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By M. W. Clegg

The application of the Laplace transformation to problems in the flow of compressible fluids in porous media has provided a large number of exact solutions. For plane radial flow, however, these solutions are either complex integrals or infinite series and are of little value to the field engineer. In the case of production at constant well pressure, the available approximate solutions me valid for large times only. In this paper it is shown that an approximate inversion formula for the Laplace transform, developed for the solution of viscoelastic problems, is applicable to radial flow problems and provides simple analytical solutions to constant terminal pressure problems. The method may be used to obtain approximate solutions to many problems, including media with radial permeability discontinuities, multi-layer formations and pressure buildup in wells after shut-in. The results are compared with the few available computer solutions as well as the large time solutions, and it is shown that this approximate method greatly extends the time interval over which a simple analytical solution is acceptable. INTRODUCTION The study of transient problems in the flow of fluids through porous media has benefited greatly from the application of transform methods. The use of the Laplace transformation for solving parabolic equations has been widely discussed in the field of heat conduction and diffusion as well as in the petroleum literature. Removal of the time variable with the Laplace transformation generally reduces the problem to a boundary value problem which may be solved by standard techniques. A much more formidable problem then faces the engineer, however, for frequently the transform does not possess a simple inverse. The result is that the general inversion integral must be used and this leads to either an infinite integral or an infinite series, both of which are difficult to handle from a computational standpoint. Asymptotic approximations for the inverse have been known for some time and these yield approximate inverse functions that are valid for very large or very small times — but frequently the times of interest lie somewhere between these two extremes. Therefore, some acceptable approximation valid over a larger interval of time is desirable. During the past few years a number of methods for achieving this have been developed and some of these are discussed briefly in this paper. The relative merits of the various methods are not evaluated here, but some general conclusions reached by other authors are given. One of these methods has been applied to problems associated with the radial flow of compressible liquids to producing wells. In the case of production at constant well pressure, the method leads to simple analytical solutions for a number of standard problems; e.g., homogeneous formation, permeability discontinuities, pressure buildup. These solutions greatly extend the range of validity of the asymptotic ones (valid for large times only) and should be of value in studying the behavior of wells producing under constant pressure conditions. METHOD FOR THE APPROXIMATE INVERSION OF LAPLACE TRANSFORMS Much of the work that has been done on the approximate inversion of Laplace transforms has originated in viscoelastic problems. Apart from the asymptotic approximations,1 one of the first approximate methods was due to Alfrey.2 If (s) is the Laplace transform of f(t) defined by

By J. F. Held

In a study of the influence of cold rolling on mechani cal properties of steel, it was found that the specific rolling procedure influenced crystallographic orientation. Properties developed by several rolling modes were determined and related to crystallographic orientation. Sanzples were cold-rolled various amounts on a laboratory mill. When palm oil was used as a lubricant, the crystallographic orientation was homogeneous throughout the thickness of the samples. Other samples were rolled without lubrication. Variations in intensity of the recrystallization texture components persisted throughout more than 50 pct of the volume of these samples. When the average plastic strain ratio, which is dependent upon crystallogvaphic orientation, was plotted as a function of percent reduction, a maximum was found at 40 pct in the samples which contained the observed texture variation. No maximum was found for the samples with the homogeneous texture distribution. Other mechanical properties, such as tensile strength and yield strength, were not influenced by the variation in crystallopaphic orientation. MECHANICAL properties of steel sheets depend, in general, upon the structural properties of the steel. For example, the Petch equation describes the relationship between yield strength and grain size. Other properties, such as hardness, vary with chemical composition. The plastic strain ratio, or R value, has been found to be dependent upon crystallographic orientation . In the course of investigating the effect of cold rolling on mechanical properties, it was found that a previously reported relationship between percent cold reduction and R value was not always observed. Published data had shown that the optimum cold reduction for best R values is 70 pct for aluminum killed steel.' However, by altering the rolling conditions, the optimum reduction can be shifted to much lower values, or it can be moved to very high values. This paper describes the rolling conditions that lead to shifting of the optimum cold reduction. The effect of rolling conditions on the various structure parameters and the resulting mechanical properties are evaluated. EXPERIMENTAL PROCEDURE Samples of three low-carbon aluminum killed steels were cold-rolled various amounts on a 9-in.-diam 2-high laboratory mill. Hot-mill thermal practice and steel chemistries are listed in Table I. Steel A was rolled with palm oil lubrication and heavy reductions on each pass; i.e., a total reduction of 75 pct was ac- complished with a maximum of five passes. Steel B was rolled without lubrication, and light reductions were given on each pass. After approximately 75 pct reduction, it was necessary to use a small amount of light oil to achieve any additional reduction in thickness. Following cold reduction, the samples were box-annealed at 1300°F for 10 hr. The heating rate between 800" and 1300°F was 50°F per hr, and the cooling rate following the soak period was 50°F per hr. Tensile specimens were machined from the annealed material and these were used to measure yield strength, tensile strength, and the plastic strain ratio (R value). Recrystallization textures were determined by an inverse pole figure technique.*'3 Integrated intensities of the (110), (002), (112), and (222) reflections were recorded for those planes lying parallel to the sheet surface. Examinations were made on both surfaces of each sample, and also at various levels beneath each surface to approximately 0.010 in. depth by etching techniques. RESULTS R Values. The R values obtained in steels A and B are shown as a function of percent cold reduction in Fig. 1. No optimum cold reduction was observed in steel A, rolled with palm oil lubrication. It is likely, however, that an optimum reduction would have occurred had higher reductions than 88 pct been employed. The optimum reduction in steel B occurred at 40 pct. The behavior in both of these steels is quite

Jan 1, 1968

By Francis C. Frary

OF the five metals that now show the highest figures for annual tonnage production in the world, three (iron, copper, and lead) have been known and used by man for many thousands of years. The fourth (zinc) did not come into general use until the Middle Ages. Only the fifth (aluminum) is of, ultramodern origin, as far as mankind is concerned. Discovered in 1825, and first publicly exhibited at the Paris Exposition in 1855, aluminum was still so difficult to obtain that it was more expensive than silver, until the development of the dynamo provided cheap electricity and the development of the present electrolytic process for its production made it possible to make large quantities cheaply. Even today, the world production of aluminum is only about one per cent of the world production of iron, although about half that of copper by weight. The increase in production from a few tons to more than a million tons per year began with ,the development of the Hall-Héroult electrolytic process, which was first commercially operated by Mr. Hall's company, The Pittsburgh Reduction Co., in 1888. During the relatively short period of time that has elapsed since that date, it has been necessary to develop all the metallurgical and fabricating information required for the production of useful articles of the metal and its alloys, together with experience in both their production and their use, so as to be able to fit them satisfactorily into their proper places in our complex modern civilization. The fundamental properties upon which the usefulness of aluminum depends are its lightness, workability, resistance to corrosion,

Jan 1, 1953

By Eric R. Jette

In order to control a chemical process by other than empirical, rule of thumb methods, two types of knowledge concerning the reactions involved must be available: (1) the thermodynamics of the reactions, and (2), by no means less important for efficient operation, the mechanisms and kinetics of the reactions. Information on the thermodynamic side enables the operator to decide upon initial and final conditions, whether heat must be added or removed from the system, whether the reactions proceed farthest in the desired direction at high pressure or low, etc. Knowledge of the mechanisms involves the determination of the individual steps by which an initial set of reactants, under given conditions, proceed to give the desired final products and kinetic studies upon which the mechanisms are based give the speed at which each of these reactions or steps take place. Thus thermodynamic studies of a reaction enable the operator to control the direction and extent to which the reaction can proceed, while kinetic studies enable him to control rates and thus the time efficiency of the operations. The thermodynamics set the limit to which the reacting system approaches; the kinetics tell how fast the system actually approaches this limit. The two types of information are complementary and not antagonistic even though in discussing the mechanism the introduction of thermodynamics is entirely needless and generally of no assistance, while in thermodynamic studies mechanism need not even be mentioned. Heterogeneous Reactions The thermodynamic side of metallurgical reactions has received much attention in the past; the mechanisms, relatively, very little. The main reason for our present lack of information on the mechanisms of these reactions lies in the fact that every one of importance is a heterogenkous reaction; i. e., the substances involved in the reaction exist in more than one phase, while, if we neglect the large amount of work which has been

Jan 1, 1931

By R. Bakish, M. A. Badiali, N. W. Kirshenbaum

One pound of ultra pul-e molybdenum has been produced containing both metallic and nonmetallic impuvities close to or less than the limits of detection. various purification methods were investigated; althouglz the use of move than one purification step was consideved, it was found that a single, caefully-controlled sublimation of MoCl5 yielded a highly puvified product without prior treatment or recourse to repeated sublimation. Hydrogen reduction of MoC1, to metal was attempted at atmospheric pressure; however, reduced pressure was necessary to obtain substantial yields. The tubular deposits of metal were consolidated into bulk fovm by electron beam melting undev high vacuum yielding a very low gas content. Boblems involved in monitoring the puvity of these materials and analytical results obtained are also presented. THE pronounced effect of even trace amounts of impurities upon fundamental properties of materials is well known to metallurgists and solid-state physicists. Consequently, groups interested in basic studies of metals have in recent years immensely stimulated the preparation and production of numerous ultra-pure metals. Increased demand by scientists for these high purity materials has necessitated development of facilities to prepare them in significant quantities; the procedures reported here were devised to produce significant quantities of ultra-pure molybdenum. Previous work performed in the field of vapor phase purification and hydrogen reduction of several other refractory metal chlorides had demonstrated valuable techniques applicable to molybdenum.' Various purification and reduction steps were individually investigated. Those procedures which showed the most favorable results with respect both to attainment of high purity and to ease of operation were then incorporated in the process utilized to produce the metal.' STARTING MATERIALS It is well known that because of differences in volatility, chlorides may be separated by fractional distillation. It was presumed that distillation of molybdenum pentachloride offered a simple and straightforward method of purification due to its relatively low boiling point. Alternatively, sublimation of the solid chloride also appeared feasible since MoC15 has both a reasonably narrow temperature range in which it exists as a liquid (a property typical of refractory metal chlorides) and a low enthalpy of sublimation. Pertinent thermochemical data of MoC15 are given in Table I. It should be noted that this compound must be handled with care as it is extremely hygroscopic. Anhydrous MoC15 was obtained from the A Metal Climax Co. METHODS OF PURIFYING MOLYBDENUM PENTACHLORIDE Distillation. It was expected that distillation methods, while affording an efficient purification, would prove simple to control and would have a higher production rate than sublimation processes. Also considered was the possibility of effecting a high degree of purification by using both these volatilization methods in conjunction—possibly a distillation followed by sublimation of the solidified condensate. Distillation of MoC15 was investigated using a single stage distillation column packed with chemically resistant glass beads. Heating coils were wound around the column and collection tube (condenser). As-received MoCl5 was charged into a flask connected with the column using a side loading arm under an argon flow. After the column and condenser were brought to about 270" and 210°C, respectively, the apparatus was lowered until the flask was fully immersed in a constant temperature fused salt bath maintained at about 285 °C. Distillation was continued for about 10 or 15 min until 50 to 70 g of distillate had been collected. Analyses of these distillations indicated that several elements, e.g., Cu, Fe, Ni, Cr, and Mg, were lowered in quantity although not all were removed to the same extent. The occurrence of Na, B, Si, and A1 in the distillates appeared to be due to contamination, possibly from corrosion of the pyrex glass. An improved distillation system of larger capacity and longer distilling column was built. Improvements were effected in lowering the amounts of such impurities as B, Mn, Ni, Na, Mg, Cr, Cu, and Fe. These studies were pursued concomitantly with efforts to purify by sublimation; it was subsequently found that although improvements in purity were obtained by distillation, sublimation processes were simpler to control and effected a high degree of purity.

Jan 1, 1963

By William A. Johnson

The mathematical analysis of diffusion curves in solid metals is carried out ordinarily by analogy with the flow of heat in a continuous medium and no account is taken of the fact that the materials involved are composed of discrete particles that move discrete distances at irregular intervals. It is possible to treat the problem on the basis of simple assumed atomic mechanisms, in which case, because of the small scale of the elementary process compared to the gross effects observed experimentally, the two procedures lead to the same expression for the variation of concentration with distance. Thus, for engineering purposes, the usual methods are quite satisfactory. If, on the other hand, our purpose is to go beyond the mere collection of data, however desirable this may be, it is necessary to recognize and understand the factors that are of fundamental importance. One factor that has not hitherto been considered when dealing with solid metals is the difference in atomic weights of the isotopes of a single metal. While all the atoms of a given element are alike chemically, their weights may vary by a small but significant amount, and atoms of different weights may have different diffusion rates. With gases this variation in isotopic weight produces a change in the rate of diffusion by a factor inversely proportional to the square root of mass. While, except for the lightest gases, this is not a large effect, it is, for example, sufficient to permit a considerable concentration of one isotope at the expense of others. If metals exhibit a similar phenomenon, some modification of the analysis of the diffusion process will be required, since the different isotopes of a given metal will have different probabilities of moving and the heat-flow analogy will contain a fundamental error. This situation cannot be rectified by using a diffusion coefficient based on the average probability of moving, and it can be shown that even when the diffusion coefficient is independent of composition, the diffusion curve will not agree with the simple theory except in the rare cases where only one isotope exists; e.g., gold. If, however, the mass effect in the solid state were no larger than in the gaseous, the errors arising therefrom in the analysis of ordinary diffusion curves would be quite negligible. Nevertheless, our desire to obtain all possible information concerning the details of the diffusion process, and the possibility of diffusion in the solid state as a means for separating isotopes are cogent reasons for undertaking an experimental study to determine whether isotopes of different masses diffuse at different rates. Experimental Procedure If isotopes of different masses diffuse at different rates, the ratio of the concentration of one relative to another will vary with the distance from the diffusion inter-

Jan 1, 1946

By William A. Johnson

The mathematical analysis of diffusion curves in solid metals is carried out ordinarily by analogy with the flow of heat in a continuous medium and no account is taken of the fact that the materials involved are composed of discrete particles that move discrete distances at irregular intervals. It is possible to treat the problem on the basis of simple assumed atomic mechanisms, in which case, because of the small scale of the elementary process compared to the gross effects observed experimentally, the two procedures lead to the same expression for the variation of concentration with distance. Thus, for engineering purposes, the usual methods are quite satisfactory. If, on the other hand, our purpose is to go beyond the mere collection of data, however desirable this may be, it is necessary to recognize and understand the factors that are of fundamental importance. One factor that has not hitherto been considered when dealing with solid metals is the difference in atomic weights of the isotopes of a single metal. While all the atoms of a given element are alike chemically, their weights may vary by a small but significant amount, and atoms of different weights may have different diffusion rates. With gases this variation in isotopic weight produces a change in the rate of diffusion by a factor inversely proportional to the square root of mass. While, except for the lightest gases, this is not a large effect, it is, for example, sufficient to permit a considerable concentration of one isotope at the expense of others. If metals exhibit a similar phenomenon, some modification of the analysis of the diffusion process will be required, since the different isotopes of a given metal will have different probabilities of moving and the heat-flow analogy will contain a fundamental error. This situation cannot be rectified by using a diffusion coefficient based on the average probability of moving, and it can be shown that even when the diffusion coefficient is independent of composition, the diffusion curve will not agree with the simple theory except in the rare cases where only one isotope exists; e.g., gold. If, however, the mass effect in the solid state were no larger than in the gaseous, the errors arising therefrom in the analysis of ordinary diffusion curves would be quite negligible. Nevertheless, our desire to obtain all possible information concerning the details of the diffusion process, and the possibility of diffusion in the solid state as a means for separating isotopes are cogent reasons for undertaking an experimental study to determine whether isotopes of different masses diffuse at different rates. Experimental Procedure If isotopes of different masses diffuse at different rates, the ratio of the concentration of one relative to another will vary with the distance from the diffusion inter-

Jan 1, 1946

By N. A. Gokcen, R. A. Dodd

Solubility of nitrogen in liquid iron-manganese system at 1550°C and one atmosphere pressure has been determined by a simple method. Results show that the solubility increases from 0.040 pct for pure iron to 1.41 pct for pure manganese. DETERMINATION of the solubility of gases in volatile metals. and alloys by the well-known Sievertsl method is unreliable. This is particularly true for the Fe-Mn system since Mn vaporizes readily from the alloys containing as little as 2 pct Mn, and, upon condensing on the cooler parts of the apparatus, it absorbs large amounts of nitrogen. Further, the condensing Mn vapor interferes with the usual method of temperature measurements with an optical pyrometer.

Jan 1, 1962

By S. LeFevre

THE solution of the housing and sanitation problem in mining communities, keeping in view both economic and humanitarian aspects, demands the best thought of the management of such enterprises. Upon the solution depend the health and comfort of the employee and his family, and as a consequence his contentment and efficiency. The following description covers briefly the methods installed for Witherbee, Sherman & Co. The operation of the system has been for about two years under the direct supervision of T. A. Hammond, Land Agent, and I am indebted to him for a compilation of the results.

Jan 2, 1915

By F. A. Loving

This paper describes experiments which represent an effort to measure preciscly the pressure-time history in detonating condensed commercial explosives. The performance of explosives in mining has been a favorite subject for experimentalists and theorists for many decades. Much useful empirical information has been developed; but it has not yet been possible to predict, or even to account for, the behavior of explosives in mining on the basis of fundamental physical principals. A basic piece of information that would appear necessary for any rigorous analysis is the pressure-time history in the detonating condensed explosive. The experiments described here represent an effort to measure this relationship precisely in commercial explosives. THE EXPERIMENTAL METHOD The experimental method, first described by Cowan and Jacksonl has been extensively evaluated by Cowan and Balchan for relatively simple explosives. The experimental procedure involves the detonation of a layer of explosive between metal plates whose external surfaces are polished to a mirror finish (Fig. 1). Precise measurements of the deflection of

Jan 1, 1967

The ten-year "supply-demand relationship" tables in this chapter for various mineral and metal commodities have been adapted from Minerals in the U.S. Economy, compiled by the Bureau of Mines, U.S. Department of the Interior, published in 1975. Acknowledgment is made to the Bureau of Mines for compilation of the tables. [ ]

Jan 1, 1976

By W. A. Tiller, J. P. McHugh

HE majority of liquidus and solidus surfaces in phase diagrams have been determined by the conventional cooling- and heating-curve techniques.' These techniques have two main shortcomings: 1) the solidus may be in considerable error due to the difficulty involved in completely homogenizing the solid and 2) the determination of liquidus and solidus in more than a two-component system does not enable one to determine tie-lines connecting the specific equilibrium solid and liquid compositions. However, in a recent paper by one of the authors,' a method was suggested whereby the liquidus and solidus surfaces plus tie-lines in an n-component system may be determined. This method utilizes a controlled solidification technique and assumes that interface equilibrium exists during freezing. The present work was undertaken with a twofold purpose; first, to determine the liquidus and solidus lines in the pseudo-binary system Bi2Te3-Bi2Se3 by heating- and cooling-curve techniques and, second, to determine the partition coefficients of Te and Se in the BizTe3-,Sex system by controlled solidifica- tion techniques. The two sets of results can be compared to test the accuracy of the controlled solidification method. EXPERIMENTAL I—The starting materials for this study were 997999 pct Bi, Te, and Se, obtained from the American Smelting and Refining Co. The compounds BizTe, and Bi2Se3 were each prepared by melting together stoichiometric amounts of the elements, followed by twelve zone-refining passes. This produced homogeneous bars of the compounds for use in the phase-diagram studies. The apparatus used to obtain heating and cooling curves is illustrated schematically in Fig. 1. The alloy samples were located in a graphite crucible placed in a stainless steel canister. The canister was supported in a heavily lagged pit furnace by a device which oscillated the canister about its vertical axis at a frequency of about 3 cycles per sec during heating and cooling-curve runs. The graphite crucible was designed to minimize the thermal coupling of the sample to the furnace. A thin graphite sleeve separated the alloy sample from the stainless steel tube that housed the thermo-

Jan 1, 1960

By Robert L. Schuster, James A. Doolittle, Ronald L. Sack

The effect of the height of a retaining-wall-supported berm on the slope stability of an idealized mine-tailings dam was investigated. The material in the dam was idealized as a two-layered system with the phreatic surface delineating the boundary between the layers. In each layer the tailings were assumed to be homogeneous and isotropic. The effect of variation in height of the berm was examined for tailings dams with three different, commonly occurring slopes. The stresses and displacements were obtained using the finite element method. An incremental analysis technique was employed to simulate sequential construction of both the tailings dam and the retaining-wall-supported berm. A one-dimensional element was used to represent all interfaces and discontinuities in the finite element model. Assuming a hyperbolic model, the nonlinear stress-strain relationship for the tailings was approximated using the method of successive increments. The stresses obtained in the finite element analyses were used in conventional slope stability analyses assuming circular failure surfaces. The results of the study show that the use of a retaining-wall-supported berm is an effective means of improving the stability of a tailings dam. This increased stability is greater for dams with steeper slopes. In addition, the increase in factor of safety is particularly notable for berm heights less than 25% of the height of the dam.

Jan 1, 1975

By Arthur B. Cummins

POWDERED nonmetallic minerals and rocks of many different types are used extensively in industry for incorporation in compositions and manufactured products The term "mineral filler" is commonly employed to designate a material that is used for a specific purpose but not as an essential or reactive component Such a definition is not without objections, and it is indeed difficult to define fillers in any fully satisfactory manner, since the term has come to have so many different meanings and to cover such a wide range of uses. A filler is defined, for the purposes of this chapter, as a substantially inert material not specifically employed as a reactive or essential component, the primary function of which is to modify the properties or processing of a composition of matter or fabricated article Emery1 has emphasized that fillers change the properties of the product but are themselves unchanged in compounding or use The term "filler" appears to be rather general when referring to usages m bituminous compositions, rubber, composition floorings, fertilizers, plastics, textile finishes, and some others. In paper manufacture, in the paint industry and with insecticides, other terms are frequently employed, as is indicated, herinafter By placing emphasis on the function of the material used in modifying the properties of the composition or article, it is believed that a more useful classification of filler products and their applications may be derived. FUNCTIONS OF MINERAL FILLERS All of the manifold functions of mineral fillers cannot be listed in a summary review. A survey of the uses for these materials, however, shows that in nearly all cases the powders are employed to modify the properties of a composition of matter or those of a fabricated article, or to perform some useful function In the manufacture of either. A generalized list of these useful functions may be given is follows 1 To Modify Optical Properties Color Surface texture Opacity Brightness and gloss (as in paper and plastics) Flatness (as in lacquers and paints)

Jan 1, 1949

By H. l. Burghoff, J. S. Porter

THIS paper presents the results of an investigation of the effect of cold-working and annealing treatments upon the occurrence of preferred orientation in annealed brass wire. The subject has received less consideration than has the same phenomenon in annealed brass sheet or strip, and perhaps very properly so in view of the obvious and undesired results obtained in the forming or drawing of strip having preferred orientation, which results are in contrast with the lack of any spectacular visual evidence in wire. The factors of cold-working and annealing that control preferredness in strip are naturally expected to function similarly in wire. Indeed, one might expect the condition to be commoner in annealed wire, because the severity of the cold-working between anneals in commercial practice is usually much greater for wire than for strip. For example, a wire that is to be finished in the annealed condition on a diameter of 0.040 in. is commonly subjected to a final reduction of 96 per cent between the last two anneals, the large reduction being accomplished in the successive drafts of a multiple-die machine. Wire for rivets, for instance, on 0.125-in. diameter, although given a slight reduction of about 10 per cent after the final anneal, may have been given a prior reduction of 75 to 80 per cent. Barrett1 states the fiber axis of annealed 70-30 brass wire to be [111] with some indication of [100] as a secondary fiber axis. Croft and Sachs2 have reported briefly on some differences in brass wire with random and with preferred orientations. They showed statistical plots of the twin-band angles with respect to the wire axis or direction of drawing as observed on an axial plane. They also pointed out that the resistance of the wire to corrosion-cracking when externally stressed and exposed to a mercurous nitrate solution decreased as the degree of the preferred orientation increased. MATERIAL AND PROCEDURE All the wire for the investigation was processed from one. portion as cut for extrusion from a cast billet of the following analysis: 70.13 per cent copper; 0.01 lead; 0.01 iron; 0.02 nickel; 29.83 zinc (by difference). The billet section, 8 in. in diameter, was extruded hot to 3/4 -in. diameter, after which it was processed by alternate cold-drawing and annealing treatments as indicated in Fig. I. The earliest anneals in process were at about 1100°F. and the next to the last reductions by drawing were 58 per cent. The diameter of the finally annealed wire was 0.132 in. Semifinal anneals were at 800°F., 950°F. and 1100°F. and reductions of 47.5, 74, 83.5 and 89.5 per cent were employed in drawing to 0.132 in. The final anneals were at 875°F., 1050°F. and 1250°F. and were

Jan 1, 1944

By William P. Blake

The numerous and copious reports of geological surveys made in the lead and zinc region of Wisconsin leave, perhaps, but little room for any original work, or for descriptive details of the nature and origin of the deposits not already given in the exhaustive memoirs of Percival, Whitney, and Chamberlin and their associates. HOWeyer, since the completion of the last survey, in 1879, much more attention has been given than before to the exploration of the ores of zinc, especially of late years, since the region has been better opened up by railways and the zinc industry of the country has assumed large proportions, giving a constantly increasing demand for zinc-ores. A residence of more than a year in the region, and the active direction during that time of mining operations over a considerable area, have familiarized me with the forms and peculiarities of many of the deposits; and it appears probable that some observations upon them, especially from the mining and commercial standpoint, may interest the members of the Institute. A few notes on the structure of the deposits from the mineralogical and chemical standpoints have already been presented by me to the Wisconsin Academy of Arts and Sciences." The presence of lead-ore in the soil at many points along the Mississippi river was well known to the aborigines, and early attracted the attention of the frontier traders, who purchased from the Indians the ore and even lead smelted out by the squaws. The demand for the lead-ore soon increased, and it became one of the early and potent factors determining the settlement of southwestern Wisconsin, and the development of its mining and agricultural resources. The mines of that section, together with those of Missouri and the Mississippi valley, may be said to have been the cradle of mining in the western United States. The deposits of ore being at or near the

Jan 1, 1894

By J. E. Elliott, K. O. Miller

Solubility studies were carried out to establish the phase distributions for various Fe-Ni-Pb-C alloys at temperatures where the metallic components exist as liquid solutions. Temperature us composition diagrams for the Ni-Pb, Fe-Pb, Fe-Ni-Pb, and Ni-Pb-C systems are derived by employing various approximations in conjunction with the data. Results are summarized for 1550°C in a quaternary phase diagram of the Fe-Ni-Pb-C system. BECAUSE surprisingly little information has been published on the phase diagrams of the Ni-Pb, Fe-Pb, Fe-Pb-Ni, and Fe-Ni-Pb-C systems, a study of these systems was undertaken to ascertain the important phase relationships in the temperature range of 1300" to 1550°C. Measurements were also made on the carbon-saturated systems in the hope that they would assist in the interpretation of the systems without carbon. This paper reports the results obtained from the simple equilibration of the various liquid and solid phases. EXPERIMENTAL PROCEDURE The experimental technique involved holding appropriati quantities of the metals in an alumina crucible, or in a graphite crucible when saturation of the melt with carbon was desired, for sufficient time at the desired temperature to ensure equilibrium. Then a sample of each liquid phase presen was drawn into a small-bore silica tube. This sample was withdrawn quickly from the furnace, cooled, and sent to the chemical laboratory for analysis. The cell assembly used is shown in Fig. 1. Durin the work on the Fe-Pb-Ni system, it was placed in a furnace wound with 20 pct Rh-80 pct Pt wire. This furnace eventually failed and subsequent studies were carried out between 1350" and 1475°C in a tube furnace heated by silicon-carbide resistance elements. A protective atmosphere of argon with approximately 10 pct hydrogen was supplied to the cell assembly at a gage pressure of 1 in. of water. Hydrogen was passed over palladized alumina and then anhydrous calcium chloride for purification. Argon was purified of oxygen and water vapor by passing it over copper gauze at 550°C and then through a calcium chloride drying column. The gases were mixed and redried before they entered the equilibration cell. Temperature was measured by calibrated Pt/Pt-10 pct Rh thermocouples and a Rubicon Type B potentiometer. The thermocouples were standardized against the melting points of pure nickel

Jan 1, 1961

By W. A. Wood, W. H. Reimann

A study is made of the creep that can be induced in armco iron at room temperature by superposing small amplitudes of alternating torsion on a tensile creep load. It is shown that the creep differs from that in comparable tests on copper in being trmsient only. At the same time, though transient, the creep can produce extensions of some 10 pct under creep loads less than the tensile yield stress of the material. The creep can be largely suppressed b$ applying cyclic strain of suitable amplitude before applying the creep load and the metal thereby stabilized. At room temperature, plastic flow in a metal under steady load is normally limited by strain-hardening processes. However, if a small cyclic stress is superposed on the steady load these processes may be more or less neutralized and, as shown in recent investigations,'-4 plastic flow may continue. In this way annealed copper, for example, can be induced to creep continuously to fracture under loads as small as 1 tsi. Dislocation mechanisms possibly responsible for this room-temperature creep have been usefully reviewed by Feltner.But discussion so far has been based mainly on creep as it is found in close-packed metals initially in the annealed state, and their behavior may not be general. In fact, recent work shows that the form of creep in annealed copper is different from that even in cold-worked copper;7 the creep thus depends on the dislocation pattern already in a metal as well as on the metal itself. This paper describes the creep in annealed armco iron, tested in the same way as the above-mentioned copper. One object was to see how creep in a typical bcc metal compared with that in the annealed close-packed metals. Another object was to utilize the fact that a bcc metal like iron has a more pronounced elastic range than close-packed metals like copper and to find to what extent the creep load or superposed cyclic stress had to exceed their re-

Jan 1, 1964

By A. W. Bethune, L. M. Pidgeon

The equilibrium vapor pressure of zinc has been determined over the systems: ZnS(s) + Fe(s) = FeS(s) + Zn (vapor) and ZnS(s) + 2Cu(s) = Cu2S(s) + Zn (vapor) by reacting the components in an evacuated tube containing a thin copper fiber, and allowing equilibrium to be established with respect to the brass formed and the zinc in the vapor phase. The composition of the brass formed was determined and equilibrium vapor pressure values obtained from existing data. Between 850' and 1000°C, values for the first reaction ranged from 8 to 58 mm Hg; for the second reaction from 1.8 to 22 mm Hg. THE direct reduction of metallic sulphides may be indicated by an equation of the form MS + X = XS + M [1] where X is some suitable reducing agent. In the case where M is a metal of relatively high volatility, the use of vacuum will displace the equilibrium to the right at comparatively low temperatures in the face of the usually unfavorable thermochemistry. For this technique to be feasible, MS, X, and XS, must of course be nonvolatile compared to M. In this regard, zinc becomes an obvious metal both from the point of view of its volatility and the fact that most commercial ore deposits of this metal occur as the sulphide, and its direct reduction would avoid the expensive roasting process necessary prior to present day reduction methods. Two reducing agents are of interest, namely copper and iron, with the former having the added attraction of being relatively easily regenerated by oxidation in the copper converter. The possibility of these reactions has been considered before. Imbert1 patented a process whereby zinc sulphide was reduced by either copper or iron. The process as described took place at atmospheric pressure and, at the high temperatures required, the system was molten, resulting in the formation of a matte with the consequent reduction in the activities of the reactants. Peterson2 did further experimental work on these reactions and, although promising results were obtained on a small scale, attempts to increase the size of the furnace led to excessive "blue powder" formation. The early workers failed to realize the large reduction in temperature afforded by the use of vacuum and its desirable results. More recently, the direct reduction of zinc sulphide by iron has been the subject of a thermody-namic investigation by Kelley,3 and Gross and War-rington' have studied the kinetics of the reaction in the temperature range 900" to 1000°C, their experiments being conducted using vacuum and indicating that the reaction would proceed practically to completion in 1 to 3 hr, depending on the temperature. A qualitative examination of the system ZnS-Cu carried out at this University indicated that 98 pct of the theoretical zinc in the charge could be recovered in 1 hr at 1000°C when operating under reduced pressure. The purpose of this research program was to study the equilibrium of the two reactions. During the investigation, reference to the experimental work of Schenk5 was found but, due to lack of detail in the report, it was felt that it would be desirable to continue the equilibrium measurements. Selection of Method The measurement of vapor pressure of metals presents obvious problems resulting from the high temperatures which must be employed. In the present case, the production of the "reaction pressure" introduces a further difficulty since a chemical reaction must proceed before any metal vapor pressure is produced, resulting in depletion of the re-

Jan 1, 1954

By Charles H. Jacoby

During the past three decades an ever increasing number of uses for underground storage space has been developed. In some instances, the value of the space created has been so great that the host rock has been wasted. The preferential use of salt to host underground cavities is based on numerous factors, the primary two being low extraction costs and low permeability. Both dry and solution mined cavities have been created for the storage of a variety of materials. As the demand for underground storage and disposal grows, so must our selectivity of the materials to be stored.

Jan 1, 1985