout this work. It is capable of the greatest accuracy and all results given are significant to the last, figure. Where analyses do not check, the samples

Jan 1, 1923

By C. Baldwin Sawyer

During the last half century, much time has been devoted to investigations of the effect of nitrogen on the physical properties of steel, but in all discussions of results there is considerable doubt as to the accuracy and interpretation of analyses. No conclusions concerning the effects of nitrogen on the physical properties of steel can be more reliable than the methods used for determining the quantities of nitrogen present. The work described in this paper endeavors to establish some additional conditions required by the customary distillation method for reliable and nccurate determinations. Results by a combustion method of analysis for total nitrogen content are presented; these indicate that all of the nitrogen in steel, exclusive of that contained in blowholes, may be determined by the distillation method. Based on these more sound and more reliable analyses, results havc been obtained that bear on the following divisions of the general subject, nitrogen in steel: Nitrification of steel by melting in nitrogen, nitrification of steel by heating in ammonia, decomposition of nitrified steel by heating, and thermal analysis of nitrified steel. Consideration of Two Methods of Analysis and Some Results The details of the distillation and combustion methods are chemical in character and of little interest to most readers. They are therefore described in an appendix. The distillation method is essentially that described by Hurum and Fay1 and was generally used throughout this work. It is capable of the greatest accuracy and all results given are significant to the last, figure. Where analyses do not check, the samples

Jan 1, 1923

CONTENTS PAGE East Texas, except the Gulf Coast-H. Vance 3 Gulf Coast-L. P. Teas 8 Texas Panhandle-C. C. Rae 16 North Central Texas-H. F. Smiley 23 North Louisiana, South Arkansas and Mississippi-B. C. Craft 25 Oklahoma-C. H. Pishny, Raymond M. Carr and E. J. Dickinson 31 Kansas-E. A. Koester 35 Rocky Mountain District-C. D. Johnson 46 Illinois and Indiana-T. Wasson 49 Michigan-T. Wasson 52 Eastern States-P. D. Torrey and W. H. Young, Jr 58 West Texas and New Mexico-W. V. Vietti. Published as a Supplement.

Jan 1, 1933

By G. Derge, R. E. Grace

A S detailed studies of mass transport in hetero- geneous systems are made, a knowledge of the chemical diffusion coefficients in various liquid and solid phases is necessary to understand the kinetics of any total reaction. For example, in zone refining some information must be available about the diffusion coefficients of various species in the liquid and solid regions near the moving interface. In liquid-liquid reactions, of which slag-metal reactions are of particular interest to metallurgists, the diffusion coefficient of a transferring species must be known accurately in both phases in order to predict a transfer coefficient for the over-all process. Diffusion data for various elements in liquid iron and iron-carbon alloys have been roughly deter-

Jan 1, 1959

By K. T. Koone, R. J. Blackwell

One of the more important problems to be solved in designing a miscible flood is related to the size of the solvent bank used. Size of the bank may be critical to economic success. Too large a bank loses money; too small a bank may deteriorate and fail to maintain the miscibility needed for high recovery. An important factor in deterioration of a small bank is permeability channeling. In a highly stratified reservoir, solvent speeds ahead in the more permeable zones and mixes laterally with fluids bypassed in adjacent, low-permeability strata. Numerical solutions have been obtained .for the differential equations that describe the movement of a slug through a two-layer system in which mixing occurs both in the direction of flow and transversely. The solvent slug is assumed to have the same density and viscosity as the resident fluid and the pushing fluid. These solutions have been verified by comparing them with similar concentration profiles obtained in the laboratory in a 36-ft stratified model packed with glass beads. The theoretical study revealed that when the dominant mechanism causing a bank to fail is lateral mixing the bank size needed for a given recovery may increase with length rather than decreasing as the square root of reservoir length, as suggested by one-dimensional mixing theory. From a comprehensive examination of the variables, a generalized correlation is developed that relates strata thicknesses, bank size, fluid velocity, mixing coefficients, system length and simple solvent-resident fluid phase behavior to the area miscibly swept. INTRODUCTION Miscible displacement, or solvent flooding, continues to receive widespread attention as a method for increasing oil recovery over that possible in conventional gas-drive or waterdrive projects. A basic economic requirement in the application of such processes is the use of as little solvent as possible. A basic physical requirement is that enough solvent be used to maintain miscibility. Economics places an upper limit on the size of a solvent slug, and physical considerations establish a lower limit. Consequently, the practicality of any given miscible process requires that the economic limit be greater than the lower limit imposed by physical requirements. Procedures exist for determining the economic limit; however, procedures for determining realistic minimum bank sizes exist for only special reservoir situations. In the past, bank size has usually been selected on the assumption of a piston-like displacement for which only longitudinal mixing is important. This assumption leads to the favorable conclusion that bank size, expressed as per cent of pore volume, is inversely proportional to the square root of length. Collins considered the problem of transverse mixing of solvent with fluids in bypassed zones with the assumptions that no forward mixing occurs and that the concentration is uniform in the permeable stratum of interest. 1 Lauwerier considered a mathematically similar problem in thermal recovery operations.2 Their work suggests the much less favorable conclusion that bank size could be directly proportional to the length or even higher powers of the length. This paper considers the physical behavior of a small solvent bank as it moves through a real reservoir, without imposing many of the restrictive assumptions of past treatments. To facilitate mathematical description, an idealized, two-layer model that permits mixing both laterally and in the direction of flow will be considered. A calculation procedure for solving the descriptive equations will be developed for a displacement involving fluids of equal density and viscosity. In addition, laboratory experiments designed to check the computational results will be described, and the coincidence of calculated and observed results will be discussed. The use of many solutions for a variety of bank sizes, strata thicknesses and characteristic system lengths to develop a usable correlation between

Jan 1, 1966