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By Harold Vance

The Lafitte field, the largest oil reserve in South Louisiana, is in Jefferson Parish, some 25 miles due south of the City of New Orleans. The discovery well, The Texas Company's No. I, Louisiana Land and Exploration Co., in the southeast corner of sec. 19, T. 17 S., R. 24 E., was completed on May 15, 1935. The initial production of this well was 960 bbl. of 34.9º A.P.I, gravity oil per day, through 1/4-in. choke, with a tubing pressure of 1600 lb. per sq. in. Producing depth was 9558 to 9572 ft., the total depth being 9572 feet. The development of the field has been at the rate of three to eight new producing wells per year. Up to Jan. I, 1944, 60 producing wells and three dry holes had been drilled, while two of the original producing wells had been abandoned, Although the field is not unitized, The Texas Company was the sole operator in the field until the Lafitte Oil Co. completed its NO. I Jefferson Parish, near the center of the west line of the NW/4 sec. 20, T. I7 S., R. 24 E., on July 27, 1941. No additional wells have been drilled by the Lafitte Oil Company. Drilling and WeLl-completion Practices All drilling operations have been conducted with the steam-driven rotary equipment mounted on submersible barges. A canal is dug to the well location and the drilling unit is floated into position. The seacocks are then opened and the barge settles to the bottom. After the well is completed, seacocks are closed and water is pumped out of the barge. This procedure permits the barge, with drilling equipment still in place, to be floated and moved off the location. The conventional open-hole and the gun-perforation method of completing wells has been used in this field. Where possible, the initial completion is from the deepest 'sand and recompletions are made progressively up the hole, by plugging back with cement to the upper sand and gun-perforating opposite the new sand. The oil string usually is 7 5/8 in., 26 to 34-lb. casing. Three wells have been completed using 9 5/8-in. 44-lb casing set below 10.000 feet. Fig. I shows the completion and recom-pletion practices on one well in the field. This figure also shows the relative locations of the different producing sands as shown on the electric well log. Structure The structure is an elongated dome, cut by two north-south faults, which divides the field into three segments. The west segment is the highest structurally and contains most of the recoverable oil and gas. The center segment is less important and the east segment is of little value. Figs. 2, 4, 6, 8 and 10 are depth contour maps on top of the five main producing sands in the field. These maps show the relative size of the five reservoirs and the

Jan 1, 1945

By J. Richter, D. Schulze

J. Richter and D. Schulze (Deutschen Akademie der Wissenschafte zu Berlin)—Introduction. In a recent paper R. G. Garlick and H. B. Probst reported on experimental results of investigations of room-temperature slip in zone-melted tungsten single crystals.17 In the paper it was pointed out that slip lines could be detected with an optical microscope only after about 10 pet plastic strain of the crystal. In our investigations we could observe slip lines in tungsten single crystals of defined orientations already with an elongation of 0.02 to 0.03 pet.18"9 Experimental Technique and Results. The tungsten single crystals were produced from 4 to 5 mm sintered rods* as starting material by electron- beam zone melting. With single-zone-pass melting a speed of 0.5 mm per min was used, while three-pass melting could be handled at a speed of 3 mm per min. Crystal axis orientations were located in the shaded area of the stereographic triangle, see Fig. 6. Orientation 1 is located at about 18 deg and orientation 2 at about 5 deg on the great circle from [011] to [ill]. This corresponds approximately to the orientations P and M referred to by Garlick and Probst. Our single crystals had a length of about 70 mm and were profiled solely by electrolytic means, leaving grip ends at both ends of the crystals. Between the latter, a cylindrical crystal of 45 to 50 mm length and about 2.4 mm diam was obtained. The crystals were deformed at room temperature in a commercial tensile-testing machine to obtain a strain of 0.02 to 5 pet. The average strain rate e = eP/t for all tensile tests amounted to approximately 10 -6 to 10-5 per sec, with ep representing plastic strain and t the duration of applied stress. In Fig. 7 a crystal is shown elongated by 0.03 pet. The picture was obtained by means of an optical microscope. Figs. 8 and 9 give electron-microscopic pictures of slip lines of crystals elongated by 0.07 and 1.1 pet, respectively. For crystals with the orientation 1, see Fig. 6, only the two main slip systems (101)[111] and (110)[111] were found. With the crystals of group 2 the two main slip systems are again evident, with

Jan 1, 1965

By E. Martinez

The effect of ultrasonic energy transmitted through a liquid on chrysotile asbestos was investigated. Ultrasonic energy was effective in fiberization of chrysotile crudes as well as standard grades of milled asbestos fibers. Treated samples of several grades of milled fibers had increased wet bulk volumes and decreased settling and filtration rates compared to untreated fibers. Ultrasonics may be a method for fiberization of chrysotile without decreasing length or use of chemical additives that alter surface properties. Cavitation of the liquid on the surface of fiber bundles is believed to be the cause of the fiberization. It was found that ultrasonic energy greatly increased the rate of precipitation of latex on asbestos. When chrysotile asbestos fibers require additional opening or fiberization, the usual method employed is some type of high speed impact or grinding to open the fibers and produce a larger surface area. These methods always cause some degradation in length due to breaking of fibers. In addition, the efficiency of mechanical methods decreases as the diameter of fiber bundles decreases. Chemical methods have been proposed and it is claimed that fiberization down to individual fibers of 200-300 A diam is possible with some wetting agents. However, large amounts of reagent are required, approximately EDWARD MARTINEZ is with Central Research Laboratories, American Smelting and Refining Co., South Plain-field, N.J. TP 63H226. Manuscript, Aug. 12, 1963. Discussion of this paper, submitted in duplicate prior to Mar. 15, 1964, will appear in SME Transactions, September 1964, and AIME Transactions, 1964, vol. 229. 50 pct of the weight of fiber treated, and some of the wetting agent remains on the surface of the chrysotile and cannot be removed by any solvent which does not destroy the asbestos.' This investigation was directed at determining whether ultrasonic energy transmitted through a liquid would be effective in fiberizing chrysotile asbestos. Samples of asbestos crudes and commercially milled fibers were treated; settling and filtration rates of treated and untreated milled fibers were obtained. EQUIPMENT A Westinghouse Corp. ultrasonic cleaning system WEHH was used in this investigation. See Table I for a breakdown of this ultrasonic unit. RESULTS AND DISCUSSION Fiberization of Chrysotile Crudes: Samples of chrysotile crudes were pulled apart with tweezers so that coarse bundles of fiber approximately 1/16 in. in diam were obtained. The bundles were put into a bottle with 200 ml of methanol and the mixture placed into the ultrasonic tank for 30 min at a power output of 1200 w. The test was repeated using water instead of methanol. During the irradiation it was noted that the surfaces of the bundles were being fiberized. The liquid eventually became cloudy with dispersed solids. Fig. 1 is an electron micrograph of the fibers, some reduced to unit dimensions, and a fine material released by the ultrasonic energy. The platy particles in Fig. 1 were identified by electron diffraction and differential thermal analysis as brucite, Mg(OH)2, which must have been intergrown in the chrysotile crudes. Electron micrographs of bulk specimens of chrysotile have shown a fine material filling the interstices between tubular fibers.2,3 Electron diffraction patterns of the fine material collected after ultrasonic treatment indicate that it is amorphous. After decanting the solution, bundles of chrysotile remained somewhat decreased in diameter. Continuing the ultrasonic irradiation of the remaining material resulted in additional fiberization. The opening of the fibers occurred in both methanol and water. Cavitation of the liquid by the ultrasonic energy is undoubtedly responsible for the fiberization. When sound waves are transmitted through a liquid at a

Jan 1, 1963

By René de Batz

From 1754 to the end of 1895 the production of gold in Russia had been approximately as follows: Kilogrammes. Russia proper (Finland and the Caucasus),. .. 890 The Ural Region,........505,386 Western Siberia,........116,937 Eastern Siberia,........1,218,372 Total,.........1,841,085 of the value of more than $1,200,000,000.

Jan 1, 1899

By J. C. Martin

Stmplified equations are developed for the flow of fluids in gas drive reservoirs in which the effects of gravity can be neglected. The results show that the pressure distribution is governed by a nonlinear heat flow type of equation, and the saturation distributions are related to the pressure by the same equations QS those developed by Muskat for the average pressure and saturations in gas drive reservoirs. Unrler certain conditions the equation for the pressure can be approximated by the linear form of the heat flow equatlon. This equation tk analogous to the equation for the pressure in single-phase compressible flow The analysis reveals that the equation for the pressure in n~ultiphase flows can be obtained directly from the equation for the pressure in slngle-phase flows by simply replacing the single-phase compressibility by the total compressibility and the single-phase mobility by the sum of the mobilities of all the fluids present. Perrine's method of pressure buildup analysis for multiphme flows is based on these same substitutions. Thus, the development presented in this paper constitutes a theoretical justification for Perrine's method of pressure buildup analysis. One of the most difficult problems associated with the production of oil is the determination of the flow of the fluids within the reservoirs. One purpose of this paper is to present the development of simplified equations for the flow in gas drive reservoirs. The other purpose is to present some of the needed theoretical foundation for the methods currently being used in the analysis of multiphase pressure buildup data. The analysis presented in this paper makes use of a partial linearization of the equations governing multiphase flows. It is felt that the process of linearizing or partially linearizing the nonlinear equations of multiphase flows can lead to useful results since this process has proved extremely valuable in the study of other fields of science and engineering where nonlinear equations are encountered. Pressure buildup data of shut-in wells have been used for many years to estimate the static reservoir pressure. These data have also been used in studying the aver- age permeability both away from and close to the well-bores. The majority of the buildup data are obtained from wells producing two or three fluids. As yet the theoretical foundations for the methods of buildup analysis used in connection with rnultiphase buildup data have not been established. A number of methods of analysis of pressure buildup data have been developed." Most of these methods apply only to single-phase flows, and almost all of the theoretical analysis is confined to single-phase flows. Perrine' developed a method of analysis for rnultiphase flows from the method for single-phase flows of Miller, Dyes, and Hutchinson.' He did this by simply replacing the single-phase compressibility by the multiphase compressibility and replacing the single-phase mobility by the sum of the mobilities of the fluids in the rnultiphase flows. Obviously, such a procedure lacks a certain amount of theoretical justification, and such practices can lead to erroneous results. Fortunately, Perrine's results have a theoretical justification, and this justification is presented in the following discussion. It is assumed that gravitational effects and the cornpressibility of the rock can be neglected. Under these assumptions the equations governing the simultaneous flow of gas, oil and water in porous media areo* The preceding equations can be expanded into the following expressions.

By D. P. Harris

This paper examines recent developments and work in progress on the application of quantitative methods and computers to the appraisal of the mineral resource potential of discrete areas by employing reconnaissance geological information and general economic relationships. The perspective of this paper might be that of a firm planning a regional exploration program or of a legislative body seeking to choose between several alternative actions on the basis of their impact upon the regional resources. In addition to this general survey and commentary, an example is presented of the use of geostatistical analysis and computer simulation to evaluate the economic mineral resources of the Seward Peninsula of Alaska.

Jan 1, 1969

By Charles R. Fettke

In connection with the gathering of data for a report on the geology of the Humacao district of southeastern Porto Rico during the summer of 1916, under the auspices of the Scientific Survey of Porto Rico and the Virgin Islands, conducted by the New York Academy of Sciences, the writer had an opportunity to make a brief examination of the magnetite deposits of the eastern portion of the island. Inasmuch as these deposits have attracted some attention as possible future sources of iron ore, and as there is only scanty reference made to them in literature,' a short description based on this reconnaissance survey was deemed to be worthy of record. The magnetite deposits of eastern Porto Rico occur in association with a belt of limestone, trending approximately S 53° E, which begins 11/2 miles east of Juncos and can be traced for about 6 miles toward the coast. Four outcrops of magnetite were observed, which are designated as Nos. 1, 2, 3, and 4, respectively, on the map shown in Fig. 1. Others are probably present, but escaped notice on account of the thick mantle

Jan 1, 1924

By Charles W. Merrill

Obsolescence in the mineral world is virtually nonexistent if the term is taken to mean that a mineral commodity, once established in commerce and industry, subsequently has fallen into disuse. We are living in an age of minerals. Each generation puts an increasing array of mineral-based commodities, in larger quantities, to more uses than ever before. Bastnasite, a museum mineral and a collector's item a few years ago, is now produced in quantity at Mountain Pass, Calif. Uranium, a minor byproduct of vanadium mining in the Rocky Mountain plateau area before World War 11, has grown to be a leading mineral product in several western States. And finally the total quantity and value of minerals both in the United States and in the World establish new records almost yearly. Surely the mineral industry as a whole is not obsolescent in our economy. Nevertheless, there are particular uses for particular minerals that are obsolescent and some applications have been supplanted entirely. Tin does not occupy the prominent place in foil manufacture that it once did, and the schoolboy's slate left most classrooms before the oldest of us were born.

Jan 9, 1964

By R. G. Turner, M. G. Hubbard, A. E. Dukler

Gas phase hydrocarbons produced from underground reservoirs will, in many instances, have liquid phase material associated with them, the presence of which can affect the flowing characteristics of the well. Liquids can come from condensation of hydrocarbon gas (condensate) or from interstitial water in the reservoir matrix. In either case, the higher density liquid phase, being essentially discontinuous, must be transported to the surface by the gas. In the event the gas phase does not provide sufficient transport energy to lift the liquids out of the well, the liquids will accumulate in the wellbore. The accumulation of the liquid will impose an additional back pressure on the formation that can significantly affect the production capacity of the well. In low pressure wells the liquid may completely kill the well; and in the higher pressure wells there can occur a variable degree of slugging or churning of the liquids, which can affect calculations used in routine well tests. Specifically, the calculated bottom-hole pressures used in multirate backpressure tests will be erroneous if the well is not removing liquids on a continuous basis, and gas:liquid ratios observed during such a test may not be correct. Several authors1,3,8,14 have suggested methods to determine if the flow rate of a well is sufficient to remove liquid phase material. Vitter14 and Duggan' proposed that wellhead velocities observed in the field would be adequate for keeping wells unloaded. Jones8 and Dukler3 presented analytical treatments resulting in equations for calculating, from physical properties, the minimum necessary flow rate. An analysis of these studies indicates the existence of two proposed physical models for the removal of gas well liquids: (1) liquid film movement along the walls of the pipe and (2) liquid droplets entrained in the high velocity gas core. Although there probably is a continuous exchange of liquid between the gas core and the film, they will be treated separately for the purposes of this study. The development and comparison of these separate models with experimental data will permit the determination of which, if either, is the controlling mechanism for the removal of liquids from gas wells. The Continuous Film Model Liquid phase accumulation on the walls of a conduit during two-phase gas/liquid flow is inevitable due to the impingement of entrained liquid drops and the condensation of vapors. The movement of the liquid on the wall is therefore of interest in the analysis of liquid removal from gas wells. If the annular liquid film must be moved upward along the walls in order to keep a gas well from loading up, then the minimum gas flow rate necessary to accomplish this is of primary interest. The analysis technique used follows Dukler2 and Hewitt5 and involves describing the profile of the velocity of a liquid film moving upward on the inside of a tube. The minimum rate of gas flow required to move the film upward is then calculated.

Jan 1, 1970

By W. A. Hockings, D. W. Fuerstenau, A. L. Mular

This paper briefly describes a simple air pycno-meter and its use for rapid determination of the composition of mixtures of solid particles. Research on such problems as the pelletizing of solids, the mixing of solid particles, and the comminution of mixtures can be simplified by means of this analytical tool. THEORY OF OPERATION Liquid pycnometers1 are commonly employed to measure volumes. These devices are time consuming and sometimes give inconsistent results. The liquid used in the pycnometer may have an undesired influence on the material to be measured; moreover, complete displacement of air by the liquid is seldom

Jan 1, 1963

By Paul H. Lu

Methods and results of measuring three basic parameters for ground stability control, ground pressure, strata movement, and geomechanical properties of mine rock are presented in this paper. It is found that these parameters can be measured in situ by simple and practical techniques with nonsophisticated and inexpensive instruments. Specifically, a drillhole dilation technique employing a cylindrical hydraulic borehole pressure cell (CPC) was used to determine the modulus of rigidity. Premining ground pressures were determined by pressure convergence tests with a combination of one CPC and two pre-encapsulated flat hydraulic borehole pressure cells (BPC) installed in a single drillhole. Abutment pressures and pillar loading were monitored with BPC's. Differential strata movements and bed separations were measured with self-recording 10-anchor-point extensometers. Roof-to-floor convergence was measured with self-recording convergence meters. Some applications of these in-situ-determined parameters to mine design and ground stability control are also discussed.

Jan 1, 1984

By D. W. Levinson, L. E. Tanner

DURING the course of an investigation of the zirconium-iron-tin system the zirconium-iron system was reexamined up to 55 pct* Fe. The alloys pre- visible melting3 and X-ray diffraction studies were made of samples of the alloys. The ferromagnetic properties of ZrFe2were determined by Professor P. W. Selwood* using a modified Faraday balance.4 The zirconium-rich portion of the phase diagram is presented in Fig. 1 and compared with the work of Hayes et al.1 The maximum solubility of iron in ß is somewhat decreased while the eutectic temperature is raised. There seemed to be no change in the eutectic composition of 16 pct Fe. Since the base material was so low in iron content, it was possible to establish the maximum solubility in a between 0.017 and 0.025 pct Fe at the eutectoid temperature. The observation of fine ZrFe, particles in the micro structure of a specimen of 0.012 pct Fe alloy quenched from 700°C indicated that the solubility drops below this composition at 700° C and lower. Further study was made of the intermediate phase ZrFe2. wallbaum5 identified the compound initially as ZrFe2 with a C 15 (MgCu2) structure, placing it at 55 pct Fe stoichiometrically. Hayes et al.1 believed they found the phase at about 47.2 pct Fe and called it Zr2Fe3 but reverted to ZrFe, in the discussion of their paper.6 Jordan and Duwez7 confirmed Wallbaum's work as well as finding the same single-phase structure to about 62.3 pct Fe or Zr0-61 Fe2-18. In order to establish the ternary phase relations in the zirconium-iron-tin systema the exact position of this phase had to be known. This was accomplished by X-ray diffraction, visible melting, and metallographic techniques. Elliott8 obtained a single-phase ZrFe2 X-ray diffraction pattern from an alloy of about 55 pct Fe. This was confirmed in the present study with an alloy of 54.81 pct Fe. However, extra lines (attributable to a or ß zirconium) were found in diffraction patterns of the 47.42 and 49.83 pct Fe alloys. The melting characteristics of these same alloys were studied by suspending 47.42, 49.83, and 54.81 pct

Jan 1, 1960

By H. F. Silliman, Daniel R. Hull, Earl W. Palmer

THE brass-rolling industry has not had a great deal of experience with antimony in its product. There have been some recent excursions with antimony as a corrosion inhibitor in tubes, but in sheet brass it has been regarded with apprehension and generally avoided. This is not to say that [ ] contaminations have never occurred, and probably a great many brass mill men have had their own ideas on the effect of such contamination. Our own views were based upon certain experiences some years ago with strip castings that split lengthwise in the early stages of rolling. The nature of this splitting is shown in Fig. I, from a photograph taken in 1922 as a record of 20 bars of 65-35 common brass made with an antimonial brand of copper. These bars were cast 6 ¾ in. wide by 1 in. thick by 45 in. long. In the first pass through the rolls, 19 of the 20 split lengthwise throughout their length, while each half curved outward in a wide arc as it emerged from the rolls. [ ] In those days, if splitting was not a frequent occurrence, it was not unfamiliar. One can recall periods of short duration when large amounts of common brass would behave in this way. There was nothing imaginary about these spells. The affected metal would split lengthwise in the breaking rolls, and no maneuvering of mill practice made any difference. The condition would descend like a plague, demoralize the mill for several days, and disappear. It is doubtful if anyone knew the cause-however many explanations may have been current. In 1921 a quantity of split brass was traced to the use of fired small-arms

Jan 1, 1943

By J. B. Gayle

PRESENT flotation processes depend almost entirely on the buoyant properties of air bubbles to effect separations of mineral and gangue, but there is no convenient method for measuring aeration in flotation cells. Consequently the relation between aeration and cell performance has not been definitely established. In connection with a comparative study of kerosene and froth flotation processes, a modification of the displacement method' was developed in which air escaping from the cell surface is measured with a wet-test meter. The arrangement shown in Fig. 1 is satisfactory for use with a number of cells and is not critical, except that care must be taken to use connections and tubing large enough to avoid excessive back pressures. Attempts to use smaller tubing resulted in back pressures that caused displacement of the liquid level in the receiver, so that some air was lost around the sides, an occurrence readily visible when measurements were taken with only water passing through the cell. With the arrangement shown, the manometer indicated an average reading of about 1/2-in. water pressure. No loss of air was evident. Fig. 2 presents typical data for a standard Denver sub-A 24x24-in. unit cell operated at impeller speeds from 0 to 710 rpm. Each plotted point represents the average for five readings distributed over the entire cell surface. Readings were taken with only water passing through the cell. Results of this type have been used in a study of the influence of operating variables on cell performance and in detecting inherent differences in the operating characteristics of cells of various kinds. Although the information presented in Fig. 2 resulted only with water passing through the cell, the apparatus is suitable for use during flotation of coal when various reagents are present. Possible modi- fications that might prove convenient under special circumstances include varying the size and shape of the receiver and substituting a calibrated, inverted, water-filled carboy or other gas-measuring device for the wet-test meter. If such modifications result in excessive back pressures, some form of draft should be applied at the discharge end of the measuring system.

Jan 1, 1959

By J. van Lookeren

In the case of a reservoir where the oil underlies a large gas cap and overlies bottom water, production can be inzproved considerably if wells are perforated below the water-oil contact rather than opposite the oil-bearing section. The theoretical arguments for this improvement, which in some cases may be tenfold, are supported by experimental evidence. INTRODUCTION Reservoirs frequently consist of one sand body containing an oil layer underlying a thick, gas-bearing section and overlying bottom water (Fig. 1). Wells in such reservoirs are customarily opened up opposite the oil-bearing interval or, rather, opposite the lower part of this interval (Fig. 2). More often than not, it is inefficient or prohibited to blow off large quantities of gas with the oil. This im-psses a severe limitation on the drawdown, which results in low oil-production rates. Because of the small difference in specific gravity between oil and water, the latter will easily cone upwards, so that the production of water together with the oil is not prevented by this completion method. In such a situation wells should be opened deeper, in the originally water-bearing zone. The gas can be shut off by not perforating over the upper part of the interval (Fig. 3) or by a tubing hung close to the bottom of the interval (Fig. 4). Initially much water will be produced, but when steady-state conditions have been established (as depicted in Figs. 3 and 4) larger drawdowns are permissible than in a conventionally completed well, and correspondingly higher oil-production rates will result. Water cuts are only slightly higher because of the small effect of gravity on the water-oil flow distribution. CALCULATIONS The ratio of improvement has been estimated by means of approximate calculations. The completion depicted in Fig. 4 is the most convenient basis for these calculations. By postulating that vertical flow gradients can be disregarded, the Appendix shows that the well-known Dupuit formula can be obtained except for some complication due to the presence of two fluids rather than one. The Appendix makes the reasonable assumption that, for suitable boundary conditions, the oil layer occupies a constant fraction of the total fluid height throughout the reservoir. The oil- and water-production rates can thus be related to the liquid levels in the borehole as follows:

Jan 1, 1966

By R. W. Bartlett

DISILICIDE coatings, MeSi2, on refractory metals are usually grown by a solid-state diffusion reaction similar to the parabolic oxidation of metals. Two or more silicide compounds occur in each of the binary silicon-refractory metal systems. When an adequate source of silicon is available during the coating process, the lower silicide compounds are usually not formed.1 However, during service application of the coated refractory metal, continued heating causes further diffusion and growth of the lower silicides. A study of the growth kinetics of the lower silicides in the molybdenum and tungsten binary systems with silicon was previously reported.2 The present study is concerned with the growth kinetics of Ta5Si3 and Cb5Si3, formed as conjugate layers between TaSi2/Ta and CbSi2/Cb diffusion couples, respectively. Diffusion couples consisting of disilicide-coated tantalum and columbium sheet coupons were subjected to diffusion heat treatments, cross-sectioned, and scanned by an electron-microprobe analyzer to determine the relative X-ray intensity profiles. These profiles correspond closely to concentration profiles for the constituents, and were used to identify phases and locate phase boundaries. The analysis of a single specimen after a diffusion-anneal provides only one value for the Me5Si3 phase thickness, corresponding to the time and temperature of the diffusion treatment. Consequently, each isothermal curve showing the rate of accumulation or depletion of silicide phases required several samples with identical diffusion temperatures but different diffusion times. The disilicide coatings were prepared by pyrolizing commercially pure silane in a hydrogen carrier gas. The hydrogen was purified by passage through a palladium membrane. Commercially pure tantalum and columbium sheet metal coupons, 0.005 by $ by 2 in., were used. All of the coated specimens for each system were prepared together in a single group in order to minimize coating variations among individual specimens. During pyrolysis, the brightness temperature was maintained at 1200°C. With suitable flow rates at this temperature, only the disilicides of tantalum and columbium were formed in detectable amounts. Coated specimens were subjected to diffusion an-neals in a tube furnace with automatic proportional control within ±10°C. A H2-Ar mixture, deoxidized and dried over anhydrous magnesium perchlorate, was used to prevent oxidation during the diffusion anneal. Diffusion couples were cross-sectioned, polished and examined with an A.R.L. electron-microprobe X-ray analyzer. Both metal constituents in each specimen were simultaneously scanned using a 1-p beam spot size and either 1- or 2-µ steps. Analyses were performed using the Ka radiation of columbium and silicon, and the La, radiation of tantalum. For all specimens, an acceleration voltage of 30 kv was used, and integration was made against the specimen current. LiF and A DP monochrometers were used to isolate characteristic radiations. Three or more traverses were made on each specimen. The intensity scales were adjusted using the constituent metals and standard samples of the silicide compounds which had been verified by X-ray diffraction. The relative intensity profiles were used directly, in conjunction with the standard samples, to identify compounds and phase boundaries. The stoichiometries differ considerably between the silicide compounds in both systems, and the homogeneity range for these silicide compounds is narrow. These characteristics result in marked differences in relative intensities of the fluorescing elements—differences which permit ready identification of phases and phase boundaries. Projections of both electron back-scattered images and characteristic

Jan 1, 1967

By P. O. Metz, E. L. Wiehe, J. S. Foster

BASED on their analyses of growth kinetics, ibbs' and Harris et al.' have recently proposed that the rate of subcritical graphitization of steel is controlled by the rate of diffusion of carbon in ferrite. illert has concluded that this is the rate controlling growth mechanism when the growing graphite particles are relatively large. Harris et al.' also propose that the matrix surrounding a growing graphite particle is plastically deformed to make room for the growing particle. If this plastic deformation does occur, then preferred recrystallization may be observed around the larger particles. If diffusion of carbon in ferrite is rate controlling, then a graphite particle growing in a matrix of, say, tempered martensite or pearlite, should be surrounded by a carbide depleted zone. Thus, the simple metallographic experiments reported here are sufficient to determine whether or not diffusion of carbon in ferrite is the dominant mechanism for the growth of graphite in steel. The present investigation considers graphitization in five alloys. The compositions are given in Table I. Graphitization was carried out at three temperatures: 900°K (627"C), 950°K (677"C), and 990°K ('717°C). Samples were reacted in both the martensitic and the pearlitic initial conditions. In the hypoeutectoid steels, Sets 7 and 8, .and in the hypereutectoid Fe-C binary, Set 6, graphitization was very limited after 1000 hr at temperature. In these samples graphite particles observed were less than 10 p in diam. In the hypereutectoid commercial steels, Sets 1 and 3, large graphite particles (100 p) did not appear until after 250 hr at temperature. The limited number of graphite particles observed and the range of sizes obtained prohibited measurement of growth rates in this investigation. However, in all samples showing graphitization, neithe a carbide depleted zone nor recrystallization was observed. illert's model predicts that diffusion of carbon in ferrite should become dominant for graphite particles larger than about 300 p in diam. The largest graphite particle observed in this investigation was approximately 450 p in diam. No evidence of carbide depletion was noted. Fig. 1 shows a typical graphite particle. This nodule is from an initially pearlitic sample from Set 3 after

Jan 1, 1970

By A. H. Larson, L. G. Twidwell

DURING the roasting of zinc sulfide concentrates and by-product recovery from flue dusts, the zinc sul-fate phase may occur in various stages of the processes. In addition to zinc sulfide, other sulfide phases are usually present such as CdS, PbS, CuzS, and FeS. Consequently, the effect of these sulfides on the thermal decomposition of ZnS04 was investigated. Merck high-purity, anhydrous zinc sulfate was used as the starting material. The sulfate was heated under an argon atmosphere, at a rate of 10°C per min. With the first slight indication of decomposition as determined by gas analysis, the sample was removed from the furnace and allowed to cool. X-ray patterns showed no other phase present. It is estimated that less than 0.05 pct of the ZnS04 decomposed. The metal sulfides were also heated under an argon atmosphere to drive off any adsorbed water. The materials were then sized (-200 to +270 mesh), mixed in predetermined mole ratios, and pressed into pellets. The experimental measurement of the reaction rate consisted of purifying the argon carrier gas, continuous flushing of the heated reacting mixture with argon, and collection and analysis of the SOn product gas. The reaction system was heated to 600°C and al-

Jan 1, 1967

By H.A. Bedworth

AlloTs of copper and silicon have been known for one hundred years or more but the commercial development of this type of alloy has taken place during the past few years. In 1905, Sperry l proposed the use of copper-silicon alloys for springs and other purposes for which copper-tin bronzes were used. Some attention was given to this proposal at the time but no one succeeded in producing a practical alloy containing more than a fraction of a per cent. of silicon. The equilibrium relations of the copper-silicon system were studied first by Rudolfi2 and later by Sanfourche 3 and Corson. 4 The constitution of the system has also been recently investigated by Matuyama, 5 and in the laboratories of the American Brass Co. by Smith. 6 Some of the physical properties of the copper-silicon alloys have been investigated by Norbury7 and by Geiss and Van Liempt.8 Summarizing the results of various investigators of the constitution of copper-silicon alloys, the solubility reaches its maximium value, 6.7 per cent. silicon, between 721" and '782" C. At 852" (1. the solubility is 5.25 per cent., while at 400" C. it is only 4.1 per cent. silicon. The copper-silicon alloy begins to get so hard at about 3 per cent, silicon that it is difficult to manage. It was found by Jacobs that the addition of manganese to this alloy considerably improved the working

Jan 1, 1929

By H. A. Bedworth

AlloTs of copper and silicon have been known for one hundred years or more but the commercial development of this type of alloy has taken place during the past few years. In 1905, Sperry l proposed the use of copper-silicon alloys for springs and other purposes for which copper-tin bronzes were used. Some attention was given to this proposal at the time but no one succeeded in producing a practical alloy containing more than a fraction of a per cent. of silicon. The equilibrium relations of the copper-silicon system were studied first by Rudolfi2 and later by Sanfourche 3 and Corson. 4 The constitution of the system has also been recently investigated by Matuyama, 5 and in the laboratories of the American Brass Co. by Smith. 6 Some of the physical properties of the copper-silicon alloys have been investigated by Norbury7 and by Geiss and Van Liempt.8 Summarizing the results of various investigators of the constitution of copper-silicon alloys, the solubility reaches its maximium value, 6.7 per cent. silicon, between 721" and '782" C. At 852" (1. the solubility is 5.25 per cent., while at 400" C. it is only 4.1 per cent. silicon. The copper-silicon alloy begins to get so hard at about 3 per cent, silicon that it is difficult to manage. It was found by Jacobs that the addition of manganese to this alloy considerably improved the working

Jan 1, 1929