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By T. S. Lundy, J. I. Federer

A graphical method has been developed and tested for separating the effects of grain boundary and lattice diffusion in polycrystalline materials. The method is based on the assumptions that for unidirectional diffusion from a plane source of radioactive material, the penetration of activity far into the specimen from the source is due solely to grain-boundary effects, and 2) pure grain-boundary penetration is described by a linear plot of log activity vs the perpendicular distance x from the source. The former is based on the fact that at any temperature the grain-boundary diffusion coefficient is always very large relative to the lattice diffusion coefficient; and the latter is based on the derivation of Fisher.1 Using these criteria along with appropriate penetration data (in this case, data for the diffusion of Cb95 in pressed and sintered UO2) one first plots the data as log activity vs x2 and as log activity vs x, as shown by curves 1 and 2, respectively, in Fig. 1. A tangent line to curve 2 for large x (curve 3) is then transferred to the x2 plot as curve 4. The subtraction of curve 4 from curve 1 yields curve 5 which represents only lattice diffusion and may therefore be related to the diffusion coefficient by using the appropriate solution to Fick's second law. It should be noted that the method has inherent inaccuracies for small and large values of x2 and only the subtraction at intermediate values can be used. For the illustrated specimen the calculated diffusion coefficient is 3.4 X 10-11 sq cm per sec at1445°C while data using a single crystal of UO2 at the same temperature yielded a value of 2.9 x 10-11 sq cm per sec.2 The same method of subtracting grain-boundary diffusion effects to obtain lattice diffusion coefficients has been successfully used to determine self-diffusion coefficients of Th230 in polycrystalline thoria.

Jan 1, 1962

By A. B. Hildebrandt

P. B. Baxendell is to be complimented for an exccllent piece of work. To our knowledge there has been no previous publication of field data on the flow of oil and gas through the annulus of a well. It is certainly gratifying to see this work on annular flow confirm the previous published correlation procedure on tubing flow. It extends considerably the range under which reliable gas-lift calculations can be made. Baxendell discussed this work with us about a year ago and was kind enough to send a large scale plot of his correlation. We had been designing gas-lift installations on flow through the annulus, assuming that the original correlation of the f factor based on tubing flow' was valid as long as we stayed within the same mass velocity range on which the correlation was based. Doing this work necessitated the use of an equivalent diameter for the annular flow. The equivalent diameter is defined as area' of stream cross section wetted perimeter and for the case of an annulus is D, — D,. Substituting this in the basic equation correlating energy loss along with the area to flow required to convert the velocity, to volumetric flow rate, D (Baxendell's Eq. 7) becomes dell's expression, D,). Similarly, the D in 1.4737 X 10 (M&/D) becomes (D, + D;) for annular flow. On receipt of Baxendell's data, we. of course, recalculated it to put it into the form we were using, and to see how well it agreed with the correlation based on tubing flow. Fig. 1 shows the results, which were certainly gratifying. For low values of (D, - D,) pv, the data coincide with the data on flow through tubing, whereas at high values the data on flow through the annuli appear to be leveling off to a constant value. For very high rates of flow where the turbulence is very high, one might expect the value f to level out and become constant. A bulletin published in 1914 by the U. of Wisconsin presented results of a large number of laboratory teats in air lifting water through short lengths of 1.25-in. tubing. It was possible to correlate a random sampling of

By E. L. Dougherty, J. W. Sheldon

A numerical method for computing the dynamical behavior of fluid- fluid interfaces is described. Results of studies made to assess the accuracy and economy of the method on a computer are reported. It is concluded that it is practical to obtain digital computer solutions for fluid- fluid interface problems with two space dimensions. PROBLEM DEFINITION We consider two-dimensional flow in a rectangle as shown in Fig. 1, where a fluid-fluid interface divides the rectangle into two regions. The pressure is specified along the lower boundary (the injection boundary) and upper boundary (the withdrawal boundary). There is to be no flow of fluid across the side boundaries, which are walls of symmetry for the flow, and px = 0 along these boundaries. The fluids are incompressible, the absolute permeability and porosity is constant, and each fluid has its own constant mobility. Thus, the pressure satisfies Laplace's equation in each region. Across the interface, pressure is continuous and the normal component of fluid flux is 1. These conditions are shown in Fig. 1. The velocity of a point on the interface in the direction of the normal from Fluid 1 into Fluid 2 is U,/ Q, where Un is the normal component of volumetric flux at the point on the interface, i.e., For brevity, we call the problem defined above "Problem A". Problem A is a simple example of a dynamical fluid-fluid interface problem. However, the same numerical methods which we use to solve Problem A can be extended to the solution of a large number of fluid-fluid interface problems which are mathematical models for various oil recovery processes,l hence our interest in Problem A. We define the interface by prescribing the x, y coordinates of a finite set of points. These points are called "interface mesh points" and are illustrated by triangles or asterisks in the figures. Fig. 2 is a procedural (flow) chart displaying the main steps in the solution. We comment briefly on some of these steps in this section and then give further details in subsequent sections. For mobility ratio greater than one it is well known that Problem A is unstable.*2 Small amplitude,

Jan 1, 1965

By Charles H. White

+1HARVARD UNIVERSITY, CAMBRIDGE, MASS. The equipment of a laboratory in which students are to be trained for practical work in metallurgical chemistry presents many difficulties not encountered in the fitting up of a commercial or works laboratory. At an industrial plant the chemical work required usually demands the frequent repetition of a comparatively limited number of methods. In a steel-works laboratory, for instance, by far the larger part of the work consists in making determinations of the usual impurities found in iron and steel; at a smelter the great bulk of the work is confined to the analysis of ores, slags, mattes, and fuels, which involve the frequent application of perhaps not more than a dozen different methods. In a laboratory of this character, therefore, those operations most frequently applied may each have a certain section set apart and fitted permanently with such apparatus as best facilitates the carrying out of this one operation. The work of a commercial or custom laboratory is perhaps more varied than that of a works laboratory, but the couditions are similar in these respects, that there is usually no great need for economy of space, and that a few skilled workmen are employed to carry the determinations through from beginning to end without interruption. On the other hand, the laboratory of a technical school should be planned on such a scale that a comparatively large number of students may work at the same time, and each desk should be equipped for general metallurgical analysis. In most institutions for technical education the student's program is so arranged that his day is divided among several subjects in the course of study; only a few consecutive hours being devoted to one subject, or spent in one laboratory. Therefore, those appliances should be provided that render possible the safe continuation of such processes as

Jan 1, 1905

By I. Fatt, D. N. Saraf

A method is described for measuring two- and three-phase relative permeabilities in sandstones or sand packs using a nuclear magnetic resonance (NMR) technique to determine fluid saturations. Two- and three-phase relative permeabilities have been determined on Boise sandstone using the NMR technique of saturation measurement. Three-phase relative permeability to water was found to depend only on the water saturation, whereas three-phase permeability to oil depended on both the water and oil saturations. Relative permeability to gas in three-phase flow was found to depend only on the total liquid saturation. INTRODUCTION Three-phase relative permeabilities are extremely useful in calculating field performance for reservoirs being produced by simultaneous water and gas drives. Three-phase relative permeability data are also needed for analyzing solution gas-drive reservoirs which are partially depleted and are being produced by water drive. Some thermal recovery processes involve three-phase flow which require three-phase relative permeability data for predicting reservoir behavior. Unfortunately, three-phase relative permeability measurements have rarely been made. Also, because of the scarcity of three-phase data, it has not been possible to date to relate other measured rock characteristics to the relative permeabilities with a great certainty. Leverett and Lewis,l Reid2 and Snell3 have reported three-phase relative permeability data on unconsolidated sands. Leverett and Lewis used ring electrodes spaced along the length of the sand sample to measure the resistivity of the sample which was assumed to be monotonically related to brine saturation. Gas saturation was determined from pressure-volume measurements. Oil saturation was obtained by material balance on the cell containing the sand sample. This method is involved and time consuming. Another difficulty arises from the fact that the resistivity of the sand is a function not only of saturation of brine but also of the distribution and saturation history of the brine in the pore spaces. Reid2 used a gamma ray absorption technique for measuring liquid saturation. This method has the disadvantage that total liquid saturation rather than oil or brine saturation is all that can be measured and still another method is required to determine the saturations of individual components. snel13 used a neutron bombardment method which also required a separate determination of the individual component saturations. Caudle et al.4 measured three-phase relative permeability on consolidated sandstones using vacuum distillation for determining fluid saturations. Distillation after each reading makes this technique very lengthy and time consuming. Corey et a1. 5 and Naar and Wygal 6 measured three-phase relative permeability on sandstones by the capillary-pressure method. Semipermeable diaphragm assemblies were used at each end of the core specimen to keep the water phase in the core. Gravimetric methods were used to determine fluid saturations. Sarem7 recently reported an unsteady-state method for measuring three-phase relative permeability on sandstones. This method is an extension of Welge's method8 for measuring two-phase relative permeability. Although Sarem's method is simple and comparatively fast, the assumptions involved may oversimplify the problem. Sarem's assumption, that in all rocks relative permeability to each fluid will depend only on the saturation of that fluid, seems to be rather unrealistic. Neglecting capillary effects at the end of the core is also a weak assumption. Donaldson and dean9 measured three-phase relative permeability using a method similar to Sarem's.

By K. E. Beu

THE integrated intensity X-ray method of meas-uring retained austenite concentrations in hardened plain carbon or low alloy steels as proposed by Averbach and Cohen1,2 has the advantages of being a highly sensitive and precise quantitative method. The various phases of this method have been studied and several modifications have been developed which aid not only in reducing the time required per determination, but which also increase the possible accuracy of the method. A fundamental step in the original calculation procedure is to plot V.A(?) curves for austenite and martensite and to obtain VM/VA ratios from these curves.' In taking this ratio the absorption factor A (8) drops out since it is constant for a. given diffraction angle 8. The reason for eliminating A(?) in this manner is because it is apparently assumed

Jan 1, 1953

By W. O. Philbrook, H. W. Hosking, N. B. Melcher

A simple and inexpensive mercury-tracer method has been develohed to study rates and Patterns of gas flow in blast furnaces. A Pulse of mercury is injected into the hot blast, and its arrival at the sampling Point is recorded by an electronic circuit that measures resonant absorbtion of ultraviolet light by mercury vapor in the gas aspirated .through the detecting. cell. A rapidly developing interest in blast-furnace technology in recent years has created a strong demand for precise knowledge of the rates and patterns of gas movement through the stock column. Classical fluid-flow theory cannot supply the desired information because the complexity of the blast-furnace situation precludes the accurate determination of many of the parameters required for solution of the equations. In fact some of the terms employed in fluid-flow treatments become almost meaningless under blast-furnace conditions. The void fraction of the stock column, for example, varies widely from place to place and is affected by the segregation of charge materials, attrition of lumps during descent, and channeling. Gas density varies with changes in local pressure, temperature, and composition, while viscosity varies with temperature and composition. Even if mean values for these functions were acceptable, they would be either impossible or extremely difficult to determine with a high degree of accuracy since the value of the mean for all gas properties would depend upon the flow distribution itself. Attempts to study gas movement by the pitot-tube determination of kinetic pressures have met with little acceptance. Reproducibility of results is extremely difficult to achieve in a situation where alignment of the tube orifice with respect to the flow direction in tortuous channels cannot be guaranteed. Because of these difficulties it would appear that progress can be achieved only with a direct method of measuring gas velocities and determining the shape of flow paths through the stock. The establishment of such a method is described in this paper. SELECTION OF METHOD Direct measurement suggests the use of a tracer by means of which the progress of a "parcel" of gas can be followed through the furnace. Several requirements must be met before any selected material can be considered a suitable tracer. First of all, it must be a substance not normally present in blastfurnace gas or dust; otherwise its presence in a gas sample will have little significance. It should be volatile at temperatures normally existing within the furnace, to ensure that it will travel with the gas, as a gas. It should possess special properties enabling its presence in the gas to be detected readily, and it should not undergo exchange reactions with any material normally present within the furnace, including refractories and coke as well as all components of the metal and slag. Radioactive materials naturally are considered because their radioactivity renders them susceptible to detection. However, of the many radioactive materials available, almost all are eliminated from final consideration by their unsuitability in terms of other properties. Radioactive silicon, carbon, calcium, phosphorus, and many others have been considered and discarded, either because they are not volatile over the whole range of significant temperatures, or because they could be expected to undergo exchange reactions with burden or refractory materials. Others which might be suitable in terms of these properties are eliminated because of a low activity, short half life, or the necessity for fragile counting apparatus. Of the many elements available in radioactive form, perhaps radon is the only one suitable for blast-furnace gas-flow studies. This has been used in several investigations1-4 with considerable success. The use of radiotracers has certain inherent disadvantages. One is the cost. An appreciable sum must be allowed for materials each time a test is made. Also, special methods of handling must be employed, and very often the progress of an investigation must be governed by the availability of isotopes and the delivery arrangements that can be made for them. An advantage is immediately gained if the tracer material can be a substance which can

Jan 1, 1960

By H. H. Evinger, M. Muskat

A methoD of calculating productivity factors for oil, gas, and water systems in the steady state is presented as an illustration of the quantitative application of the fundamental data on the flow properties of heterogeneous fluid systems. While the numerical results of the calculations cannot be applied directly to field conditions, because they are based on permea-bility data for unconsolidated sands and involve specific assumptions regarding the nature of the reservoir fluids, the methods of analysis and interpretation should havc significance in considering certain specific field situations when the necessary field and laboratory data become available. Moreover, it is felt that even under the idealized conditions to which the numerical calculations refer they should serve to give at least the orders of magnitude of the effects of gas-oil ratio and connate water on observed productivity factors. Within the indicated limitations, the computations imply that the foregoing factors can explain only a part of the apparent discrepancy between the homogeneous fluid productivity factors and those obtained recently in field measurements on the West Coast. IntroductioN Sufficient laboratory research has been carried out in the last several years on the fundamental features of the flow of heterogeneous fluids through porous media to call for consideration of what can be done with this type of information. It has, of course, already led to a, much clearer general understanding of the mechanics of oil production. However, examples of the quantitative application of the results of such laboratory studies are few in the literature. part of the explanation for this fact lies undoubtedly in the lack of sufficient laboratory data relating to practical fluids and sand systems such as would occur ill actual oil reservoirs. However, unless it can be shown that if such data were obtained quantitative applications could be made, serious doubt may be cast upon the desirability of carrying on further extensive experimental research work on fluid flow. The purpose of this paper is to present one approach to the problem of quantitative application of laboratory data to practical field problems. Because the published results on the basic experiments with three-phase fluid systems in porous media are limited entirely to uncon-solidated sands, the numerical applications made here will not pertain directly to any actual field situation. However, they should serve to illustrate what could be done with fundamental laboratory data if they were extended to cover the field of consolidated sands. From this point of view, it is hoped it will serve to encourage further laboratory research on this problem. The particular application to be treated here relates to the calculation of the productivity factors for oil-gas-water systems in the steady state. This specific problem seems especially appropriate for discussion in view of the recent publication by Johnston1 of the results of produc-

Jan 1, 1942

By M. Muskat, H. H. Evinger

A methoD of calculating productivity factors for oil, gas, and water systems in the steady state is presented as an illustration of the quantitative application of the fundamental data on the flow properties of heterogeneous fluid systems. While the numerical results of the calculations cannot be applied directly to field conditions, because they are based on permea-bility data for unconsolidated sands and involve specific assumptions regarding the nature of the reservoir fluids, the methods of analysis and interpretation should havc significance in considering certain specific field situations when the necessary field and laboratory data become available. Moreover, it is felt that even under the idealized conditions to which the numerical calculations refer they should serve to give at least the orders of magnitude of the effects of gas-oil ratio and connate water on observed productivity factors. Within the indicated limitations, the computations imply that the foregoing factors can explain only a part of the apparent discrepancy between the homogeneous fluid productivity factors and those obtained recently in field measurements on the West Coast. IntroductioN Sufficient laboratory research has been carried out in the last several years on the fundamental features of the flow of heterogeneous fluids through porous media to call for consideration of what can be done with this type of information. It has, of course, already led to a, much clearer general understanding of the mechanics of oil production. However, examples of the quantitative application of the results of such laboratory studies are few in the literature. part of the explanation for this fact lies undoubtedly in the lack of sufficient laboratory data relating to practical fluids and sand systems such as would occur ill actual oil reservoirs. However, unless it can be shown that if such data were obtained quantitative applications could be made, serious doubt may be cast upon the desirability of carrying on further extensive experimental research work on fluid flow. The purpose of this paper is to present one approach to the problem of quantitative application of laboratory data to practical field problems. Because the published results on the basic experiments with three-phase fluid systems in porous media are limited entirely to uncon-solidated sands, the numerical applications made here will not pertain directly to any actual field situation. However, they should serve to illustrate what could be done with fundamental laboratory data if they were extended to cover the field of consolidated sands. From this point of view, it is hoped it will serve to encourage further laboratory research on this problem. The particular application to be treated here relates to the calculation of the productivity factors for oil-gas-water systems in the steady state. This specific problem seems especially appropriate for discussion in view of the recent publication by Johnston1 of the results of produc-

Jan 1, 1942

By D. Walton

The effect of small solute additions of Cu on the activation energies for creep A1 single crystals were determined over the range from 78° to 850° K. Below 240°K and above 800°K activation energies were unchanged. Between 240°K and 400°K strain aging causes the creep rate to become vanishingly small and the flow stress was independent of the temperature. Between 500° and 50°K the activation energy was increased to 41,000 cal per mole. NUMEROUS investigationsL have shown that solid solution alloying invariably increases the flow stress. A typical example is documented in Fig. 1. Such increases in flow stress can arise from two general effects: Alloying can increase the long-range stress fields through which dislocations must move by causing appropriate clustering; modification of dislocation densities, and so forth. Alloying can also modify the short-range stress fields that determine the activation energies for thermally stimulated migration of dislocations, such as occurs in some solute atom pinning processes, and so forth. Actually both long- and short-range stress-field effects can occur simultaneously. It was the purpose of this investigation to evaluate the effect of alloying on the short-range stress fields by determining the effect of alloying on the activation energies for creep. The resulting observations also shed some light on the effect of long-range stress fields on dislocation processes. EXPERIMENTAL TECHNIQUE Single-crystal bars (6 in. long 3/8 in. wide and l/4 in. thick) of dilute solutions of Cu in A1 were seeded, so as to provide extensive single slip, with the pole of the tensile axis located in the standard stereographic projection as shown in Fig. 2. Each crystal was grown under an argon atmosphere in a graphite mold containing a large reservoir of molten alloy for the purpose of obtaining rather uniform composition of Cu along the length of the bar. The nominal compositions of the alloys which were produced from 99.99 pct Cu and high-purity A1 containing 0.001 pct Fe and 0.001 pct Si, are given in Table I. Strains, measured by linear variable transformers attached by quartz rods to a 3 in. gage section were sensitive to and the stresses were ap- plied by direct loading of the specimen. Temperatures were determined by thermocouples attached to the gage section of the specimens. Below 400°K the apparent activation energies for creep, Q, were determined by the effect of small, rapid changes in temperature of about + 10°K from T1 to T2 on the corresponding creep rates ?1 and ?2 during primary creep according to where R is the gas constant.' Above 400°K, Q was evaluated from Eq. [1] for the secondary creep rate using temperature changes of about ±20K. A typical set of results is shown in Fig. 3. RESULTS AND DISCUSSION The previously obtained effect of temperature on the apparent activation energy for creep of single crystals of high-purity A12 is shown by the broken curve of Fig. 4. The datum points on the same graph illustrate the effect of dilute a solid solution alloying with Cu on the activation energy between 600" and 750°K. Each plotted point is the average of not less than five independent test values between 600° and 750°K and not less than three at other tempera-

Jan 1, 1962

By A. G. Taylor, H. P. Ehrlinger, U. C. Tainton

FOR the last 15 years lead has been the standard material for anodes in electrolytic zinc production and it has been generally accepted that this lead should be as free as possible from impurities. Laistl says, "Next in importance to the purity of solution is the purity of the electrodes and tank lining material. The purest lead obtainable should be used for anodes." The same conclusion is expressed by Ingalls2 and by two German investigators who say that experiments have demonstrated that the purer the lead, the greater is its resistance to corrosion during electrolysis.3 Pure lead, however, while the best material hitherto available for anodes, is not entirely free from objection. The plain lead anode gradually disintegrates under electrolysis, so that the life of an anode, say 1/4 in. thick, is frequently not more than two years. Part of the lead from the anode finds its way to the cathode, lowering the purity of the deposited zinc and decreasing the hydrogen overvoltage. The rest of the lead that comes from the disintegration of the anode goes into the manganese dioxide which is precipitated in the cells, rendering unsaleable what might otherwise be a valuable by-product. Yet a further disadvantage of plain lead anodes comes from their tendency to bend or buckle during electrolysis, as a result of intercrystalline oxidation. This makes it necessary to use a fairly aide spacing between anode and cathode to avoid short circuits, and thus leads to a higher power consurnption than would otherwise be necessary. The power consumption is also affected by the high decomposition voltage at a lead peroxide surface.

Jan 1, 1929

By G. Vaux, M. L. Fuller

AN apparatus and procedure for the determination by X-ray reflection of preferred orientation of crystals in rolled metal with the Geiger counter X-ray spectrometer was described by Schulz.' This is an excellent procedure and we have used it continually for several years. In our use of the procedure, two modifications have been made and used during most of this period. One of these provides for automatic scanning and recording of the reflections, and the other makes possible the application of the procedure to coarse-grained specimens and permits measurement of almost all orientations without resort to the transmission technique. The automatic scanning and recording are accomplished by a motor drive of the inner ring of the Schulz apparatus (see R, in Fig. 2 of his paper and R2 in Fig. 1 of this note) in synchronism with the chart recorder of the North American Philips 90" X-ray spectrometer. A rate of 10" per min is used. A scan of 180" is obtained corresponding to poles on the stereographic projection whose locus is a great circle. The modification for coarse-grained material is accomplished by allowing a larger area of the specimen to contribute to the X-ray diffraction. In the Schulz apparatus the incident X-ray beam is confined by a slit system to rays in the plane of the spectrometer. Schulz demonstrated that this restriction of the X-ray beam permits a survey of the X-ray reflections without correction up to about 80" on either side of that specimen position in which the specimen is perpendicular to the plane of the spectrometer. This is the angle + of rotation of the inner ring R2. One of these slits is horizontal and extends across the X-ray source side of the specimen. In the modification this slit is removed, thus permitting greater divergence in the X-ray beam and the irradiation of a larger area of the specimen surface. Fig. 1 shows the apparatus with the motor drive and with the slit removed. Discontinuities in the recorded X-ray intensity plot due to the few participating crystals in coarse-grained metal are much lessened. The increased divergence does not cause reflections from other crystal planes to enter the Geiger counter slit. An important advantage of the original Schulz scheme is thus lost and a system for correction is required. To do this, a compact of atomized copper powder was prepared and tested by the original Schulz method for the absence of preferred orientation. The horizontal slit was then removed and a curve recorded showing the variation of intensity with angle +. In our arrangement the intensity was uniform within the range + equals ±30°. Beyond this the intensity fell off rapidly reaching zero at ±90°. The curve thus produced is then used to correct measurements made on preferred orientation specimens. In practice this is accomplished by constructing from this calibration curve a family of curves which, as a transparency, can be superimposed on the recorder chart to read corrected intensity directly. Not only does this method permit the handling of coarse-grained material but it also makes possible the plotting of intensities almost to the circumference of the stereographic pole figure projection. Thus, nearly the entire pole figure can be plotted without the necessity of using the transmission technique. Moreover, intensities are much greater, an advantage when surveying crystal planes of poor reflecting power.

Jan 1, 1954

By E. M. Cox, A. S. Skapski, N. H. Nachtrieb, M. C. Bachelder

As a result of using copper-containing scrap in the steelmaking process, the copper content of steels has been steadily increasing for years. Consequently the possible role copper may play in the steelmaking process and in the finished product begins to attract the metallurgists' attention. Some time ago one of the present authors forwarded the idea—based on the results of the analysis of nonmetallic inclusions extracted electrolytically from steels—that sulphur in plain carbon steels is distributed mainly between copper and manganese, the amount of iron sulphide being very small; and that, consequently, the problem of copper and that of sulphur in steel cannot be treated separately.' At the time of the publication of the quoted paper little was known about the relative affinities of copper and manganese for sulphur at high temperatures except that at moderate temperatures (below 1000°C) the affinity of manganese for sulphur is much greater. To gather more experimental data on this subject, the present authors undertook the investigation of the equilibrium constants of the reactions: 2Mn(8 or 1) + S2(g) = 2MnS(s) 4Cu(s or 1) + S2(g) = 2Cu2S (S or I)* 2Fe(s) + S2(g) = 2FeS (s or 1) over a range of temperatures wide enough to establish the dependence of these equilibrium constants on temperature. From the equilibrium constants (K = l/Ps2) the free energy of formation (affinity) can be calculated from F° = -RTln 1/PSt (1) where the standard conditions chosen are: 1 atm of sulphur pressure and the activities of condensed components equal one. The decomposition pressure, Ps2, of sulphur over the respective sulphides is too small to be measured directly, but there is a way of eliminating this difficulty by measuring the equilibrium constant of the reaction between the sulphide and hydrogen. From the latter and from the equilibrium constant of the thermal dissociation of H2S we then calculate Ps2 for the respective sulphide. 2Mn + 2H2S = 2MnS + 2H, 2H2 + S2 = 2H2S_________ 2Mn + S2 = 2MnS The numerical values of the equilibrium constant of the thermal dissociation of H2S at different temperatures were taken from Kelley's paper, "The Thermodynamic Properties of Sulfur and its Inorganic Compounds."² In previous experimental work published by Jellinek and Zakowski3 and by Britzke and Kapustinsky4 the equilibrium constants of the reactions Metal sulphide + H2 = H2S + metal were determined by passing hydrogen, at different rates of flow, over the sulphide, analyzing the resulting H2S + H2 mixture and then extrapolating the H2S/H2 ratio (which is a function of the rate of flow) to the zero speed of flow, a method necessarily involving considerable uncertainty. In the present work the equilibrium ratio was actually measured instead of being extrapolated. The apparatus is shown in Fig 1. Experimental Procedure The sulphides were prepared by the following methods: FeS Powdered iron which had been reduced with hydrogen (ferrum reduc-tum) was mixed in stoichiometric ratio with sublimed sulphur and carefully ground. The mixture was put into an alundum crucible, covered with pure sulphur, and the reaction started by touching the mixture with a glowing iron rod. After the reaction was completed the product (still containing some metallic iron) was again ground with sulphur, put into a Rose crucible, covered with sulphur, and heated in a strong current of pure hydrogen. Analysis of the final product showed 62.46 pct Fe and 36.59 pct S. Theoretical for FeS: 63.53 pct Fe and 36.47 pct S. MnS Manganese sulphide (precipitated and carefully washed with distilled water containing H2S) was dried in a Rose crucible in an atmosphere of H2S and heated in a current of hydrogen for 2 hr at red heat. The product was then ground and ignited for several hours at 1000°C in a current of hydrogen sulphide. Analysis showed 64.53 pct Mn and 36.63 pct S. Theoretical: 63.15 pct Mn and 36.85 pct S. Some MnS samples were prepared from metallic manganese and sublimed sulphur by mixing and grinding them and then heating in a current of hydrogen sulphide in an alundum tube.

Jan 1, 1950

By T. P. Papazoglou, N. A. D. Parlee, W. C. Phelps

HE high vapor pressures of metals such as lead, calcium, lithium, bismuth, and magnesium at steel-making temperatures present experimental problems which have thus far rendered it almost impossible to obtain really reliable data for their solubilities in liquid iron. Many investigators have attempted to equilibrate liquid iron in the same crucible with the undissolved liquid phase of such volatile metals. The published results,l-6 although useful, are often questionable on the grounds of not being obtained under true equilibrium conditions. Such information is not always of practical value in any case since the equilibrium vapor pressure is often several atmospheres and steel is not currently made at these pressures. Solubility measurements at lower partial pressures (< 1 atm) appeared to be more practical and easier to make. These data could be used to calculate solubilities at other pressures where Henry&apos;s Law is obeyed, and to estimate solubilities under other conditions of temperature and pressure with useful accuracy. This note outlines the development of a general technique for the measurement of solubilities in systems of this kind. The method involves equilibration of the high-boiling metal at known temperatures with the vapors of a low-boiling metal at known partial pressures. Analyses of quenched samples provide vapor pressure-solubility data and make calculations of alloy thermodynamics possible. The principle involved is similar to the closed-system diffusion-transport method which is difficult to apply with most high-melting liquid metals like iron, due to closure problems. A two-zone horizontal (molybdenum wire element) tube furnace, Fig. 1, provides two constant-temperature zones in a reaction tuve (3/4 in. ID by 1 in. OD by 36 in.). A high-boiling metal sample, 9, introduced in the higher-temperature zone, is maintained at temperature T1, and a volatile metal sample, 7, in the lower-temperature zone, is held at T2. A stream of argon with 10 pct hydrogen is passed via flowmeters, 1, and mixing-drying towers, 2 and 3. through the reaction tube at a favorable flowrate and acts as a carrier gas which entrains vapor from the volatile liquid metal at a specific constant partial pressure. The gas mixture passes through a system of constrictions, 6 and 8, to the higher-temperature zone, establishes intimate contact with the high-boiling liquid sample, 9, and exits through a small condenser tube. The entire system is at (nearly) atmospheric pressure and the volume of carrier gas passed is measured with a wet gas meter. When the high-boiling sample attains equilibrium with the vapor phase, both samples are removed and quenched. Analysis of the high-boiling sample for solute content reveals its solubility for the low-boiling metal at a vapor pressure calculated from carrier-gas volume and either a) weight loss of volatile metal or 6) weight gain of high-boiling sample plus condenser (which collects the undissolved vapors). To test the capabilities of the method, liquid silver at 1403&apos;C was equilibrated with lead vapor at various partial pressures. The relatively simple Pb-Ag system was particularly suitable for uncovering experimental problems and providing the first step toward investigations with more volatile metals and more difficult combinations.

Jan 1, 1965

By W. E. Newell

The basic principles and assumptions involved in D. L. White&apos;s solution5 for ultrasonic wave amplification in piezoelectric semiconductors are summarized. If the gain per unit length is maximized at each frequency without regard to the drift-field power density, the gain increases linearly with frequency. Therefore it would seem that very high gain is possible for frequencies in the hundreds of megacycles. However, with present materials the resulting drift-field power density is so large that cooling would be a major problem. For this reason it is more realistic to judge the capabilities of an ultrasonic amplifier in terms of the gain that is possible with a specified power density. In this case the gain at high frequencies does not increase but decreases more rapidly than l/f. The calculation of the gain us frequency at a fixed power level involves the repeated solution of a cubic equation and is therefore tedious. For the purpose of comparing different materials, sufficient accuracy can be obtained from an approximate solution which may easily be plotted as three straight lines on logarithmic graph paper. This method is used to compare the Performances of CdS, CdSe, ZnO, and GaAs. At a power density of 10 watts per cu cm, the first three give maximum gains of 60 to 80 db per cm in the vicinity of 60 megacycles. At the same power density, GaAs has a maximum gain of about 7 db per cm near 150 megacycles. Although an increase in mobility usually increases the gain for a specified power density, it is shown that there is an optimum mobility above which the gain decreases. An approximate expression for the optimum mobility is established. It is well-known that the interaction between charged particles and an electromagnetic wave can be used to amplify the electromagnetic wave. In the conventional traveling-wave tube, electrons in a vacuum are caused to move at a velocity slightly greater than the wave velocity, thereby coupling energy into the wave.&apos; In principle, the same effect would be evident in a solid except that repeated collisions prevent the electrons from attaining a velocity greater than that of an electromagnetic wave. However, the drift velocity of electrons can be made to exceed the velocity of an acoustic wave in a solid. In 1956, weinreich2 noted that the deformation potential provided one means of coupling energy from drifting electrons into an acoustic wave, but the effect was too small to be of any practical importance. It was not until 1961 that White and Hutson demonstrated that the piezoelectric effect provided a strong enough coupling to give appreciable amplification of an ultrasonic wave and awakened wide interest in electron-phonon interactions. Qualitatively the effect may be described as follows. An acoustic wave propagating through a piezoelectric material is accompanied by an electric-field wave. If the vibrations are properly oriented with respect to the crystal axes of a piezoelectric semiconductor, the local electric fields are axially directed and cause bunching of the charged carriers. If the drift velocity of these carriers is less than the velocity of sound, they tend to be dragged along by the acoustic wave. This electroacoustic effect results in a net potential appearing across the material and in attenuation of the acoustic wave. On the other hand, if the drift velocity exceeds the velocity of sound, energy is coupled from the carriers to the acoustic wave and amplification results. Related effects which are being investigated include ultrasonic amplification in semimetals6-&apos; and semi-conductor, and current saturation in piezoelectric semiconductors.&apos;4-17 There are various problems which hinder the immediate application of ultrasonic amplification in a practical device. First, there are the traditional problems encountered in the design of acoustic delay lines: attenuation in the electromechanical transducers, reflected waves (which can lead to self-oscillation in an amplifying device), mechanical tolerances necessary to maintain phase coherence, and so forth. Second, there is the problem of selecting the best material from among the various piezoelectric semiconductors as they become available in single-crystal form with a wide choice of characteristics. This paper deals with the second problem and shows that the most realistic way of comparing materials is in terms of the gain which can be obtained without exceeding a

Jan 1, 1964

By T. D. Yensen, R. K. McGeary

While we have not been primarily interested in the determination of hydrogen in the alloys that we have been dealing with, we arc very glad to cooperate in this symposium on sampling and analysis for hydrogen, as we can never tell when we may find it desirable to perform such analyses. Vacuum-fusion Method Our primary interest has been oxygen and carbon, in the analysis of which we think we have become very proficient. Our oxygen-analyzing apparatus is of the vacuum-fusion type (Fig. I). This employs Dr. Derge&apos;s type of graphite cruciblc and slit sleeve, with graphite powder between, for heat insulation (Fig. 2) supported in a clear quartz bulb connected to the Pyrex glass system by means of a carefully made ground joint. The latter is kept cool by means of an air blast from a circular copper tube surrounding the joint. The crucible is heated by high-frequency induction and the 24 one-gram samples successively dropped in from the horizontal tube at the top by means of a magnet. The gases (H², CO, N2) are passed through the CuO catalyst held at 300°C. (converting CO to CO²I, H² to H²O) and the CO² and H2O frozen out in the main liquid air trap, while N2 is evacuated. At the end of the operation, shown by the termocouple vacuum gauge indicating a pressure of 10-4 mm. Hg, the analyzing system is isolated by means of the mercury cutoffs, and the CO² and H2oare determined by transferring first the CO2 and then the HzO to the small trap at the right. This is done by placing liquid air on the small trap, then removing the liquid air from the large trap for one minute, which is sufficient to evaporate the Co2 and transfer it to the small trap. The CO2 is then measured by closing the mercury cutoff at the extreme right, removing the liquid air from the small trap, warming it up to room temperature, adjusting the mercury level to one of the three marks on the glass tube (corresponding to three volumes calibrated so that I mm. Hg of CO² corresponds to 0.001, 0.002 and 0.010 mg., respectively, of oxygen) and finally reading the pressure. Liquid air is now replaced on the large trap, the mercury cutoff at the right opened, transferring the COz back to the large trap. The cutoff to the pumps is then opened, the liquid air removed for one minute, thus evacuating the CO², the pumps again cut off and the H2 O transferred to the small trap as before, except that it is now necessary to warm the large trap with a Bunsen burner in order to evaporate all the H2O. This requires about three minutes, as the inner tube must be heated to at least 100°C. In order to prevent H²O from being adsorbed on the glass walls, the glass tubing beyond the catalyst (i.e., to the right in Figs. I and 3) is kept heated to about 150°C. by means of Nichrome ribbon as shown in Fig. 3. For a I-gram sample the above amounts of oxygen (0.001, 0.002 and 0.010 mg.) 35

Jan 1, 1945

By Jasinder S. Jaspal, John A. Reeves, Bradley J. Bourquin

INTRODUCTION The United States has an abundance of coal reserves in thick seams. Most of these resources are in the West. Surface mining operations in thick seams are highly efficient, particularly in the West, but methods for mining thick seams underground are very limited. The percentage of resource recovery in deep mining of thick seams is often as low as 30 percent. It is estimated that there are 45 billion tons of coal reserves for underground mining in seams greater than 10-ft thick in the western states alone. With such a large available reserve base and low rates of recovery, the need to develop the technology to mine these thick reserves is quite evident. As the definition of a thick seam varies widely from country to country, a thick seam is defined here as any seam where the height is such that it is not minable in a single pass with available mining equipment.

Jan 1, 1981

By H. R. Cooper, T. S. Mika

T. S. Mika (Department of Mineral Technology, University of California, Berkeley, Calif.) - Dr. Cooper&apos;s attempt to establish a correlation between process behavior and operational variables on the basis of a statistical analysis after imposing a reasonable process model is a very commendable improvement on the use of standard regression techniques. However, it must be recognized that the imposition of a model has the potential of yielding a poorer representation if its basic assumptions or mathematical formulation are invalid. It appears that at least two aspects of his treatment require some comment. First, the limitations on the kinetic law where xta represents a hypothetical terminal floatable solids concentration (cf. Bushell1), should be mentioned. Most current investigations2-9 appear to utilize the concept of a distribution of rate constants rather than a single unique value, k, to describe flotation kinetics. A distributed rate constant is certainly a more physically meaningful concept than that of a terminal concentration. The study of Jowett and safvi10 strongly indicates that xta is merely an empirical parameter, whose actual behavior does not correspond to that expected from a true terminal concentration. Rather than being a strictly mineralogical variable, as Dr. Cooper&apos;s treatment implies, it apparently represents the hydromechanical nature of the test cell as well as the flotation chemistry. The extension of batch cell kinetic results to full-scale continuous cell operation is a suspect procedure if the effect of such nonmineralogical influences on x,, remain unevaluated. There is evidence that introduction of a terminal concentration is necessitated by the inherent errors which arise in batch testing and are eliminated by continuous testing methods.&apos; Possible lack of validity of the author&apos;s use of Eq. 1 is indicated by two unexpected results of the statistical analysis of his batch data. The first is the apparent corroboration of the assumption that the rate constant, k, is independent of particle size, i.e., of changes in the size distribution of floatable material. This assumption directly contradicts numerous results 2,4,11-l8 for cases where first order kinetics prevailed and ignores the phenomenological basis for the analysis of flotation in terms of a distribution of k&apos;s. It must be recognized that, if the rate constant is size dependent, the lumped over-all k would be time dependent; Eq. 1 would then no longer be valid. Cooper&apos;s x,, is determined by batch flotation of a distribution of sizes for an arbitrary period of time. If the size dependence of k is artificially suppressed, x,, will become a function of the experimental flotation time used in its determination. Upon reviewing the rather extensive literature concerning batch flotation kinetics, there appear to be few instances where constant k and x,, adequately adsorb variations in floatability due to particle size. The second surprising result is the low values of the distribution modulus, n, determined. Contrary to Cooper&apos;s assertion, most batch grinding (ball or rod mill) products yield values of n > 0.6, which increase as the material becomes harder.&apos;&apos; It is likely that the values of n = 0.25 and n = 0.42 for Trials 1 and 2, respectively, are completely unreasonable, and even the value n = 0.54 obtained for Trial 3 is unexpectedly low. Possibly, this indicates inherent flaws in the three trial models considered, in particular the assumed particle size independence of the rate constant, k. The above does not necessitate that Eq. 1 (and the terminal concentration concept) is invalid; it could constitute a good first approximation. However, the qualitative arguments used by Dr. Cooper in its justification are somewhat frail and require verification, particularly since much of the flotation kinetics literature is in opposition. Apparently, no effort was made to test these hypotheses on the actual data; in fact, since they pertain to a single batch test time, his data cannot be utilized to evaluate the kinetics of flotation. To evolve a control algorithm on the basis of this infirm foundation seems a questionable procedure. Another difficulty in his analysis arises in consideration of the froth concentrating process. As Bushel1 &apos; notes, for Eq. 1 to be valid it is necessary that the rate of recycle from the froth be directly proportional (independent of particle size) to the rate of flotation transport from the pulp to the froth, a restrictive condition." Harris suggests that it is more realistic to assume that depletion occurs in proportion to the amount of floatable material in the pertinent froth phase volume (treating that volume as perfectly mixed).12,21,22 The physical implications of

Jan 1, 1968

By K. R. Waugh, Barbara S. Brown, D. W. James

AN electronic data-processing system is described which permits rapid, accurate, low-cost processing of strain-dependent damping data utilizing equipment normally available within the service facilities of most large laboratories. On analyzing the record of a stress-dependent damping test, the operator usually measures the double amplitudes at several points on the decay curve. The logarithmic decrement is then calculated for decay between consecutive amplitudes. These values of 6 are plotted against the corresponding maximum surface shear stress, T, which is proportional to the average of the two amplitudes between which is calculated: where d is the specimen diameter. The period of the vibration is not necessarily constant during decay; thus, each cycle must be counted. A decay curve may extend to, perhaps, 1000 cycles, and at least two curves are always obtained for each specimen or set of conditions. It can, therefore, be seen that manual analysis of decay curves is both tedious and costly in terms of man-hours. Furthermore, the resolution of the record is often such that accurate measurement of amplitude is extremely dif-

Jan 1, 1969

By Thomas J. Pike, Keith G. Kirk, Mark F. Weider, Lawrence E. Welborn

As part of the mine permitting process as delegated by the Surface Mining Reclamation and Control Act of 1977 the regulatory authority must assess the probable hydrologic consequences and cumulative hydrologic impacts of surf ace mining. The U.S. Office of Surface Mining (OSM), in conjunction with Energy & Minerals Technology Assessment and ENCORE Systems Inc., has developed a user friendly groundwater model that is capable of predicting the effects of surface mining on groundwater quality and quantity. The model is a variation of the Prickett-Lonnquist model which has been modified to be specifically applicable to surface mine applications. This model is presently being used by OSM, the states, and industry to determine mining impacts on groundwater resources. The model is designed for use by the hydrologist with minimal computer training. The model accounts for multiple pumping wells, injection wells, multiple mine pits, and mine pit movement through time. This paper presents an example of how the model may be used in permit application review and how the model can be used by industry to simplify permit preparation.

Jan 1, 1983