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By A. H. Geisler

INTRODUCTION THE correlation of property changes during precipitation with structure has progressed, sometimes rapidly but other times more slowly, since the fundamental discovery of Merica, Waltenberg and Scott.1 The predominent factor that hampered the progress has been limitations imposed by the various detection methods. Refinements in X ray diffraction techniques and in metallographic methods, which have been extended by the electron microscope, have contributed new information within the last few years. These permit an extension of the theory as proposed by Mehl and fetter in 1940.2 Now that a suffcient number of alloys has been investigated to establish a general mechanism of the precipitation process, a correlation of the facts into a generally applicable theory of age-hardening is both warranted and desirable. 'I he purpose of the paper is to provide an orderly correlation of the phenomenological facts of precipitation hardening. Speculation on mechanism of hardening will be confined to that consistent with existing theories of hardening. Age-hardening accompanies the formation of a new structure, the precipitate, as provided by an alloy system in which solid solubility decreases with decreasing temperature. Upon this premise alone all such systems would be expected to include age-hardenable alloys. Alas, this is not always the case. Few attempts have been made to explain the variable degree of age-hardening among different alloys or to explain the influence of small alloying additions upon the hardening. Dispersion hardening as originally postulated3 is not adequate.* Coherency hardening-the term that will be used to distinguish the properties of a two-phase mixture in the unique and unstable transition state at which the phases are strained into precise atomic registry (continuity or coherency) in planes

Jan 1, 1948

By Walter A. English

CONTENTS PAGE Introduction. By WALTER A. ENGLISH 1 Theory of Seismic Reflection Prospecting. By WILLARD H. TRACY 2 Instruments for Reflection Seismograph Prospecting. By ARTHUR NOMANN 9 Seismograph Field Operations. By FRANK ITTNER 15 Determining Geologic Structure from Seismograph Records. By P. C. KELLY 22 INTRODUCTION BY WALTER A. ENGLISH,* MEMBER A.I.M.E. THE four papers making up this symposum have been prepared espe-cially for those who have no knowledge of seismograph prospecting. To many people mathematics is a formidable subject, and many are discouraged from studying seismograph prospecting under the mistaken assumption that the mathematical requirements are severe. In the papers presented here there is not a single mathematical equation. We believe that considerable competence in dealing with some of the most important problems of this work can be attained without any mathe-matical training whatever. At the present time, there is a real need for interpretation of results by persons thoroughly competent to bring geologic experience and imagination to bear on data that are subject to multiple interpretation from a strictly physical viewpoint. Likewise, those charged with the responsibility of planning seismo-graph exploration campaigns would do well to become familiar with as . much as possible of the technical aspects of the work. They would then be in better position to judge of its success in individual cases. It has often been said that the seismograph is a new structure-finding tool for the geologists to use. Using a tool and using its product are two different things. One does not use an automatic screw-threading machine when he buys a box of screws at the hardware store. Neither does the geologist

Jan 1, 1939

By W. B. Gogarty

With the use of polymer solutions in secondary recovery operations, the need has developed to understand the mobility control mechanism. This study investigated mobility control by considering both permeability and rheological effects. Experiments used a high molecular weight, partially hydrolyzed polyacrylamide polymer. Flow studies took place in reservoir and Berea cores having zero oil saturation. Effective size of the polymer flow unit was inferred from Nuclepore filter tests. Clay studies indicated the particle size capable of decreasing the core permeability. Flushed permeabilities measured the approximate core permeabilities with flowing polymer solutions. These permeabilities were considerably lower than original values. With mobility data and the flushed permeability, maximum effective viscosities were determined for polymer solution flow in a core. Effective viscosities showed that rheological properties play an important part in mobility control with polymer solutions. The study showed that permeabilities decrease and stabilize with polymer flow. At the lower permeabilities, high shear rates exist in the cores. Because of the pseudoplastic character of the polymer solution, the high shear rates caused low effective viscosities. This condition pointed to the inefficient use of the potentially high viscosity of the polymer solution at low shear rates. INTRODUCTION In the oil industry, a great deal of interest is being shown in the use of polymer solutions for secondary recovery and a number of polymer floods are being performed in the United States.1 Some of these floods have become commercial while others have been reported as failures. A number of floods are still in progress and remain to be evaluated. With the advent of polymer flooding, the need developed to understand the mobility control mechanism in porous media. Rheologically, the polymer solutions behave as pseudoplastic fluids. Investigators have studied the rheology for this type of non-Newtonian fluid in porous media?-6 Results have also been reported on the ability of polymer solutions to decrease mobility.7-10 Some investigators indicated that polymer solutions show a different rheological behavior in cores than on the viscometer.7,8 This study is representative of an initiatory investigation on mobility control with polymer solutions. Some effects are considered on a qualitative basis. Mobility control is considered from the standpoint of both permeability and rheology and, to the extent possible, permeability and rheological effects are considered separately. Results show that mobility control occurs from a reduced permeability caused by polymer retention and an effective viscosity determined by the average shear rate in the core. In this respect, rheological behavior is as important in mobility control as permeability. PROCEDURES A high molecular weight, partially hydrolyzed, polyacrylamide polymer was used in the investigation. Solutions of various concentrations were made with this polymer in different types of water. Some solutions used distilled water and others used tap water. The tap water contained approximately 500 ppm dissolved solids. As used in this paper, concentrations in ppm refer to parts by weight solute to one million parts by weight of solvent. In the tap water, calcium and magnesium accounted for from 60 to 80 ppm of the solids, the remainder being mostly sodium chloride. All solutions contained a bactericide, and anti-oxidants and antiprecipitants were added to the tap water. Capillary and concentric-cylinder* viscometers determined the rheological properties of solutions. The capillary viscometer is described elsewhere.6 Berea and reservoir sandstone were used as core materials for this investigation. Cores were 1 in. in diameter by approximately 2 to 3 in. long. Prior to mounting, the Berea cores were heat-treated for 3 hours at 850F. This treatment decreased the water-sensitivity of the clays in the cores. The reservoir cores were cleaned with solvent and

FREderick H. Davis, Electrical Engineer of the Westinghouse Electric and Manufacturing Co., in charge of the plant at Bodie, Cal. (communication to the Secretary): I beg to offer, to complete the information conveyed in Mr. Leggett's paper, the following report of tests of the electrical efficiency of the power-transmission he has described:

Jan 1, 1895

By E. S. Machlin, A. J. McEvily

HE results of an experimental investigation by McEvily and Machlin have indicated that a strong relationship exists between the processes of cross slip and fatigue. Whenever dislocations can cross onto an intersecting plane and expand thereon, as in AgCl crystals, the usual type of S-N behavior is obtained, but when such a process is difficult, as in NaCl crystals, fatigue does not occur in its usual manner, if at all. MgO, because of its crystal structure (NaCl type) and slip systems ({110}<110>) would not be expected to fail in fatigue. However, Cornet and Gorum2 have found something akin to the usual type of fatigue behavior for MgO crystals. The purpose of this note is to attempt to resolve this apparent discrepancy. In Cornet and Gorum&apos;s work as-cleaved crystals were tested under cyclic axial loading, whereas in McEvily and Machlin&apos;s work chemically-polished crystals were tested in reversed bending. Because of the difference in specimen preparation, the major effort of the present work was directed toward comparing the behavior of as-cleaved as opposed to chemically-polished specimens. The effect of type of loading seemed less important, but a check was made on this also. Eighteen bend tests and one axial load test were made. The specimens were cleaved from Norton magnorite blocks, and measured 1 by 3/16 by 1/8 in. To avoid failures in the grips, the thickness of the bend specimens was reduced from 1/8 in. near the ends to 0.04 in. in the central portion. This reduction was from one side of the crystal only. Twelve specimens were polished in orthophosphoric acid to remove the damage due to cleavage. The other six specimens were not chemically polished so as to maintain the as-cleaved condition of the crystal faces which had not been reduced. The axial-load specimen was reduced from both faces to a thickness of

Jan 1, 1962

By Ezequiel Ordoñez

THE great activity with which the oil resources of the northern Cantons of the State of Veracruz have been developed has largely resulted from the great success obtained by the important explorations carried out since 1902 in the Ebano district in the North, and several years later near Tuxpam, in the South. It must not be thought that these successes were quickly obtained, since the preliminary studies by good experts, the acquisition of what were thought to be the most promising coast lands, the extensive clearing thereof, and finally the number of unsuccessful drillings at great depth, signified an original outlay of some ten&apos;s of millions of dollars before finding commercial oil. The discovery of oil in industrial quantities at Cerro de la Pez, Ebano district, and the famous Dos Bocas gusher some years later, which was burned, once and for all made famous the Veracruz coast, where today is concentrated the Mexican output of mineral oil. In .1917, this production was nearly 50,000,000 bbl. It is well known that this output represents only a fraction of what the wells in actual production can furnish, because with adequate means of transportation and storage, the present extraction could be somewhat over 300,000,000 bbl. a year. These enormous potential oil resources of the Veracruz coast proceed from a relatively small number of wells, scattered over a few oil fields, separated from each other by large unexplored areas, wherein may be found other favorable fields which, in time, will undoubtedly become just as great centers of oil production. Experts who know our Gulf Coast believe that lands with commercial oil resources lie not only between the Panuco amid Tuxpan Rivers, but that indications are that the oil zone of Mexico, with more or less interruption, takes in the coast zone from Northern Tamaulipas to the foot of the Sierra Madre of Chiapas, and the banks of the Usumacinta River. This generalization is not merely the outcome of optimism, but is the result of the persistency with which one finds, throughout this Gulf Coast, the most usual characteristics upon which we depend for recognizing oil-bearing lands.

Jan 5, 1918

By R. Silverman, H. Blumenthal

It was found that despite the similarity of chemical analyses of different titanium carbides used as base materials for cermets, the physical properties, especially transverse-rupture strengths, of test bars were different. Hence this metallographic study attempts to link physical properties to micro-structures. It is shown that microstructure, grain shape, and grain growth are functions of three interrelated factors: 1—powder production procedure, 2—surface conditioning of the particles, and 3—impurities either contained in the original powder or acquired during ball milling. An explanation is offered for the "coring effect," long observed, but heretofore of unknown origin. The explanation is based on assumption of an oxide film and on chemical analyses which substantiate these findings. TITANIUM carbide has become in recent years a material of great interest in the high temperature field. Consequently, many manufacturers in the United States and Europe are producing titanium carbide for cermet applications as well as for additions to the well known tungsten carbide tools. All present commercial processes of titanium carbide production utilize the chemical reaction of titanium dioxide and carbon to form as nearly as possible stoichiometric Tic. This reaction is carried out in three ways: 1—in a menstruum of molten metal,&apos; 2—in the solid state, either in a protective atmosphere2 or in vacuum;" or 3—in an are-melting operation. In spite of the fact that the pure carbides obtained in these operations are almost identical chemically, the physical properties vary considerably when they are combined with a binder (Ni, Co) to form cermets. This fact led the authors to examine metal-lographically nickel-bonded titanium carbide in order to find the possible reasons for this behavior. Materials and Methods Five different titanium carbides were used in this investigation. They are identified in Table I. The first four materials were used in the as-received condition. Material E, received in lumps, was crushed to —100 mesh and carried through a flotation process in order to bring its graphite content in line with the other products. A Galagher flotation cell was used with pine oil as frothing agent. The chemical analyses of the investigated materials are given in Table 11. The binder used was carbonyl nickel of 9 to 14 microns particle size, supplied by A. D. Mackay. The materials were ball milled at a ball to charge ratio of 6:1 using procedures described under "Experiments and Results." All particle sizes mentioned are averages determined with a Fisher Sub-sieve Sizer. Test bars (lx0.40x0.16 in.) were prepared by 1—hot pressing to 85 to 95 pct of theoretical density at pressures between 1 and 1½ tsi and temperatures from 1600" to 1800°C, 2-—-cold presssing after 3 pct camphor had been added, or 3—wet pressing, both 2 and 3 at pressures between 5 and 10 tsi. All pressed bars were sintered in a vacuum of 105 to 10-6 mm Hg for 2 hr at 1350 °C. Transverse-rupture strengths were determined by breaking on a Baldwin Universal Testing Machine over a 9/16 in. span. Densities were measured by water displacement. The preparation of the specimens for micrographs was done according to Silverman and Doshna Luscz." All magnifications are at X1000. A sodium picrate electrolytic etch was used. Experiments and Results The influence of ball-milling procedure, ball-milling medium, pressing procedure, and sintering procedure on the microstructure of 80/20 — TiC/Ni were investigated. Ball Milling of Materials A, B, and C in a Steel Mill: Figs. 1 and 2 show microstructures of hot-pressed and vacuum-sintered test bars of materials A and B after the respective materials had been ball milled to 2.1 microns particle size in a steel mill and mixed with 20 pct Ni binder. Material A (Fig. 1) shows considerable grain growth. Also evident is a tendency of the carbide grains to coalesce. The density is 98 pct and the low transverse-rupture strength of 111,000 psi is probably caused by many large grains and an unfavorable packing factor. Almost all grains show a slight indication of "coring." Material B (Fig. 2), although showing grain growth, still has many small particles and a better distribution of binder and carbide due to the relative absence of the coalescing tendency. "Coring" can be observed in almost all grains. The high transverse-rupture strength of 179,000 psi and the density of 100 pct are believed to be due to the many small grains completely surrounded by the binder phase. There is also a preference to form spherical grains with material A, while most grains of material B preserve their angular shapes. Material C, of which no picture is given, stays between A and B in every respect. Rounding of some grains can be observed as well as coring, but the latter to a lesser degree than with material B. Its densification is good and the transverse-rupture strength obtained is 142,000 psi. Ball Milling of Materials A, B, C, and E in a WC Mill: When the Tic powders were ball milled to 2 microns particle size in a we mill, then ball-mill mixed with 20 pct Ni binder, hot pressed, and vacuum

Jan 1, 1956

By C. B. Post, G. V. Luerssen

It is generally recognized that non-metallic inclusions in steel come from two principal sources. First are the chemical reactions in the furnace, or in subsequent deoxidation, resulting in slag which does not free itself from the metal. Much information has been published concerning these chemical reactions and their control through proper attention to slag viscosity, composition of deoxidizers, and other qualities. The studies of this subject by C. H. Herty, Jr. and others through the medium of physical chemistry have yielded much information for the steelmaker. The second source is erosion of ladle refractories, such as lining brick, stoppers, nozzles and runners, causing entrapped particles of globules of fluxed silicate material. In contrast with the large amount of information available on the first source, relatively little has been published on the subject of erosion which, in the case of basic electric melted steel, is the principal source of nonmetallics. This is probably due to the fact that the problem was assumed to be one of simple mechanical erosion, which could be solved primarily by modification of ladle practices. Good improvements have been made by elimination of slurries in the ladle, better ladle and runner refractories, and more attention to pouring temperatures. It is doubtful, however, that this problem has been recognized in its true light since it is not one of simple mechanical erosion but rather one of chemical reaction between the metal and the refractories; and in this sense is as much a problem of physical chemistry as the reactions involved in the actual steelmaking process. The influence of ladle refractories on the resulting cleanness of steels was early recognized by A. McCancel who examined large inclusions in steels made by both acid and basic practices. His chemical analyses showed the large influence exerted by the manganese content of the steel on erosion of the ladle and nozzles used in those days. The presence of MnO in such inclusions led McCance to the hypothesis that both basic and acid steels react chemically with the ladle refractories so that small globules of fluxed refractories are carried in the stream into the molds. This early work of McCance was checked by one of the present authors on basic electric bearing-steel, and it was found that on steels containing as low as 0.40 pct manganese the fluxed surface of the ladle lining after delivering such a heat showed as high as 25 pct MnO by actual analysis. Furthermore, by lowering the manganese content of the steel to 0.20 pct, ladle erosion was decreased with a corresponding decrease in silicate inclusions in the steel. Limitations placed on the manganese content for the required inherent properties made it impossible to pursue this line further, and subsequent attention was concentrated on improved ladle refractories, care in keeping the ladle clean and free from loose refractories up to the time of tapping, and pouring the steel at optimum temperature. Our study of the chemical reactions at the metal-brick interface between steel and ladle refractories was revived in 1939 as a result of an experimental observation made on the cleanness of alloy steels of the SAE types. This observation showed that the relative cleanness of such steels made in basic electric arc furnaces of 12 ton capacity and poured in ingots ranging from 1100 to 2200 lb weight was determined to a large extent by the ratio of the manganese and silicon contents, provided other steelmaking variables such as tapping temperature, pouring temperature, pouring time, amount of aluminum added for grain size control, and degree of deoxidation in the furnace were kept reasonably constant. Detailed studies made on the deoxidation and slag practice during the refining period of basic electric furnace practice showed that these two variables exerted some influence on the resulting cleanness of steel in the form of bars and forgings. The important variable, the manganese-silicon balance, was not apparent until heats were made in succession by the best furnace practice kept under fairly rigid metallurgical control. Another observation pertinent to this work concerned the similarity in the microscope of slag particles causing magnaflux or step-down indications in subsequent rolled bars, and the patches of slag frequently seen on the surface of ingots. These patches are generally believed to come from the glassy metal-brick interface in the ladle and represent an entrapment of such glass (both from the ladle brick and nozzle) in the metal as it flows over the refractories in the neighborhood of the nozzle. These glassy particles are carried down into the mold with the liquid steel, and gradually coalesce into a slag "button" which floats on the surface of the steel as it rises in the molds. Periodically the button is washed to the side of the ingot where it is trapped between the surface of the ingot and the mold, later appearing as a slag patch on the surface of the ingot after stripping. Even though most of the small glassy particles coalesce into a slag button while the ingot is being poured, it is logical to suspect this step in the steelmaking process as being a source of slag lines large enough to cause trouble

Jan 1, 1950

By Richard H. Olson

"Rarely in our technological society does the discovery of a new class of inorganic materials result in such a wide scientific interest and kaleidoscopic development of applications as has happened with the zeolite molecular sieves." That opening sentence in a landmark volume on zeolite molecular sieves by D. W. Breck (1974), is, if anything, an understatement. Zeolites were recognized as a new group of minerals in the 1750s, but it was not until 1930 that the first analysis of the crystal structure of a zeolite mineral was made. In the late 1940s research workers at Union Carbide Corp. began a program of zeolite synthesis and study which has resulted in one of the major research achievements of all time. Naturally, with the vast research and development efforts devoted to the synthetic molecular sieves, Union Carbide became concerned in the mid-1950s about its position should minable deposits of natural analogues be discovered. Zeolite minerals have diverse origins, and even a brief discussion of these is beyond the scope of this paper. The early work on zeolites was confined to igneous rock occurrences (e.g., amygdules and veins) which were formed by "space-filling;" these crystals tend to be euhedral, thereby rendering them appealing to both mineralogists and collectors. During the first year or so of Union Carbide&apos;s exploration (which began in mid-1957) attention was devoted solely to such igneous, occurrences. A landmark paper by Bramlette and Posnjak (1933) heralded the potential significance of the occurrence of zeolite minerals as alteration products of vitric ash and similar materials. In the summer of 1958, full attention was directed by Union Carbide to the search for deposits of this type in the western United States. Since then, such exploration has been continuous by both commercial firms and private parties. The future economic potential for natural zeolite deposits seems to be restricted to those of the "open-and-closed system" types as described by Sheppard (this chapter). Therefore, this and the following discussions will concentrate upon these types; the other types of zeolites in sedimentary rocks (e.g., deep-sea sediments, burial metamorphic, and hydrothermal) will be, for the most part, ignored. Despite the relative cheapness of natural zeolite deposits as compared with the cost of synthetic molecular sieves, there has been minimal development of zeolite mining in the US over the past 25 years or so. Mumpton (this chapter) discusses the present commercial utilization of natural zeolites and their future potential in detail, but perhaps the following will serve as useful background. In the early days of synthetic molecular sieve research and production, the efforts were concentrated largely upon such high-value applications as physical separation of components in a stream (based upon molecular size and geometry) and in catalysis. Due to a number of reasons (some of which are difficult for an outsider to understand), natural zeolite ores (beneficiated or not) have not made substantial inroads upon the use of the higher-priced synthetic molecular sieves for the foregoing applications, but this is not to say that such a condition will exist forever. Furthermore, in view of the many other uses which are now known, or which loom in the future, the competitive position of the natural zeolites vs. the more expensive

Jan 1, 1983

By Joseph Lindmayer, Karl M. Busen

If silicon is in contact with silicon oxide, a heterojunction is formed which induces an inversion layer ("channel"). Influences of impurities and structural parameters on the channel are discussed. There seems to be no relation between surface damage in silicon and the channel. Phosphorz~s doping of the silicon oxide has no pronounced effect on the channel. Channels which were well above the range predicted by the heterojunction model were related to the action of H* at the silicon/silicon oxide interface. Channels which were well below tlze range predicted by the heterojunc-tion model were related to a transition region in the oxide adjacent to the interface. In support of the assumed transition region and the H+ are the ex-periments described on the paper. Furthermore, the concept of metastable OH groups in silzca, known from other publications, has been used to explain certain channel characteristics by the formation and the accommodation of hydrogen in the silicon oxide. THE electrical characteristics of a semiconductor device in many cases are influenced by the conditions of its surface. Because these conditions often are changing with temperature, time, ambient, or other parameters, numerous attempts have been undertaken to stabilize them by suitable processes. Several years ago Atallal studied the silicon/silicon dioxide interface and since then increasing attention has been given to the silicon dioxide as a means to stabilize silicon surfaces. This led to the evolution of the planar silicon devices where oxide layers are used to protect places at which the junctions are intersecting the surface. The formation of the oxide layers on silicon can be carried out by a variety of processes: high-temperature thermal oxidation (exposing the silicon surface to oxidizing agents such as 02, HzO, COz), evaporation of SiOz, or anodic oxidation of silicon. Originally the oxides were considered able to "passivate" the silicon surface and it was understood that they 1) protected the surface against any influence from the ambient and 2) stabilized surface conditions which were necessary for proper device performance. It soon was realized that the second quality was not always obtainable: Atalla and Tannenbaum showed that, in the process of forming a layer on doped silicon by thermal oxida- tion, electrically active impurities in the silicon near the interface are redistributed, thus giving rise eventually to the formation of unwanted charge distributions. The degradation of planar junctions during reoxidation of silicon was observed by Barson et a. Surface studies with silicon planar junction structures indicated that the breakdown voltage depended on the kind of procedure which was applied during or after oxidation.*" Yamin and worthinge report on charge storage and dielectric properties of SiOz films at elevated temperatures. Another influential parameter on the silicon surface is discussed by Lindmayer and usen,&apos; namely the appearance of a surface potential on silicon as a consequence of the heterojunction formed by the silicon/silicon oxide interface. In the present paper the influence of impurities and structural parameters in silicon oxide in connection with the heterojunction is a particular object of our investigations. I) EXPERIMENTAL The material used was 10 ohm-cm p-type silicon slices with either damaged surfaces (mechanically lapped or polished) or damage-free surfaces (chemically polished). The majority of the slices were oxidized for 1 hr and 20 min at 1250°C in a steam + oxygen atmosphere generated by passing O2 through HzO at 90°C (wet oxygen). This led to oxide layers of about 9000 A. On some slices oxide layers were grown in pure oxygen (dry oxygen). By a photoresist process a set of 20 by 200 mil windows was then etched out from the oxide layer. The pattern of the windows is shown in Fig. 1. In a subsequent process n-type pockets with surface concentrations between 2 x 10" and 5 x 10" cm"3 were formed by phosphorus diffusion. This allowed ohmic contacts between the silicon surface and tungsten probes which for electrical measurements were placed into two adjoining windows and

Jan 1, 1965

William P. Blake, TUCSON, Ariz. (communication to the Secretary): As one who in youth, now nearly half a century ago, had the privilege of participating in the initial explorations which have alreacly resulted, within a single lifetime, in the establishment and Development of a vast continental empire, so well described by Dr. Douglas, I may be permitted to supplement with some additional details the comprehensive sketch given in his paper. Before the War Department, in 1853, sent out the Pacific railroad exploring parties, Fremont had already made his memorable expeditions, exploring the Great Basin and the passes into California; Sitgreaves had traversed, from east to west, the Zuni and Moqui country; and, still later, Emory had examined the region along the boundary-line between the United States and Mexico. The services of these pioneers deserve to be mentioned in even an outline of the history of continental development. Concerning the five practicable railroad-routes, suggested in the Reports of Explorations aid Surveys," etc., as published

Jan 1, 1900

By M. T. Hepworth, R. Schuhmann

Hydrogen solubility measurements were made on a series of Ti-O alloys, and a portion of the 800°C isotherm for the Ti-O-H system was determined. Activities of oxygen and titanium were calculated from the experimentally measured activities of hydrogen, using ternary Gibbs-Duhem integrations. The data were extrapolated to obtain thermo-dynamic properties of binary Ti-O solutions. The thermodynamic properties of a Ti-0 solid solutions thus determined were compared with properties predicted from interstitial models. The Gibbs-Duhem equation, long used to calculate activities in binary systems, has been extended. recently to ternary systems.1"3 When the activity of one component in a ternary system is known as a function of composition, the activities of the other two components can be calculated from that of the first by an integration procedure, provided certain restrictions are observed on the path of integration. Often the activity of one component in a ternary system can be measured readily, while the activities of the other two components are difficult to measure. Gibbs-Duhem calculations are especially applicable to such systems. The further possibility arises of developing a new and indirect approach to activity measurement in binary systems. The proposed new method for binary systems consists of adding varying amounts of a third component whose thermodynamic behavior is easily measured. The activity of this added component is determined experimentally as a function of composition. Then the activities of the two components of the original binary system are calculated by Gibbs-Duhem integrations and extrapolations. For the work to be described in this paper, the Ti-0-H system was selected as a promising system for evaluating this approach. Investigations of the Ti-H system have shown that the activity of hydrogen can be measured precisely with little difficulty. Pure titanium transforms from a low-temperature a form (hcp) to a higher-temperature /3 firm (bcc) at 882.5"~ The phase transformation occurs in a temperature range where hydrogen pressures are easily measured. Also, the diffusivity of hydrogen at temperatures above 600" or 700"~ is large enough that equilibrium can be reached within a reasonable time.

Jan 1, 1962

By Henry Hibbard

THE process of making washed metal now followed is in principle that described by Holley before this Institute in 1879, as the Krupp washing process. Sir Lowthian Bell also experimented extensively in England during 1877 and 1878 on refining iron and joined his interest with Krupp, the process being often referred to as the Bell-Krupp process. The only plant in this country now operating this process is that of the Brier Hill Steel Co., Youngstown, Ohio. This process may be considered as the sole survivor of the numerous methods conceived for refining crude iron, when the removal of phosphorus from steel-making material was the great desideratum affecting large districts. The east coast of England and all northern Germany, the homes of Bell and Krupp, respectively, could at that time make steel only from imported ores. These processes were in use or in various stages of development 40 years ago and all except the Bell-Krupp received their quietus from the development of the basic steel processes, both pneumatic and open hearth. The aim of the early refining processes was, first, the removal of the silicon; which could be clone on a sand bottom, and later, the removal of the phosphorus, requiring a bottom which would give or permit a basic slag. The incidental advantages of increased yield and small fuel consumption were not generally recognized or considered; the aim of the later. operations was the saving of the difference in value between low and high phosphorus irons, as well as hastening the removal of the metalloids. The chemistry of the washing process follows in part that of the puddling process, and indeed washing might, be considered as the first half of puddling, since all the non-ferrous elements of the crude iron, except the carbon, are eliminated and the iron is maintained molten until cast. In puddling, the iron loses its carbon as well, and because of that, its fusion point rises above the hearth temperature; it freezes into a pasty malleable form, and is worked at once by squeezer, hammer, or rolls.

Jan 12, 1915

By W. R. Crane

Mining of the red iron ores of the Birmingham district has been carried on energetically during the past 60 years, and their development has created a large iron and steel manufacturing center, the only important one in the South. The district produces approximately 10 per cent. of all the iron ore of the United States (80 per cent. of the Alabama ore mined is red ore); also, 40 of the 400 blast furnaces of the country are in the district tributary to Birmingham. The rapid growth of the district has been made possible through investigations that resulted in radical changes in furnace practice, and a still greater impetus will come from the study of the low-grade, high-silica ores, as a result on which they will be made amenable to treatment by concentration. Mining practice in this district has been comparatively simple because of the occurrence of the ore; but with the rapid extension of the workings and the disturbed condition of the ore bed at some distance from the outcrop, more difficult conditions are encountered and the tendency is toward worse rather than better conditions. Should the high-silica ores of the lower bench of the Big Seam become available through beneficiation, mining practice will have to be modified to meet the new conditions, which will be rendered more difficult by the increased weight of cover that will exist at considerable distances from the outcrop. Support of workings will require greater attention and the efficient and economical operation of the mines will depend largely on the successful solution of the problems of working and handling the ore. History and EaRly Development The first explorers of the coal and mineral lands of Alabama were blacksmiths and mechanics mustered out of the army after the war of 1812. These men recognized the red rock of the Birmingham district as iron ore, and utilized it in making cooking utensils and farm implements. The first blast furnace was built and operated at Russellville in 1818, where also was a foundry and rolling mill. Soft ore was used at that time, but, in 1864, the first red hematite ore of Red Mountain was smelted, near Irondale. Birmingham was founded in 1871, and the successful use of coke in making pig iron in 1876 was the beginning of

Jan 1, 1925

By W. F. Kieschnick, C. C. Miller, E. R. Brownscombe

The possibility has been mentioned that large pressure gradients in a solution gas driven field caused by high production rates might lead to a reduction in the ultimate recovery obtainable compared to that which would be obtained by a very slow rate of production. In the present study the reservoir conditions accompanying a high rate of production and the corresponding ultimate recovery were compared with those obtained if the reservoir were produced at some marginal rate throughout its entire life. The method of calculation involved the application of fluid flow - material balance analysis to a series of successive steady state conditions in the reservoir. In the case studied very little difference in recovery was obtained at the abandonment pressure. An analysis of the basic factors involved indicates that the sane results would hold for considerable variation in properties of reservoir fluids, permeability of the formation or well spacing. Even if the reservoir has a water drive it appears that no harm will be done by- open flow production if the rate is cut back before any appreciable free gas is produced. However, any condition which leads to disproportionate withdrawal rates and which causes large pressure differences over large areas might result in substantial loss in ultimate recovery. INTRODUCTION When the pressure declines in a reservoir, gas is evolved from solution causing a shrinkage in the reservoir oil so that a stock tank barrel of oil with its residual dissolved gas occupies a smaller volume than originally. For a given reservoir oil saturation, therefore. stock tank oil content will be higher at the lower pressure. At the same time the evolved gas which remains in the reservoir reduces the reservoir oil saturation, and this would be expected perhaps to cause a reduction in stock tank oil content. However, around the well the shrinkage occurs so rapidly that stock tank oil may actually accumulate in this region in spite of the simultaneous reduction in reservoir oil saturation. If this accumulation should continue, spreading into a larger zone, the loss might be appreciable and because larger pressure gradients accompany higher rates the accumulation might possibly be large if wells are produced at too high a rate. It is the purpose of this paper to determine the effect of rate of flow on ultimate recovery by solution gas drive. The problem under consideration involves the unsteady state flow of oil in a closed radial system from which oil is produced by the evolution of gas as a finite drawdown is estalllished and the reservoir pressure declines. A somewhat similar unsteady state production problem dealing, however, with a linear system has been considered by Muskat and Meres, but these authors do not discuss the effects which rate may have on recovery. Other methods have been reported for estimaling recovery as a function of pressure decline when producing at an infinitesimal rate, and Muskat and Taylor&apos; have shown the effect of fluid and reservoir characteristics on recovery under these conditions. Assuming steady state to exist, Babson has given a procedure for computing the decline in well productivity as the field is depleted, and Moyer has combined these methods to estimate abandonment conditions and the resulting ultimate recovery. These latter approaches to the problem either do not consider the effect of rate or assume steady state can be established. In detail this paper presents the behavior of the reservoir producing under unsteady state conditions and considers the effect of production rate during this unsteady state flow on the recovery attained. The analysis also shows that there will exist at abandonment a type of steady state, and on this basis a method has been clevelopetl for rapid calculation of abandonment conditions.

Jan 1, 1949

By C. C. Miller, W. F. Kieschnick, E. R. Brownscombe

The possibility has been mentioned that large pressure gradients in a solution gas driven field caused by high production rates might lead to a reduction in the ultimate recovery obtainable compared to that which would be obtained by a very slow rate of production. In the present study the reservoir conditions accompanying a high rate of production and the corresponding ultimate recovery were compared with those obtained if the reservoir were produced at some marginal rate throughout its entire life. The method of calculation involved the application of fluid flow - material balance analysis to a series of successive steady state conditions in the reservoir. In the case studied very little difference in recovery was obtained at the abandonment pressure. An analysis of the basic factors involved indicates that the sane results would hold for considerable variation in properties of reservoir fluids, permeability of the formation or well spacing. Even if the reservoir has a water drive it appears that no harm will be done by- open flow production if the rate is cut back before any appreciable free gas is produced. However, any condition which leads to disproportionate withdrawal rates and which causes large pressure differences over large areas might result in substantial loss in ultimate recovery. INTRODUCTION When the pressure declines in a reservoir, gas is evolved from solution causing a shrinkage in the reservoir oil so that a stock tank barrel of oil with its residual dissolved gas occupies a smaller volume than originally. For a given reservoir oil saturation, therefore. stock tank oil content will be higher at the lower pressure. At the same time the evolved gas which remains in the reservoir reduces the reservoir oil saturation, and this would be expected perhaps to cause a reduction in stock tank oil content. However, around the well the shrinkage occurs so rapidly that stock tank oil may actually accumulate in this region in spite of the simultaneous reduction in reservoir oil saturation. If this accumulation should continue, spreading into a larger zone, the loss might be appreciable and because larger pressure gradients accompany higher rates the accumulation might possibly be large if wells are produced at too high a rate. It is the purpose of this paper to determine the effect of rate of flow on ultimate recovery by solution gas drive. The problem under consideration involves the unsteady state flow of oil in a closed radial system from which oil is produced by the evolution of gas as a finite drawdown is estalllished and the reservoir pressure declines. A somewhat similar unsteady state production problem dealing, however, with a linear system has been considered by Muskat and Meres, but these authors do not discuss the effects which rate may have on recovery. Other methods have been reported for estimaling recovery as a function of pressure decline when producing at an infinitesimal rate, and Muskat and Taylor&apos; have shown the effect of fluid and reservoir characteristics on recovery under these conditions. Assuming steady state to exist, Babson has given a procedure for computing the decline in well productivity as the field is depleted, and Moyer has combined these methods to estimate abandonment conditions and the resulting ultimate recovery. These latter approaches to the problem either do not consider the effect of rate or assume steady state can be established. In detail this paper presents the behavior of the reservoir producing under unsteady state conditions and considers the effect of production rate during this unsteady state flow on the recovery attained. The analysis also shows that there will exist at abandonment a type of steady state, and on this basis a method has been clevelopetl for rapid calculation of abandonment conditions.

Jan 1, 1949

By R. C. Allen

About four years ago the writer proposed a revision of the correlation of the Huronian formations in Michigan, and noted the bearing of the question on the correlations of the Huronian rocks in Wisconsin and Minnesota.1 Dr. C. K. Leith opposed this revision and argued for the retention of the correlations of the United States Geological Survey, published in 1911,2 for which he and Dr. Van Hise were mainly responsible. As late as June, 1917, Harder and Johnson, following Leith, thought it "premature to change radically a correlation based on years of careful field work."3 The work of Wolff on the Mesabi and Cuyuna Ranges, of Hotchkiss on the Gogebic Range (unpublished), and of the writer and assistants on the Michigan ranges, together with data developed by exploratory and mining operations, has introduced so many new facts not recognized in the scheme of the U. S. Geological Survey that the correlations of 1911 must be considered, in some important respects, obsolete. Indeed, new data are accumulating so rapidly that any classification, which for the moment may seem best to explain the facts, is almost immediately modified or refined by further observations. The problem of Huronian correlations is difficult, but interesting and important. With the aid of fossils, stratigraphers of the post-Algonkian formations have been able to show that slight disconformities mag separate strata of vastly different ages, and that within physically conformable strata may be concealed a hiatus of great magnitude. In the non-fossiliferous Huronian group, minor physical breaks in the strata are only beginning to attract attention, and it is too early to discuss what bearing these will have in correlating the formations of one area with those of another, but it is safe to say that the "lost intervals" which are not disclosed by physical relationships will remain forever lost; therefore we may not hope to discover the ultimate truth concerning the

Jan 1, 1920

By Michael B. Jones, Wayne R. Bruce, Cyrus W. Field

For more than a decade the Pacific Northwest has been a frontier of successful porphyry copper-molybdenum exploration. This vast region (about 2100 miles long, 350-500 miles wide) occupies a geologically complex mobile tectonic belt. It parallels the Western Cordillera from northern California-Nevada to southern Alaska-Yukon Territory, and west from the northern Rocky Mountain-Tintina Trenches to the Pacific margin. Right lateral displacement has occurred along major transcurrent faults that are sub parallel to the region and the transform Fairweather-Queen Charlotte fault zone separates the North American continental plate from the Pacific oceanic plate. Porphyry-type deposits are widespread, but producing mines are restricted to south and central British Columbia. Size and grade are variable (25 to +300 mt; 0.18 to 0.65% Cu with 0.014 to 0.049% MoS2; 0.14 to 0.28% MoS,) and secondary enrichment is normally unimportant. Metallization is genetically and spatially related to late quartz-feldspar porphyries that are within, marginal, or satellitic to composite batholithic intrusions. Radiometric ages of the plutons range from Miocene to Triassic-Jurassic (18 to 217 m.y. [million year] ). Country rocks are typically eugeosynclinal metasedimentary and metavolcanic assemblages of Permian to Jurassic age. Several of the older (pre-Late Cretaceous) deposits formed in submarine island arc environments and they may be genetically related to occurrences of volcanogenic sulfides in the greenstone country rocks. Deposition of bornite-chalcopyrite-molybdenite ores is controlled by contacts, breccias, and fault-fracture zones. Associated hydrothermal gangue minerals include biotite, orthoclase, sericite, kaolinite, quartz, anhydrite, and tourmaline. Isotopic data suggest a deep source for ore, gangue, and plutonic host rocks. Significant exploration features include porphyries, dike swarms, breccias, potassic alteration, barren quartz cores, gossans, and fringing halos of pyrite and propylitic alteration.

Jan 1, 1975

By John Chipman

IT has been long known that the gas evolved during the boil in the open-hearth furnace is mainly carbon monoxide associated with smaller quantities of other gases. A number of attempts have been made to determine the precise effects of carbon and oxygen content of the bath, and of other factors, such as temperature, upon the evolution of carbon monoxide. In his investigation of the carbon-iron oxide product in liquid steel, Herty1 showed that the value of this product at equilibrium could be approximated by plotting the value of the product observed in open-hearth reactions against rate of carbon elimination, and extrapolating to zero rate. The results of this study showed a slight but definite effect of temperature upon the carbon-iron oxide reaction. Experimental studies of the evolution of gases from rimming-steel ingots have not yet attained the degree of precision necessary for an exact understanding of the effects of pouring temperature, carbon content, and iron oxide in the metal upon the composition of these gases. Klinger2 showed that the gas consists mainly of carbon monoxide, and that con-siderable variation in its composition occurs during the solidification of the ingot. In order that these variations may be understood in their proper relationship to the progress of solidification of the ingot and the segrega-tion that accompanies solidification, it is essential to have a knowledge of the condition of equilibrium in the several chemical reactions by which the gases are being formed. It is also necessary to understand the effects of temperature upon the equilibria, and further, to know the manner in which the temperature of the liquid metal within the ingot changes as the skin of the ingot is being built up. The reactions in which we will be chiefly interested are those involving in the one case the oxides of carbon, and in the other case steam and hydrogen, with iron oxide and carbon in the liquid metal. The reactions as they occur in unalloyed liquid iron, and their respective equilibrium constants are written as follows:

Jan 1, 1937

By E. T. Wessel

UNEXPECTED brittle failures of metals in practical applications are a serious problem to many industries and to the nation as a whole. Considerable effort has been devoted to studies of the brittle behavior in metals. However, the major portion of this effort has been directed at developing techniques and apparatus for the purposes of determining the susceptibility of metals to brittle failure and of making various types of observations of the phenomena. Relatively minor effort has been made to understand the basic mechanisms involved in initiating brittle failures. A more complete understanding of the nature and mechanism of the brittle failure problem would be very helpful in efforts directed toward predicting and avoiding brittle failure and toward the development of suitable materials and designs that are not susceptible to a brittle behavior. The intent of the present investigation is to acquire this basic understanding. The pronounced transition from a ductile-to-brittle behavior is most prevalent in metals having the body-centered-cubic lattice structure, primarily be- cause metals of this structure exhibit a strong dependence of yield strength upon temperature and the rate of straining. The generally recognized qualitative concept of the ductile-to-brittle transition is that brittle (cleavage) failure occurs when the yield strength exceeds the cleavage fracture strength. This condition can apparently be achieved by decreasing temperature or increasing strain rate. Likewise, a normally ductile metal can be made to fracture in an apparently brittle manner by the introduction of triaxial stresses (notches) where the ratio of normal to shear stresses can be increased to such an extent that the normal stress exceeds the fracture strength before the critical shear stress for plastic flow is achieved. Neither of these concepts require any prior plastic deformation or explain why the observed fracture strengths are so much less than the theoretical cohesive strength. The results of several investigations of the ductile-to-brittle transition in body-centered-cubic metals illustrate rather conclusively that measurable amounts of nonelastic deformation do precede cleavage fracture, even at extremely low temperatures. These studies suggested that the early stages of plastic flow, particularly abrupt yielding, and their relationship to brittle fracture should be examined

Jan 1, 1958