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By Warren J. Jackson, John L. P. Campbell

Automatic recording of the radioactivity of the earth's formations provides a log of relative intensities that, if properly interpreted, can be applied to oil-field engineering. Production, engineering, and geological departments regard the radioactivity log as a forward step in the securing of more conclusive information for successful well completions. Explanations of the technique, together with some of the problems to which radioactivity logging have been applied, are presented in this paper. Introduction Those responsible for the completion of new oil and gas wells, or with planning workover operations on old wells, have followed closely the development of radioactivity well logging because they are interested in reducing the number of unknowns that usually are present in such work. Many operators have made use of the log, or are acquainted with at least one of the applications, but it is unlikely that any one operator is familiar with all of the many applications that are possible. The purpose of this paper is to present a representative example of each of the many applications, wherever the information has been released by an operator, and to illustrate by hypothetical examples other applications, releases for which have not been given. In this way, it is hoped that a better understanding of the scope of this new engineering tool may be obtained. Although the literature contains many references that describe in detail the theory, development, and application of radioactivity well logging, a brief discussion of the technique may be helpful to those who are investigating the subject for the first time. All rocks contain radioactive material in varying concentrations. In general, shales contain relatively more radioactive material than sandstones or limestones. These radioactive materials disintegrate with time into other materials of lower atomic weight, and in that process of disintegration the rocks are emitting many rays, the most penetrating of which is the gamma ray. The intensity of emission of the gamma ray is proportional to the quantities of radioactive materials present. A higher rate of emission would be observed, therefore, opposite a shale than opposite a sandstone or limestone. Since measurable intensities of gamma rays are capable of penetrating as many as five concentric strings of casing, and as the gamma-ray intensity is relative to the formations, the measurements of variations in gamma-ray intensities offer a means of identifying cased-off formations in their proper stratigraphic sequence. The Gamma-ray Curve The measurement of gamma-ray intensities is accomplished by means of an ioniza-tion chamber that consists of a heavy cylinder, about 3 ft. long, that contains two insulated electrodes and is filled with an inert gas under high pressure. Under normal conditions no current will flow through the gas when an electrical potential is set up between the electrodes, but when

Jan 1, 1946

By T. H. Dunn, P. L. Menaul

This paper discusses the results of an investigation made to develop a method of combatting corrosion of subsurface oil-well equipment caused by brines containing hydrogen sulphide. Carbon monoxide, aldehydes, and certain cyanide compounds were found by laboratory tests to effectively inhibit corrosion of steel by sulphide brines. Experiments were made for one year in eight wells in West Texas fields using formaldehyde as an inhibitor. It was found that the inhibitor treatment successfully prevented the severe corrosion previously experienced in these wells, and effected important net savings in operating costs. Introduction Corrosion of oil-field equipment has long been a problem in areas producing sour crudes. These areas include the major fields of Arkansas, Western Kansas, West Texas and New Mexico. Corrosion in these fields is caused primarily by the chemical action of hydrogen sulphide in the presence of water and by electric currents entering the wells through flow lines. Hydrogen sulphide is noncorrosive to iron or steel in the absence of water but under the usual conditions prevailing in oil wells where more or less water is present, hydrogen sulphide is very corrosive. This type of corrosion occurs over the pH range below 9, which includes all natural oil-field brines. If air is present in addition to hydrogen sulphide and water, corrosion proceeds at an extremely rapid rate. It was reported several years ago that a string of oil-well tubing was literally dissolved within 50 days where an air lift was used on a well producing considerable water and hydrogen sulphide. Air is generally absent in wells producing sour crude. After hydrogen sulphide corrosion starts, it proceeds with increasing severity and its correction becomes progressively more difficult. This characteristic of sulphide corrosion has been attributed to the formation of galvanic couples between the iron and steel equipment on one hand and the products of corrosion on the other.' Severe corrosion of subsurface oil-well equipment leads to a multitude of troubles. In addition to destruction of costly equipment, producing sands often are damaged by flooding with water leaking through corroded casing; bad mechanical conditions may develop in a well due to obstructions caused by corroded equipment lost in the hole, or partly collapsed casing; pumping operations are interfered with, and severe emulsification problems may result from the homogenizing action of corroded balls and seats.% A typical case of severe corrosion caused by hydrogen sulphide was reported in Howard County, Texas, where it was necessary to pull tubing once a week to repair leaks after the tubing had been in use for only one year. On one well in this area a string of tubing was pulled 11 times in 8 months; 11 joints of tubing being replaced because of leaks. In Ector

Jan 1, 1946

By V. J. Driscoll

A method is given for checking pore volume reserve estimates and transient water inflzix factors utilizing early well performance. Principal applications are based on the observation that there is a convenient transient time-range in terms of well spacing in which observed pressure drop will give a good indication of fluid-in-place. Primary quantity determined is a porosity-feet value applicable in the vicinity of an observation well. Checks on porosity or net pay thickness and permeability values also are obtained. These are particularly valuable in improving quality of interpretive factors entering into pore-volume reserve determinations for larger fields. In smaller fields, direct determination of total field reserves and approximate location of boundaries may be made in some cases. Well interference and production data plus a build-up curve on the observation well are needed. The build-up curve may be taken at any time. Field applications are given. The method can be applied with the completion of the second well on a new discovery or to older reservoirs by major changes in withdrawal rates from a local area. Appropriate test length permits results to be obtained with equal accuracy on widely spaced wells. Criteria for optimizing test conditions are given. Provision is made for various boundary and well effects including incomplete observation well build-up. INTRODUCTION Due to low quality data, initial pore volume reserve and water influx estimates may often vary by a factor of two or more from results obtained at a later date. Unfortunately, by conventional methods, more reliable answers from performance usually are not available until after most significant economic decisions have been made. Furthermore, in older reservoirs, uncertainties may still exist as to original oil-in-place, recovery factors and residual oil saturations due to incomplete or inaccurate performance data. This paper outlines situations and appropriate arrangements of basic transient theory whereby well interference data can be utilized to improve the quality of estimates under certain conditions. In addition to production data on offset producers, key information required is a measured pressure drop at an observation well, corrected for any incomplete build-up due to previous production, plus a formation capacity value derived from a conventional pressure build-up plot on the observation well. The method, as outlined, is strictly applicable only to a horizontal single-layered system of uniform rock characteristics containing a homogeneous fluid of low and constant compressibility. However, under the set of test conditions devised, requirements can usually be relaxed so that it should be applicable to most low permeability gas, water and undersaturated oil reservoirs. This is an area where more reliable information is certainly needed. BASIC CONSIDERATIONS A, B, C and F as subscripts or in the text refer to producing Well A, observation Well B, a more remote producing Well C and field boundary F. Combinations such as AB refer to distances and dimensionless times in terms of distances between these points, while single letters refer to distances and dimensionless times in terms of the well-bore or field radius. Equations covering definitions of quantities and complex situations are given in the Appendix. Key equations in practical units are given in Table 2. Transient Pressure Behavior Fig. 1 illustrates pressure drop at Point B with time due to initiation of a constant rate of withdrawal from Point A. This is shown as since a quantitative under-

By D. B. Kibler

THE Florida hard-rock field extends from Suwanee and Columbia Counties in northwest Florida to south of Croom, Florida, in Hernando County. This area is approximately 100 miles long and varies from 2 to 30 miles in width. Florida hard-rock phosphate was discovered at Hale Springs, about one mile northwest of the town of Dunnellon, Marion County, in the year 1888, by Albertus Voight, who lived within a few hundred yards of the spring. Soon after this discovery there was a great influx of land speculators and wildcat operators into the vicinity of Dunnellon. A few years later phosphate was found in Alachua, Levy, Citrus and Hernando Counties, and a great number of small crude plants were built from Newberry, Alachua County, all the way to Croom, Hernando County. Phosphate was found in many places as "outcrops." Looking for outcrops was the first method used by the early prospectors in searching for deposits. Several years passed before any systematic method of prospecting was used. EARLY MINING The early method of mining hard-rock phosphate was with picks and shovels, wheelbarrows, mules and wagons. The pick-and-shovel method was used altogether until about 1900, when some of the larger operators began to use railroad-type steam shovels of from ½ to 1-yd. capacity. Picks and shovels, with negro labor loading the phosphate ore (called "matrix") into wooden side-dump skip-cars, was continued until about 1907. From the discovery of hard-rock phosphate until approximately 1905, overburden was removed with mules and scrapers. At some places, the overburden was loaded into side-dump skip-cars by negro laborers and the cars were then pulled up an incline with a steam hoisting engine. The maximum depth of overburden that could be economically removed by hand labor, mules and scrapers was approximately 15 feet. About 1905 one of the companies erected a producer-gas powerhouse near Dunnellon and generated its own electricity and about the same time the larger companies began using hydraulic methods for the removal of overburden. From the year 1888 through the year 1939, approximately 75 companies were operating at one time or another in the hard-rock territory, on approximately 500 locations. The hard-rock deposits are more irregular and have higher mining costs than the pebble-rock deposits, therefore they have not been competitive in the domestic market, but because of the higher grade of the hard rock it is in demand for the export trade. Discovery of phosphate outside of the United States has made it increasingly difficult in recent years for the hard-rock companies to survive, so today only three companies are operating. These

Jan 1, 1941

The Geophysics Education Committee has devoted several years to a consideration of the problem of training geophysi-cists. Past reports have dealt largely with fact finding and with the discussion of particular aspects of geophysical education. In the present report it is proposed to review the subject more comprehensively. This involves the question of what educational qualifications the geophysicist of the highest professional standards should possess, and the related question of what changes must be effected in existing educational institutions in order that prospective professional geophysicists may obtain instruction of the desired quality. The type of geophysicist here contemplated is one familiar with what is known already in the several branches of earth physics, and capable not only of following contemporary progress in any of these branches, but of contributing to that progress in a research capacity. Geophysics in its broadest sense, as has been emphasized repeatedly by this Committee, is the study of the physics of the earth and of terrestrial processes. This includes both the static and the dynamic characteristics of the gaseous, the liquid, and the solid portions of the earth, as well as its gravitational, thermal, and magnetic and electrical manifestations. Some branches of earth physics have been cultivated but slightly; others have reached an advanced state of development. Those branches whose development is sufficient to warrant explicit recognition in the form of organized Sections of the American Geophysical Union are: geodesy, seismology, tectonophysics, and volcanology, dealing with the rock constituents of the earth; oceanography and hydrology with the aqueous constituents; meteorology with the atmospheric constituents; and terrestrial electricity and magnetism with the electromagnetic manifestations. At present, instruction on the professional level in any of these branches of earth physics can be obtained in but few universities in North America. In most institutions where such instruction is undertaken different subjects are given in different and independent departments. Geodesy and hydrology are taught, if at all, as a part of civil engineering. The nearest approach to volcanology and tectonophysics ordinarily is represented by petrology and structural geology given

Jan 1, 1946

By John L. P. Campbell, Warren J. Jackson

Automatic recording of the radioactivity of the earth's formations provides a log of relative intensities that, if properly interpreted, can be applied to oil-field engineering. Production, engineering, and geological departments regard the radioactivity log as a forward step in the securing of more conclusive information for successful well completions. Explanations of the technique, together with some of the problems to which radioactivity logging have been applied, are presented in this paper. Introduction Those responsible for the completion of new oil and gas wells, or with planning workover operations on old wells, have followed closely the development of radioactivity well logging because they are interested in reducing the number of unknowns that usually are present in such work. Many operators have made use of the log, or are acquainted with at least one of the applications, but it is unlikely that any one operator is familiar with all of the many applications that are possible. The purpose of this paper is to present a representative example of each of the many applications, wherever the information has been released by an operator, and to illustrate by hypothetical examples other applications, releases for which have not been given. In this way, it is hoped that a better understanding of the scope of this new engineering tool may be obtained. Although the literature contains many references that describe in detail the theory, development, and application of radioactivity well logging, a brief discussion of the technique may be helpful to those who are investigating the subject for the first time. All rocks contain radioactive material in varying concentrations. In general, shales contain relatively more radioactive material than sandstones or limestones. These radioactive materials disintegrate with time into other materials of lower atomic weight, and in that process of disintegration the rocks are emitting many rays, the most penetrating of which is the gamma ray. The intensity of emission of the gamma ray is proportional to the quantities of radioactive materials present. A higher rate of emission would be observed, therefore, opposite a shale than opposite a sandstone or limestone. Since measurable intensities of gamma rays are capable of penetrating as many as five concentric strings of casing, and as the gamma-ray intensity is relative to the formations, the measurements of variations in gamma-ray intensities offer a means of identifying cased-off formations in their proper stratigraphic sequence. The Gamma-ray Curve The measurement of gamma-ray intensities is accomplished by means of an ioniza-tion chamber that consists of a heavy cylinder, about 3 ft. long, that contains two insulated electrodes and is filled with an inert gas under high pressure. Under normal conditions no current will flow through the gas when an electrical potential is set up between the electrodes, but when

Jan 1, 1946

By J. D. Testerman

A statistical technique to identify and describe naturally occurring zones in a reservoir and to correlate these zones from well to well is described. The technique is particularly useful in describing a reservoir where cross flow between adjacent strata is important in determining reservoir behavior. Although it has been used primarily for permeability zonation, the technique is general and can be used to correlate any reservoir property or related data, such as the information contained in well logs. INTRODUCTION One of the first problems encountered by the reservoir engineer in predicting or interpreting fluid displacement behavior during secondary recovery processes is that of organizing and using the large amount of data available from core analysis. Permeabilities pose particular problems in organization because they usually vary by more than an order of magnitude between different strata. Due to the sheer volume, it is almost always necessary to group data and to use an average value to represent a number of measurements. Perhaps the most common method now used to group permeability data is the capacity-fraction technique, which ranks permeabilities in order of magnitude, regardless of the physical location of the permeabilities within the reservoir. The cumulative per cent capacity is plotted against cumulative per cent thickness. This plot is divided into an arbitrary number of zones, generally of equal thickness. Five zones (or averaged groups of data) usually are obtained, each of which is treated as homogeneous in subsequent calculations. The division so obtained has no physical meaning; strata in the same zone, calculation-wise, are usually not adjacent in the reservoir. Reservoir engineering techniques being developed will handle crossflow that occurs between adjacent communicating reservoir strata because of imbibition and gravity segregation. Since crossflow occurs between physically adjacent layers within the reservoir, a new zonation technique recognizing the actual location of strata within the reservoir is necessary. Similarly, the recognition of natural zones is important for predictions of oil recovery by processes involving diffusion. One such process is miscible displacement, where predictions of lateral diffusion within the reservoir must recognize the actual location of the invaded zones in relation to the rest of the formation. Natural zones must also be adequately recognized to account for heat transfer within the reservoir during thermal exploitation. Because of the complexity of the problem, statistics appear to offer the only practical hope of dividing a reservoir into physically-meaningful natural zones. This paper presents a statistical technique for identifying these natural zones and for ascertaining which ones are likely to be continuous between adjacent wells. The zones defined have minimum variation of permeability internally and a maximum variation between zones. The technique is general and can thus be applied to reservoir properties other than permeability. The method will guide the reservoir engineer in estimating which zones are likely to be continuous between wells. However, a statistical correlation based on permeabilities in two different wells is no guarantee that the zones so defined are, in fact, continuous. Rather, the assumption of continuity must be consistent with geological data concerning the depositional environment, as well as justified on the basis of engineering judgment in combination with statistics, just as judgment is required with conventional zonation methods. CALCULATION PROCEDURE The reservoir zonation technique is a two-step operation. The steps are individually described, and a sample calculation is presented in the Appendix. ZONATION OF INDIVIDUAL WELLS First, the set of permeability data at a single well is zone, into Zones. These zones are selected so that variation is minimized within the zones and maximized between the zones. The equations4,6 used to zone the data are where B = the variance between zones, , = the number of zones, i = the summation index for the number of zones, j = the Sumation index for the number of data within the zone, mi = the number of data in the ith zone, k,. = the mean of the permeability data in the ith zone, k . = the over-all mean of the data in the well, W = the pooled variance within zones, N = the total number of

By John Wulff, Robert Kamm, Steinberg Morris

In powder metallurgy it has often been observed that shrinkage may occur in one direction and growth in another during sintering. Even in long-time sintering experiments the rate of shrinkage may be different in different parts of the compact. In the fabrication of some parts requiring a constant permeability it is even questionable in some cases whether pressing from one direction should be attempted. These observations require for their interpretation a more detailed study of green or pressed density than has heretofore been available. Usually average density measurements of the whole compact are made and in some cases carefully cut sections are measured. A different approach to the problem was first mentioned by Rakowskil and also used by Balshin.2 Balshin's diagram is reproduced in Fig I and schematically shows the result of pressing three layers of metal powder with fine intervening layers of graphite. The retarding effect of the die walls and a qualitative example of the density distribution is evident. More quantitative information about the distribution of density within a cold-pressed powder compact would be useful in showing the variation in density in as as influenced by the type of poKder, shape of die, lubricatioll during the process, and other variables. Furthermore, information about the cracking of cold-pressed compacts may be obtained from an analysis of the stress distribution within a, powder compact, and some information about the stress distribution can be obtained in turn from the derlsity and strain distributions. A more detailed report on some of the present experiments appears in reference 3. Present Investigation In order to ascertain the density gradients in cold-pressed metal powders, a deformable lead grid within the powder was employed. After pressing in cylindrical di" the ejected compact was radiographed, giving a pattern of the deformed grid. From the radiograph density and deformation from point to point is readily measured. From the radiograph strain distribution and stress trajectories were also determined. The latter also permits the determination of the coefficient of friction at the die wall. This technique indicates that the densest Part of a compact pressed from one side is at the top outer circumference and the least dense region at the bottom circumfercnce near the stationary plunger. For Some heights of compacts the density at the axis is such that the lower density is at the top rather than at the bottom. SO irregular a density distribution is due primarily to die-wall friction. As the ratio - diameter to height of compact is increased the die walls play a correspondingly smaller role. More uniform density

Jan 1, 1947

By H. I. Najarian

This paper is a companion piece to the description of the electrothermic process that begins on page 141. It will be confined to a brief story of the development. of the Weaton-Najarian vacuum condenserf at this plant, together with up-to-date design and operating data. The Josephtown smelter was designed primarily for production of zinc oxide. However, the development of a method for production of zinc metal had always been under consideration, and accordingly one of the original eight units of the elcctro-thermic furnaces built in 1930 was set up to produce metal. The design of this furnace was identical with that of the oxide furnaces except that in place of oxide tewels opening into oxide manifolds, conventional conical clay condensers—similar to condensers used in horizontal retort smelting—were installed around the periphery of the furnace and in several tiers vertically for condensing the zinc vapors. The early experimental work in trying to condense zinc out of the mixtures of zinc vapor and carbon monoxide gas from the electrothermic furnaces indicated that, while the gases from electrothermic smelting would condense in surface-type condensers, the formation of blue powder was excessive and condenser efficiency low. Furthermore, operating a large unit of electric furnace with several hundred small condensers, with attendant high labor cost and unfavorable operating conditions, did not appeal to us. We also realized that a single unit of surface condenser capable of condensing 12 torg tons of metal per day would be of huge dimensions and possibly difficult of control. So we took as our aim the development of a method whereby a single condenser unit of reasonable dimensions would condense zinc, in one step, from the large volume of gases that the electric furnaces produced. We set about searching for knowledge on zinc metallurgy and design of zinc condensers in particular. Our study of the prior art focused our attention on the oft-repeated statement by earlier experimenters, that the most efficient way to condense metallic vapors, such as zinc vapors, was to bring the vapors into "intimate contact" with molten metal; but the methods offered for securing this "intimate contact" in any practical manner left much to the imagination. We were handicapped by not having some-one on the Josephtown smelter staff who could lay claim to being an expert zinc metallurgist and could give guidance from actual experience on the practicability of various schemes that haunted our imagination. Laboratory Experiments However, we had an expert ex-steam engineer in the person of George I?. Weaton, manager of the Josephtown smelter, who had had long experience with steam-jet condensers and would reiterate his belief at every opportunity that the logical and the most efficient way to condense zinc would be with a jet-type condenser. We became intrigued by the possibilities of a zinc con-

Jan 1, 1944

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

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

Jan 1, 1942

By C. R. Kuzell

ALTHOUGH furnaces constructed of refractory brick have been oper-ated for many decades, there has always been an unfulfilled desire by the operators for a less arduous and more satisfactory method of patching weak spots and burned-out zones in order to postpone and to effectively extend the termination of a furnace campaign. Not only has this desire frequently arisen when small spots have approached incipient failure while the furnace structure as a whole was still in good condition, but also when larger areas showed signs of needing replacement. The availa-ble methods have been arduous, sometimes dangerous, inefficient with respect to the life of new refractory material used, and nearly always have necessitated interruption of the continuity of the furnace operations and therefore reduction in furnace production during the period of time required for the repair work. Most of these older methods have involved the replacement of masonry by refractory shapes in the weakened areas. Many attempts have been made to develop a method of patching the burned-out areas by spraying granular refractory material upon old surfaces. While some success has been attained in attempts to renew the grooved, corroded side walls and fettling, and the edges of hearths, there have been no known successful applications of the spraying method in patching the underside of arches of operating furnaces. The method developed recently at the Clarkdale smelter of the United Verde Branch of Phelps Dodge Corporation, at Clarkdale, Ariz., and described in this paper, has been found to be not only convenient and successful with respect to patching vertical or inclined surfaces, but has met with a marked degree of success in patching the parts of furnace arches that are exposed to flame, the successful result being obtained with-out interruption or interference with the continuity of furnace operations. ? It may be described as a method of renewing the interior refractory sur-faces of operating furnaces by pneumatic spraying of an aqueous suspen-sion of finely divided particles of refractory material. It has been used

Jan 1, 1939

By J. M. McDowell, Morris Muskat

In both production and refining operations of the oil industry many processes are controlled by the gas-liquid phase relationships of the hydrocarbon mixtures of interest. The quantitative behavior of fractionating or distillation columns and stills depends on the changes in the equilibrium distributions of the hydrocarbon components between the gas and liquid phases as the pressure or temperature conditions may vary along the length of the column or as the gross operating parameters and compositions are varied. In oil producing operations the nature and amount of gas phase developed within an underground reservoir as it is being depleted and its pressure declines also involve the basic equilibrium gas-liquid phase interactions. The influence of surface conditions of temperature and pressure and various separation procedures on the nature and amount of stock tank oil and natural gas recovered from a given well stream is likewise determined by the same basic phase equilibrium characteristics of the hydrocarbon systems. Such equilibrium separation of the gas and liquid phases in a well stream is of importance both in establishing optimum separator conditions for obtaining maximum stock tank oil yields and in the general problem of crude stabilization. The phenomena involved in these problems and their quantitative aspects can, of course, be established in each individual instance by appropriate laboratory experimentation. It has been found, however, that by associating with the individual hydrocarbon components functional characteristics de- scribing their individual gas - liquid phase equilibrium behavior, the phase properties of the composite mixtures can be predicted by mathematical computation. These characteristics have been termed "equilibrium constants", or "equilibrium ratios"," and are defined by the general equation: where K, is the equilibrium ratio for the jth component, y, is the rnol fraction of that component in the gas phase, and xj is the corresponding mol fraction in the coexisting liquid phase. Considering the Kj as representing available and measurable properties of the individual components of a mixture, and as defined by Eq. (l), it is readily shown that in a coexisting gas-liquid system the rnol fraction concentrations of the individual components in the gas phase, y,, and those in the liquid phase, x,, are given by the expressions: where the nj are the corresponding rnol fraction concentrations in the composite system, and ng is the mol fraction of the whole which is in the gas phase. The basic unknown in Eq. (2) is n,: which gives the gross separation between the gas and liquid phases. This may be determined in principle by imposing the requirement that the sums of the mol fractions in both the gas and liquid phases are unity, i.e. by the equations: The solution of the equivalent Eqs. (3) lying between 0 and 1, when inserted into Eqs. (2), provides a complete description of the compositions of the coexisting gas and liquid phases. While the Eqs. (3) are essentially equivalent to polynomial equations, such transformations are of little value when dealing with multicomponent sys-

Jan 1, 1949

By John Wulff, Steinberg Morris, Robert Kamm

In powder metallurgy it has often been observed that shrinkage may occur in one direction and growth in another during sintering. Even in long-time sintering experiments the rate of shrinkage may be different in different parts of the compact. In the fabrication of some parts requiring a constant permeability it is even questionable in some cases whether pressing from one direction should be attempted. These observations require for their interpretation a more detailed study of green or pressed density than has heretofore been available. Usually average density measurements of the whole compact are made and in some cases carefully cut sections are measured. A different approach to the problem was first mentioned by Rakowskil and also used by Balshin.2 Balshin's diagram is reproduced in Fig I and schematically shows the result of pressing three layers of metal powder with fine intervening layers of graphite. The retarding effect of the die walls and a qualitative example of the density distribution is evident. More quantitative information about the distribution of density within a cold-pressed powder compact would be useful in showing the variation in density in as as influenced by the type of poKder, shape of die, lubricatioll during the process, and other variables. Furthermore, information about the cracking of cold-pressed compacts may be obtained from an analysis of the stress distribution within a, powder compact, and some information about the stress distribution can be obtained in turn from the derlsity and strain distributions. A more detailed report on some of the present experiments appears in reference 3. Present Investigation In order to ascertain the density gradients in cold-pressed metal powders, a deformable lead grid within the powder was employed. After pressing in cylindrical di" the ejected compact was radiographed, giving a pattern of the deformed grid. From the radiograph density and deformation from point to point is readily measured. From the radiograph strain distribution and stress trajectories were also determined. The latter also permits the determination of the coefficient of friction at the die wall. This technique indicates that the densest Part of a compact pressed from one side is at the top outer circumference and the least dense region at the bottom circumfercnce near the stationary plunger. For Some heights of compacts the density at the axis is such that the lower density is at the top rather than at the bottom. SO irregular a density distribution is due primarily to die-wall friction. As the ratio - diameter to height of compact is increased the die walls play a correspondingly smaller role. More uniform density

Jan 1, 1947

By I. R. Kramer, P. D. Gorsuch, D. L. Newhouse

Although many methods have been suggested for the calculation of tensile strength and yield point from chemical composition, their usefulness has been limited to a particular cooling rate or section size. Further limitations have been imposed by failure to take into account many of the alloying elements that exert a considerable influence on the tensile strength or yield point. These systems, nevertheless, have filled an important need in many instances. The value of a system for the calculation of the tensile properties from the chemical composition and cooling rate is that it permits the prediction of the effect of alloying elements and heat-treatment on the mechanical properties, so that more efficient use of alloying elements may be made. Furthermore, it aids in the choice of steel for a given application aid tends to decrease the number of steels that otherwise would have to be tested. It is the purpose of this work to present a method of calculating tensile strength and yield point from the chemical composition and to suggest a method of correlating the tensile-strength and yield-point factors and cooling rate. Steelmakers have been interested for many years in the calculation of the tensile strength of hot-rolled steels. Quest and Washburn' summarize several of the attempts that have been made to devise formulas. They show the inadequacy of each of these formulas and present one of their own. It is apparent from their work that a simple additive equation of the type TS = A + BX + Cy + DZ + . . . , where A, B, C, D, etc. are experimentally determined constants and x, y, z, etc., are the percentages of alloying elements present in the steel, is not adequate to analyze fully the situation encountered in the calculation of tensile strength. For example, it was found that the difference between the calculated and observed values became progressively greater as the carbon and manganese contents were increased. Therefore, the effect of manganese was given as a function of the carbon content. Grossmann, in his work on the harden-ability of quenched steels, and Walter, in his method of calculation of tensile strength of normalized steels, present two cases in which multiplying factors were successfully used to express the combined effect of alloying elements. The factors in both cases were obtained from the fractional increase in hardenability or tensile strength with increase of alloy content. Yield point often is more important in design than tensile strength. For quenched and tempered steels a linear correlation exists between yield 2nd tensile strength.4 This is not true, however, for normalized

Jan 1, 1948

By George A. Morrison

THE Columbia Chemical Division of the Pittsburgh Plate Glass Co. is at Barberton, Ohio, 35 miles south of Cleveland. For many years large tonnages of limestone have been brought to the Barberton plant from distant points. The stone is here burnt in vertical kilns, the resultant product then hydrated and the hydrated lime used in chemical processing. To eliminate the expense of these shipments, the company decided to investigate a limestone bed known to exist on company property at Barberton, where the stone is used. The bed lay at a depth of more than 2000 ft. and was known locally as the "Deep Lime." Chemical analyses of sludge from churn-drill holes made some years ago proved that the limestone was of sufficient purity to warrant diamond-drill exploration. Four diamond-drill holes were put down at well-spaced intervals, to represent fairly an area of four miles by one mile. Cores logged as to chemical and physical conditions were found to compare closely, and to corroborate the earlier evidence that the limestone was of superior quality for chemical use. A plant of 300 tons per hour was subsequently decided upon. SITE The yard at the chemical plant was already so congested that location of the projected mine within its area could not be considered. Eventually a site was selected 2 miles northwest of the plant, near the main line of the Erie Railroad. Here 412 acres were owned outright by the company and stone rights were obtained on 250 additional acres. This location required a transportation line of nearly 2 miles (8800 ft.), crossing two major highways, and to avoid interruption of deliveries to the plant, overpasses were planned. GEOLOGY The limestone in the immediate vicinity lies about 2200 ft. below the surface. Geologists* identify this stone as Delaware of Devonian age. It is overlain by 18 ft. of unconsolidated (sand and gravel), 100 ft. of water-bearing sandstone, and finally 2080 ft. of shale into which sandstone in thin layers is interbedded. The contact of shale and limestone is abrupt, flat-lying and very pronounced. Berea sandstone, often found at 520 ft., is absent, but Euclid sandstone was encountered, together with a seepage of oil and a small amount of methane gas. The limestone bed itself is 345 ft. thick, and overlies 200 ft. of gypsum. The lower part becomes dolomitic as it approaches the gypsum. A detailed study of the drill cores indicates that the upper 50 ft, are highest in lime and reasonably low in silica. The physical make-up shows several separating cherty layers. These occur at definite horizons and cause distinct partings, which become horizontal planes of

Jan 1, 1943

By H. A. Schwartz

FROM time to time, one of the authors has had occasion to investigate the graphitizing reaction and has published the results mainly as discussion1 of the work of other investigators. In view, therefore, of the diversity of both observations and interpretation, it seemed well to attempt a revision of the entire subject in the Research Laboratory of the National Malleable Castings Co. The work consisted of a careful study of a single, impure, iron-carbon alloy. The material, which may be considered typical low-carbon white cast iron of the malleable industry, was an air-furnace iron of the following composition: carbon 2.30 per cent., silicon 1.20 per cent., manganese 0.29 per cent., phosphorus 0.156 per cent., sulfur 0.048 per cent. The freezing range extended from 1213° to 1132° C., the latter figure agreeing with Gontermann's data .2 We have attempted to define the equilibrium diagram of this alloy, in the stable condition as related to the metastable diagram, from a temperature somewhat below the eutectic freezing point to a temperature below Ar1 and for a graphitic-carbon content from practically nothing to the original total carbon of the specimen (see Fig. 6). More especially we desired to locate the line in the stable diagram corresponding to the Acm line of the metastable system, which is designated by analogy, the Atm line (tm from temper carbon) ; also to determine the location of Aim with respect to Acm toward their lower extremities at Ar1 in order to determine whether or not graphitization is completed by the separation of an iron-carbon eutectoid analagous to pearlite in the iron-cementite system. This would involve further a comparison of the locations of the stable and metastable A1 points.

Jan 8, 1922

By J. B. Pullen

The United Verde mine is in the north central part of Arizona, on the northeasterly slope of the Black Hills, near the town of Jerome. Ore was first discovered in the district about 1875, and the first mining claims were located by M. A. Ruff-ner and associates in 1877. In 1888 the late Scnator William A. Clark secured control of the property and under his ownership it developed into one of the country's most important copper producers. The property was sold to the Phelps Dodge Corporation in 1935, and since then has been under this Corporation's management. Except for shutdowns caused by general world-market conditions, production has been continuous from 1890 to date. Geology The mineralized zone ranges in area from approximately 12 acres to less than 5 acres. All mineralization occurs in the pre--Cam-brian intrusives. The first intrusion, according to geologic records, was the quartz porphyry, which later was intruded by augite diorite. Following the diorite intrusion through a series of intrusions of lesser magnitude, a pipelike mass of massive sulphide, quartz and rock was formed. The diorite forms the hanging wall of this mass, and the porphyry the footwall. Between the footwall and the sulphide a band of chlorite schist was formed, probably owing to metamorphic conditions. Commercial ore occurs along the contact of the schist and sulphide extending into the sulphide, sometimes entirely through the schist, and fingering out into the porphyry. The ore deposit was formed by replacement similar to deposits formed in limestone areas. Faulting and deformation occurred in pre-Cambrian times and again in the Tertiary period, removing approximately 2000 ft. from the top of the main United Verde ore body, forming the United Verde Extension ore body, the only other major ore body in the district. Major development work has shown that the sulphide mass extends to the 3300-it. level, and diamond drilling below this level has indicated that the mass might extend below the 3700-ft. level, but in a diminished quantity. While many copper minerals exist in the mine, the chief commercial mineral is chalcopyrite. Aplan and vertical section of the mineralized zone showing the principal geological eatures is shown in Figs. I and 2. General Description and Physical Condition or Mine After over 50 years of active production, ore still exists on almost every level of the mine. This condition is due to many causes —-mine fires, which broke out as early as 1894, caused the abandonment of certain areas; subsidence and ground movements retarded the cleaning up of others. Furthermore, in the early days there was such an abundance of ore that when mining became dificult it was a simple matter to replace the production by going to a deeper level. Several attempts were made to recover the ore in the fire zone, both by glory-holing

Jan 1, 1943

By Zay Jeffries

THIS paper will include a brief discussion of Prof. Howe's paper on The Supposed Reversal of Inheritance of Ferrite Grain Size from that of Austenite.1 The general subject of grain refining in steel and iron will also be treated. The conclusions reached are stated in the following hypotheses which are discussed more in detail below. 1. The ferrite grain size in pure iron, the ferrite and pearlite grain size in hypoeutectoid steel, the pearlite grain size in eutectoid steel and the cementite and pearlite grain size of hypereutectoid steel are not inherited from the grain size of the mother austenite. 2. The only structural feature that is generally inherited from the austenite of hypo- and hypereutectoid steels on cooling through their transformation ranges is the position of the excess ferrite or cementite at the austenite grain boundaries, sometimes causing complete and sometimes incomplete networks which outline the old austenite grain boundaries. Rapid cooling through the transformation range will cause the non-inheritance of this structural (network) feature. 3. The austenite grain boundaries themselves are nearly always effaced in all steels and also in pure iron during the Ar transformations. 4. The grain-size refining of steel and iron is brought about by the combined. effect of non-inheritance of the transformation products on either heating or cooling, i.e., the austenite transformation .products do not inherit their grain size from the austenite on cooling through the transformation range for does austenite inherit its grain size from the products which form austenite on heating. 5. In general, in both iron and carbon steel the larger the austenite ,grain size, the larger will be the grain size of the transformation products on cooling. This, of course, assumes all other conditions constant except the austenite grain size. An exception is found to this general rule in very pure iron such as electrolytic iron. 1n this instance small austenite grains may form very large ferrite grains on cooling through Ar3.

Jan 11, 1917

By E. T. Turkdogan, L. S. Darken

Using the quadratic formalism, thermodynamic equations are derived for the composition dependence of the heat and entropy of mixing. The applicability of these equations is confirmed by available experimental data on the activities and heats of mixing for binary metallic systems of Group ZZB elements. In a recent paper arkeen' introduced a quadratic formalism describing the composition dependence of the activity coefficient in the terminal regions of binary metallic solutions. That is, in the terminal region, which may extend to as much as 60 at. pct, the logarithm of the activity coefficient, log y,, of component 2 is a linear function of (1 - N,)' where N2 is the atom fraction of component 2. Similarly, for the other component, log yl is a linear function of (1 - N,)'. A number of iron-base binary liquid alloys were shown to obey this quadratic formalism. arkeen' extended this formalism also to any corner of a ternary system and showed that the activity coefficients of the components 1, 2 and 3 (1 is taken as the solvent) can be represented by quadratic terms involving five parameters, four of the binaries and one for the ternary system. Numerous examples given by arkeen' demonstrated the general applicability of the quadratic formalism to iron-base systems over a wide composition range. In this paper further examples are given of binary liquid systems (Group IIB elements, Zn, Cd, and Hg) and of several solid solutions, again demonstrating the appropriateness of this concept. A further purpose of this paper is to extend the quadratic formalism to the enthalpy and excess entropy of binary metallic solutions and to test the equations so found using available experimental data. QUADRATIC FORMALISM FOR HEATS AND ENTROPIES OF MIXING OF BINARY METALLIC SOLUTIONS The following equations, reproduced from Darken's paper, are for the two terminal regions of binary systems. at infinite dilution and a's are temperature dependent parameters to be determined from the experimental data. Although the quadratic formalism is an assumed representation of the data, Eqs. [I] to [4] are thermo-dynamically consistent with the Gibbs-Duhem relation and satisfy Raoult's and Henry's laws as limiting cases. As pointed out previously,' the following form of the Gibbs-Duhem equation facilitates the integration in general but particularly in regions I and 11, where each of the derivatives is constant. The partial molar enthalpy of solution i, (and i; the value of i, at infinite dilution) are related to the activity coefficients y, and y," by the thermodynamic relation Differentiating Eq. [l ] with respect to 1/T and substituting the above thermodynamic relation gives for region (I) It is reasonable to assume that over a temperature range of experimental interest, the enthalpy of mixing is essentially independent of temperature, implying from Eq. [7] that the derivative da,,/d(l/) is also independent of temperature. On the basis of this argument, the temperature dependence of a has the form where £ and S have the units of enthalpy and entropy respectively; they are characteristic parameters for a terminal region of a binary system, e.g. for region (I), C12, S12 and for region (II), d:,,, S2,. Using this equation gives for dff ,/ d(l/), From Eqs. [7] and [9] an expre_ssion is obtained for the composition dependence of L,. Similar calculations are made for El and the results are summarized below for the two terminal regions. For region (I), The corresponding expressions for the molar heat of solution, AHM, are readily obtained from the above equations for the two terminal regions: For region (I),

Jan 1, 1969

By Richard L. Gordon

THE PROBLEMS AND POSSIBLE SOLUTIONS Toward the end of the 19th century, American industry began a drastic reorganization. The many, small, often-regional firms were supplanted by large national corporations-often produced by mergers among the existing firms. Giant companies appeared throughout American industry and many of them were engaged in the mineral industries.a The largest combines, by far, to emerge during the period were United States Steel and Standard Oil. Long before the restructuring had run its course, widespread concern arose over the process of concentration. Efforts were made to control, if not stop, the transformation. The concern produced the Sherman Antitrust Act of 1890 and the first of many federal regulatory agencies-the Interstate Commerce Commission (see Refs. 24, 31, 42). The basic objectives of these policies remain unclear to this day. The crucial issue is whether the goal is primarily to insure development of a more competitive economy or to preserve a social structure leaving more scope for small businesses. Complications arise from difficulties in agreeing upon the meaning of these terms. Studies of the early years of the antitrust movement suggest that it involved no particular concern over the mineral industries. Objections were directed at big companies in general. To be sure, the conservation movement arose in roughly the same period and did stress the evils of monopoly control of minerals. However, direct, continuing influence of conservation policy on antitrust is not apparent. Many of the most important antitrust cases, nevertheless, involved minerals. This, of course, may be sheer coincidence; the choice of cases has never followed any obvious pattern. Certainly, no simple hypothesis can explain the interest consistently. Once it may have been true that mineral industries were more likely than other sectors to be dominated by a few large companies. Yet, often sharp reversals of such tendencies -e.g., in oil and aluminum-have not removed antitrust interest. The importance of minerals to the economy cannot satisfactorily rationalize antitrust interest. The equally

Jan 1, 1976