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By P. B. Baxendell

The performance of a water-drive reservoir having a gas cap depends primarily on the movement of the gar-oil and oil-water contacts. The movement of the contacts during production depends in turn on fluid withdrawals and how the reservoir pressure changes as fluids are produced from the reservoir; that is, on how effectively the aquifer maintains pressure by replacing withdrawals. inasmuch as pressure changes, fluid withdrawals, contact positions, and produced gas-oil and oil-water ratios are interdependent, the analysis and prediction of the performance of a reservoir produced in a given way must take into account this interdependence throughout depletion. This paper presents an analysis which, within the limitations of the assumptions made, yields an engineering approach to predicting future performance based on reservoir pressure and production history. The most significant assumption is the method of extrapolation of future gas-oil and water-oil ratios. The extrapolation procedure smoothly increases both ratios to preselected values as the remaining oil column undergoes a specified decrease in thickness. This preselection is made on the busis of previous field experience in depletion of similar reservoirs under similar conditions. For computing future performance a vdumebic balance L combined with the differential equation defining pressure distribution in the aquifer to obtain positions of water-oil and gas-oil contacts. From these positions are extrapolated produced water-oil and gas-oil ratios. Reservoir performance can be investigated when oil production rates are dependent upon various factors including the performance of the reservoir itself. Examples of practical application of the procedure are included. INTRODUCTION To predict performance of water-drive reservoirs with gas caps and thin oil columns, it is necessary to describe the motions of the fluids within the reservoir during the entire production period to depletion. These motions depend on the pressure changes and on the withdrawal of oil, gas and water. Production of oil from the oil zone primarily causes water to move in to take its place; production of gas from the cap tends to cause oil to migrate into its place. In addition, the volumes of oil and gas remaining in the reservoir depend on changes in the pressure, since a decrease in pressure causes fluid expansion, gas liberation and oil shrinkage. A method of relating the future pressure to total withdrawals is used to describe the motions of fluids within the reservoir under conditions arising in possible modes of production. The analysis is based on two relationships and will reduce the problem to one amenable to digital computation. The first of these concerns the dependence of the pressure distribution in the entire aquifer furnishing the water drive upon the total reservoir withdrawals. This dependence is dictated by the permeability distribution and the extent of the aquifer; at present, such information is most readily obtained from the performance history by means of the resistancecapacitance reservoir analyzer. The second relation involves withdrawals, pressure in the reservoir, and movement of oil, gas, and water within the reservoir. The analysis is subject to certain simplifying assumptions that are necessary to permit solution of the problem. A comparison of the methods of this paper with those presently practiced is pertinent. One method of analysis is to use the reservoir analyzer to predict reservoir behavior based on aquifer characteristics determined from production history. Inasmuch as the total withdrawal rate depends upon the gas-oil and water-oil ratios, which depend in turn upon, among other things, the positions of the gas-oil and water-oil contacts, these ratios must be assumed in advance. In this paper these ratios are, instead, related to the computed positions of gas-oil and water-oil contacts. Thus, our method can be applied to problems in which the oil production rate is limited by produced gas-oil ratio, or to problems in which it is desired to determine the variable gas injection rate that will maintain the gas-oil or water-oil contact stationary. These problems cannot be worked satisfactorily on the analyzer. Another method presently used is based on a paper by Hurst.' Since his procedure is dependent upon using the solution of the heat flow equation, which requires constant permeability within the aquifer, and our procedure recognizes variations of permeability in

By R. C. Padfield

Experience over a 3-year period in Bethlehem Steel Corporation's plants has demonstrated the reliability of open-hearth roofs of bonded sprung-arch constructzon with burned basic brick. The design principles lor constructing these roofs include a minimum hot-strength requirement for the basic brick, expansion allowances that extend the full roof thickness, structural members to control arch contour, and a specified minimum roof rise. The greater stability of bonded roofs is explained in terms of the basic stress patterns of ring constrution and bonded construction. PRIOR to the development of successful sprung-arch roofs of basic brick, the majority of open-hearth furnaces in the United States were operated with sprung-arch roofs built of silica brick. Although many silica roofs used on open-hearth furnaces were ring-arch construction, Bethlehem Steel Corp. used bonded-arch construction because of its greater stability. In ring construction, each ring of brick is separately keyed and comprises an independent arch with the straight joints between rings traverse to the longitudinal axis of the furnace. In bonded construction, the bricks are laid in rows starting from the skewbacks so that the straight joints run parallel to the longitudinal axis of the furnace. Each brick in a given row is laid so that it spans the joint between two bricks in the row beneath it. Thus, the transverse joints across the arch are broken and the arch rings are thereby interlocked or bonded. When basic roofs were first being developed, the basic brick that were available had low hot strength. Such brick could not be safely used in sprung-arch construction without some means of suspending them. With the development of higher firing techniques by brick manufacturers and the recently introduced direct bonded bricks with high hot strength, the use of burned basic brick in sprung-arch roofs became feasible. The availability of high hot strength basic brick coupled with the potentially lower cost and proven stability of bonded construction prompted Bethlehem's Research Department to study the possibility of using basic brick in bonded roofs. With the full cooperation of plant ceramic engineers and open-hearth superintendents, particularly in 3 years of fur-nace trials, we developed the design criteria for bonded roofs and the corresponding property requirements for the basic brick that are discussed in this paper. DESIGN PRINCIPLES OF SPRUNG-ARCH BRICK ROOFS Stresses in Fixed Arches. A sprung-arch open-hearth furnace roof is generally built on rigidly held skewbacks. The constraint of the fixed support at each end adds a bending moment to the horizontal and vertical reactions at the ends of the arch. Fig. 11 shows the positive direction of forces acting on an arch fixed at both ends. Fixed arches can be analyzed when the members are continuous and have elastic properties. However, brick are inelastic, and arches built with individual brick segments cannot carry tensile stresses. Therefore, for practical solution of brick arches, empirical formulas have been derived from elastic theory that place design restrictions on arch dimensions to avoid development of tensile stresses. McDowell2 cites three main conditions for stability in sprung brick arches: 1) the thrust line of the arch should be maintained in the middle third of the thickness to avoid tensile stresses and resulting open joints in inner and outer curves of the arch; 2) the angle between the line of thrust at any joint and a line perpendicular to the joint must not exceed the angle of repose between brick; and 3) the maximum pressure at any point must not exceed the strength of the arch materials at furnace operating temperatures. The first and third conditions are particularly important in designing sprung-arch basic roofs because of the comparatively low hot strength of basic brick. According to McDowell's equation, if the thrust line is maintained within the middle third of the arch thickness, the unit pressure is obtained as follows: where p = unit pressure in psi, F, = resultant thrust normal to skewback in pounds per foot, t = arch thickness in inches, and z = distance in inches of thrust line from arch axis. When the resultant thrust normal to the skewback acts along the arch axis, z equals zero and unit pressure is simply the thrust divided by the cross-sectional area. If the thrust line moves to the limits of the middle third of the arch thickness, beyond which tensile forces would develop, z then equals one-sixth of the arch thickness and the unit pressure is double that when the thrust line is acting

Jan 1, 1968

By P. E. Rider, K. A. Gschneidner, O. D. McMasters

The solid solubilities for thirteen rare-earth metals in gold were determined by using the X-ray parametric method. Solubilities ranged from 0.1 at. pct for lanthanum in gold up to 8.8 at. pct for scandium in gold. The solubilities from lanthanum to gadolinium were very small and essentially constant, but a sharp increase occurred from gadolinium to scandium. The large solubilities for the heavy rare-earth metals were not expected because of the large size and electrochemical differences between rare-earth atoms and the gold atom. Contributions from first- and second-order elasticity theory plus an electronic contribution were found to reasonably account for a more favorable size factor. Electron transfer from the rare-earth metal to the gold Is thought to occur such that the resultant rare-earth and gold electronegativities are favorable for solid-solution formation. It was also found that this mutual adjustment of size and electronegutivity does not occur if the pure-metal size factors are greater than a critical value of 25 pet. The eutectic temperatures for ten systems were determined and these remained fairly constant at approximately 809 "C for the lighter lanthanide metal-gold systems until the Er-Au system was reached, at which Point the eutectic temperature successively increased reaching a maximum of 1040°C in the Sc-Au system. This rise was correlated to the size factor becoming more favorable for solid-solution formation at erbium. The valence state of ytterbium was found to change from two in the pure metal to three when ytterbium is dissolved in the gold matrix. RECENT results1 reported concerning the solubility of holmium in copper, silver, and gold, showed that the solubility of holmium in gold was quite large, 4.0 at. pct, compared with 1.6 in silver and 0.02 in copper. The small solubilities of holmium in silver and copper are quite reasonable in view of the large size difference (22.2 and 38.2 pct, respectively), large electronegativity difference (0.59 for both systems), and possible unfavorable valency factor (assuming one for silver and copper and three for holmium). The large solubility in gold, however, is unexpected because these same factors are also unfavorable for holmium and gold (22.5 pct size difference and 0.69 electronegativity difference), and because the light rare-earth metals, lanthanum, cerium, and praseodymium, have negligible solid solubilities in gold.2 In view of this unexpected behavior, it was felt that a study of the solid solubilities of most of the rare-earth metals in gold would be desirable to better understand the factors involved in the formation of solid solutions. Of the rare-earth metals added to gold in this study, only ytterbium is divalent in the pure metallic state (the other rare-earth metals are all trivalent) and many of its physical properties (such as the metallic radius, electronegativity, and so forth) are much different from those of the normal trivalent rare-earth metals.' The properties of ytterbium are such that one would expect solid-solution formation to be less favorable for ytterbium in gold than for any of the normal trivalent rare-earth metals. But chemically ytterbium is known to possess a stable trivalent state, and it is quite possible that ytterbium may alloy as a trivalent metal under certain conditions rather than as a divalent metal. Because of the dual valency nature and because so little is known about the alloying behavior of ytterbium, the gold-rich ytterbium-gold alloys are of special interest. EXPERIMENTAL PROCEDURE Materials. The gold used in this investigation had a purity of 99.99 pct with respect to nongaseous impurities. In general the rare-earth metals were prepared by reduction of the corresponding fluoride by calcium metal.3 The impurity contents of the metals used in this study are given in Table I. Preparation of Alloys. Two- or 3-g alloy samples were prepared by arc melting. The samples, with the exception of some of the Er-Au alloys, had weight losses of 0.5 pct or less. All alloy concentrations noted in this paper are nominal compositions. After arc melting, the alloys were wrapped in tantalum foil, sealed off in quartz tubing under a partial atmosphere of argon, homogenized for approximately 200 hr at 780°C, and then quenched in cold water. X-Ray Methods. The X-ray parametric method was used in determining the solubility of the rare-earth metals in gold. filings were sealed in small tantalum tubes by welding under a helium atmosphere. The tantalum tubes were then sealed in quartz tubing under a partial argon atmosphere, and annealed for times ranging from 1/2 to 3 hr (the length of time was inversely proportional to the an-

Jan 1, 1965

By F. F. Craig

Many full-scale waterflooding operations are preceded by pilot floods, one purpose of which is to provide an estimate of recoverable oil. A laboratory model study was made to determine the influence of the producing wells' effective productivity on the oil recovery efficiency of single five-spot pilots, as well as single injection well pilot floods. The effective productivity is indicated by the value of Condition Ratio, defined as the actual well productivity to that of on undamaged and non-stimulated, normal-sized well in the same formation. The effects of initial gas satrcration and mubility ratio on recovery eficiency were also investigated in this model study. Model test results skowed that at favorable mobiliry ratios, a five-spot pilot flood can provide a direct quantitative estimate of the recoverable oil in the pilot area. If the pilot producer's Candition Ratio is 2.2 or more, upwards of 90 per cent of the recoverable oil in the pilot area is recovered from the inside producer, regqrdless of the mobility ratio or initial gas saturation. This Condition Ratio can be achieved with preyent fracturing techniques. Model studies also showed that over the range of imposed injection pressure differences and regional pressure gradients normally encountered in field operations, there was no effect on the recovery efficiency of a five-spot pilot waterflood. Model studies of single injection well pilot waterfloods showed that with no initial gas saturation, the total oil recovery at the offset producing wells can indicate the oil recovery possible by full-scale waterflooding. It is essential that the Condition Ratios of the offset wells be above 1.4. If an initial gas saturation exists prior to water injection, the recoverable oil cannot be directly evaluated by a single injection well pilot flood. However, the production per formance of such a flood can be used to provide information on volumetric sweep efficiency. INTRODUCTION Oil reservoirs are conlplex structures and cannot always be fully studied in the laboratory. Therefore, many operators consider it prudent to evaluate a waterflood prospect by means of a pilot flood. Pilot waterfloods generally involve one of two well arrangements: a single five-spot pilot waterflood, involving four injectors and an internal pilot producing well; and a single injection well pilot flood (sometimes called an inverted five-spot pilot) having one injector and four sur- rounding pilot producers. Some pilot floods are composed of multiple five-spot pilot patterns. To yield information applicable to field-wide performance, the pilot must be located in a representative portion of the reservoir. Pilot floods generally are conducted for one or more of the following reasons: (1) to determine whether water could be injected at desirably high rates, (2) to determine whether an oil bank or zone of increased oil saturation is formed by water injection, and (3) to estimate the oil recovery by waterflooding. Many of the early pilot water-floods were conducted for only the first two reasons. As soon as a buzz in oil production was obtained in the pilot, water injection was initiated throughout the entire lease or field. A number ot laboratory studies have been directed toward determining conditions under which a pilot flood could yield a quantitative estimate of the oil recovery possible by full-scale pattern flooding. One of the early studies of single five-spot pilot flooding' showed that well damage to the inside pilot producer could reduce the total amount of oil recovered. In a study of the single injection well pilot flood pattern,' the results indicated that if the model boundaries were no closer than a half-well spacing beyond the pilot pattern, the pilot performance in the laboratory is unaffected by these boundaries. In another study,? he effect of initial gas saturation and mobility ratio on the ratio of production to injection rate for various groupings of five-spot patterns was defined by mathematical and analog methods. In a study4 involving both potentiometric and flow model experiments at a mobiliry ratio of unity, four different pilot patterns were studied. These included a single five-spot, a single injection well pilot, a cluster of four single injection well pilots and six inverted five-spots. In this study the ratio of well diameter to the distance between injection and producing wells was held constant at 1:1000. The effect of the 7 ratio-—the ratio of the pressure drawdown at the producing wells to the pressure build-up at the injection wells on the pilot performance-was studied. The values of 7 ratio ranged from 0 to 0.34. Results showed that both the total oil recovery and the total fluid production from the pilot relative to the cumulative injection increased with increasing values of the 7 ratio. The effect of both the ratio of injection to producing rates and mobility ratio on the oil recovery performance of a liquid-saturated single five-spot pilot flood was studied in a series of flow model tests.5 Rate ratios ranged from one to four, and mobility rates ranged from 0.1 to 10. Resulls of these tests showed that at low rate ratios, the pilot producers may recover up to four times the recover-

Jan 1, 1966

Jan 1, 1940

Jan 1, 1940

Jan 1, 1881

Jan 1, 1914

By P. H. Delano, Will H. Coghill, G. D. Coe

Data concerning the actual net energy required for pulverizing coal are lacking from the literature on coal pulverization. Power data given in the literature concern gross power and frequently include the power expended on the air blast or product-conveyor system, as well as power lost through friction in the pulverizer itself. Consequently, such data supply no information regarding the net energy consumed in pulverizing or the relative grinding resistance of various coals. In the study of coal pulverizing much work has been done on what is known as " grindability-index numbers," but grind-ability tests have seldom considered the energy input (that is, the "cause" part of the system "cause and effect"). There are many records of the effect, but even these have questionable value because the "grindability" tests did not make a pull'erized product by a method comparabLe with- commercial pulverizers. In many of the tests, only a selected part of the coal was ground, and the remainder continued to be an unknown factor. Furthermore, none of the grindability tests provide the balanced circulating load common to all modern commercial pulverizing. In order to obtain better understanding of the fundamental principles of coal pulvcrizing, the Bureau of Mines is investigating the "cause" phase; that is, the net energy input or net power excluding friction between the moving parts of the machine. As a first step in the investigation,it was necessary to design and construct a laboratory machine in which no friction-loss corrections are involved, which could grind and finish a minus-¾-inch feed, which could be emptied rapidly and completely, which could operate with a continuous feed and finish in an air separator; and, most essential of all, which would be equipped with a measuring device for recording only that portion of the total power consumed in actual pulverizing, hereafter referred to as "net energy input" or "net horsepower-hours." The channel-roller pulverizer hereinafter described is believed to meet these requirements. History oF the Machine The, work started when Ralph W. smith, engineer, St. Genevieve Lime Co., St. Cenevieve, Mo., was appointed one of the consultants of the Bureau of Mines, United States Department of the Interior, in cooperation with the University of Alabama, to develop a machine for testing the abrasiveness of coal. Smith had already developed a machine for testing the abrasive-ness of dentifrices,1 and it was thought the same principles might be applied to coal, Smith's machine had a revolving disk with an annular channel in which the sample was placed. Riding in the channel was a small block or runner of selected soft metal held

Jan 1, 1942

By Marie L. V. Gayler

Without diffusion taking place in liquid metals and alloys, no castings could be made; it is therefore the most important factor affecting the structure of metals. Diffusion involves the interchange of atoms, a process which takes place during the life history of an ingot. In the liquid, atoms are in a state of high thermal agitation, but this thermal vibration is reduced in amplitude with falling temperature. When solidification sets in, the atoms arrange themselves on an ordered space lattice and the changes in structure which take place in the solid are due to the interchange of atoms on this space lattice. The rate of atomic interchange—e.g., of diffusion—is most rapid at temperatures close to the melting point and decelerates as the temperature is lowered. At room temperature, the rate of diffusion is practically negligible in most alloys, and any change in structure can only be brought about by using methods which will accelerate the rate of diffusion. The rate of diffusion depends on three factors (I) temperature; (2) concentration gradient and (3) activation energy. The growth of grains and particles in the solid alloy also depend on these factors and are therefore intimately associated with diffusion. The rate of homogenization in a cast alloy depends on several factors, such as: (I) rate of solidification, which involves grain and particle size which, in their turn, depend on diffusion: (2) the nature of the constituents; (3) the temperature interval between the melting point of the metal or alloy and the temperature at which it is being heat-treated. It is well known that coarse, cast structures are extremely difficult—if possible— to homogenize, and the finer the grain size and particle size, the more readily solid solution will take place. The rate of diffusion depends, also, largely on the nature of the constituents; for instance, copper and magnesium form solid solutions with aluminum quite readily but nickel and iron do not; neither do certain intermetallic compounds, such as alpha and beta FeSi. Furthermore, the actual formation of intermetallic compounds may be a very slow process, particularly when they are formed in the solid state as equilibrium products. For example, BFeSi is formed in the solid as the result of the reaction aFeSi + A1 —+ PFeSi. The particles of aFeSi become surrounded with a reaction ring of PFeSi. This layer is formed as the result of diffusion of atoms taking place between the aluminum matrix and aFeSi. As the amount of aFeSi surrounding the core of aFeSi increases the concentration gradient becomes low and so the rate of diffusion of atoms also decreases until it practically ceases. This occurs after a comparatively thin layer of ßFeSi has been formed. It follows that when intermetallic compounds of this type are formed in the solid, as the result of diffusion, it is generally impossible ever to attain equilibrium, since the forma-

Jan 1, 1944

By Will H. Coghill, P. H. Delano, G. D. Coe

Data concerning the actual net energy required for pulverizing coal are lacking from the literature on coal pulverization. Power data given in the literature concern gross power and frequently include the power expended on the air blast or product-conveyor system, as well as power lost through friction in the pulverizer itself. Consequently, such data supply no information regarding the net energy consumed in pulverizing or the relative grinding resistance of various coals. In the study of coal pulverizing much work has been done on what is known as " grindability-index numbers," but grind-ability tests have seldom considered the energy input (that is, the "cause" part of the system "cause and effect"). There are many records of the effect, but even these have questionable value because the "grindability" tests did not make a pull'erized product by a method comparabLe with- commercial pulverizers. In many of the tests, only a selected part of the coal was ground, and the remainder continued to be an unknown factor. Furthermore, none of the grindability tests provide the balanced circulating load common to all modern commercial pulverizing. In order to obtain better understanding of the fundamental principles of coal pulvcrizing, the Bureau of Mines is investigating the "cause" phase; that is, the net energy input or net power excluding friction between the moving parts of the machine. As a first step in the investigation,it was necessary to design and construct a laboratory machine in which no friction-loss corrections are involved, which could grind and finish a minus-¾-inch feed, which could be emptied rapidly and completely, which could operate with a continuous feed and finish in an air separator; and, most essential of all, which would be equipped with a measuring device for recording only that portion of the total power consumed in actual pulverizing, hereafter referred to as "net energy input" or "net horsepower-hours." The channel-roller pulverizer hereinafter described is believed to meet these requirements. History oF the Machine The, work started when Ralph W. smith, engineer, St. Genevieve Lime Co., St. Cenevieve, Mo., was appointed one of the consultants of the Bureau of Mines, United States Department of the Interior, in cooperation with the University of Alabama, to develop a machine for testing the abrasiveness of coal. Smith had already developed a machine for testing the abrasive-ness of dentifrices,1 and it was thought the same principles might be applied to coal, Smith's machine had a revolving disk with an annular channel in which the sample was placed. Riding in the channel was a small block or runner of selected soft metal held

Jan 1, 1942

By Alexander Squire

A brief study of the effects of material and processing variations upon the tensile properties of steel formed from mixtures of iron and carbon was made in order to provide information regarding the properties obtainable in iron-carbon compacts as influenced by forming pressure, sintering temperature, and graphite particle size. Sintered steels formed from mixtures of iron and graphite have been studied by Stern,' who investigated the effect of various percentages of graphite on compacts formed from electrolytic iron that were repressed and heat-treated after sintering. A further study, by Stern and Greenberg,l is concerned with the heat-treatment of steels formed by the car-burization of iron compacts, and Margolies3 has reported work on the simultaneous sintering and carburization of iron-powder parts. Glauch4 investigated the effect of various types of graphite on the properties of iron-carbon powder alloys but did not determine the effect of different particle sizes of the same graphite alloyed with different types of powder. In the investigation reported in this paper, powders typical of those produced by electrolytic deposition and the decar-burization of shotted steel scrap were used. The powders were mixed by tumbling in a jar mill with graphite powder ground to an average particle diameter of 2, 4, 6, and 16 microns (as determined by microscopic measurement). The properties of the iron and graphite powders are presented in tabular form as Table I. In order to obtain the maximum information from a minimum number of test specimens, the study was divided into two sections with one set of specimens treated identically in each section as a basis for comparison. In the first section, iron powder produced by the shotting and subsequent decarburization of scrap steel was mixed with 2-micron graphite powder, pressed at 50,000, 100,-000, and 200,000 psi, and sintered in hydrogen at 1200°C for the periods of time ranging from 15 to 120 minutes. In the second section of the investigation, electrolytic iron powder was mixed with graphite of an average particle diameter of 2, 4, 6, and 16 microns, pressed at 100,000 psi, and sintered at temperatures ranging from 1000° to r200°C'. for periods of time of 30 to 180 minutes. By following this procedure an indication of the effect of the following variables upon the density and tensile properties of iron-carbon powder compacts was obtained: (I) forming pressure, (2) sintering time, (3) particle size of graphite powder, (4) sintering temperature, (4) type of iron powder.

Jan 1, 1947

By Wilbur H. Grant

THE property of the United Comstock Mines Co. lies in the eastern foot-hills of the Sierra Nevada Mountains, in the Washoe mining district of Storey County, Nev. Commencing at the boundary line between Virginia City and Gold Hill, covering all the town of Gold Hill, it extends south to American Flat; the main camp, or the new town of Comstock, the mills, shops, residences of employees, and the main haulage-tunnel portal are located on American Flat. The property extends for about 10,300 ft. along the lode; this covers the southern end of the main Comstock lode, the Knickerbocker branch, and the junction of the Silver City branch with the Comstock lode. Within the property, 5000 ft. of the main Comstock lode is known to have been productive, 1000 ft. of the lode at the northern end of the property is thoroughly developed, and 1000 ft. south of this is partly developed; this leaves about 3000 ft. of the known productive portion that has not been opened up by this company. The northern end of the property, or the Imperial mine, has been intricately developed by five main levels and numerous sublevels. The Yellow Jacket ground to the south has been partly developed by the reopening of three old levels. In addition, the main haulage level is driven from the portal at Comstock for 9250 ft., to the north end of the property; about 5500 ft. of this `is in the foot wall of the lode and parallel to it.

Jan 11, 1922

By W. A. Wood, W. H. Reimann, K. R. Sargant

A study is made of the microstructural changes produced in armco and pure iron subjected to alternating torsion at amplitudes above and below the knee of the S/N curve. The aim was to identify the basic mechanisms of fatigue and to find why they should give rise to a sharp S/N knee in contrast to the type of S/N curve shown by fcc metals. It is found that the basic structural change above the knee in the iron is a pronounced cell formation in the grains, which determines irregular micro-cracks, and below the knee a dispersion of fine slip that determines a dispersed pore formation in the grains. Comparison of these changes with those in fcc metals similarly tested shows that they do not include an intermediate structural change, a concentrating of slip in narrow bands with associated slip-band cracking, that characterizes the fcc metals and accounts for their different type of S/N curve. RECENT conferences on basic mechanisms of fatigue emphasize that fatigue damage takes many forms: for example, cracking in slip bands (Thompson1), at grain boundaries and inclusions (Hempel'), at precipitation zones in alloys (Han-stock, Forsythe), or at surface notch-peak effects, both hypothetical (Mott, cottrel16) and observed (Wood). Evidently it is not easy to see in this diversity a basic mechanism. At the same time the contributions suggest that some reconciliation may be possible if distinctions are drawn between three phases of the fatigue process: initiation of damage at nuclei, distribution of these nuclei, and the final macroscopic crack system. In initiation, the relevant features appear to be that nuclei may appear early, at least by 1/100th to 1/1000th of the life of a test specimen; that they may do so at many independent centers, appearing according to some observationsa as pores or voids; and that they are not necessarily self-propagating, damage spreading rather by their multiplication. In distribution, the relevant feature appears to be that they form preferentially in zones where the microstructure becomes abnormally strained (as defined more closely below). Now in these two phases the basic fatigue process should be systematic. But, at the same time, the "abnormal strains" in particular set the stage for considerable diversity in the final phase of macroscopic cracking, for where zones of abnormal strain develop will depend on what kind of fatigue deformation is applied and what kind of prior processing the test material has had. On this view it seems desirable to know what in

Jan 1, 1964

By D. A. Stevenson, T. Alden, J. Wulff

A portion of the liquidus curve has been determined for the binary alloy systems Ni-Pb and Cr-Pb. The solubility of nickel is 0.53 atomic pet at 372° and 18.63 atomic pet at 1200°C. Chromium shows low solubility, 0.634 atomic pet at 1210°C. Molybdenum and tungsten were also studied and found insoluble in lead, less than 0.005 atomic pet at 1200°C. INCREASED use of liquid metals of low melting X point for heat transfer, coating, joining, and other purposes has renewed interest in the solubility of structural metals in these liquids. A study of Hansen1 and current literature indicates that few liquidus curves at the low melting end of the binary diagrams have been accurately delineated. This statement applies particularly to the binaries of lead. The present paper is limited to nickel, chromium, tungsten, and molybdenum in lead. In early studies2, 3 of the lead end of the Pb-Ni system, a monotectic at 1340°C was established. Tammann and Oelsen' determined the solid solubility of nickel in lead at 20°C to be 0.023 wt pet. Recently Pelzel5 determined the liquidus curve from the eutectic temperature of 327° up to 727°C using a segregation method. In the present paper this part of the curve has been checked and extended to 1244°C. The Pb-Cr system was first studied by Hindrichs.6 He pointed out the existence of a monotectic at 1470°C and indicated a tentative liquidus. Recent corrosion studies of Fe-Cr alloys in lead suggest that chromium is more soluble than iron in lead.7-8 The solubility of tungsten in lead according to Inouye8 is about 30 wt pet at 1200°C. Appreciable solubility of molybdenum in lead might therefore be expected. Experimental Various experimental techniques have been employed in the determination of solubility in liquid metals. For low solubility, thermal analysis is unsatisfactory. A segregation method was used by Pelzel3 in his study of the Pb-Ni system. In this procedure separation of liquid and solid is possible due to difference in density. In the technique of Kleppa10 a single piece of material is maintained in contact with the liquid metal in evacuated Vycor vials. After equilibration, solid and liquid are separated by tilting. Keck and Broder" measured the weight of a piece of the solid solute before and after immersion in a pure solvent bath; the weight loss was a measure of the solubility. All of the above procedures are time-consuming since they permit only one determination per run. Numerous samples for analysis may be taken from the melt in the method described by Gurinsky and CO-workers.10 The rate of extraction of samples is limited only by the time required for equilibration. In the present work, a modification of this method was employed. A 150-g charge of analytical reagent grade lead and the added metal* were contained in an Alun- dum crucible. It rested on firiely divided silica at the closed end of a 45 mm Vycor tube, 500 mm long. The top of the tube was provided with an inlet and

Jan 1, 1959

By T. A. Wright

The sampling of waste materials containing copper, lead and tin has taken on a new significance within recent years, and is of increasing importance, on account of the entry of some of the copper refineries into this field and the tendency towards consolidations among the smelters. In the past, such material was sold on the basis either of a rough or grat) sample or of casual inspection of the lot. The two principal sources of this waste are the processes of fabrication and the scrapping of automobile, electrical, plumbing, railroad and other equipment. In both cases rnuch material can bc sorted, salvaged and sold by classification and grade to be melted "as is" or with the addition of new or virgin metal. The increasing care in classifying exercised in the large manufacturing plants tends to incrcase the proportion of this usable scrap; on the contrary, the increasing use of more complex and special non-ferrous alloys tends to makc sorting and grading more difficnlt in turnings, borings, clippings, etc., and conseqllcntly is making sampling of more moment. In tin, lead, alumiinum, and zinc furnace by-products such as ashes, drosses, skimmings, etc., the trade practice of evaluation has not varied much. For instance, tin drosscs, battery lcad, and aluminunl skimmings are ordinarily sold on what is called "metallic button" or "metallic recovery" or "metallic yield." Coppcr and Icad wastcl, howcvcr, is being sold more and more on actual copper and lead contents bascd on sarrlple and chemical analysts. This paper will be dcvotctl chiefly to the sampling of niaterials suitablc only for refining and recovery of one or more of the metals present. The methods described are often bascd on thc fact that but one, metal, such as copper, is to be paid for. The loss of volatile constituents in melting does not appreciably affect thc final copper result, as the "after-melting" assay can be readily calculated to the "bcfore-nltltingl' basis, but if smelter efficiency continues to increase, so that in tiltie zinc, for instance, may be rccovrred on a paying basis, thc method of sampling dirty brass, for example, will have to bc changed also. As a matter of fact, we may cxpect that improved refining proresses will make possible the partial reeovrry of lcad and tin which are now lost

By Heinrich Freyn

THE American iron and steel manufacturer finds himself to-clay barely at the threshold of enormous possibilities for practicing rational economy in the use of fuels. The fuel cost is by no means the smallest of items which enter into the cost of manufacture of iron and steel products, but the great wealth of this country in high-grade fuels, together with a protective tariff, has heretofore made fuel economy relatively unimportant. In Germany, the use of raw coal for the purposes of iron and steel manufacture has been all but abandoned and large sums of money, formerly irrevocably wasted, are now being saved. When scanning the literature of this country devoted to the application of gas power, but little information will be found on a subject which, however, is destined to become of considerable importance in the United States, namely, the use of coke-oven gas for the generation of power in gas engines. This lack of information can be traced to the fact that the regenerative by-product coke oven with its large amount of surplus gas is still far from having attained in this country the universal application which it has found in Europe. This statement needs hardy any corroboration other than the evidence of statistical investigations made by E. W. Parker of the United States Geological Survey, according to which only approximately 25 per cent. of the total coke produced in this country in 1912 was made in by-product coke ovens, whereas 75 per cent. was produced in bee-hive ovens. This entailed the enormous loss of over $80,000,000 in non-recovered by-products, such as gas, tar, and ammonia, without considering the substantial loss due to the non-recovery of benzol from the coal. There are two more or less distinct fields of application of the by-product coke oven: one, to furnish as the main product metallurgical coke of specified quality, and surplus coke-oven gas as the by-product, and the other, to carbonize high-volatile coals, and thus produce as the main product large quantities of gas, high in heat value and rich in illuminants, adapted primarily for domestic heating and lighting, while domestic coke becomes the by-product.

Jan 4, 1914

By Marie L. V. Gayler

Without diffusion taking place in liquid metals and alloys, no castings could be made; it is therefore the most important factor affecting the structure of metals. Diffusion involves the interchange of atoms, a process which takes place during the life history of an ingot. In the liquid, atoms are in a state of high thermal agitation, but this thermal vibration is reduced in amplitude with falling temperature. When solidification sets in, the atoms arrange themselves on an ordered space lattice and the changes in structure which take place in the solid are due to the interchange of atoms on this space lattice. The rate of atomic interchange—e.g., of diffusion—is most rapid at temperatures close to the melting point and decelerates as the temperature is lowered. At room temperature, the rate of diffusion is practically negligible in most alloys, and any change in structure can only be brought about by using methods which will accelerate the rate of diffusion. The rate of diffusion depends on three factors (I) temperature; (2) concentration gradient and (3) activation energy. The growth of grains and particles in the solid alloy also depend on these factors and are therefore intimately associated with diffusion. The rate of homogenization in a cast alloy depends on several factors, such as: (I) rate of solidification, which involves grain and particle size which, in their turn, depend on diffusion: (2) the nature of the constituents; (3) the temperature interval between the melting point of the metal or alloy and the temperature at which it is being heat-treated. It is well known that coarse, cast structures are extremely difficult—if possible— to homogenize, and the finer the grain size and particle size, the more readily solid solution will take place. The rate of diffusion depends, also, largely on the nature of the constituents; for instance, copper and magnesium form solid solutions with aluminum quite readily but nickel and iron do not; neither do certain intermetallic compounds, such as alpha and beta FeSi. Furthermore, the actual formation of intermetallic compounds may be a very slow process, particularly when they are formed in the solid state as equilibrium products. For example, BFeSi is formed in the solid as the result of the reaction aFeSi + A1 —+ PFeSi. The particles of aFeSi become surrounded with a reaction ring of PFeSi. This layer is formed as the result of diffusion of atoms taking place between the aluminum matrix and aFeSi. As the amount of aFeSi surrounding the core of aFeSi increases the concentration gradient becomes low and so the rate of diffusion of atoms also decreases until it practically ceases. This occurs after a comparatively thin layer of ßFeSi has been formed. It follows that when intermetallic compounds of this type are formed in the solid, as the result of diffusion, it is generally impossible ever to attain equilibrium, since the forma-

Jan 1, 1944

By C. Scala, F. Bernstein

General expressions are derived relating the streaming potential to the electrochemical potential of a permeable junction separating two electrolytic solutions. By the methods of irreversible thermodynamics, these potentials are related to the flux of mobile species arising from differences in pressure and chemical composition. The flux is conveniently expressed as a transference number, the equivalents of a mobile species transferred through the junction per faraday of electricity. At constant pressure, the flux equation gives the electrochemical potential across the permeable junction. The streaming potential across the junction is obtained by imposing the condition of constant chemical composition. The familiar expression for the borehole SP is shown to be a particular solution of the general flux equation. The derived exprersions were verified in experiments with seven shale samples. Both the theory and experimental data provide additional proof of the presence and magniturle of the streaming potential in shales. INTRODUCTION In the interpretation of electric logs, there has been much concern over the correction to be made to the recorded SP for an electrokinetic or streaming potential originating from the difference in pressure between the mud column and the formation. It was long recognized by M. R. J. Wyllie that such an electrokinetic potential source mas in the mud cake opposite permeable sands.' More recently, M. Gondouin and C. Scala2 showed an additional but opposing electrokinetic source of potential to be in shale beds. Their work was supported by the very extensive and excellent work of Hill and Anderson.3 n the present contribution, the general relationships between the electrochemical potential and the corresponding streaming or electrokinetic potential are examined and clarified. A notable advance towards understanding the relation between the various sources of electrical potential in a borehole has been the application of the now common methods of irreversible thermodynamics to describe the passage of ions and water through charged electrolyte junctions such as in shales.' The advantages of these methods are twofold. Unlike classical thermodynamics, they can be applied to non-equilibrium sys- tems, i.e., systems in which flow takes place, provided the flow processes have reached a steady state. They also permit conventional thermodynamic properties to be related to the steady-state dynamic properties. These methods arc used here specifically to derive expressions relating the potential behavior of shales in terms of ion and water transport. Experimental verification of the expression for the shale streaming potential is given which in turn offers theoretical support to the existence of a streaming potential in shales.' Importantly, the relative contribution of transport parameters to the SP is clarified. The theoretical treatment is essentially that of Lori-mer, Boterenbrood and Hermans3 ut has been extended to derive the general expression for the SP.

By F. W. Miller

A brief history of byproduct coking in Alabama with short general descriptions of plants and the state's production of beehive and byproduct coke. PRIOR to the Civil War, there were several small charcoal furnaces for smelting the brown limonite ore that is found, in comparatively small bodies, throughout the central and north-central portions of the state. During the Civil War, these furnaces furnished charcoal iron to the Confederate Government. No attention was paid to the large bodies of lime-bearing hematite ore that now supplies the bulk of the ore used in the various blast-furnace plants of this district until the latter part of the 19th century. Red Mountain, which is the southernmost and one of the smaller ranges of the Appalachian Chain, lying immediately south of the Birmingham and Bessemer, is the principal source of this ore. The orebody outcrops on the northern face, extends through the mountain, and underlies Shades Valley on the southern side. When it was found that these ores could be worked satisfactorily in the blast furnaces, there was a comparatively rapid growth in the blast-furnace industry in the Birmingham district. As these ores are far more refractory than the limonite ores, this blast-furnace development was accompanied by the construction of beehive ovens to carbonize the coal, in order to supply the necessary fuel. The state's production of bee-hive coke in 1880 was 60,781 tons; ten years later this had increased to 1,072,942 tons; and, in 1897 the production had reached 1,443,017 tons. In 1898, the first byproduct oven built in the state was put in operation. This plant consisted of 120 horizontal-flue Semet-Solvay ovens, three flues in height by thirty flues in length with an average width of 16 in. The plant was constructed by Semet-Solvay Co., for the Tennessee Coal, Iron & Railroad Co., and was located adjacent to the blast-furnace plant of that company at Ensley. Coal was delivered from the Pratt mines, by gravity tracks, directly into bin's of the ovens after having

Jan 9, 1924