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By M. C. Cheney

The active development of the vast East Texas oil field, the attendant effects of the rapidly increasing flow from its prolific wells and the efforts to bring order out of chaos precluded or dwarfed other oil development in Texas during 1931. In a paper by Dr. F. H. Lahee1 presented at the October, 1931, meeting, the early history of the East Texas oil field is described and the sequence of events in connection with its development and efforts to control its production up to Sept. 25 is narrated. At that time the Railroad Commission of the state reduced the production of the field to a maximum of 400,000 bbl. per day by restricting the allowable daily production per well to 185 bbl. By further reduction in the daily production per well to 100 bbl., the field was held below that maximum figure during the remainder of the year. Meanwhile, as a result of an injunction against the Railroad Commission, its authority in the field was superseded on Oct. 13 by the Governor of the state, and after that date production was controlled directly by his orders issued under authority of martial law. Suits to contest this authority were brought in the Federal courts and were pending at the close of the year. On March 5, 1931, as a result of the East Texas production, posted prices for Mid-Continent 40' A.P.I. crude slumped from $1.07 to $0.67. As East Texas production continued to mount, posted prices in East Texas were reduced to $0.37 on June 3 and $0.22 on July 8, although in that field most of the oil was sold for much less, bringing the producer and royalty owner as low as $0.025 per barrel. Northeast Texas To the information contained in Dr. Lahee's paper, it can now be added that the East Texas field has produced over 105,000,000 bbl. and registered about 3700 successful completions during 1931. There may be some merit to the recent prediction that a large part of the field will have passed its flowing period by the middle of 1932 unless

Jan 1, 1932

By Henry S. Mackay

The interesting paper recently submitted by Messrs. Tobelmann and Potter1 shows that chemical problems have developed which are of great interest in this new and important branch of metallurgy. Those who realize what a process of this kind really involves will agree that it deserves a better name than '(leaching process." The word leaching conveys the idea that the copper is simply leached out of the ore with acid and then precipitated on iron; the chemistry of such a process would be of little interest. As, however, during the first year's operation of this plant 24,400,532 lb. (11,067,837 kg.) or about two-thirds of the produce, was electrolytic copper, while 7,992,033 lb., or about one-third, was cement copper, it would seem more appropriate to term the process electrochemical. It further appears, from the particulars given, that efforts have been made to have the entire production in the form of electrolytic copper. This could be done if the chemistry of the problem were kept in balance, so that it would not be necessary to discard any solutions that carried copper and acid of commercial value. A process, such as that under consideration, in which the copper is precipitated from solution by electrolysis, the solvent being at the same time regenerated, is one that requires special chemical and electrochemical knowledge and experience if all the copper in solution that has been extracted from the ore is to be successfully and economically produced as electrolytic copper. The object of this paper is to discuss, from the practical and theoretical standpoints, the chemical and electrochemical problems involved in the working of a process of this kind, and which must be solved to keep it in chemical and electrochemical equilibrium. In such a process, if the chemical balance is maintained, a solution can be used alternately as a solvent for the copper in the ore and as an electrolyte of high efficiency for the precipitation of the copper. To maintain the chemical equilibrium and so attain this result, the process must be so controlled that the solu-

Jan 1, 1921

By Alden B. Greninger

Although the crystallography of lattice transformations has been studied extensively during the past few years, these studies have been limited, with few exceptions1'2, to specimens in which the transformed lattice appears as a segregate phase. A realization of the technical importance of the segregation mechanism, especially in the formation of martensitic structures and in age-hardening phenomena, has undoubtedly stimulated research in this direction. In the crystallographic studies of segregation, the general problem has been to relate the orientation of the parent crystal to that of the segregate crystals. The technique has been complicated by the fact that it has been necessary to deal with the presence of as many as 24 ideal segregate orientations within one parent lattice; furthermore, the segregate lattices are invariably scattered (seldom less than ±2º, often as much as 15" or 20') about these ideal positions. It is probable that a more complete picture of phase transformations may result from a study in which complete lattice relationships between individual grains are evaluated, thereby providing an additional parameter which when it is necessary to work with multiple segregate orientations, cannot be evaluated. The present paper presents the results of such a study, ? wherein a peritectic reaction is made use of to produce the transformed lattices. Matebials and Methods Pem'tectic Reaction.—In Fig. 1 is reproduced a portion of the copper-zinc equilibrium diagram, which includes the peritectic reaction a + liq. —ß. A liquid of composition between B and D upon solidifying will

Jan 1, 1937

By B. Otto Pixler

Mud-analysis logging provides identification of the fluid content of formations drilled by the rotary method and permits the accurate correlation of oil and gas shows with the depth. Mud-analysis logging eliminates much coring and has an especially important application in drilling programs when coring is particularly hazardous or the electric log is difficult to interpret correctly. An appreciation of the factors that influence the results of the mud analysis, such as rate of penetration, mud properties, coring, and characteristics of reservoir rock as related to the "flushing effect," permits a better understanding of the mud-analysis log. Recent studies of the relationship of the two gas readings obtained by the gas-detector instrument have proved significant. The difference between the total combustible gas reading and the higher molecular weight gas reading indicates the presence of methane. With few exceptions, zones not showing an increase of methane probably can be condemned. Mud-analysis logging furnishes valuable information, which generally cannot be obtained by other methods. Introduction Logging by mud analysis of wells drilled with rotary tools is a direct method of locating oil-and-gas-bearing formations. The use of this method of logging has increased each year until now more than 20 field units are being used in 13 oil-producing states and in some foreign countries. Several papers1-9 have been published in the petroleum trade journals describing in detail the equipment and the application of mud-analysis logging. This paper will discuss briefly the method and review its application and some of the late developments. Method As the drilling of a well progresses, the drilling bit dislodges and disintegrates a cylindrical section of the formation. If oil or gas is contained in the pore spaces of the cylinder, some of the contents of these porous spaces will be entrained in the drilling fluid. In wall logging by mud analysis, the mud is continuously examined for oil and gas on its return to the surface, and the results are correlated back to the actual depth of the hole at the time the mud was clearing the eyes of the bit. The test for gas is made by diverting a portion of the circulating mud from the flow line to a separator or gas trap, where the mud is thoroughly mixed with air and a portion of the gas entrained in the mud is removed. A stream of air is drawn coun-tercurrent to the flow of mud in the gas trap, thus materially assisting the separation of the gas from the mud. The air-gas mixture is then drawn into a "hot-wire" gas-detector instrument where the percentage of the combustible gas is determined. The presence of oil in the formation drilled is detected by a physical examination of the drilling mud under ultraviolet light. A sample of the mud is treated to reduce the surface tension and gel strength, after which it is placed in a viewing box. This box is so constructed that all external light is excluded and so that the sample may be subjected selectively to either ultra-

Jan 1, 1946

By B. Otto Pixler

Mud-analysis logging provides identification of the fluid content of formations drilled by the rotary method and permits the accurate correlation of oil and gas shows with the depth. Mud-analysis logging eliminates much coring and has an especially important application in drilling programs when coring is particularly hazardous or the electric log is difficult to interpret correctly. An appreciation of the factors that influence the results of the mud analysis, such as rate of penetration, mud properties, coring, and characteristics of reservoir rock as related to the "flushing effect," permits a better understanding of the mud-analysis log. Recent studies of the relationship of the two gas readings obtained by the gas-detector instrument have proved significant. The difference between the total combustible gas reading and the higher molecular weight gas reading indicates the presence of methane. With few exceptions, zones not showing an increase of methane probably can be condemned. Mud-analysis logging furnishes valuable information, which generally cannot be obtained by other methods. Introduction Logging by mud analysis of wells drilled with rotary tools is a direct method of locating oil-and-gas-bearing formations. The use of this method of logging has increased each year until now more than 20 field units are being used in 13 oil-producing states and in some foreign countries. Several papers1-9 have been published in the petroleum trade journals describing in detail the equipment and the application of mud-analysis logging. This paper will discuss briefly the method and review its application and some of the late developments. Method As the drilling of a well progresses, the drilling bit dislodges and disintegrates a cylindrical section of the formation. If oil or gas is contained in the pore spaces of the cylinder, some of the contents of these porous spaces will be entrained in the drilling fluid. In wall logging by mud analysis, the mud is continuously examined for oil and gas on its return to the surface, and the results are correlated back to the actual depth of the hole at the time the mud was clearing the eyes of the bit. The test for gas is made by diverting a portion of the circulating mud from the flow line to a separator or gas trap, where the mud is thoroughly mixed with air and a portion of the gas entrained in the mud is removed. A stream of air is drawn coun-tercurrent to the flow of mud in the gas trap, thus materially assisting the separation of the gas from the mud. The air-gas mixture is then drawn into a "hot-wire" gas-detector instrument where the percentage of the combustible gas is determined. The presence of oil in the formation drilled is detected by a physical examination of the drilling mud under ultraviolet light. A sample of the mud is treated to reduce the surface tension and gel strength, after which it is placed in a viewing box. This box is so constructed that all external light is excluded and so that the sample may be subjected selectively to either ultra-

Jan 1, 1946

By A. A. Smith

The application of indium to bearings was first advocated by C. F. Smsrtl in 1938, for the purpose of inhibiting corrosion of certain bearing alloys. He found that a thin layer of indium plated on the bearing surface and subsequently diffused at elevated temperatures markedly decreased the rate of corrosion in lubricating oils containing organic? acids. Most of his work was done on cadmium-base alloys, although he showed that the treatment was also effective for copper-lead and other; alloys. Since their introduction, indium-treated bearings have found considerable use, particularly in connection with airplane motors.2 Undoubtedly the effectiveness of the indium plate in resisting corrosion depends upon its relative concentration on the bearing surface after the diffusion treatment and after prolonged use at operating temperatures. Some diffusion experiments were made on a number of base metals that had been indium plated, to determine the depth of penetration after heating for reasonably long periods of time. As only the practical aspects were desired, no attempt was made to determine actual diffusion constants. Method Two different series of experiments were carried out to study the diffusion of indium into several base metals. Cast cylinders about one-inch diameter were machined to 0.750-in. diameter, so as to remove all surface imperfections, and final finishing was done with oo sandpaper. The original diameters were very carefully measured with micrometers and then a layer of indium was electrolytically deposited on the cylinders from a sulphate bath.3 In the first series of experiments, about 0.002 in. of indium' was deposited and diffusion, was carried out at 150°C. for a period of 500 hr. in a thermostatically controlled electric oven. After the diffusion period, successive layers were machined from the specimens and analyzed spectro-graphically and chemically—the spectro-graphic examination serving as a guide to determine which layers should be chemically analyzed. Apparently there was some surface oxidation of the indium plate due to the long heat-treatment, which may have had some effect on the diffusion. A1so, the cadmium alloy showed some incipient melting, which probably was caused by the formation of a low-melting eutectic. To eliminate these factors, another series of experiments was carried out by heating in an electrically heated, automatically controlled, oil bath at lower temperature. The preparation of the specimens was the same as before except that a layer of indium 0.0001 in. thick, an amount commonly used commercially on bearings, was deposited on each of the cylinders. Diffusion was carried out at 120°C. for a period of 200

Jan 1, 1944

By A. A. Smith

The application of indium to bearings was first advocated by C. F. Smsrtl in 1938, for the purpose of inhibiting corrosion of certain bearing alloys. He found that a thin layer of indium plated on the bearing surface and subsequently diffused at elevated temperatures markedly decreased the rate of corrosion in lubricating oils containing organic? acids. Most of his work was done on cadmium-base alloys, although he showed that the treatment was also effective for copper-lead and other; alloys. Since their introduction, indium-treated bearings have found considerable use, particularly in connection with airplane motors.2 Undoubtedly the effectiveness of the indium plate in resisting corrosion depends upon its relative concentration on the bearing surface after the diffusion treatment and after prolonged use at operating temperatures. Some diffusion experiments were made on a number of base metals that had been indium plated, to determine the depth of penetration after heating for reasonably long periods of time. As only the practical aspects were desired, no attempt was made to determine actual diffusion constants. Method Two different series of experiments were carried out to study the diffusion of indium into several base metals. Cast cylinders about one-inch diameter were machined to 0.750-in. diameter, so as to remove all surface imperfections, and final finishing was done with oo sandpaper. The original diameters were very carefully measured with micrometers and then a layer of indium was electrolytically deposited on the cylinders from a sulphate bath.3 In the first series of experiments, about 0.002 in. of indium' was deposited and diffusion, was carried out at 150°C. for a period of 500 hr. in a thermostatically controlled electric oven. After the diffusion period, successive layers were machined from the specimens and analyzed spectro-graphically and chemically—the spectro-graphic examination serving as a guide to determine which layers should be chemically analyzed. Apparently there was some surface oxidation of the indium plate due to the long heat-treatment, which may have had some effect on the diffusion. A1so, the cadmium alloy showed some incipient melting, which probably was caused by the formation of a low-melting eutectic. To eliminate these factors, another series of experiments was carried out by heating in an electrically heated, automatically controlled, oil bath at lower temperature. The preparation of the specimens was the same as before except that a layer of indium 0.0001 in. thick, an amount commonly used commercially on bearings, was deposited on each of the cylinders. Diffusion was carried out at 120°C. for a period of 200

Jan 1, 1944

By A. B. Cook

Gas cycling is generally considered a much less efficient oil recovery mechanism than water flooding. HOWever, recoveries from some fields have been exceptionally high as a result of gas cycling. Recovery from the Pick-ton field, for example, was calculated to be 73.5 perceni of the stock-tank oil originally in place. In evaluating pressure maintenance projects, determining how much of the recovery is due to displacement by gas and determining how much is due to vaporization of the imrnohile oil in the flow path of the cycled gas is very difficrilt. Even though most of the oil is recovered by displacetr~ent, the success of a project may depend on the amount of oil vaporized. A limited number of experiments have heen performed with a rotating model oil reservoir that simulates gas cycling operations and allows a separation of the oil from, tile free gas flowing into the laboratory wellbore at reservoir conditions, thus revealing which is displaced oil and which is vaporized oil. It Iras been determined that the amount of varporizatio'n is .significant if proper conditions exist These experiments show that oil vaporization depends on pressure, temperature, volatility of the oil and amount of gas cycled. Increases in each of these conditions increase the volume of oil vaporized. Data from six experiments affecting vaporization are presented to illustrate reservoir condition that range from favorable to unfavorable. 111 these eaperitnenis recovery by vaporization ranged from 73.6 to 15.3 percent of /he immobile oil (oil not produced by gas displacerrlt). INTRODUCTION Between 1930 and 1950, gas cycling was a popular. oil recovery practice. especially for the deeper reservoirs. Later, with many case history-type studies published for both gas cycling and waterflooding, it was generally believed that waterflooding was far superior to gas cycling, even when gas cycling was conducted as a primary production procedure by complete pressure maintenance. A good example illustrating the advantage of water-flooding over gas cycling is given in a paper by Matthews' on the South Burbank unit where gas injection was followed by waterflooding. The author concluded in part that "Early application of water injection, without the intervening period of gas injection, would have recovered as much total oil as ultimately will be recovered by waterflooding following the gas injection, and total operating life would have been shortened". This appears to be a logical conclusion. However, it should not be applied to all fields. Pressure maintenance with gas in the Pickton field, as reported by McGraw and Lohec;' will result in a much larger percentage of oil recovery than was obtained in the South Burbank unit. The great success in the Pickton field resulted partly from vaporization of the immobile oil in the flow path of the cycled gas. The amount of vaporization is related to the following conditions: volatility of the oil as reflected by the APT gravity of the stock-tank oil; reservoir temperature; reservoir pressure during gas cycling; and the amount of gas cycled. Therefore, the U. S. Bureau of Mines is investigating these effects on vaporization in a research project using a model oil reservoir. Three different stock-tank oils having 22, 35 and 45" API gravities are being used as base stock to synthesize reservoir oils. Experiments are being performcd to determine vaporization at 100, 175 and 250F and at 1,100, 2,600 and 4,100 psia. This is a progress report showing the results from six experiments. Other Bureau of Mines reports"- concerning vaporization are listed. LABORATORY EQUIPMENT AND PROCEDURES The equipment ' consists of an internally chromium-plated steel tube packed with finely sifted Wilcox sand. The tube is approximately 44 in. long and has an ID of 13/4 in. The sand section contains approximately 570 ml of voids, has a porosity of 32 percent, and a permeability to air of 4.3 darcies. A unique feature of the laboratory reservoir (Fig. 1) permits the tube part to rotate at 1 rpm while the outlet and inlet heads are held stationary. The outlet end contains diametrically opposed windows to permit observatlon of the flowing fluids, and two valves, one on the top and the other at the bottom. Oil and free gas. when being produced simultaneously, can be separated by manipulating the two valves to keep a gas-oil interface in view through the windows. Thus, only gas is produced through the top valve and only oil flows through the bottom valve. The laboratory equipment was designed to study vaporization. Therefore, a uniform reservoir was made using dry sifted sand as opposcd to using a consolidated sand core with interstitial water. Furthermore. the reservoir was tilted to minimize fingering of gas. This tilting also in-

By R. H. Moore

The data for diffusion in dilute binary alloys with the Solvents Ag, Cu, Ni, Fe. Al. and Pb hare been correlated as a function of atomic volume. Linear equations of the form: Q = b - a log V are obtained with constants "a" and "b" ciuirac-teristic of each solvent metal. In most cases. 3-d In recent years measurements of diffusion coefficients in solid binary alloys. using small concentrations of radioactive isotopes. have resulted in accumulation of highly reproducible data. Such and 4-d transition elements correlate on separate straight lines from those which serve to correlate the non/ransition elements. The data for the uon-transilion elements diffusing in silver and copper liave been fitted by least-squares analysis. It is concluded that the size and charge effects which determine the magnitude of the activation energy for diffusion are a function of atomic volume. systems represent the simplest possible examples of chemical diffusion since solute interaction effects can be neglected and Kirkendall-like phenomena do not occur. Generally it is found that thc diffusion rate of the solute is within an order of magnitude of the diffusion rate of the solvent. The differences have been attributed to the effect of size and to electrostatic interactions between the solute and solvent atoms.

Jan 1, 1965

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

THE phase diagram of the Ge-Te system was first investigated by Klemm and Frischmuth.' They arrived at the phase diagram shown in Fig. 1 indicating the presence of a peritectic phase boundary at the 50 at. pct Ge composition. Later, Schubert and Fricke2 obtained data which suggested to them the possible existence of a eutectic at about 55 at. pct Ge. In order to resolve these differences, we have carefully studied this system in the region 40 to 60 at. pct Ge using both the conventional thermal analysis technique and a new solidification technique.3y4 The alloys were prepared from semiconductor grade germanium and 99.999+ Te by reacting the elements in evacuated, graphite coated, vycor tubes. The samples were placed in a thermal analysis apparatus described elsewhere4 and cooling curves were taken of each alloy to determine the liquidus surface. The cooling curve for a 50 at. pct alloy shows two distinct arrests about 1°C apart which

Jan 1, 1961

By G. E. Archie

The usefulness of the electrical resistivity log in determining reservoir characteristics is governed largely by: (I) the accuracy with which the true resistivity of the formation can be determined; (2) the scope of detailed data concerning the relation of resistivity measurements to formation characteristics; (3) the available information concerning the conductivity of connate or formation waters; (4) the extent of geologic knowledge regarding probable changes in facies within given horizons, both vertically and laterally, particularly in relation to the resultant effect on the electrical properties of the reservoir. Simple examples are given in the following pages to illustrate the use of resistivity logs in the solution of some problems dealing with oil and gas reservoirs. From the available information, it is apparent that much care must be exercised in applying to more complicated cases the methods suggested. It should be remembered that the equations given are not precise and represent only approximate relationships. It is believed, however, that under favorable conditions their application falls within useful limits of accuracy. Introduction The electrical log has been used extensively in a qualitative way to correlate formations penetrated by the drill in the exploitation of oil and gas reservoirs and to provide some indication of reservoir content. However, its use in a quantitative way has been limited because of various factors that tend to obscure the significance of the electrical readings obtained. Some of these factors are the borehole size, . the resistivity of the mud in the borehole, the effect of invasion of the mud filtrate into the formation, the relation of the recorded thickness of beds to electrode spacing, the heterogeneity of geologic formations, the salinity or conductivity of connate water, and, perhaps of greatest importance, the lack of data indicating the relationship of the resistivity of a formation in situ to its character and fluid content. On the Gulf Coast it is found that the effects of the size of the borehole and the mud resistivity are generally of little importance, except when dealing with high formational resistivities or extremely low mud resistivities. Fortunately, little practical significance need be attached to the exact values of the higher resistivities recorded. Low mud resistivities are not common, but when this condition is encountered it may be corrected by replacing the mud column. With the present advanced knowledge of mud control, invasion of mud filtrate into sands can be minimized, thereby increasing the dependability of the electrical log. The effect of electrode spacing on the recorded thickness of a bed is often subject to compensation or can be sufficiently accounted for to provide an acceptable approximation of the true resistivity of the formation. As development of a field or area progressively enhances the knowledge of the lithologic section, the resistivity values of the electrical log take on greater significance, ultimately affording acceptable interpretations. The salinity, and

Jan 1, 1942

By G. E. Archie

The usefulness of the electrical resistivity log in determining reservoir characteristics is governed largely by: (I) the accuracy with which the true resistivity of the formation can be determined; (2) the scope of detailed data concerning the relation of resistivity measurements to formation characteristics; (3) the available information concerning the conductivity of connate or formation waters; (4) the extent of geologic knowledge regarding probable changes in facies within given horizons, both vertically and laterally, particularly in relation to the resultant effect on the electrical properties of the reservoir. Simple examples are given in the following pages to illustrate the use of resistivity logs in the solution of some problems dealing with oil and gas reservoirs. From the available information, it is apparent that much care must be exercised in applying to more complicated cases the methods suggested. It should be remembered that the equations given are not precise and represent only approximate relationships. It is believed, however, that under favorable conditions their application falls within useful limits of accuracy. Introduction The electrical log has been used extensively in a qualitative way to correlate formations penetrated by the drill in the exploitation of oil and gas reservoirs and to provide some indication of reservoir content. However, its use in a quantitative way has been limited because of various factors that tend to obscure the significance of the electrical readings obtained. Some of these factors are the borehole size, . the resistivity of the mud in the borehole, the effect of invasion of the mud filtrate into the formation, the relation of the recorded thickness of beds to electrode spacing, the heterogeneity of geologic formations, the salinity or conductivity of connate water, and, perhaps of greatest importance, the lack of data indicating the relationship of the resistivity of a formation in situ to its character and fluid content. On the Gulf Coast it is found that the effects of the size of the borehole and the mud resistivity are generally of little importance, except when dealing with high formational resistivities or extremely low mud resistivities. Fortunately, little practical significance need be attached to the exact values of the higher resistivities recorded. Low mud resistivities are not common, but when this condition is encountered it may be corrected by replacing the mud column. With the present advanced knowledge of mud control, invasion of mud filtrate into sands can be minimized, thereby increasing the dependability of the electrical log. The effect of electrode spacing on the recorded thickness of a bed is often subject to compensation or can be sufficiently accounted for to provide an acceptable approximation of the true resistivity of the formation. As development of a field or area progressively enhances the knowledge of the lithologic section, the resistivity values of the electrical log take on greater significance, ultimately affording acceptable interpretations. The salinity, and

Jan 1, 1942

By C. G. Dunn, E. F. Koch, K. T. Aust

Strain-induced grain boundary migration was studied in a series of silicon-iron (3% pct Si) bicrystals of controlled orientations. Each bicrystal was given a 7 pct cold-rolling strain rind annealed at 1100°C. The direction of boundary migration was found to depend on orientation; results for several orientations related by a common [110] axis are given. Analysis of the micrographic and X-ray data is made in terms of the residual strain-energy densities within the crystals (energy per unit volurne) and a driving force on the boundary due to an energy density difference across the boundary. Relative strain energies were obtained for the various orientations investigated. A CHROME-acetic acid electroetching method for revealing dislocation sites in silicon iron was previously applied to clarify the structural features and the energetics involved in strain-induced grain boundary migration.',' The present paper is a continuation of this study, but is primarily concerned with the influence of crystal orientation. Sperry, as reported by Beck,3 attempted to determine the factors that influence the preferred growth of one grain over another in aluminum due to strain-induced boundary migration. He found that the particular grain of a pair which work hardened more was invaded, although exceptions to this correlation were noted. The index of work hardening was determined from microhardness measurements of each grain before and after cold-rolling. In the present study, orientation itself was taken as a useful variable for studying the behavior of individual grains in a bicrystal and the direction of boundary migration, since the extent of work hardening is orientation dePendent." The effect of strain on boundary migration is evident from a consideration of driving forces. Thus, in the absence of inclusions, the driving force (per unit area of boundary) for growth of grain A into grain B when a bicrystal is strained and annealed may be expressed as follows:2

Jan 1, 1960

By Randolph Specht

A two year study was made of the waste disposal of the pebble rock phosphate industry. Solid slimes are impounded in large settling areas and the process water is re-used. Clear effluent was not found to be toxic to fish or animal life in field tests or in controlled experiments.

Jan 7, 1950

By Richard B. Reese, George R. St. Pierre, Robert A. Rapp

The vapor pressures of pure iron and pure chromium have been measured using a Knudsen cell coupled with a mass spectrometer. The experimental results agree well with some previously reported data; heats of sublimation and vaporization have been calculated. From vapor pressure rr~easurernents, the activities of iron and chromium in their binary alloys have been determined for NcY = 0.10 to 0.65 over a 1400" to 1700~ temperature range. The activity of chromium in the liquid alloys was found to exhibit positive deviation from ideal behavior when referred to solid chromium as the standard state; however, for the activity of chromium referred to nonequilibrium undercooled liquid chromium as standard state, the activity behavior is almost ideal. ALTHOUGH the Fe-Cr system is important as the basic system of alloy steels, the thermodynamic properties of this system have not been thoroughly investigated at elevated temperatures. In view of the potential practical applications of such data as well as their contribution to alloy theory, further study of the Fe-Cr system was undertaken. In addition, further development of experimental techniques for equilibrium measurements at high temperature is required. The present research involved an application of the Knudsen effusion method in conjunction with a time-of-flight mass spectrometer. Belton and ~ruehan' have measured the activities in Fe-Ni and Fe-Co alloys by a similar method. Speiser, Johnston, and lackbburn' have determined the vapor pressure of pure solid chromium between 1283" and 1561°K by a Langmuir free evaporation technique. The vapor pressure of chromium was described by the expression: over the temperature range 1283" to 1561°K. McCabe, Hudson, and paxton3 have measured the vapor pressures of pure iron and pure chromium by the Knudsen cell technique around 1500°K. The vapor pressure and heat of sublimation at O°K, AH,", for pure chromium agreed within experimental error with the measurements of Speiser et al. at 1200°C. Kubaschewski and HeYmer~ determined the vapor pressure of pure solid chromium in the temperature range 1170" to 1400°C by the Knudsen effusion technique combined with a radioactive tracer analysis of crS1. Their results agreed with the work of previous investigators. Edwards, Johnston, and Ditmars5 have measured the vapor pressure of pure solid iron by the Langmuir technique between 1356" and 1519°K. The vapor pressure of solid iron in the temperature range studied was given by: The data of McCabe, Hudson, and paxton3 on the vapor pressure of pure iron around 1500°K by the Knudsen effusion technique were in good agreement with those obtained by Edwards et a~.~ Hultgren, Orr, Anderson, and Kelley give the selected values for the AH: of pure iron and pure chromium as 98,990 *200 and 94,340 * 500 cal per mole, respectively. These values are the average values determined in the several investigations by different methods. The Fe-Cr phase diagram7 is shown in Fig. 1. Previous determinations of activities in this system have been carried out by several investigators, but most of the work has been done on solid alloys. Using a Knudsen effusion method with cr5', Kubaschewski and Heymer4 reported that the Fe-Cr system exhibits positive deviation from the ideal behavior for compositions ranging from NCr = 0.0398 to 0.699 at 1170"

Jan 1, 1969

By G. R. Fitterer

Trends in slag composition in acid open hearth practice, particularly the variation in iron and manganese oxides during refining, are reviewed. A procedure which is currently being used to control the refining reactions is described and partially explained through slag phase diagram considerations. In addition, the ionic nature of these slags is considered and it is proposed that silica combines with the oxide ion and forms a series of complex silicate ions. The effect of basic oxides such as FeO, MnO, and CaO is apparently additive in furnishing the oxide ion for this purpose. IT is now possible to control192 the refining of steel in an acid open hearth furnace to a surprising degree. This control has been brought about through the knowledge and use of several facts and tests. These are: 1—A planned charge analysis based on a knowledge of the type of fuel, the bath depth, etc. 2—Knowledge and control of rate of fuel input as well as its method of atomization, if any. 3—Determination of the slag fluidity. 4—Bath temperatures (use of the Pt-Pt-Rh thermocouple). 5—Periodic determination of carbon content (use of the Carb-analyzer or Carbometer). Through the use of these control methods, a heat may be made to "melt-in" with or without residual manganese and silicon. The rate of refining or carbon elimination may be controlled accurately, and the desired tapping (or "go-ahead") carbon may be approached at a rapid or slow rate according to preference and type of steel being made. Thus operating time may be predetermined and greatly reduced. Further, all of the refining can be done without any ore or other oxidizing additions, and the heat may be brought to the desired tapping temperature simultaneously with the attainment of the desired carbon analysis. This control procedure is being used in most acid plants in the United States today and has been de- scribed.', ' Although the slag metal relations are sufficiently well known to control the heat as stated, yet it is possible to account for only about two-thirds' of the 0, which must have been used for the elimination of the carbon and other metalloids. Phase diagram studies' of the slags, slag weights, the metal particle theory,' ore additions, limestone additions, etc., may all be taken into consideration; yet, the mechanism of oxidation and source of all the oxygen remain to be explained. This paper reviews some of the principles upon which the control methods were based and proposes other possibilities regarding the unexplained phenomena. Old and New Acid Open Hearth Practice Some of the recent statements in the literature regarding acid open hearth operation are based on old heat data which are not typical of modern American practice. These old heat logs have been responsible for many misconceptions regarding the acid hearth practice and represent heats which do not coincide with modern methods. In recent years, American practice has been altered materially and these changes will be briefly described. Modern American Practice: A typical log of a modern American acid open hearth heat' is shown in Fig. 1 which indicates that the refining time was only two hours, during which the carbon was eliminated rapidly and the bath temperature increased at a fast rate. The manganese and silicon contents of the metal were essentially eliminated and their oxides had become constituent parts of the slag at the "melt-down" period. During the course of the heat, the MnO content of the slag remained practi-

Jan 1, 1954

By John G. Simmons

A tutorial account of the tunnel effect between metal electrodes separated by a thin insulating film is presented. Energy diagrams of metal-insulator -metal sandwiches are briefly discussed, and the isothermal and thermal J-V characteristics for symmetric and asymmetric tunnel junctions are derived from a generalized expression. Experimental data from tunnel junctions are presented, and it is shown how, correlation between theory and experiment permits a determination of some of the oxide properties. Finally, the barrier heights in AT-Al2O3-A1 junctions determined by various inr3estigators are discussed. The object of this paper is to give a tutorial account of the electric-tunnel effect between metal electrodes separated by a thin insulating film and to illustrate its utility in the study of metal-oxide interfaces. This paper will emphasize the theoretical aspects of the electric-tunnel effect: however, a brief account of the more recent experimental work will be presented. A more comprehensive experimental study of the tunnel effect will be presented in the following paper by Drs. Pollack and Morris, see p. 497. We will open with a discussion of the energy diagrams for metal-insulator-metal junctions and what we mean by the electric-tunnel effect. Following this is an account of the theoretical studies of Sommerfeld and Bethe, and Holm, and the recently reported calculations on symmetric and asymmetric junctions using the generalized formula. The theoretical presentation is concluded with calculations on the temperature dependence of the tunnel J-V characteristic. In the experimental section, it is shown how barrier heights and thicknesses are determined by comparing the experimental data with the theory. Finally, the results of various investigators on the determination of the barrier heights in Al-Al2O,-A1 systems are discussed. I) POTENTIAL BARRIERS BETWEEN CLOSELY SPACED ELECTRODES Since it is necessary to supply energy to a metal in order to observe electron emission from its surface, it is evident that the potential energy of an electron within a metal is lower than that of an electron at rest outside the metal. It follows, then, that the electron must undergo a change in potential as it crosses the metal-vacuum interface. In the Sommerfeld1 free-electron theory of metals it is assumed that the free electrons, the electrons responsible for the electrical characteristics of metals, move in a constant potential environment in the metal, and are contained within the metal by a potential barrier at the metal-vacuum interface. It will be evident that the idea of a constant potential environment is a very idealized model, since the potential energy of an electron is influenced by all of the atoms and the other electrons within the metal; however, its use is justified by the many excellent results it gives.2 Fig. l (a) is the energy diagram of the model envisaged by Sommerfeld; the metal is represented by a potential-energy well of depth V,; the vacuum level represents the energy of an electron at rest outside the metal. At 0°K the electrons, which exist in pairs in discrete energy levels, fill up the well to an energy ?, the Fermi level. The distance, Vo - ?, from the Fermi level to the vacuum level is known as the work function of the metal, and represents the minimum energy required to free electrons from the interior of the metal at 0°K.

Jan 1, 1965

By W. H. Emmons

Although gold is one of the rarer metals, it is widely distributed; it is found on all of the continents and in each of the grand metallogenic provinces of the earth. It is prominent particularly in the shield areas of the earth; these areas have produced a large part of the world's lode gold and in most of them gold lodes are more important than the lodes of other metals. The Scandinavian shield is the only one that has not produced much gold. Nearly all of the world's gold has been derived from lodes and from sands and gravels where gold placers formed by the destruction of lodes. The gold derived from magmatic segregations, from pegmatites and from contact metamorphic deposits is quite subordinate to that derived from auriferous lodes. The lodes include all veins and related deposits that are formed by hot waters that move along fissures or other openings and that deposit vein 'matter :in the fissures and by replacement of the country rocks along the fissures. All of the shield areas of the earth are characterized by large areas of granitic rocks including granitic gneisses, granodiorites and other acid intrusives which here are included in the general term "granite." The granites are intruded into schists, ancient lavas and other rocks which here are designated as the "invaded" rocks. The granites are parts of what once were great batholiths: that is, they are the remaining portions of great deep-seated bodies that slope outward, have very irregular roofs and so far as known have no floors but extend downward to great though unknown depths. Some of them are scores or hundreds of miles across and contain islands or "roof pendants" of the invaded rocks at places where the roofs of the batholiths were low—that is, where erosion has not yet completely unroofed the batholiths. It is in these islands of older rocks and in the narrow marginal belts and cupolas of the batholiths that practically all of the gold lode deposits of the shields are found. Valuable lodes are lacking generally in the granites themselves except in grahite within a mile or less from .the contacts with rocks of the islands (Fig. 1). It is probable that the great areas of granites and gneisses that surround the islands are not all of the same age, and that at places unmapped granite intrudes gneiss or older

Jan 1, 1932

By Edgar Marburg, William R. Webster

The desirability of bringing about greater uniformity in specifications governing iron and steel is generally recognized, and has found expression within recent years, in the efforts of numerous technical societies in that direction. When the International Association for Testing Materials was organized at Zurich in 1895, a committee was appointed, charged as follows: " On the basis of existing specifications, to seek methods and means for the introduction of international specifications for testing and inspecting iron and steel of all kinds." The American representation on this international committee consisted originally of five, and now of eight members. In view of the magnitude and importance of the subject, the Executive Committee of the American Section of the International Association for Testing Materials, since incorporated as the American Society for Testing Materials, appointed a committee of 34 members, including the American members of the above-named international committee, to frame standard American specifications for iron and steel. This committee reported on specifications for (1) Structural Steel for ridges and Ships; (2) Structural Steel for Buildings; (3) Open-Hearth Boiler-Plate and Rivet-Steel; (4) Steel Rails; (5) Steel Splice-Bars; (6) Steel Axles; (7) Steel Tires; (8) Steel Forgings; (9) Steel Castings ; (10) Wrought-Iron. These specifications were designed to be fairly representa-tive of the best current American practice, and were adopted by letter-ballot of the Society in August, 1901. The leading engineering societies have participated at various times in the discussion of these specifications and have lent valuable assistance through the appointment of special committees on like, or closely related, subjects. The American Society of Civil Engineers discussed the spec-

Jan 1, 1905

By N. Rowlands, J. A. Finch, R. Espinosa-Gomez

The sulphation roast-leach process for complex sulphides results in phase changes due to roasting and leaching. The phases in the calcine, and in the neutral and hot acid leach residues were identified and their degree of liberation determined in order to design and Interpret separation tests on the residues. The hot acid leach residue was composed of hematite, silica, and lead sulphate with some associated silver. Magnetic separation was selected as the process for producing a lead concentrate, as the non-magnetic product. Separation was limited by -1 pm hematite reporting to the product, and hematite/lead sulphate agglomerates reporting to the magnetics.

Jan 1, 1984