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By D. R. Uhlmann, T. P. Seward, K. A. Jackson, J. D. Hunt

microscopic ohservations on alloys of organic trzaterials show that dendrite arms can melt off under normal conditiorzs of growth. This occurs because of the interactiorz of' heat and matter fluxes during dendritic growth. The re melting occurs where the den-drite arms are joined onto the main deizclrite sterrz. Many detached crystals can be produced in this fashion. It is postulated that this remelting phenornenon occurs in metal alloys, giving rise to the equi-axed region in castings. Experiments peyformed orr castings of transparent materials support remelting as a primary source of detached crystals. Ob~ervations an equiaxed tones in metal castings are discussed in terms of this and other mechanisms. It is concluded that the partial remelting of dendrites is on important mechanisnl for producing the equiaxed regions in castings. THE freezing of a casting can be divided into three regions: a chill zone formed near the mold wall, a columnar region, and a third region, at the center of the casting, which is called the equiaxed zone. The origin of the grains that comprise the equiaxed region is the subject of this paper. We will first outline the mechanisms which have been proposed to account for the origin of the equiaxed region and discuss some recent experiments which cannot be explained by these theories. We will then present some microscopic observations of dendritic growth which have led us to conclude that the equiaxed zone in castings can arise from partial remelting of dendrites. This proposal is supported by observations on transparent castings. Finally, we will discuss several observations on metal castings which could not be explained previously, and which can be accounted for by the present proposal. Previous Mechanisms. Winegard and Chalmers3 pointed out that the molten central region of an ingot could be constitutionally supercooled, because of the solute layer at the growing interface. In this supercooled region, nucleation on particles could occur, giving rise to the equiaxed crystals. Another mechanism has also been suggested,4y5 that the nuclei originate in the chill zone then float or are carried by convection to the center of the casting, where they grow to produce equiaxed crystals. In this case, all the crystals nucleate immediately on casting, so this mechanism will be termed "big-bang" nucleation. Walker's Experiments. J. L. Walker has made observations on the solidification of nickel and Ni-Cu alloys which cannot be accounted for by either of the above mechanisms. In studying the grain size resulting from freezing of nickel at various undercoolings, walker6 found that at large undercoolings the grain size was small, due to mechanical nucleation, as discussed by walker7 and Horvay.' At small undercoolings, the grain size was large, and the growth dendritic. In Ni-Cu alloys, however, for initial undercoolings starting from just below the melting point and extending for a hundred or so degrees of undercooling, fine grains were also observed. Samples were undercooled 200 Centigrade degrees without nucleating, and were then heated 130 Centigrade degrees so that the undercooling was 70 Centigrade degrees, and nucleated. The samples had a small grain size, indicating multiple nucleation. There were no heterogeneous nuclei in the liquid which could operate at the temperature of growth. Constitutional supercooling could not have been greater than the supercooling of the initial melt, since the temperature rose as the freezing continued. walker -as also shown that a Ni-Cu alloy which can be undercooled to below its solidus will produce typical columnar and equiaxed regions when cast into a cold mold. This alloy could not reach a temperature below its solidus by constitutional supercooling. It could not, therefore, have nucleated heterogeneously. Neither the big-bang mechanism nor the Winegard-Chalmers mechanism can account for the fine grain

Jan 1, 1967

By J. M. Boutwell

I. Introduction. THE object of this paper is to present a concise statement on the genesis of the copper- and lead-deposits of the Bingham Mining District, Utah. It is essentially a condensation of a chapter in a detailed report on this district, together with so much on geologic features, and on the character and occurrence of the ores as bears on the problems of ore-deposition. The studies upon which the paper is based were undertaken in 1900 under the direction of S. F. Emmons, Geologist-in-Charge of the Section of Metalliferous Deposits, U. S. Geological Survey; and a little additional data was secured in subsequent years. The evidence then obtained as to the genesis of the replacement copper-ores has led, to conclusions which differ somewhat from explanations hitherto current. Accordingly, it seems desirable briefly to present the facts together with the resulting conclusions in a separate paper.

Nov 1, 1905

By S. Jess Larsen

Modern technology has provided the world with many innovations to improve living standards, ease of job performance, efficiency, and managerial control. While not expected to compete with the computer revolution, Kerr-McGee Coal Corporation has found a way using laser technology to solve one of their haulage problems. Operating successful and profitable surface coal mine facilities in Wyoming's Powder River Basin require economies of scale, flexibility of operation, conscientious cost control, and ever-present innovative effort. Because haulage costs are the major source of expenditure in surface mining, Kerr-McGee recognized early the need for maximum haulage productivity and the economies of scale provided by large haulage trucks. Special conditions that exist in the Powder River Basin coal fields require consideration. The coal thickness (up to 100 feet and more) and varying depths of overburden dictate that a haulage unit with good gradability characteristics be used to avoid undesirable long ramps. Two and often three coal seams are encountered by most mines, which necessitates operating from several coal and parting faces simultaneously. This situation consumes much space, and to minimize the scope of problems, a coal haulage unit with good maneuverability and stability is needed. Finally, the low density of coal (±1500 pounds/loose cubic yard) demands a large volume capacity to utilize truck load carrying capability effectively. These conditions prompted Kerr-McGee to select unitized two-axle bottom dump trucks of the 160-170 ton size for primary coal haulage at its two Gillette-area mines. Use of 170-ton bottom dump trucks at the Clovis Point Mine handles most of the coal haulage, but the truck

Jan 1, 1983

By Arthur Winslow

Location.—The Liberty Bell gold-mine is in the San Juan region, in the southwestern corner of Colorado. It is situated about 2 miles from the town of Telluride, near the summit of the Uncompahgre range, at the head of Cornett basin, at an altitude of 11,000 feet, and in a district of excellent record in the past and of great promise for the future. In the immediate vicinity are such well-known and important mines as the Smuggler Union, with a total production of over $12,000,000; the Virginius and Revenue Tunnel group, with a production of probably $5,000,000; the Tom-Boy, with a production of probably at least $3,000,000; the Japan, the Cimarron, and a number of others. History.—The first prospecting in this district is reported to

Jan 1, 1900

By A. M. Skov, L. F. Elkins

First response to large-scale water flooding in the fractured very low permeability Spraberry sand has led to a new unique cyclic operation. Capacity water injection is used to restore reservoir pressure. This is followed by marly months production without water irzjection and the cycle repeated. Expansion of the oil, rock and water during pressure decline expels part of the fluids but capillary forces hold much of the injected water in the rock. At least with reservoir pressure restored and with partial water flood development, field performance has proved this cyclic operation is capable of producing oil from the nzatrix rock at least 50 per cent faster and with lower water percentage than is imbibition of water at stable reservoir pressure. INTRODUCTION The Spraberry Field of West Texas presents unusual problems for both primary production and water flooding. Extensive interconnected vertical fractures in the fractional-md sandstone permitted recovery of oil on 160-acre well spacing, but they made capillary end effects dominant. Primary recovery by solution gas drive is less than 10 per cent of oil in place. The concept of displacement of oil from the sand matrix by capillary irnbibition of water has led to field techniques which promise greatly increased oil recovery. Free exchange of laboratory research, reservoir information and results of field pilot tests among the various companies has been very important in development of this technology. Five units covering a total of 170,000 acres have been formed for water flooding, and 10 other areas covering an additional 175,500 acres are in various stages of unitization. Part of the Driver Unit reaching fillup first has demonstrated very unusual waterflood behavior and indicated numerous operating problems that will develop within and among the various units. SPRABERRY ROCK AND PRIMARY PERFORMANCE The Spraberry, discovered in February, 1949, is a 1,000-ft section of sandstones, shales and limestones with two main oil productive members: a 10-15 ft sand near the top and a 10-15 ft sand near the base. In part of the field some thinner intermediate sands are oil productive, and others are water bearing. All sands have permeabilities of 1 md or less and porosities of 8-15 per cent. Ordinary core analysis and electric and radiation logs are ineffective in differentiating between oil productive and nonprcductive sands. Sands capable of containing producible oil are best identified by mercury injection capillary pressure measurement and, in some cases, by core water saturation. About 3,500 wells have been drilled in the 500,000-acre trend. Vertical fractures were observed in practically all Spraberry cores. Continuity and interconnection of fractures were confirmed by pressure interference among wells during early development.' Major fractures trend northeast-southwest as indicated by oriented cores and confirmed by five fluid injection tests, by analysis of the pressure transients observed during development,''' and by three interference tests in the Driver Unit Water Flood reported herein. Fracture spac- ing probably averages inches to a few feet. Spraberry wells typically produced 100-400 BOPD initially after hydrauLic fracture treatments. By 1962 oil production had declined to an average of 12 bbl/well/day, near the economic Limits of operation. Reservoir pressure had declined from 2,300 psi initially in the Upper Spraberry and 2,500 psi in the Lower Spraberry to 500-1,000 psi. Partial closing of the fractures with declining reservoir pressure is believed to be the cause of such low oil production rates at these relatively high reservoir pressures. Cumulative recovery of 208 million bbl of oil is 80 to 90 per cent of that recoverable by primary means. Performance of the entire reservoir is summarized in Fig. 1. IMBIBITION WATER FLOODING By 1952 reservoir performance indicated low primary recoveries. Most engineers, expecting serious channeling of injected fluids through the fractures, held little hope for secondary recovery. With its extensive background of research on the fundamentals of fluid flow within reservoir rocks, Atlantic's Research and Development Division on short notice in 1952 conceived that displacement of oil by capillary imbibition of water into the rock might significantly increase Spraberry recovery. Laboratory data reported by Brownscombe and Dyes scaled to probable reservoir conditions showed potential waterflood recovery equal to or greater than primary recovery with a 10-15 year flood life.= A pilot test using three 40-acre injection wells, one central producing well and 18 surrounding observation wells demonstrated technical feasibility of the process. Injection of 1.5 million bbl of water from November 1952 to August 1955 proved water entered the rock and displaced oil

By Homer G. Turner

Coals, other than anthracite, have been so thoroughly studied under the microscope during recent years, that we now know what kinds of plants and what parts of plants form the bulk of lower rank coals from peat to bituminous coal. The microscope has also shown the state of preservation of such vegetation as well as the nature and distribution of products of plant decay. These and further details have been ascertained mainly through the employment of two methods of attack, section cutting and maceration. Anthracite has failed to respond to these methods, so well adapted to the study of lower rank coals and, therefore, has been neglected by investigators to such an extent that there is much doubt as to its microscopical characteristics. The object of this paper is to lift anthracite from its realm of obscurity by demonstrating the wealth of microscopical detail that is revealed when reflected light is used on a properly polished and etched surface and, further, to show the relationship between anthracite and bituminous coal. Technique The method adopted in this investigation is similar to that described in an earlier paper.' Because of slight modifications recently made, the process is again described. It consists, briefly, of etching a polished surface of coal with heat. Although pieces of various sizes and shapes are used, blocks of coal about 2 or 3 cm. square take the most uniform polish and are large enough to be handled with ease. Larger pieces can be used if one has the equipment for polishing them and they rnay be desirable when one wishes to study some particular form that extends for some distance through the coal. Large surfaces, however, require greater care in polishing and etching; for this reason, they are not recommended for ordinary work.

Jan 1, 1925

By L. H. de Wald, J. Walter Scott

The removal of lead by fire refining methods from copper of electrolytic quality is growing in importance. Particularly is this true of the refining of secondary copper and copper cathodes obtained from electrolytic cells where lead is used as the anode material, as in the electrolysis of ore-leaching solutions and foul electrolyte. When investigating the removal of small amounts of lead from molten copper in a reverberatory furnace during the refining of secondary copper of otherwise electrolytic copper quality,' it was found necessary first to know something about the distribution of the lead throughout the bath. The authors believe that it is not generally known how small amounts of lead as an impurity are distributed in a molten copper bath; that is, whether the lead is concentrated at the bottom or at the top, or whether it occurs more or less uniformly throughout the bath. The data contained in this report may help, therefore, in the development of a satisfactory fire refining method for the removal of this obstinate element from a molten copper bath. The first step was the development of a method for taking samples from various locations in the bath, at the surface and at various depths. The sampling device used, shown in Fig. 1, consisted of a 10-gram fireclay assay crucible fitted into a ring on the end of a steel rod handle of suitable length. A fireclay scorifier, 2 in. dia., with a ½-in. hole bored in the

Jan 1, 1930

By I. Fatt

A recently developed system for measuring electrical resistivity of liquids without use of electrodes offers some interesting possibilities in electric logging technology. The equipment as supplied by the manufacturer is satisfactory for continuous mud logging on a drilling rig or for measuring mud or filtrate resistivity in the laboratory. A simple modification of the commercially available instrument makes it suitable for measuring resistivity of core samples in the laboratory. The continuous measurement of mud resistivity on a drilling rig is a convenient means for detecting mixing of formation water with the drilling mud. Such information is useful to the geologist, the mud engineer and the logging engineer. However, continuous mud resistivity logging by conventional electrode-type resistivity cells is beset with difficulties. The mud, sand and rock chips abrade the electrodes, thereby changing the cell constant and eventually destroying the cell. Also, additives and crude oil in the mud may poison the electrodes by coating them with a nonconductive material. An electrode-type resistivity cell. therefore, may give erroneous readings under certain conditions. Electric logging companies circumvent the electrode poisoning problem by using a four-electrode resistivity cell for measurement of mud resistivity. In this cell, change in electrode area does not change the cell constant. However, the four-electrode cell is difficult to adapt for continuous reading and does not solve completely the problem of electrode abrasion by the sand and cuttings in the mud. The measurement of electric logging parameters on core samples in the laboratory encounters some of the same problems discussed in connection with mud logging. Ideally, the electrical resistivity of a core sample should be measured by placing platinum black electrodes in direct contact with the plane ends of a cylindrical or rectangular sample. Platinum black electrodes however, are much too fragile and easily abraded to be brought in contact with a rock sample. Also, oil or other constituents in the fluid contained in the sample will poison platinum black. In practice, gold-plated brass electrodes, in an AC bridge circuit operating at about 1,000 cps, are used for routine core analysis. For more precise work in research studies, a four-electrode scheme is used.',' Preparation of the samples for the four-electrode method is much too involved for routine core analysis. An apparatus for measuring resistivity of liquids without use of electrodes was described by Guthrie and Boys3 in 1879. They suspended a beaker, containing the electrolyte, by a torsion wire and rotated a set of permanent bar magnets around the vessel. The eddy currents induced in the electrolyte reacted against the rotating magnetic field to develop a torque, which was measured as a deflection of the torsion wire. In 1879 this method could not be made precise or convenient because of the lack of strong permanent magnets. The writer described a very greatly improved apparatus similar to that of Guthrie and Boys, but it was not suitable for continuous measurements or core samples.' Many electrodeless resistivity devices using radio frequency current are described in the literature.5, 6 These generally are suitable only for noting the end-point in a chemical titration. They do not measure resistivity, instead measuring a complex quantity which includes the dielectric constant and the magnetic permeability. The first description of the apparatus to be discussed in this paper was given by Relis.7 Improvements and modifications are described by Fielden,s Gupta and Hills,> and Eichholz and Bettens.10 DESCRIPTION OF APPARATUS The apparatus used in this study is based on the principle that the solution under measurement can form a loop coupling two transformer coils, as shown in Fig. 1. For a fixed AC voltage applied across Coil A, the voltage appearing across Coil B is a function of the resistance of the liquid-filled loop. The details of the voltage generating and measuring circuits are given in Refs. 7, 8, 9 and 10. A block diagram of the equipment is given in Fig. 7. Special features worth mentioning are the operating frequency of 18,000 cps and the automatic temperature compensation which results in the given resistivity readings being automatically correlated to 25°C. The liquid loop supplied by the manufacturer, shown in Figs. 1 and 2, was modified for use in core analysis (Fig. 3). The core sample under test is substituted for a section of the original loop. As shown in Fig. 3, the unit accepts only plastic-mounted cylindrical core specimens. A Hassler-type sleeve easily can be designed for the unit if unmounted cores are to be measured. EXPERIMENTAL PROCEDURE MUD LOGGING A simulated mud line was set up in the laboratory.

By E. L. Raymond

The effect of heat treatment on the microstructure and resultant notch-bar rupture life of ZNCONEL alloys X- 750 and 718 was studied. It was found that the primary effect of heat treatment in rendering these alloys notch-ductile is the elimination of any y' denuded zone adjacent to the pain boundaries. The mechanisms by which such a denuded zone can arise and be eliminated by heat treatment are discussed. InCONEL Ni-Cr alloy X-750 and INCONEL Ni-Cr alloy 718 are age-hardenable austenitic materials. Alloy X-750 is used for its corrosion and oxidation resistance and high creep-rupture strength up to 1500°F. Alloy 718 is used most effectively up to 1300°F. One of the most important areas in their development has been establishment of consistently good rupture properties, especially in the presence of a stress concentration, such as imposed by a notch. A desire to improve these properties has led to extensive studies of the effect of heat treatment on the micro structure of these alloys and their performance in stress-rupture tests. In earlier investigations"~ of INCONEL* alloy X-750, *INCONEL i s a Registered Trademark of The International Nickel Co., Inc. grain boundary carbide morphology was linked with stress-rupture properties. If, during heat treatment, the carbide MZSC was precipitated in the grain bound-ary in a cellular form, poor rupture properties re-

Jan 1, 1968

By G. L. Simard, D. J. Salley, J. Chupak

DITHIOPHOSPHATES and xanthates are the principal collectors for sulphide minerals, and consequently any knowledge of mineral-collector systems of this type is of value. In the present investigation an attempt was made to obtain information on the interaction of a typical dithiophosphate with galena. In carrying out this study, radioiso-topes, so much discussed in the past few years,', ' were extensively employed. By using radioactive dithiophosphate synthesized from radioactive phosphorus, a rapid and sensitive analytical procedure G. L. SIMARD is in the Research Division, Stamford Research Labs., American Cyanamid Co., Stamford, Conn.; J. CHUPAK, formerly in the Research Division, Stamford Research Labs., is now at Camp Detrick, Frederick, Md.; and D. J. SALLEY is in the Research Division, Stamford Research Labs. AlME New York Meeting, Feb. 1950. TP 2815 B. Discussion (2 copies) may be sent to Transactions AlME before April 30, 1950. Manuscript received Oct. 17, 1949. was at hand. This permitted determination of such important quantities as the rate of uptake of dithiophosphate by the mineral, the amount existing at equilibrium on the mineral surface and in the solution, and the desorption of the agent from the surface. Such measurements were possible even on single crystals of galena. In addition the exchange of dithiophosphate between the solution and the sorbed phase was examined, a matter which could be accomplished only by the use of isotopes. It is desired to point out at this time that throughout this paper the term "sorption" has been employed to designate the uptake of agent by mineral, without implication as to the nature of the process by which the uptake was accomplished. Experimental Materials: Galena: The galena was from the Tri-State district. For studies on ground mineral four preparations were used during the course of the investigation. These were prepared from selected large crystals by wet grinding in order to reduce surface oxidation. Alcohol was chosen as a convenient medium for this purpose. The ground mineral was then fractionated by sedimentation in alcohol, dried by evacuation, and stored in a nitrogen-filled desiccator. Data on the preparations are tabulated in table I. The size analysis indicated that the areas of the preparations were of comparable magnitude, even though the absolute values may be somewhat incorrect. Dithiophosphates: Nonradioactive dithiophbsphate (di-isopropyl or di-secondary butyl) was obtained by purification of a commercial product. An aqueous acid solution of the agent was extracted with petroleum ether, the ether layer dried, and the dithiophosphate precipitated as ammonium salt with anhydrous ammonia. Several repetitions of this process resulted in a nearly colorless, flaky product of good purity. (General formula (RO,)PSSNH,). Radioactive dithiophosphate was synthesized by heating radioactive elementary red phosphorus* • For early experiments (1943 to 1944), the elementary red phosphorus was obtained from the cyclotron group at the Crocker Radiation Laboratory of the University of California. Berkeley, through the courtesy of Dr. Joseph W. Hamilton. For more recent work (1946 to 1949). the elementary radioactive Phosphorus has been supplied by the Oak Ridge National Labarotories on allocation from the U. S. Atomic Energy Commission. with sulphur at 270" to 300°C to produce radioactive P,S,. The latter was then treated with the desired purified alcohol (isopropyl or secondary butyl) at 60" to 80°C to form the dithiophosphoric acid derivative. Purification was effected in the same manner as for the nonradioactive material. The effectiveness of the purification method was established by the isotopic dilution method." The same technique was used to show that only negligible decomposition of neutral or of carbonate solutions of the dithiophosphate took place over a period of a day; this was true whether or not galena was suspended in the solutions. Procedures: Radioactivity: The activity of a solution was obtained by counting with a small glass-jacketed, silvered Geiger counter, using a conventional scaling circuit.' Crystals and other solids were counted under a bell-shaped, mica-window counter tube. Sufficient counts were made so that the probable error of counting was of the order of +I-3 pct. The specific activity in terms of counts per minute

Jan 1, 1951

By J. Chupak, D. J. Salley, G. L. Simard

DITHIOPHOSPHATES and xanthates are the principal collectors for sulphide minerals, and consequently any knowledge of mineral-collector systems of this type is of value. In the present investigation an attempt was made to obtain information on the interaction of a typical dithiophosphate with galena. In carrying out this study, radioiso-topes, so much discussed in the past few years,', ' were extensively employed. By using radioactive dithiophosphate synthesized from radioactive phosphorus, a rapid and sensitive analytical procedure G. L. SIMARD is in the Research Division, Stamford Research Labs., American Cyanamid Co., Stamford, Conn.; J. CHUPAK, formerly in the Research Division, Stamford Research Labs., is now at Camp Detrick, Frederick, Md.; and D. J. SALLEY is in the Research Division, Stamford Research Labs. AlME New York Meeting, Feb. 1950. TP 2815 B. Discussion (2 copies) may be sent to Transactions AlME before April 30, 1950. Manuscript received Oct. 17, 1949. was at hand. This permitted determination of such important quantities as the rate of uptake of dithiophosphate by the mineral, the amount existing at equilibrium on the mineral surface and in the solution, and the desorption of the agent from the surface. Such measurements were possible even on single crystals of galena. In addition the exchange of dithiophosphate between the solution and the sorbed phase was examined, a matter which could be accomplished only by the use of isotopes. It is desired to point out at this time that throughout this paper the term "sorption" has been employed to designate the uptake of agent by mineral, without implication as to the nature of the process by which the uptake was accomplished. Experimental Materials: Galena: The galena was from the Tri-State district. For studies on ground mineral four preparations were used during the course of the investigation. These were prepared from selected large crystals by wet grinding in order to reduce surface oxidation. Alcohol was chosen as a convenient medium for this purpose. The ground mineral was then fractionated by sedimentation in alcohol, dried by evacuation, and stored in a nitrogen-filled desiccator. Data on the preparations are tabulated in table I. The size analysis indicated that the areas of the preparations were of comparable magnitude, even though the absolute values may be somewhat incorrect. Dithiophosphates: Nonradioactive dithiophbsphate (di-isopropyl or di-secondary butyl) was obtained by purification of a commercial product. An aqueous acid solution of the agent was extracted with petroleum ether, the ether layer dried, and the dithiophosphate precipitated as ammonium salt with anhydrous ammonia. Several repetitions of this process resulted in a nearly colorless, flaky product of good purity. (General formula (RO,)PSSNH,). Radioactive dithiophosphate was synthesized by heating radioactive elementary red phosphorus* • For early experiments (1943 to 1944), the elementary red phosphorus was obtained from the cyclotron group at the Crocker Radiation Laboratory of the University of California. Berkeley, through the courtesy of Dr. Joseph W. Hamilton. For more recent work (1946 to 1949). the elementary radioactive Phosphorus has been supplied by the Oak Ridge National Labarotories on allocation from the U. S. Atomic Energy Commission. with sulphur at 270" to 300°C to produce radioactive P,S,. The latter was then treated with the desired purified alcohol (isopropyl or secondary butyl) at 60" to 80°C to form the dithiophosphoric acid derivative. Purification was effected in the same manner as for the nonradioactive material. The effectiveness of the purification method was established by the isotopic dilution method." The same technique was used to show that only negligible decomposition of neutral or of carbonate solutions of the dithiophosphate took place over a period of a day; this was true whether or not galena was suspended in the solutions. Procedures: Radioactivity: The activity of a solution was obtained by counting with a small glass-jacketed, silvered Geiger counter, using a conventional scaling circuit.' Crystals and other solids were counted under a bell-shaped, mica-window counter tube. Sufficient counts were made so that the probable error of counting was of the order of +I-3 pct. The specific activity in terms of counts per minute

Jan 1, 1951

By R. J. Blackwell, J. R. Rayne, W. M. Terry

This paper presents results of an experimental investigation of factors that control the efficiency with which oil is displaced from porous media by a miscible fluid. The study was made to elucidate the relevant processes both on microscopic level (within individual or between neighboring pore spaces) and on macroscopic level (within a large sand body). Mixing of miscible fluids on the microscopic level was studied in sand-packed tubes. It was found that molecular diffusion is the dominant dispersion mechanism for reservoir conditions of rate, length and pore sizes. Macroscopic channeling was studied for various mobility ratios in reservoir mode1s scaled to relate viscous, gravitational, and diffusional forces. The formation of channels was due to viscous firzgering, gravity segregation and variations in permeability. With adverse mobility ratios, it was found for reservoirs of realistic widths that diffusion will not be effective in preventing the formation and growth of fingers, even in homogeneous sands. At sufficiently low rates channeling was eliminated by gravity segregation in tilted reservoirs. The dependence of recovery on mobility ratio, length-to-width ratio, flow rate and angle of dip is presented. INTRODUCTION Oil recovery by solvent flooding is finding increasing application in the field. While the process promises high recoveries from the region swept by solvent, under adverse conditions only a small fraction of the reservoir volume may be swept at the time solvent breaks through to the producing well. Further, the high cost of the solvent encourages its use only as a bank whose size must be kept at a minimum. Thus, two important questions arise: (1) what fraction of the reservoir can be swept, practically, by solvent? and (2) what is the minimum size solvent bank that can be used to carry out the displacement? The answers to these questions require knowledge of both macroscopic channeling processes and microscopic mixing processes. The studies described here were carried out to gain this knowledge. Microscopic mechanisms which cause mixing will be discussed first, because an understanding of these mechanisms is necessary for proper interpretation of the experimental work on channeling described later. INVESTIGATION OF MICROSCOPIC DISPLACEMENT PHENOMENA FOR MISCIBLE FLUIDS The questions to be resolved concerning microscopic displacement behavior are: (1) how much mixing occurs between oil and solvent in the direction of flow? and (2) does the solvent completely flush the oil from the pore spaces in the region invaded by solvent? The classic work of Sir Geoffrey Taylor' and its extension by Aris2 have shown that it is possible from theory to describe the amount of mixing in single straight capillaries when solvent displaces a fluid of equal viscosity and equal density. Aris showed that the lengths of the mixing zones, 81, corresponding to the 10 per cent and 90 per cent concentration levels of the solvent can be calculated from the formula, 81 = 3.62 \/Kt, .........(1) where 8l is the length of the mixing zone, cm; t is the time, sec; and K is the effective dispersion coefficient, cm2/sec, given by K/D = 1 + (1/48) (au/D)2......(2) where a is the radius of the capillary, cm; D is the molecular diffusivity, cm2/sec; u is the average velocity

By E. Buehler, E. Berry

HE magnetic properties of dilute palladium alloys are of fundamental interest.''' Neutron diffraction studies3 have indicated that a better understanding of the behavior of these alloys could be realized with the availability of high-purity single crystals of palladium. Crucible melts of 99.999 pct pure palladium were found inadequate for such research. In a successful effort to fill this need, floating zone refining of palladium was undertaken. In this note the results of the initial experiments are reported. Zoning was accomplished in an argon atmosphere using 450 kc rf generator for an energy source. Samples 5 to 6 mm in diam were suspended in a gastight quartz envelope which could be moved vertically through the rf coil. A nominal upward traverse rate of 1.5 mm per min was maintained during a pass. Close coupling was found to be essential for stable retention of the liquid in the zone. Single crystals averaging 3.5 cm in length were obtained. Laue photography showed them to be continuous single crystals without gross imperfections. Several criteria were used for evaluation of the purity of the zoned material: magnetic behavior, low-temperature specific heat and residual resistivity ratios. Table I shows the residual resistance ratios obtained for two samples, one subjected to a single pass, the other zoned four times. It is appilrent that palladium can be zone refined with the electrically active impurities being transported toward the tail end. A decrease in susceptibility for zone-melted specimens over any previously measured material from 1.5" to 80'~ has been obserted by H. J. Williams and R. C. Sherwood4 substantiating the residual resistance data. The specific heat measurements are currently being made3 and will be published at some later date. Discussions with J. H. Wernick and S. C. Abrahams are acknowledged. We also wish to thank G. F. Brennert for the residual resistance measure ments.

Jan 1, 1962

By Nicholas J. Grant, Yoichi Ishida, Arthur W. Mullendore

An inert particle -marker technique was developed to provide a direct measurement of grain boundary sliding during creep in tile interior of aluminum specimens. Groin boundary sliding in the interior as measured by this technique was found to be nearly the same or slightly lower than that measured on the surface. These data disagree with those obtained by the grain-counting technique developed by W. A. Rachinger. In tests where both techniques were used, the grain-counting technique gave large and variable values of grain boundary sliding. It is shown that the grain-counting technique gines erroneozcs results because of a preferred direction of grain growth during creep. A question which has long plagued those who study grain boundary creep is whether or not surface measurements yield a true representation of the deformation in the interior of a specimen. The first attempt to measure grain boundary sliding in the interior of a creep specimen was made by Rachinger.1 His technique is based on the measurement of average grain diameters, both parallel and perpendicular to the tension axis, followed by a calculation of the grain elongation from these measurements. The difference between total elongation, Et, and the calculated grain elongation, Eg, is considered to be the result of grain boundary sliding, Egb. Surprisingly large values of Egb/ Et (90 pct) came out of creep tests of pure aluminum at temperatures above 250°C (480°F), utilizing the Rachinger technique. This value is very much larger than the values of 8 to 15 pct measured by numerous investigators on the surface of a specimen. Values obtained on the surface by Rachinger, however, were consistent with those measured by the displacement of reference scratches. Chaudhuri and Grant2 repeated the Rachinger method for A1-10 pct Zn, and found the same large values of Egb/Et inside the specimen. However, from purely geometrical considerations, grain boundaries cannot slide without grain deformation; therefore, they questioned the validity of Rachinger's grain-counting method. Several authors2,3 have suggested that grain boundary migration during high-temperature deforma- tion may tend to restore the equiaxed grain shape in order to minimize interfacial energy. Rachinger4 tested this hypothesis and found that it did not hold. Grains elongated by rapid extension retained their elongated shape during a subsequent slow creep test. It appears that some other factor was responsible for the abnormally high values of .Egb/El. McLean and Gifkins5 made a survey of the effect of grain size on the ratio Egb/ Et, and proposed that the high values were the consequence of a small grain size. They failed to explain the low value of Egb/Et which Rachinger observed on the surface of the small grain size specimens, and suggested that the surface effect on the value of Egb/Et does not always occur. Many of the disagreements arising from Rachinger' s work stem from the fact that there was only one method of estimating grain boundary sliding in the interior of a specimen, and that method was of an indirect nature. If a marker line of some sort could be introduced inside of the specimen, one could make measurements just as clearly as on the surface. In the present investigation, the technique utilizes a layer of finely dispersed oxide particles inside the specimen introduced by hot press-bonding of two pieces of aluminum. Rachinger attempted a similar technique but with the oxide distribution he obtained there was so much interference with grain boundary motion that quantitative measurements were not attempted. MATERIALS AND EXPERIMENTAL PROCEDURE A) Materials Preparation. Two pure aluminum rods (impurity content in percent: Si, 0.002; Cu, 0.004; Fe, 0.002; Mg, 0.000: Zn, 0.000; V. 0.001) 1 in. diameter by 2 in. high were jacketed end to end in a 4-in.-diam cylinder of commercial-purity aluminum, 4 in, high, which had a l-in.-diam hole. The l-in.-diam mating surfaces of the two pure aluminum rods had been electropolished initially. This interface provided the oxide-film internal -marker plane after the hot press-bonding process, see Fig. 2. The composite was annealed for 1 hr at 900 F and hot upset more than 50 pct reduction in height in one step. The resulting slab was then rolled to 1/2 in. thickness; the pure aluminum test material was cut out and annealed at 900°F for 1 hr and cold cross-rolled to 1/8 in. thickness. The sheet was machined into specimens with a 1/8-in.-square cross section and a 1/2-in. gage length. The following heat treatment was given the specimens: Specimen 5A series: annealed at 1000°F for 5 min for grain-size control and then cooled to 700°F and held for 15 hr for stabilization.

Jan 1, 1965

By J. T. Brown

AS far as could be ascertained, no one had previously investigated the creep strength of silicon poly-crystals. Literature has appeared showing evidence for plastic deformation in silicon single crystals and whiskers.*1"6 Also the fact that germanium, a material of similar crystal structure to silicon undergoes plastic deformation under stress at temperatures above about 60 pct of its melting temperature, has been known for some time.2"4'7 This investigation was performed for the purpose of determining the strength and ductility of silicon polycrystals under creep conditions that would give fairly long times to rupture. PROCEDURE The silicon specimen blanks were obtained by first placing granulated transitor grade silicon (99.999 + pct pure) in a silica crucible. The crucible was surrounded by a graphite susceptor, and induction heating was used for melting the silicon in a vacuum furnace. Blank specimens were formed by freezing molten silicon onto a polycrystalline seed of silicon in a vacuum furnace. The seed was attached to a motor driven revolving rod. As silicon solidified, this rod was gradually withdrawn from the melt. A shape with a contracted center section was obtained by varying the rate of withdrawal from the melt. Specimens for the creep-rupture tests were ground from these "pulled" blanks. Creep-rupture tests were performed in spring loaded machines under constant load at 1800" and 2000° F. RESULTS AND DISCUSSION A test specimen which was sectioned longitudinally is shown in the photomacrograph in Fig. 1. Very little deformation has taken place in the portion of the specimen shown, however, slip lines from several slip systems within the same grain, and deformation band formation was seen. The elongated appearance of the grains is due to the method of growing the specimens. One of the most interesting aspects of the results obtained from the creep-rupture tests was the high strength and the accompanying large amount of ductility. The data obtained is listed in Table I which shows the stress to rupture in 100 hr at 2000°F is between 8000 and 9000 psi. This indicates that silicon's strength at 2000°F is about equal to that of the best commercial super-alloys. It is important to mention that silicon has less than 1/3 the density of iron-, nickel-, and cobalt-base alloys. The usual type alloys for high-temperature applications

Jan 1, 1960

By Julius Pohlman

Considering the truly wonderful natural resources of the United States, and the variety and extent of uses for hydraulic cement at the present day, it seems strange that the manufacture of the artificial product called Portland cement has not been introduced here. Possibly the reason may be we have in different States of the Union rock deposits from which a cement can be obtained that is as good, and some claim even better, because of a more uniform quality, than the English product after it has been subjected to transportation across the ocean. One of these natural cement-rock deposits is found in the northern part of the city of Buffalo, and its manufacture has been carried on successfully for the past eleven years by the Buffalo Cement co., Mr. L. J. Bennett, President. The quarries cover an area of about two hundred acres, of which only twenty-five acres have been exhausted up to date; and the supply is assured for years to come. One acre yields on an average 80,000 barrels of cement; hence 12,000,000 barrels is a low estimate of what these quarries will yield before they are exhausted. According to the Geology of New York this cement-rock deposit is called the Water-Lime group, and forms in this section the uppermost member of the Upper Silurian. Its outcrop can be traced along the base of the second limestone terrace of Western New York, but at Buffalo a very large part of the overlying Corniferous limestone has been removed by natural agencies, leaving only about eight feet (six feet of rock and two feet of clay) on the top of the cement-rock, and thus furnishing the conditions for successful quarrying at a minimum expense. This rock is really an impure limestone, a mixture, as it were, of the underlying shales of the Onondaga Salt group with the overlying

Jan 1, 1889

By E. H. Dix

During an investigation of high-strength manganese bronze by til Engineering Division of the Air Service, at McCook Field, Dayton, Ohio, particles of a "blue constituent" were noted in the microstructure of most of the bronzes examined. The constitution of the simple copper-zinc base alloy is still a matter of dispute in spite of the fact that the copper-zinc series is one of the oldest industrially important groups of alloys, and has received thc carly co~l+itlcl-ntio11 of scirntific rcsc:trch. Thc diagram, according to the rnost rcrent \vork.' IS shown in Fig. 1. The disputed questions involve the tcrmi~r:~tiorl of the beta field and the lint at 470' C. The parliest expc~imc>ntcr, Rol)erts--~1~11stcri, detectrd an arrest in some of his cooling curves :it approximately this temperature and ascribed them to the formation of a cutectic; it has since been proved that there arc no eutectics in this series. Shepherd? was unable to detect any thermal arrests at this temperature, his. diagram was essentially as shown in Fig. 1, except that the line at 470" ('. was omitted and the beta phase carried down to normal temperature. 1,:ttcr. carpenter and Edwards, by a very painstaking research, definitely established the authenticity of the line but attributed it to the breakdown of the BETA constituent into a cutectoid of alpha and gamma. microscopic evidence of the formation of the cutectoid is doubtful and it seems more likely to he due to an allo-tropic change in the beta constituent as shown by Fig. 1. At least for practical purpose?, it is more convenient to think of the structure of a 60-40 brass as a mixture of alpha and beta prime crystals rather thin alpha plus an unresoluble eutectoid of "apparent beta" as it has often been called. * Chief, Metals branch, Engineering Division, Air Service. 1 0. F. Hudson: Jnl. Inst. of hlvtals (1913) 12, 2 E. S. Shepherd: Jnl. Phys Chrm. (10141 8, 421. H. C. H. Carpenter and O. A. Edwards: Jnl, Inst. of Metals (1911) 5, 127.

Jan 1, 1923

By E. H. Dix

During an investigation of high-strength manganese bronze by til Engineering Division of the Air Service, at McCook Field, Dayton, Ohio, particles of a "blue constituent" were noted in the microstructure of most of the bronzes examined. The constitution of the simple copper-zinc base alloy is still a matter of dispute in spite of the fact that the copper-zinc series is one of the oldest industrially important groups of alloys, and has received thc carly co~l+itlcl-ntio11 of scirntific rcsc:trch. Thc diagram, according to the rnost rcrent \vork.' IS shown in Fig. 1. The disputed questions involve the tcrmi~r:~tiorl of the beta field and the lint at 470' C. The parliest expc~imc>ntcr, Rol)erts--~1~11stcri, detectrd an arrest in some of his cooling curves :it approximately this temperature and ascribed them to the formation of a cutectic; it has since been proved that there arc no eutectics in this series. Shepherd? was unable to detect any thermal arrests at this temperature, his. diagram was essentially as shown in Fig. 1, except that the line at 470" ('. was omitted and the beta phase carried down to normal temperature. 1,:ttcr. carpenter and Edwards, by a very painstaking research, definitely established the authenticity of the line but attributed it to the breakdown of the BETA constituent into a cutectoid of alpha and gamma. microscopic evidence of the formation of the cutectoid is doubtful and it seems more likely to he due to an allo-tropic change in the beta constituent as shown by Fig. 1. At least for practical purpose?, it is more convenient to think of the structure of a 60-40 brass as a mixture of alpha and beta prime crystals rather thin alpha plus an unresoluble eutectoid of "apparent beta" as it has often been called. * Chief, Metals branch, Engineering Division, Air Service. 1 0. F. Hudson: Jnl. Inst. of hlvtals (1913) 12, 2 E. S. Shepherd: Jnl. Phys Chrm. (10141 8, 421. H. C. H. Carpenter and O. A. Edwards: Jnl, Inst. of Metals (1911) 5, 127.

Jan 1, 1923

By B. Chalmers

THE practical importance of the phenomena of melting and freezing must have been recognized for a very long time. The difference between ice and water, for example, has had a profound influence on the history of mankind and the evolution of society. The possibility of melting a metal and allowing it to freeze in a mold of chosen shape has been an essential ingredient in our mastery of the art of shaping metals, and therefore in the evolution of the: machine age in which we find ourselves. The importance of melting and freezing, as applied to metals and alloys, has been so great, in fact, that empirical solutions have been found for the multitude of practical problems that have arisen. This approach has been so successful that relatively little attention has been directed to arriving at an understanding of the fundamentals of the processes. But metallurgy has come to a stage at which we may expect that some, at least, of the more complex problems that have not yet been solved (or perhaps even recognized) may be handled more effectively by scientific study, theoretical understanding, and logical experimentation than by trial and error. In this lecture, therefore, I propose to describe in outline what I think really happens when a metal freezes. In doing so I hope to explain many of the phenomena which have been observed, and in particular to account for the structures that are obtained in actual ingots and castings. The basic problem, to which this lecture represents a tentative partial answer, is this: a mass of metal, containing known proportions of various elements, is melted, heated to a given temperature, and then allowed to freeze under specified conditions. What will be the "structure" of the resulting metal? The term structure includes: 1—crystal size, shape, and orientations, 2—distribution of chemical elements, and 3-—shape, including cracks, cavities, pores, etc. The Solid-Liquid Interface We will first consider what takes place if a single crystal of a metal in the form of a rod is heated, not uniformly, but so that one end is hotter than the other. If this heating process is continued long enough, the hotter end will eventually melt; we will suppose that the rod is in a containing vessel so that the molten metal does not run away, Fig. 1. When some of the metal has melted, we have some solid, some liquid, and an interface or surface of contact between them. If the source of heat is now removed, the interface will move so that some of the liquid freezes, and if the supply of heat is suitably adjusted the interface will remain at rest. This very simple arrangement allows us to study the basic processes of melting and freezing, and if we fully understand this simple case, we may be able to account for what takes place under practical conditions where the heat does not all flow in the same direction, and where the heat flow is determined not by a controllable source of heat but by the heat capacity and temperature of metal and mold, and by the heat loss from the mold surface. The solid-liquid interface is evidently the region of the greatest interest to us; on one side of it there is crystalline solid, and on the other, liquid. In the solid, each atom has a well defined position, around which it vibrates as a result of thermal agitation. It only leaves this position in the relatively rare event of a "diffusion jump." The liquid is much less systematically organized. The atoms are about as far from their neighbors as in the solid, but the arrangement is much less systematic and is continuously changing. The solid and the liquid are represented diagrammatically in Fig. 2. The average energy of the atoms in the liquid is greater than in the solid by an amount that corresponds to the latent heat of fusion, i.e., the amount of heat that has to be supplied to convert unit mass of solid into liquid at the same temperature. The Two Processes As has recently been shown by Jackson and Chalmers,3 many of the features of the processes of freezing and melting can be understood if it is assumed that a continuous and rapid interchange of atoms between solid and liquid always takes place at a solid-liquid interface." It is necessary to con- sider two distinct processes, that of melting, in which atoms leave the surface of the solid and become part of the liquid, and the converse process,

Jan 1, 1955

On the Art of Metallography (Howe Memorial Lecture), by F. F. Lucas; Beneficiation of Iron Ore. Abstract of paper by C. E. Williams followed by Round Table Discussion; A Statistical Analysis of Blast-furnace Data, by R. 8. McCaffery and R. G. Stephenson; Air Discharge of Circular Tuyeres, by R. S. McCaffery and D. E. Krause; Open-hearth Steel Process as a Problem in Chemical Kinetics. by E. R. Jette; Carbon-oxygen Equilibrium in Liquid Iron, by H. C. Vacher and E. H. Hamilton; A Thermodynamic Study of the Phasial Equilibria in the Bystem Iron-carbon (Abstract), by Yap, Chu-Phay; Influence of Dissolved Carbide on the Equilibria of the System Iron-carbon (Abstract), by Yap, Chu-Phay; Inclusions and Their Effect on Impact Strength of Steel, I and 11, by A. B. Kinzel and W. Crafts: Method for Electrolytic Extraction of MnO, MnS, FeS and Si02, Inclusions from Plain Carbon Steels, by G. R. Fitterer; Permanent Growth of Gray Cast Iron, by W. E. Remmers; Some Notes on Blue Brittleness, by L. R. van Wert; Austenite-pearlite Transformation and the Transition Constituents, by A. Sauveur; Age-hardening of Austenite, by F. R. Hensel; Transformational Characteristics of Iron-manganese Alloys, by H. Scott; Composition Limits of the Alpha-gamma Loop in the Iron-tungsten System, by W. P. Sykes; Magnetic Properties Versus AUotropic Transformations of Iron Alloys, by T. D. Yensen and N. A. Ziegler; Dilatometric Study of Chrome-nickel-iron Alloys, by V. N. Krivobok and M. Gensamer; Low-carbon Steel, by H. B. Pulsifer; Bright Annealing of Steels in Hydrogen, by F. C. KeUey; Development of Continuous Gas Carburieing, by R. J. Cowan. Transactions, Institute of Metals Division, 1931. 500 pages. Index. Papers and discussions presented before the Division at Chicago, Sept. 22-26, 1930 and New York, Feb. 16-19, 1931. X-ray MetallograpIhy: X-ray Determination of Alloy Equilibrium Diagrams (Annual Lecture), by A. F. Westgren; Suppressed Constitutional Changes in Alloys. by G. Sachs; Texture of Metals after Cold Deformation; by F. Wever. Theoretical Metallurgy: Studies upon the Widmanatitten Structure. I.—Introduction. The Aluminum-eilver System and the Copper-silicon System; by R. F. Mehl and C. S. Barrett; Studies upon the Widmanstatten Structure, 11.—The Beta Copper-einc Alloys and the Beta Copper-alumnum Alloys, by R. F. Mehl and 0. T. Mareke; Application of X-rays in the Manufacture of Telephone Apparatus, by M. Baeyerts; Thermal Conductivity of Copper Alloys. 11.—Copper-tin Alloys; 111.—Copper-phosphorus Alloys, by Cyril Stanley Smith; Thermodynamic Study of the Equilibria of the Systems Antimony-bismuth and Antimony-lead, by Yap, Chu-Phay. Ganeral: Cemented Tungsten Carbide; a Study of the Action of the Cementing Material, by L. L. Wyman and F. C. Kelley; Influence of Casting Practice on Physical Properties of Die Castings, by C. Pack; Fabrication of the Platinum Metals, by C. S. Sivil; Effect of Certain Alloying Elements on Structure and Hardness of Aluminum Bronze, by 9. F. Hermann and F. T. Sisco. The WorkinG oF Metals: Metal Working in Power Presses, by E. V. Crane; Forming Properties of Thin Sheets of Some Nonferrous Metals, by W. A. Straw, M. D. Helfrick and C. R. Fischrupp; Die Pressing of Braas and Copper Alloys, by J. R. Freeman. Jr.; Plasticity of Copper-sina Alloys at Elevated Temperatures. by A. Morris: Directional Properties in Cold-rolled and Annealed Copper, by A. Phillips and E. 9. Bunn; Effect of Combinations of Strain and Heat Treatment on Properties of Some Age-hardening Copper Alloys by W. C. Ellis and E. E. Schumacher; Constituents of Aluminum-iron-silicon Alloys, by W, L. Fink and K. R. Van Horn; Equilibrium Relations in Aluminum-antimony Alloys of High Purity, by E. H. Dix, Jr., F. KeUer and L. A. Willey; Equilibrium Relations in Aluminum-magnesium Silicide Alloys of High Purity, by E. H. Dix. Jr., F. Keller and R. W. Graham; Constitution of High-purity Aluminum-titanium Alloys, by W. L. Fink, K. R. Van Horn and P. M. Budge; Experiments on Retarding the Age-hardening of Duralumin, by E. H. Dix. Jr. and F. KeUer; Aluminum-silicon-magnesium Casting Alloys, by R. S. Archer and L. W. Kempf; Modulurr of Elasticity of Aluminum Alloys, by R. L. Templin and D. A. Paul; Quenching of Alclad Sheet in Oil, by H. C. Knerr.

Jan 1, 1931