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By John I. Yellott

Since the days of Newcomen and Watt, when men first sought to turn the energy of fuels to useful purposes, coal-generated steam has supplied most of the power needed for both stationary and mobile applications. The low efficiency and large water requirements of the nineteenth century steam-power plant caused many engineers to turn their thoughts toward more direct means of converting heat into power. As far back as 1791, John Barber secured an English patent on a combination' which he might well have called a "gas turbine." He proposed to generate producer gas from coal or charcoal, to burn it under pressure in air obtained from a reciprocating compressor, and to drive a turbine wheel with the resultant hot combustion products. With the optimism characteristic of the inventor, he hoped that the turbine would not only operate his compressor but also perform useful work. There is no record that Barber ever built his machine, but if he had done so he would have learned that useful power can result from such a combination only when both turbine and compressor are highly efficient and when the temperature of the gas entering the turbine is not far below 1000°F. Hot-air prime movers continued to attract attention, and both Stirling in England and Ericsson in America2 built reciprocating engines that operated with some success upon coal-heated air. The internal-combustion engine, burning liquid fuels, supplanted the hot-air type, and, for the first time, challenged the supremacy of both the steam cycle and its familiar fuel, coal. Liquid Fuels Compete with Coal As the increasing use of the automobile multiplied the demand for gasoline, the supply of residual fuel increased rapidly, and heavy oil declined in price to the point where it became competitive with coal. First in the marine field and later in stationary plants in areas adjacent to refineries, oil began to be widely used. Oil's greater convenience and higher heating value per pound of weight or per cubic foot of bunker space have caused it to take over much of the marine field. The introduction of the highly efficient diesel engine, capable of burning a fuel that is cheaper than gasoline, again threatened the position of coal, for the operating costs of the diesel became directly competitive with those of coal-burning equipment. In isolated power plants and smaller marine installations, the diesel provided the medium by which oil again successfully invaded fields formerly dominated by coal. The diesel engine, provided with an electrical transmission, found an excellent application in railroad service. The high availability of diesel-electric locomotives, resulting in part from freedom from water

Jan 1, 1947

By W. B. Stephenson

In the pumping of sands, slurries and slimes, practices developed over the years are the real keystones of 'successful operation. These practices are necessarily based on modifications of familiar theories. Practical methods used in the solution of problems involving the pumping of materials are set forth in the following discussion. Basic Requirements To pump sands and slurries economically, a few basic requirements must be met by the pumping system as a whole. A pipe-line velocity must be established that will move the fluid mixture throughout the entire system without any possibility of the solids settling out. To accomplish this, the velocity of flow must be slightly in excess of the critical velocity of the mixture. The critical velocity of a mixture varies from 3 ft. per sec. to 18 ft. per sec., depending on the screen analysis, concentration, and specific gravity of the solids in the mixture. Most tailings are pumped at a minimum velocity of 4 ft. per sec. if they include slimes, whereas the pipe lines of sand and gravel dredges require velocities as high as 18 ft. per second. A number of articles have been written on the determination of the minimum velocities required to maintain solids in suspension. Studies have also been made on the friction and pumping heads developed when handling solids in suspension.1-4 Our experience so far has shown that, within the normal operating limits of a pumping system, the friction factor follows more nearly the basis described by Howard,' who says, among his conclusions: "... values of f (friction factor) . . . will decrease with an increase in velocity." This conclusion is borne out by our actual experience. When the velocity in a pipe line is not sufficient to keep the solids in suspension, the total friction head' is greater than when the velocity is increased to a point where the solids are in suspension. A slight increase in the volume of feed to the pump and a slight increase in the pump speed are usually all that is necessary to put the system in balance. Maintaining Constant Volume Within reasonable limits, the volume of mixture to be handled through a pipe line should be held constant, so that the required velocity will be provided at all times. There are several ways in which this can be accomplished. The commonest is to provide a sump of sufficient capacity to take care of slight surges in the volume of mixture being fed to the pumping systen]. This sump, however, should not be as large as a settling chamber. The use of a float-controlled, fresh-water make-up valve in a sump will guarantee a constant volume. Where variations in volume are slight,

Jan 1, 1947

By John I. Yellott

Since the days of Newcomen and Watt, when men first sought to turn the energy of fuels to useful purposes, coal-generated steam has supplied most of the power needed for both stationary and mobile applications. The low efficiency and large water requirements of the nineteenth century steam-power plant caused many engineers to turn their thoughts toward more direct means of converting heat into power. As far back as 1791, John Barber secured an English patent on a combination' which he might well have called a "gas turbine." He proposed to generate producer gas from coal or charcoal, to burn it under pressure in air obtained from a reciprocating compressor, and to drive a turbine wheel with the resultant hot combustion products. With the optimism characteristic of the inventor, he hoped that the turbine would not only operate his compressor but also perform useful work. There is no record that Barber ever built his machine, but if he had done so he would have learned that useful power can result from such a combination only when both turbine and compressor are highly efficient and when the temperature of the gas entering the turbine is not far below 1000°F. Hot-air prime movers continued to attract attention, and both Stirling in England and Ericsson in America2 built reciprocating engines that operated with some success upon coal-heated air. The internal-combustion engine, burning liquid fuels, supplanted the hot-air type, and, for the first time, challenged the supremacy of both the steam cycle and its familiar fuel, coal. Liquid Fuels Compete with Coal As the increasing use of the automobile multiplied the demand for gasoline, the supply of residual fuel increased rapidly, and heavy oil declined in price to the point where it became competitive with coal. First in the marine field and later in stationary plants in areas adjacent to refineries, oil began to be widely used. Oil's greater convenience and higher heating value per pound of weight or per cubic foot of bunker space have caused it to take over much of the marine field. The introduction of the highly efficient diesel engine, capable of burning a fuel that is cheaper than gasoline, again threatened the position of coal, for the operating costs of the diesel became directly competitive with those of coal-burning equipment. In isolated power plants and smaller marine installations, the diesel provided the medium by which oil again successfully invaded fields formerly dominated by coal. The diesel engine, provided with an electrical transmission, found an excellent application in railroad service. The high availability of diesel-electric locomotives, resulting in part from freedom from water

Jan 1, 1947

By A. William Johnson

It was pointed out in an earlier paper1 that our understanding of the atomic mechanism by which diffusion occurs in metallic alloys is scarcely in an advanced state. This unsatisfactory condition is the result not of any lack of interest, but of the difficulty of designing experiments that .will yield suitable data. The diffusion coefficient of an alloy, measured in the usual way, is simply a number specifying the rate of homogenization of a nonhomo-geneous metal; this number, of itself, can furnish neither the rate at which the individual atoms move nor information as to the mechanism by which they move. It does not necessarily follow, however, that such information cannot be obtained, even if the path to be followed is still not clear. Much success has been attained in the study of diffusion in ionic crystals. A number of experiments, for which there are few counterparts in connection with metals, yield information often indicating a detailed mechanism by which diffusion probably occurs. From such work, quite acceptable theories of lattice imperfections have been developed by Wagner, Schottky, Frenkel, Jost and others.2 It is postulated that real crystals of stoichiometric composition contain, in equilibrium, certain imperfections of which the most importarlt types are: (I) vacant cation sites, with an equal number of interstitial ions; (2) vacant anion sites, with an equal number of interstitial ions; (3) equal numbers of anions and cations in interstitial positions; (4) equal numbers of vacant anion and cation sites. The classification of a particular crystal according to this scheme then follows from studies of the variation of electrical conductivity with pressure of the electronegative component surrounding the crystal, with ion size, and with temperature; other physical phenomena, such as the Hall effect, have aided in establishing the classification. The relative mobility of the anion and cation may be determined by chemical analysis of the salt at the electrodes following electrolysis. With such information, and knowing that one ion never occupies the lattice site normally belonging to an ion of opposite sign, it is usually possible to ascertain the diffusion mechanism. It is clear that the same experiments are not applicable to metal crystals, and substitute experiments that yield as much information have not yet been devised. Much can be learned, however, about the mobilities of the two* kinds of atoms in alloys by the use of radioactive metals as indicators. Only one such experiment has been performed in the past. In 1933, Seith and Keil,3 in an effort to explain the great difference between the rate of diffusion of gold in lead and of lead in lead, measured the rate of diffusion of radioactive lead in 3 gold-lead

Jan 1, 1942

By J. J. Arps, T. G. Roberts

Since the introduction of the relative permeability concept in the middle thirties1,2 various investigators have shown3,10,11,12,15 how the basic equations for the flow of oil and gas through porous media can he utilized to compute the recovery from depletion type or solution gas drive type reservoirs under certain conditions, when the necessary physical data pertaining to the reservoir rock and its reservoir fluids are known. In the study by Muskat and Taylor" in 1945, the effects of viscosity, gas solubility, shrinkage, and the permeability-saturation characteristics of the producing formation on the production histories and the recovery of gas drive reservoirs were analyzed. Each parameter was varied a limited number of times, while keeping the others constant. The work was not carried to the point where the data could be used directly to estimate the primary recovery in those cases where certain rock and fluid characteristics were known or could be assumed. Since the publication of this classic study, the work by Beal in 194616 and Standing in 1952'" has established general correlations of oil viscosity and shrinkage with gas solubility and oil gravity. In addition. a considerable number of relative permeability relationships for different types of reservoir rocks has been published2,5,13,17,19,20. Also, the burden of the numerical work required in the solutions of the differential equation has. during the last few years, been greatly reduced with the availability of modern electronic computing facilities. The purpose of this paper is therefore to present the results of a large number of such recovery computations covering the normal range of variation of the main parameters such as the type of rock, the API gravity of the oil, and the amount of gas in solution. As is to be expected, the ultimate recovery is found to increase with the oil gravity. except for the higher solution gas-oil ratios. Within the normal range of solubilities, the ultimate recovery generally appears to decrease with the amount of gas in solution for the higher oil gravities, and to show a slight increase for the lower oil gravities. Intermediate oil gravities seem to fall between the two trends. The type of reservoir rock, as identified by its relative permeability relationship, appears to have a very pronounced effect on the ultimate recovery. In general, sands and sandstones show higher recoveries than limestones and dolomites, although certain intergranular limestones seem to show a higher theoretical recovery than unconsolidated sand. The recovery from sands and sandstones generally decreases with increasing cementation and consolidation, while the recoveries from limestones and dolomites are highest for the intergranular type and lowest for the fracture type porosity.

Jan 1, 1956

By J. E. Hilliard

It is proposed that shape anisotropy in the internal structure of materials be defined by distribution functions which specify what fraction of the total line length or boundary area lies in a given direction. Methods are descriibed for determinirg these distribution functions from measurements on sections through an opaque material. New derivations, that have certain advanifages over those given previously, are Provided for well-known expressions used in estinzating the total density of lineal or areal features. INCREASING attention is being given to the quantitative description of imicrostructures in metals and other materials. This interest stems from the recognition that the structure often provides a convenient half-way point between the properties on the one hand and the processing variables on the other. Such cross correlations become increasingly desirable as materials become more complex and the demands on them more stringent. One of the principal aims in structure analysis is therefore to find parameters that are readily measurable and specific enough to be correlated with other properties of the material. Certain properties, such as magnetic and mechani cal behavior, are strongly influenced by structural anisotropies; in order to relate such properties to the structure it is obviously necessary to have means of specifying and measuring the type and degree of anisotropy. For the determination of preferred orientations in crystal structure, X-ray diffraction methods are available and are widely used, but scant attention has been given to the estimation of anisotropy in the shape of grains and particles. It is the latter problem that will be considered in this paper. It is evident that shape anisotropy can be describe in terms of preferred orientations of lineal and area elements of the structure. It will be shown that these preferred orientations can, in turn, be specified by distribution functions that define what fraction of the total line length or boundary area lies in a given direction. Methods will be given for determining the distribution functions from measurements on sections through the structure. Even when the orientation distributions are of no interest per se, they still have an important bearing on the measurement of the total line length or boundary area by means of an intercept analysis. The treatment in terms of orientation distribution functions leads to new derivations, that have certain advantages of those given previously, for the well-known expressions used in estimating the total density of lineal or areal features. The treatment is divided into two main sections. The first deals with the orientation distribution of a two-dimensional array of lineal features such as occurs in the projected image of dislocations in electron transmission microscopy. The other section treats the estimation of the distribution of lineal and areal features dispersed in three dimensions.

Jan 1, 1962

By W. B. Stephenson

In the pumping of sands, slurries and slimes, practices developed over the years are the real keystones of 'successful operation. These practices are necessarily based on modifications of familiar theories. Practical methods used in the solution of problems involving the pumping of materials are set forth in the following discussion. Basic Requirements To pump sands and slurries economically, a few basic requirements must be met by the pumping system as a whole. A pipe-line velocity must be established that will move the fluid mixture throughout the entire system without any possibility of the solids settling out. To accomplish this, the velocity of flow must be slightly in excess of the critical velocity of the mixture. The critical velocity of a mixture varies from 3 ft. per sec. to 18 ft. per sec., depending on the screen analysis, concentration, and specific gravity of the solids in the mixture. Most tailings are pumped at a minimum velocity of 4 ft. per sec. if they include slimes, whereas the pipe lines of sand and gravel dredges require velocities as high as 18 ft. per second. A number of articles have been written on the determination of the minimum velocities required to maintain solids in suspension. Studies have also been made on the friction and pumping heads developed when handling solids in suspension.1-4 Our experience so far has shown that, within the normal operating limits of a pumping system, the friction factor follows more nearly the basis described by Howard,' who says, among his conclusions: "... values of f (friction factor) . . . will decrease with an increase in velocity." This conclusion is borne out by our actual experience. When the velocity in a pipe line is not sufficient to keep the solids in suspension, the total friction head' is greater than when the velocity is increased to a point where the solids are in suspension. A slight increase in the volume of feed to the pump and a slight increase in the pump speed are usually all that is necessary to put the system in balance. Maintaining Constant Volume Within reasonable limits, the volume of mixture to be handled through a pipe line should be held constant, so that the required velocity will be provided at all times. There are several ways in which this can be accomplished. The commonest is to provide a sump of sufficient capacity to take care of slight surges in the volume of mixture being fed to the pumping systen]. This sump, however, should not be as large as a settling chamber. The use of a float-controlled, fresh-water make-up valve in a sump will guarantee a constant volume. Where variations in volume are slight,

Jan 1, 1947

By Kurt Stock

The grades of spelter demanded by the consuming industries were not definitely established until the American Society for Testing Materials undertook to fix specifications, based on the varying percentages of the common impurities (lead, iron, and cadmium) as follows: Total, Not Leap, Iron, Cadmium, Over. Per Per Cent. Per Cent. Per Cent. Cent. A. High grade.................. 0.07 0.03 0.05 0.10 B. Intermediate................ 0.20 0.03 0.50 0.50 C. Brass special................ 0.75 0.04 0.75 1.20 D. Prime western............... 1.50 0.08 The question which grade was the best for certain purposes and why was left unanswered. The conservatism of the zinc-smelting industry and the unwillingness of the spelter-consuming industries to engage in research work prevented the full benefits being obtained that such standardization promised. The custom smelters, producing spelter in pigs or plates, found it impossible to adhere closely to the established limits on account of the variety of ores treated; and the smelters with long-established and known brands, or those manufacturing their metal into marketable products, like sheet zinc, did not have to abide by the newly established grades based on chemical percentages. Smelters engaged in the smelting of custom ores had occasional complaints about the quality of their metal, as some of the consumers, especially brassmakers and some galvanizers, used the rigid standards of the A. S. T. M. as a basis for obtaining redress from zinc smelters whenever some of their work was faulty. Indirectly, much good resulted from such complaints; for while the brassmakers and galvanizers, on the whole, did not know what was wrong, the metallurgists in charge of zinc smelters were induced to abandon their conservatism and study the influence of impurities in spelter from the point of view of the consumer. For some of us, spelter gradually ceased to be considered merely spelter; it

Jan 1, 1925

By J. S. Marsh

OPPORTUNITY to pay tribute to the memory of Professor Henry Marion Howe is a strenuous assignment as well as an honor. Upon recalling Howe lecturers and lectures of the past 25 years, glancing over the list of those earlier, and rereading Howe's books, I arrive at several conclusions: 1—Many lecturers either worked under or knew Professor Howe. 2—It is virtually impossible to pick a subject on which Professor Howe did not touch. 3—There is precedent for a technical paper based upon pursuit of a single subject. 4—There have been listening lectures and reading lectures. There is solid comfort only in 2: the subject field is wide open. I did not know, nor even ever saw, Professor Howe, so can supply no fitting reminiscence. As a college student I was dimly aware that he counted among the giants. Fuller appreciation of his stature came with reading his books and papers, growing acquaintance with some of his associates, and the intrinsic dignity of the climax of the Annual Meeting, beginning at four o'clock of a Thursday afternoon in the auditorium of the Engineering Societies Building in New York. As for producing the technical paper sort of thing, it is my lot to have reached an age and assignment such that to do so would be to filch information from those who did the work and whose story is theirs to tell; for this I have no enthusiasm. As for the final conclusion, Professor Howe was one of the chosen few so highly expert at expository writing that he could produce a lecture or paper that reads as though it would also have listened well. One of his tricks was the free use of words not ordinarily part of the technical vocabulary, provided that such words were likely to communicate most precisely what he had in mind. How wonderful it would be for all who must read reports by the ton if ability at exposition could be taught with the effectiveness open, say to, differential calculus! Perhaps Professor Howe should be required college reading even if for no other reason than to prove that technical writing need be neither dull nor diffuse. My assignment is clearly still strenuous. Another point to consider is the fact that metallurgy is now so tremendously diversified that hope of finding a topic of universal appeal is negligible, even if one were competent enough to be permitted free choice. That which follows is, therefore, a compromise composed of necessity and of the obligation to attempt to avoid boring to slumber those of you who are not especially interested in the general subject chosen. The Iron and Steel Div. is now essentially a process metallurgy division, heavily concerned with the smelting of iron and the making of steel. The American Iron and Steel Inst. figure for present steel capacity of this country is 125,828,310 net tons; how this is divided among processes is indicated by the production totals for 1953, shown in Table I. The glamor girls and boys make the front page and so it is with steelmaking processes. If there is an Antarctic Daily Bugle, it undoubtedly has carried stories of revolutionary development, such as oxygen processes and vacuum melting, and stories of the incomparably rosy destiny of electric arc melting. All such certainly have their place and their future; meanwhile, it is the sturdy and old reliable open hearth that accounts for the bulk of production reported back on the financial page, and it is the old reliable that is most likely to continue to account for the bulk for some perfectly sound raw material, technologic, and economic reasons. This, plus the fact that next year marks a centennial (for it was in 1856 that Frederick and William Siemens conceived the regenerative open hearth), is reason enough to talk about open hearth furnaces, but is not the real one. The real reason is that in some years of association with open hearths, I have accumulated—in addition to a genuine liking and respect for them—certain odds and ends of fact and fancy that this lecture provides a unique chance

Jan 1, 1956

By R. J. Quigg, G. S. Doble

Commercial stress -relieved TD Nickel bar was shown to retain room- and elevated-temperature tensile strength after exposure up to 2501°F. Cold swaging increased both room -temperature and 2000°F tensile strength. After annealing at 2500°F the strengthening due to swaging was retained at 2000°F hilt eliminated at room temperature. Annealing produced changes in hardness and X-ray half peak width indicating the presence of recovery processes as 1071° as 1000°F but no recrystallization of swaged material was noted at any temperature. In contrast to swaging, rolling induced a recrystal-lized structure after annealing. The tensile strength of this recrystallized structure was comparable to the cold-worked condition. High-temperature tensile properties of as -received bar were highly anisotropic with the transverse tensile strength being one fifth the longitudinal value. The aniso-/ropy is affected by working direction and may he partially reversed by changing the direction of metal flow. The divergence in tensile strength, beginning above 550°F or- approximate one third the absolute melting point, is strain-rate dependent. T D Nickel is a commercial dispersion-hardened alloy containing 2 vol pct thoria. The dispersion, consisting of spherical particles 0.030 to 0.050 in diameter with an interparticle spacing of less than 1 is reported to maintain stable properties up to 2400°F.1 This stability of second phase results in maintenance of elevated-temperature strength at higher temperatures and longer times than normal nickel-base superalloys.2 The purpose of this paper is to describe the effect of various mechanical working operations on the strength and microstructural stability of TD Nickel bar. MATERIAL AND PROCEDURES All material used in this study was commercial TD Nickel bar. This material is produced by a chemical process which results in a nickel powder containing a dispersion of thoria particles. The powder is then pressed, sintered, extruded, and subsequently worked to bar stock. Three starting materials from three separate lots were used: as-extruded bar. 1-in.-diam stress-relieved bar, and 1/2-in.-diam stress-relieved bar. Since TD Nickel bar stock is cold-worked without a recrystalliza-tion anneal, the accumulated deformation or degree of cold work in these materials increases as the bar diameter decreases. Some of the 1/2-in.-diam bar was swaged to 1/4 in. diameter at room temperature in order to produce an as-worked condition for comparison with the stress-relieved stock. Tensile testing was performed on an Instron Tensile Tester at a constant crosshead speed of 0.020 in. per min. The 0.2 pct offset yield strength was measured from the load-crosshead movement plot. Specimen gage dimensions were 0.080 in. in diameter by 0.40 in. in length, producing a strain rate of approximately 0.050 min-1. Specimens were tested in air and heated within a resistance-wound furnace controlled to ±5°F. A 15-min soak at temperature was employed before testing. Samples were heat-treated in air and specimens machined after exposure with sufficient material removed to eliminate any surface contamination. X-ray line breadth was determined from a diffractometer scan of a transverse face of a bar using copper K, radiation. Metallographic preparation utilized standard mechanical polishing with Carapella's etch. Specimens for electron microscopy were electropolished in a 1:7 sulfuric/methaol solution and chromium-shadowed collodion replicas prepared. RESULTS AND DISCUSSION I) Effect of Elevated-Temperature Exposure on the properties of TD Nickel. The effect of various elevated-temperature exposures on the room-temperature tensile strength of TD Nickel is shown in Table I. In the unexposed condition the tensile strength, reduction in area, and hardness all increase with increasing accumulated deformation while the elongation decreases. After exposure at 2500°F the strength of all three materials decreases to about 65,000 psi and the elongations increase slightly. The apparent increase in strength of the 1-in. bar after a 2000°F treatment is probably experimental scatter. These results indicate that the room-temperature strengthening due to additional deformation is annealed out upon elevated-temperature exposure. In contrast to the room-temperature data, the 2000°F tensile strengths increase in order of increasing deformation even after exposure. Although some loss of strength occurs after exposure, much of the effect of working is still maintained at 2000°F. The room-temperature hardness after various

Jan 1, 1965

By G. A. Moore

A brief review is given of methods designed to produce metallic iron of high purity, and typical results are listed. A recent method, utilized at the National Bureau of Standards, consists of the extraction of ferric chloride by ether, reduction of this ferric chloride to ferrous chloride, further purification of this chloride, and the subsequent electrolytic deposition of metallic iron. iron produced by this procedure apparently is softer than, and otherwise different in properties from, any iron previously prepared and contains appreciably smaller amounts of impurities. THE history of attempts to produce "pure" iron reaches to antiquity and it may be presumed that each ancient armorer who succeeded in making a better steel concluded, correctly, that he had done a better job of removing the "base metals," and incorrectly, that he now at last had a "pure" metal. Early metallurgical papers mentioned use of "pure iron" in making alloys—this "pure" iron in most cases being inferior to some commercial stocks of the present time. Improvement has been continuous, and usually at a sufficient rate to convince each succeeding group of workers that they, at last, were using the really pure metal (until the analysts also improved their techniques to again discover the impurities). These adventures were reviewed in some detail by Cleaves and Thompson.' Although the ores of a metal may be abundant, difficulties in extracting it may make the pure metal very rare. When impurities are restricted to a total of a few parts per million, nearly all pure metals become rarities. Lead, copper, gold, mercury, silver, zinc, aluminum, bismuth, and the six platinum metals are claimed to be available with total impurities ranging from 2 to 50 ppm. The present small and scattered world supply of so-called "pure" iron holds an unimpressive place in another group of 16 metals having approximately 100 ppm of foreign material. Of about 20 less rare metals, only the platinum metals are more costly to prepare. While the production of such rare varieties of iron may appear insignificant in the presence of thousand-ton operations with 95 to 99 pct metal, it must be emphasized that all researches on commercially interesting irons and steels are in fact studies of the modifications of the properties of iron by additional materials. Until the properties of high purity iron are directly measured, all ferrous research must operate without known base values. Traces of impurities may affect the properties of a metal in many ways. Infinitesimal traces of solutes, by disturbing the electronic configuration, greatly change the electrical properties of transistors and semiconductors2-3 and slightly larger traces might alter these quantities in iron. Soluble impurities which disturb the perfection of lattice arrangement not only may alter the magnetic constants and electric properties, but by their close association with dislocation phenomena probably control the very existence of the "yield point"; determine the value of yield stress; and perhaps control the selection of slip and cleavage planes. It has been speculated that impurities might even cause the allotropic transformation in iron, but in any case their rearrangement must contribute to the unreliability of heat capacity and other thermodynamic measurements. Impurities which do not remain in solution may cause even greater effects on the properties. Microscopically visible amounts of phases other than ferrite can be found in all high purity irons which have come to my attention. It can be calculated that from 50 to as little as 2 ppm of an insoluble material might be sufficient to completely film all grain boundaries in irons having grain sizes from ASTM Nos. 10 to 1. Should this occur, such films, even though invisible, may be very important in fracture problems, especially at extremes of temperature:' Studies of grain growth and diffusion normally imply consideration of a single-phase system, hence, in the presence of insoluble impurities they can be expected to give ambiguous data." High purity iron is also in demand for use as chemical and spectro-chemical standards; for work in classifying the lines of the iron spectrum; for biological work in nutrition; and for work in nuclear physics. where the presence of some sensitive

Jan 1, 1954

By Morris Muskat

It is pointed out that the application of capillary pressure curves obtained by drainage or desaturation processes to the calculation of the fluid distribution in interphase transition zones involves a number of difficulties; namely: (I) the development of very low nonwetting phase saturations appears to be in contradiction with the lack of mobility of such distributions indicated by permeability-saturation curves, (2) dispersed nonwetting phases are thermodynamically unstable, and (3) discontinuous phases should not be subject to hydrostatic equilibrium requirements. While these difficulties could be obviated by assuming that the capillary pressure drainage curve has an initial horizontal segment, they are automatically circumvented by application of the imbibition capillary pressure curve to the lower part of the water-oil transition zone. These generally show zero displacement pressure at only partial wetting-phase saturations. The countercurrent upward flow of oil into the main oil-saturated pay and downward drainage of water also suggests that wetting phase imbibition processes will control the saturation distribution immediately above the water-saturated section. Similar considerations, with a generalized interpretation of the apparent wetting-phase behavior of the oil and gas phases, provides a basis for constructing the curve for fluid distribution in the oil-gas transition zone. In the transition zones so derived, the oil begins with a nonvanishing saturation at the water-oil contact and terminates with a similar saturation at the top of the gas-oil contact. The gas-oil transition zone begins with an equivalent nonvanishing gas saturation. Introduction It has been a common assumption for some years that the nature of the fluid dis- tribution in virgin reservoirs, and in particular that in the transition zones between the oil and water and between the oil and gas sections, can be computed by a simple application of capillary pressure data. The results of such calculations appear to have been first reported by Leverett.' The latter, however, indicated only the numerical values of the parameters used in the computations, without explicitly describing the procedure. Leverett's illustrative calculated transition zones are reproduced in Fig I. Although no critical study of the apparently obvious method of calculation has been published, one cannot proceed very far in the computation without encountering some rather fundamental questions not yet answered in the literature. This paper is not written under the pretense that the whole transition-zone problem has been fully and satisfactorily solved. Its purpose, rather, is to discuss suggestions for its treatment, much of it admittedly hypothetical, and emphasize the nature of the uncertainties arising therein; for the literature, as now available, gives little indication that there are any problems still outstanding. The Transition-zone Equation The basic equation, which presumably gives directly the fluid distribution without recourse to any further consideration, is: Ap = (r1 - r2)gh [1] where r1, y2 are the densities of the two contiguous fluids, h is the height above the "capillary-free" zone of complete saturation with fluid I, g the acceleration of gravity, and Ap is the capillary pressure across the average interface at the height

Jan 1, 1949

By K. H. Coats

This paper describes an approximate technique for handling the problem of percolation of evolved gas upwards through the oil column in computer simulation of natural depletion. This technique has been incorporated into a general model for simulating three-phase flow in one, two or three dimensions. The mathematical model for perfonning these calculations is described in detail in a separate article. 1 While vertical gas percolation occurs during natural depletion in a reservoir of any configuration, it is especially pronounced in the pinnacle reel or bioherm. The reel may have an areal extent less than one section with a thickness of up to 800 It. The upward percolation of evolved gas often limits the time step in calculations as little as one day. Using this small time step, computer expense for a single 30- to 40-year simulation on even a one-dimensional basis has exceeded 92,000. The method described here for handling the percolation allows time steps of 60 days or more (depending on reservoir size and production rate), resulting in a considerable reduction in computing expense. The method also allows calculations in which secondary gas caps build up in tight zones of the oil column below the main gas cap. The validity of the method is indicated in connection with an example pinnacle reef field. Calculated results using a 2-day time step (where the method in question is not needed and not invoked) are compared with results using the method and a 60-day time step. The comparison shows good agreement. Results from one- and two-dimensional simulations of the reef are presented along with the corresponding computing times on the CDC 6600 computer. A three-dimensional simulation was also performed and the required computing time is given. INTRODUCTION A general analysis for simulating three-dimensional, three-phase flow in reservoirs has been developed. 1 In applying this model to reservoirs undergoing natural depletion, a time-step restriction was encountered due to the flow of evolved gas upwards through the oil column and toward the gas cap. A remedy for this problem has been incorporated in the analysis and is described here. The time-step restriction is encountered only in calculations which include flow in the vertical or near vertical direction. The restriction occurs to some extent in reservoirs of any geometrical configuration, but it is especially pronounced in the pinnacle reef or bioherm where the ratio of thickness to areal extent is unusually large. This paper describes the problem, a method of handling it, incorporation of the method in the three-dimensional, three-phase model, and, finally, a test of the method's validity in an application to an example pinnacle reef reservoir. THE PROBLEM During the early stages of reservoir depletion, pressure falls below bubble point in progressively lower regions of the oil column. Continuing production results in evolution of dissoived gas throughout the oil column. This gas then percolates upwards toward the top of the reservoir. If the gas encounters a sufficiently low permeability zone in its travel upward, then it can accumulate and form a secondary gas cap. If no zones are encountered which are tight enough to hold gas against the gravity forces, then the gas travels on until it reaches the top of the sand or the main gas cap. Numerical simulation of multiphase flow in reservoirs is generally performed with time steps such that the flow of a fluid into or out of a block in one time step is a fraction (considerably less than one) of the total amount of that fluid present in the block. Use of a time step where the time step's

Jan 1, 1969

By W. O. Philbrook, R. H. Spitzer, F. S. Manning

The steady-state operation of an isothermal, counter-current reactor in which a mouing bed of hematite particles is reduced by hydrogen has been modeled mathematically using a generalized single-particle kinetic formulation for topochemical reduction with formation of the intermediate oxides, wustite and magnetite. Reduction prof iles have been generated for various oper- REDUCTION of iron ore, as practiced industrially, approaches counter current, granular-bed operation. The total process is extremely complex. Quite under- ating conditions selected to demonstrate the influence of major variables such as gas and solid flow rates, bed length, and particle size. These profiles illustrate , among other things, that the reducing-gas requirement in a countercurrent bed hinges upon the iron-wüstite equilibrium or 'pinch-point" in much the same way as in a staged reactor. standably, nearly all research has been focused on reduction of single particles of oxide under controlled conditions. While this approach simplifies the problem by eliminating interparticle interactions, the remaining intraparticle transport and kinetic processes still constitute a most formidable challenge. Only within the last few years has knowledge of single-particle reactions been developed sufficiently to make modeling of counter current-bed reduction a realistic and useful study of process behavior. The authors have analyzed1"3 extensive laboratory

Jan 1, 1969

By M. Nicholas, D. M. Poole

The diameters of sessile drops have been found to increase linearly with time in five reacting binary metal systems. The spreading rates of the drops are markedly dependent on temperature and on prior alloying of the solid with the lower melting point metal, hut are independent of the drop volume, wetting atruosphere , solid-surface roughness, and prior alloying of the drop with the substrate metal. A mechanism has been suggested that relates the linear-spreading rate to lateral diffusion of the liquid-metal atoms into the solid at the drop edge. An Arrhenius- type equation has been derived that describes the temperature dependence 0) the spreading rate, and although the agreement between the actual and the predicted pre-exponen-tial terms is poor that between the activation energies is excellent and the variation in the spreading rate of copper on Ni-Cu alloys produced by different extents of alloying can be predicted with considerable accuracy. CHEMICAL interactions frequently change the wetting behavior of solid-liquid systems causing, for example, "secondary spreading1 of sessile drops beyond the size defined by the surface and interfacial tensions of the unreacted components. The kinetics of the contact-angle decreases associated with this spreading are similar for many systems, but few studies have been made with the objective of determining whether the similarities are a reflection of a common mechanism. Some workers2,3 have assumed the secondary spreading is controlled by changes in the liquid surface and liquid-solid interfacial tensions and hence by the composition of the liquid, and contact-angle changes measured by the vertical-plate technique have been used to follow the course of liquid-solid chemical reactions.4 Other processes that have been invoked to explain these time-dependent changes in specific systems include the removal of adsorbed gas from the liquid-solid interface.5 penetration of containment layers on the solid Surface,6 interdiffusion,1,7 reori-entation of the solid surface into a wettable configuration: vapor-phase transport of the liquid onto the solid in advance of the drop,9 and, from vertical-plate studies. capillary flow between oxide layers and the solid surface.10 One of the reasons for the profuseness of these suggestions may be the complexity of the contact-angle change kinetics. However, in an analysis of secondary spreading gold and copper on UC,11 it was found that the diameter of the contact area between the sessile drop and the solid surface showed a simple linear increase with time although contact-angle changes were more complex. To check whether the linearity was merely fortuitous! additional exploratory work was conducted with four reacting metal-metal systems: Au on Ni. Cu on Ni, Cu on Fe, and Ag on Au. Linear spreading was observed in every case even though the kinetics of the contact-angle changes were complex. A further detailed study of the kinetics of linear spreading of five reacting metal-metal systems has been made with the object of determining the mechanism involved. The influence of variables such as temperature, drop volume. and the initial composition of the drop on the linear-spreading rate has been measured and compared with those predicted by a number of possible mechanisms. The systems employed in this study (Cu and Au on Ni and Pt, and Ag on Au) were selected because of the availability of potentially relevant chemical and physical property data. the simplicity of their phase diagrams at the wetting temperatures, and the ease of experimentation. EXPERIMENTAL TECHNIQUES The purities of the metals used in the study were: copper, 99.9 pct; gold. 99.96 pct; nickel, 99.2 pct; platinum 99.99 pct; and silver, 99.999 pct. The wetting tests were performed in a split tantalum tube vacuum resistance furnace of a conventional design. The furnace element was held vertically and was 1 $ in. in diam and 6 in, long. Viewing ports were provided in the water-cooled chamber to enable the specimens to be observed in both the horizontal and vertical planes. The temperature in the hot zone of the furnace could be held at 1500" i 5°C for an indefinite time. The surfaces of the solid-plaque metals were ground flat on Microcut paper and both the sessile drop and substrate metals were ultrasonically cleaned in methyl alcohol prior to their insertion in the furnace. After loading, the furnace was pumped down to a pressure of 2 x 10-5 mm of mercury and degassed for 30 min at 900° to 950°C. The temperature was then increased at more than 100°C per min to that used in the wetting test. The vacuum at the wetting temperature was better than 5 x 10-5 mm of mercury. Dewetting and retraction of the drop on cooling did not occur and the contact-area diameters, therefore, were measured after solidification with a vernier traveling microscope. The diameters quoted later are arithmetic means of ten measurements. The standard error of the mean never exceeded 3 pct and was often less than 1 pct.

Jan 1, 1967

By J. Paces, E. Miller, K. L. Komarek

The resistivity was determined as a function of temperature over the composition range from pure cadmium to 40 at. pct Cd. Melts with cadmium contents less than 85 at. pct had negative temperature coefficients of resistinity. On cooling below a transition temperature close to the liquidus temperature, the slope of the resistivity-temperature curve changed sharply. The activation energy calculated from the slope was 0.07 ev above the transition temperature and 0.14 ev below. The resistivity vs composition curve shows two maxima corresponding in composition approximately to CdSb and Cd3Sb2. THE relationship between the structure of a liquid and that of the crystal formed on solidification is at present not well-under stood. Various experimental determinations of the properties of liquids indicate that deviations from random atomic arrangements in liquids occur and that the properties of a solid and of its melt are closely related. Thermody-namic activities of liquids usually show negative deviations in systems where compound formation occurs in the solid,' and X-ray data indicate that close-packed solids and their melts frequently have nearly the same coordination number. Electrical resistivities and viscosities of liquids frequently exhibit maxima at compositions corresponding to compounds in the solid state. It should be of interest to study systems which have both stable and metastable compounds in the solid, and to determine if the short-range order in the liquid is affected by the existence of the metastable solid phase. The Cd-Sb system exhibits such a metastable phase. The phase diagram is shown in Fig. 1.3 The stable system has one intermetallic compound, CdSb, crystallizing in the orthorhombic crystal structure, with a melting point of 456°C. The metastable system also has one compound, Cd3Sb2, melting at 420°C and crystallizing in the monoclinic structure. Metastable alloys transform to the stable crystal structure in the temperature range from 250o to 350°C. Several distinct indications of very strong short-range order in the liquid phase have been reported in this system, with a close relation between the ordering in the liquid and the existence of both the stable and metastable solid phases. Scheil and Baach4 have observed distinctly different vapor pressures for liquid Cd-Sb alloys depending on whether the liquid solidified to the metastable- or stable-phase configuration. They observed an unusually sharp increase of the activity in a limited temperature interval immediately above the liquidus temperature of stable alloys, followed by a sudden decrease in slope to what they considered normal values. On cooling, the activity data reproduced the values in the normal range but then deviated from the values obtained on heating. They also observed that specimens of the stable phase upon melting and resolidifying always crystallized in the stable crystal structure as long as the melt was not heated to more than 485° to 525°C; otherwise solidification to the metastable phase occurred. However, in a later investigation, these results were not reproduced (13). The resistivity of liquid Cd-Sb alloys has been investigated by Matuyama 5, Oleari and Fioram, 8 and Belaschenko (141, but only above 500°C, the temperature region where Scheil and Baach observed no vapor-pressure anomalies. The data of Matuyama and of Oleari and Fiorani are reproduced in Fig. 5 and show a maximum in resistivity at 50 at. pct Cd. The data of Oleari and Fiorani, however, show the maximum as being rounded, and their values in general are slightly higher than those of Matuyama.

Jan 1, 1964

By L. W. Davies

A problem often encountered is the provision of materials which have impurity contents below a certain specified level. This problem is in some cases solved by making use of the segregation of the impurity with respect to the liquid and solid states of the material: an ingot of the material is subjected to directional solidification and the ends of the ingot. which are richer in solutes which respectively raise and lower the melting point of the solvent, are removed. An important extension of this process is the zone-refining process invented by pfann,' in which molten zones are passed successively along the length of an ingot and displace solutes towards the ends. Pfann's process is particularly appropriate in cases for which the segregation coefficient k does not differ greatly from unity, or when the impurity content must be kept extremely low (-=,6 atom fraction); it is widely used, particularly in the purification of materials for use in semiconductor electronic devices. It is the purpose of this paper to investigate theoretically the efficiency of the above refining processes; that is! we determine the most economic method of attaining a given yield of solvent of specified purity, taking into account the variables of the process. One variable of interest is the effective value of the segregation coefficient. which depends on the rate of movement of the liquid-solid interface and on the degree of stirring in the liquid; in addition to this, in the zone-refining process we are also interested in the choice of zone length for most efficient operation. A mathematical determination is made here of the lengths of successive molten zones which give, for an initially uniform distribution, the most efficient removal of a solute of arbitrary distribution coefficient. In order to be able to give a quantitative treatment of efficiency, we first define figures of merit applicable to a given distribution of solute. FIGURE OF MERIT Let an ingot of length L contain a distribution y(x) of solute: we confine our discussion to mono-tonic distributions, in order to avoid inconsistencies in the subsequent analysis. The first moments of the distribution about the origin and x = L are respectively L F = hy{x)dx [I] G = f(L -x)y(x)dx = YoL2-F, [21 where yoL is the total amount of solute present. We shall see that the quantities F and G are useful figures of merit for a discussion of the efficiency of zone-refining processes. In the first place, it is

Jan 1, 1960

By L. W. Davies

A problem often encountered is the provision of materials which have impurity contents below a certain specified level. This problem is in some cases solved by making use of the segregation of the impurity with respect to the liquid and solid states of the material: an ingot of the material is subjected to directional solidification and the ends of the ingot. which are richer in solutes which respectively raise and lower the melting point of the solvent, are removed. An important extension of this process is the zone-refining process invented by Pfann,' in which molten zones are passed successively along the length of an ingot and displace solutes towards the ends. Pfann's process is particularly appropriate in cases for which the segregation coefficient k does not differ greatly from unity, or when the impurity content must be kept extremely low (=10-6 atom fraction); it is widely used, particularly in the purification of materials for use in semiconductor electronic devices. It is the purpose of this paper to investigate theoretically the efficiency of the above refining processes; that is! we determine the most economic method of attaining a given yield of solvent of specified purity, taking into account the variables of the process. One variable of interest is the effective value of the segregation coefficient. which depends on the rate of movement of the liquid-solid interface and on the degree of stirring in the liquid; in addition to this, in the zone-refining process we are also interested in the choice of zone length for most efficient operation. A mathematical determination is made here of the lengths of successive molten zones which give, for an initially uniform distribution, the most efficient removal of a solute of arbitrary distribution coefficient. In order to be able to give a quantitative treatment of efficiency, we first define figures of merit applicable to a given distribution of solute. FIGURE OF MERIT Let an ingot of length L contain a distribution y(x) of solute: we confine our discussion to mono-tonic distributions, in order to avoid inconsistencies in the subsequent analysis. The first moments of the distribution about the origin and x = L are respectively L F = hy{x)dx [I] G = f(L -x)y(x)dx = YoL2-F, [21 where yoL is the total amount of solute present. We shall see that the quantities F and G are useful figures of merit for a discussion of the efficiency of zone-refining processes. In the first place, it is

Jan 1, 1960

By N. J. Grant, D. S. Bloom

THE development of high temperature, high stress alloys had proceeded with such rapidity during the war, and for a short time afterward, that our knowledge of the constitution of the alloys had become seriously inadequate. To interpret correctly alloy behavior it is not only necessary to recognize the phases present, but also to know the properties of the phases under all varieties of conditions and treatments. Chromium in these high temperature alloys holds the unique distinction of being the only one element which must be present when an oxidizing or generally corrosive atmosphere is present and when a long life is desired in service. Carbon and nitrogen must also be considered where chromium is present. Carbon is always present, either as an impurity in the raw alloying elements, or as a deliberate addition agent to increase the strength. Nitrogen is generally picked up from the atmosphere during melting or may be added as an alloying element. The effect of nitrogen additions is not too dissimilar to that of carbon additions. As such, chromium carbides and nitrides become of great interest since they are present in a very large number of alloys, including alloy steels, stainless steels, super alloys, and the like. In the chromium-carbon system there are three accepted, carbides: Cr,C, Cr7C8, and Cr3C2. The existence of one more carbide, a still higher carbon form CrC, has been advanced. The phase diagrams of chromium and carbon as published by Friemann and Sauerwald² and by Tofaute, Kuttner and But- tinghaus³ -do not extend beyond the carbide Cr3C2, which contains 13.3 pct carbon; but Hatsuta has extended the diagram up to 20 pct carbon, and in doing so hypothesized, with the use of some questionable experimental results, the compound CrC. This carbide would contain 18.75 pct carbon, 81.25 pct chromium, by weight. It is further known that as the chromium carbides increase in carbon the acid resistance increases but the oxidation resistance decreases4,5 This is of great importance in high temperature alloys where time-temperature stability, as well as oxidation resistance, is of prime importance. The possible existence of a carbide of the formula CrC thus becomes of prime importance and it was considered important to recheck the chromium-carbon binary constitutional diagram for such a compound. In view of the wide spread of values listed for the melting point of chromium (1500° to 1850°C) and 1930°C8, it was considered .that the liquidus temperatures might well be redetermined more ac-

Jan 1, 1951

Diffusion in Solid Metals. BY ROBERT F MEHL (Institute of Metals Division Lecture Tech Pub 726 in Metals Tech, Aug , also Trans, vol 122 22,500 words ) Diffusion in solid metals constitutes one of the important fundamental phenomena in metallurgical behavior Apart from its obvious importance in processes such as chromizing, carburizing, nitriding and calorizing, it plays an important part in the processes of homogenization, age-hardening, and transformations in steel, its scientific importance is no less great Diffusion may occur within a grain, along a grain boundary, or upon a surface, though the exact and even the relative values of these separate processes are known for only a very few cases The requirement of solid solution formation presents the possibility of identifying solid solution phases by a study of diffusion layers Some distortion accompanies diffusion, leading to little¬ understood grain-size changes Distortion assists diffusion though usually it dis¬appears before diffusion has become extensive In a binary system the rate of diffusion is the more rapid in the lower melting metal Many of the published data are too qualitative to permit sound scientific conclusions Age-hardening data may be treated as diffusion data and rates of reaction in steel could profitably be studied from this point of view Studies on diffusion are of great importance to the develop-

Jan 1, 1937