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By P. H. Griffin

WHEN a subject, such as the manufacture and service of chilled car wheels, as has been fruitlessly discussed for ten or fifteen years, it is difficult to revive interest and action by the mere repetition of statements and arguments that have been made before. And when a situation involves serious responsibilities for conditions that have grown up under circumstances beyond the control of any particular individuals or authority, it is even more difficult to deal with. But there is one phase of every subject that need not involve these particular points if presented in a, proper manner; and that is, " the future state." I will try to present the subject of this communication from the latter standpoint and with the hope that all of those interested will feel disposed to give the matter attention from the basis that it is a, vitally important one to all that travel on railroads, whether as employees or officials, or as dependent on those in charge of the operation, or in the matter of materials and equipment used. The conditions of chilled wheel service have been changed so radically in the past ten or fifteen years by the use of freight cars of 40 and 50 tons capacity, that it is fair to say in the interest of all concerned in the use and in the manufacture of such wheels, that the increased strains and loads have been quite sufficient to account for much of the service results that have transpired. That proper provision was not made for increased possibilities of strength and wear, in fact that previous factors of the kind were allowed to deteriorate, is no proof that such wheels cannot be made equal to heavy service conditions as shown in the data given herein.

Jan 10, 1913

The Committee, appointed early in May, met and organized in Washington, May 9, 1923, and were then advised that such data as they required would as far as obtainable be submitted to them in tabulations, and that they could not be allowed to see the individual reports nor know the identity of the operators on whose reports the figures submitted were based, therefore the Committee's valuation is based on data received from your statisticians, and on tonnages estimated by your staff and by the United States Geological Survey. Various methods of valuation for mining properties have been suggested, but all authorities seem to agree in accepting, as the fairest and most practicable and logical, a capitalization of the estimated future earnings, when such estimate can reasonably be made. Hoover and Finlay both emphasize this. The United States Supreme Court says in Cleveland, Cincinnati, Chicago & St. Louis Railway Co., v. Backus, 154 U. S. 439: But the value of the property results from the use to which it is put and varies with the profitableness of that use, present and prospective, actual and anticipated. There is no pecuniary value outside of that which results from such use. The amount and profitable character of such use determines the value. The Committee on Federal Taxation of the American Institute of Mining and Metallurgical Engineers, appointed in 1919, in its report states: A proper value of a mining property is the present value of the prospective net earnings, taking into account probable variations in output and value. Ingalls ("Wealth and Income of the American People," p. 97) says: The fundamental principle of mine valuation is the present worth of an annual dividend accruing during the period of years corresponding with the lie of the mine. It is a convention that the estimated period shall not be more than 30 years.

Jan 1, 1924

THE COMMITTEE, appointed early in May, met and organized in Washington, May 9, 1923, and were then advised that such data as they required would as far as obtainable be submitted to them in tabulations, and that they could not be allowed to see the individual reports nor know the identity of the operators on whose reports the figures submitted were based, therefore the Committee's valuation is based on data received from your statisticians, and on tonnages estimated by your staff and by the United States Geological Survey. Various methods of valuation for mining properties have been suggested, but all authorities seem to agree in accepting, as the fairest and most practicable and logical, a capitalization of the estimated future earnings, when such estimate can reasonably be made. Hoover and Finlay both emphasize this. The United States Supreme Court says in Cleveland, Cincinnati, Chicago & St. Louis Railway Co., v. Backus, 154 U. S. 439: But the value of the property results from the use to which it is put and varies with the profitableness of that use, present and prospective, actual and anticipated. There is no pecuniary value outside of that which results from such use. The amount and profitable character of such use determines the value. The Committee on Federal Taxation of the American Institute of Mining and Metallurgical Engineers, appointed in 1919, in its report states: A proper value of a mining property is the present value of the prospective net earnings, taking into account probable variations in output and value. Ingalls (" Wealth and Income of the American People," p. 97) says: The fundamental principle of mine valuation is the present worth of an annual dividend accruing during the period of years corresponding with the life of the mine. It is a convention that the estimated period shall not be more than 30 years.

Jan 1, 1924

By A. S. Richardson

Ventilation of the Butte mines has long been a rather difficult problem because of the natural high temperature of the rock. With increase* in mining depth, higher rock temperatures have been encountered, and this has caused a constantly growing demand for more effective ventilation measures. During recent years the hazards of dust in mine air have been more clearly recognized, and have necessitated the adoption of dust-prevention methods. To meet these ventilation problems in the mines of the Anaconda Copper Mining Co., a mines ventilation department was organized in 1918, to act under the direction of the general superintendent of mines. At the present time, under normal operating conditions, the force employed includes the ventilation engineer, two chief assistant ventilation engineers and eight assistant ventilation engineers. The activities of the department are, briefly: (1) planning and supervising operation of the general ventilation system; (2) planning and supervising the operation of dust-prevention measures, together with dust sampling and related microscopic work for the quantitation of the dust samples and determination of particle-size distribution; (3) the design and development of air-conditioning methods to meet present exceptionally severe temperature conditions and in anticipation of future requirements. To a large extent the technical features of the ventilation methods have been described in earlier papers by the author. This paper is written mainly to summarize past accomplishments bearing most closely on health and safety, with a somewhat more detailed account of the dust-prevention measures that have been developed comparatively recently. Facilitating Flow of Am As a basic requirement for the safety of the mcn, all ventilation plans are subject to a ruling that the main operating shafts must be maintained as inlet air courses. Under this condition, a safe, fresh-air escapeway is assured if a fire occurs within the mine, and the shaft; is available as a base

Jan 1, 1940

By J. E. Burke

THE origin of so-called annealing or recrystalli-zation twins in face-centered-cubic metals continues to be a matter for speculation, and in the present report an attempt is made to explain their origin and to account for at least a majority of the observations concerning their behavior. The fact that annealing twins are prominent only The speelmen was deformed 8 pet in compression and then indented over the lower left-hand corner in a Rockwell in-denter, and then annealed to cause partial recrystallization. Note intense twinning in heavily deformed part and slight twinning in less deformed part. The upper right-hand corner is unrecrystalized. Area reduced approximately 25 pot for reproduction. after recrystallization suggests that deformation may be necessary for their formation. In 1926, Mathewson1 reported the observation by Phillips that annealing twins are frequently parallel to strain markings which delineate octahedral planes in the deformed (and partially recrystallized) matrix, and suggested that strain markings are mechanical twins which grow into annealing twins during recrystallization. Later work by Burke and Barrett' has shown that strain markings are traces of planes upon which slip has occurred, and that there is no evidence for the formation of mechanical twins of microscopically resolvable width in face-centered-cubic metals. Mathewson3 has pointed out, however, that slip may produce twin faults, and later modifications of this hypothesis have assumed that twin faults rather than true mechanical twins serve as the nuclei for annealing twins. Carpenter and Tamura5 suggested, also in 1926, that annealing twins might form by accidents of growth. A close-packed layer of atoms can be added to the octahedral plane of a face-centered-cubic metal in two possible positions, the right position

Jan 1, 1951

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

It is usual practice in the copper industry to use open horizontal molds for casting tough-pitch copper wire bars.' A wire bar cast in this manner is partly characterized by heavy wrinkles and a comparatively deep skin of oxide on the top of the bar, corresponding to the open side of the mold. On the theory that the rough, high-oxide surface might have an adverse effect on the rolling and drawing properties of a wire bar and might account for some of the irregularities of mill behavior, several bars which had been planed to remove the wrinkled surface were processed into wire. These bars responded to mill treatment more satisfactorily than did the regular wire bars. Realizing that machining the surface of one face of each bar would not be commercially feasible, it was decided that casting the metal into a vertical mold and cropping off the pouring end would accomplish approximately the same result. Several wire bars of commercial size (250 Ib.) were so cast and processed into wire for comparative test with bars cast in the usual horizontal molds. It is the purpose of this paper to present the results obtained from this investigation, in which commercial bar sizes and processing technique were used throughout. The results show that in general copper wire bars cast vertically are superior to those cast horizontally. Experimental Procedure A horizontally cast bar and a vertically cast bar were obtained from each of several regular reverberatory furnace heats of copper which had been refined and poled to tough-pitch metal in accordance with usual methods.' Both bars were cast from the same part of the melt and within five minutes of each other, in order to produce as nearly as possible, in each case, wire bars of identical composition.

Jan 1, 1930

By J. L. Shafer, Christopher L. Caenepeel, Martha L. White

Often an in situ leach is the only practical economic method for copper recovery from small low grade oxide deposits. The decision to develop a copper property by an in situ blast and leach is strongly dependent on ore grade, tonnage, hydrology, and the copper extraction and acid consumption rates. The inherent leachability of the ore will in part determine the desired amount of fracturing of the ore deposit by the blast in order to obtain a copper extraction rate that is economical. For the last several years Occidental Research Corp. (ORC), has undertaken a modest effort to address the question of how to best identify and determine the information necessary to predict and control the operation of an in situ leach for the economic recovery of copper. Modelling of the Leaching Process During the past 10 years the activity in the mathematical modelling of the leaching of copper sulfides in copper dumps and heaps has increased dramatically. The modelling of copper oxide leaching has not received as much attention. The acid leaching of non-sulfide copper minerals while chemically less complex, compared to sulfides, does generate a vertical acid concentration gradient in the ore heap being leached due to the acid-base nature of the reaction. This is generally not observed in sulfide deposits that are biologically active, due to the buffering action of opposing reactions involving the generation of sulfuric acid from sulfide minerals and acid consuming host rock. Thus, the objective of ORC 's copper oxide modelling efforts is to determine the leaching parameters which will account for this vertical acid concentration gradient. Knowledge of this gradient will result in the correct choice of the feed acid concentration to the top of the ore dump or heap, such that the effluent will have the desired pH.

Jan 1, 1980

By M. E. Wadsworth, G. W. Warren

INTRODUCTION Hydrometallurgical processes for the extraction of metal values can be divided into two broad categories: (a) Processes involving the treatment of high grade material (e.g. finely divided mineral concentrates); and (b) processes which treat lower grade material (ores, waste dumps, etc.). This discussion will be directed primarily toward the first category, but in either case a fundamental knowledge of the intrinsic kinetics and thermodynamics is necessary to understand the behavior of the system. The bulk of research efforts in the last decade along these lines has been aimed at the recovery of copper (1-8). However much information has also been reported on uranium (9, 10) , zinc (11) , cobalt and nickel (12, 13). More comprehensive reviews on these areas are also available (14). As discussed by Sepulveda and Herbst (15, 16) one of the most difficult problems facing process designers is the acquisition and scale-up of reliable information concerning the intrinsic kinetics of leaching systems. The scale-up or modeling of these multiparticle systems is far more complex than that of homogeneous ones. This is due to the numerous rate determining steps which are possible with heterogeneous reactions and the broad distribution of properties of a multiparticle feed such as particle size and mineralogical composition (16). In addition, other factors must also be considered such as interactions between particles, the anisotropic nature of individual particles, the effect of solution chemistry, and electrochemical phenomena. All of these factors must be taken into account, often simultaneously. The thrust of this paper will be to more closely examine how the factors mentioned above can be treated. Some elementary examples of

Jan 1, 1980

By Ripu Daman Lama

The size of coal pillars in mines until recently has been determined by experience without being based upon scientific investigations. As a consequence, the size of pillars had invariably been larger than could be accounted for because of the number of unknown factors involved which influence the strength, dictating the use of large safety factors. With the mining going deeper, the size of the pillars greatly increases and sometimes a considerable portion of the mineral property are blocked in the mine pillars required to support the superincumbent strata. With the advances in the field of Rock Mechanics, attention of mine planning engineers has been focused upon the design of mine pillars for safe and efficient working as well as decrease losses of coal. The problem involves the study of three factors: (1) Presence of stresses in the area and their distribution on pillars in the course of extraction. (2) The influence of external factors on the strength of coal. (3) The inherent mechanical properties of coal. These aspects have been studied by a large number of investigators, the first by in-situ stress measurements and photoelastic studies and the second and third aspect by studies conducted in the laboratory on small size specimens (Bunting, 1911; Evens & Pomeroy, 1961; Gaddy, 1956; Greenland et al, 1941; Steart 1954). The size of the specimens tested in the laboratory has been limited to a few inches and the results obtained have been extrapolated by large factors, sometimes several hundred times the largest specimen tested. In these tests much consideration has not been given to

Jan 1, 1971

By C Macquarie, Maurice Cook

Normally the grain size of cold-rolled and annealed copper sheet is of the order of 0.02 to 0.06 mm., and 0.1 mm., for example, would, for many purposes, be regarded as undesirably large. The occurrence of very large grain sizes in a few isolated cases of copper sheet led the authors to inquire into the causes giving rise to such unusual results. During the course of this work a very large number of experiments have been carried out to determine the effect of varying the conditions of the final and penultimate rolling and annealing operations, as well as of earlier rolling and annealing treatments. A correspondingly large number of observations have been made, but within the space of one paper it is possible only to outline relatively briefly what appear to be the more important of these experiments and observations. The presentation of the results does not follow chronologically the order in which the experiments were carried out and they have been rearranged for the sake of simplicity. In recent years a considerable amount of work has been done in connection with the recrystallization and grain growth in metals arid alloy. that take place on annealing, and a number of generalizations have beell reached. It is known that the crystal size in wrought material in the annealed condition depends on a number of factors, including the time and temperature of the annealing operations and the nature and amount of cold-work to which the material has been subjected. Results. however that are not covered by these generalizations can be obtained, which, in some instances, may even appear to be contradictory to them. Xccortling to these generalizations gradual changes in grain size are effected by progressive variation of the factors involved in annealing or cold-working. The work recorded in the present paper, however, relates to the development of grain sizes which are far beyond those normally encountered in ordinary annealing operations and far in excess of grain sizes which,

Jan 1, 1939

By S. S. Arentz

PLANNED health and safety programs have become an essential part of American industry because such programs lead to increased operating efficiency, improved labor relations, better public relations, and to substantial savings in compensation insurance. Those of you who have had the unpleasant duty of informing the wife or widow of one of your men of his serious injury or death while on the job, know that all the benefits of a successful safety program do not show on the balance S. S. ARENTZ, Member AIME, is General Superintendent, Nevada Operations, Combined Metals Reduction Co., Pioche, Nevada. AIME San Francisco Meeting, February 1949. TP 2741 A. Discussion of this paper (2 copies) may be sent to Transactions AIME before March 31, 1950. Manuscript received Jan. 6, 1949. sheet. These programs are of particular importance to the mining ,industry because mining's reputation as an unusually hazardous industry and the commonly isolated location of mining operations tend to focus attention on these problems. Description of Operations: Before proceeding with a discussion of our health and safety programs at Pioche, it may be proper to give a brief description of Pioche and of our operations there. Pioche is one of the early Nevada mining camps. It was founded shortly after the discovery of high grade silver ore in 1863 and mining has continued with more or less regularity to the present day. In an era of lawlessness, Pioche was notorious. The story persists that 75 men died with their boots on before one died a natural death, and old payroll records show that nearly as many gunmen were employed to stand off claim jumpers as there were miners working the mine. That was probably as close to a safety program as the times permitted. Pioche is situated in southeastern Nevada on the main highway between Ely and Las Vegas. The camp is on the flank of "Treasure Hill," near the original silver discovery, at an elevation of about 6000 ft. The present day population of about 2000 is primarily dependent upon the mines of the area, although Pioche also serves as the county seat of Lincoln Couqty and as the center of the surrounding livestock industry. The camp is served by a branch of the Union Pacific Railroad and receives power from the generators at Hoover Dam. The Pioche operations of the Combined Metals Reduction Co. were started in 1923 when the first complex lead-zinc ore was shipped to the company's mill at Bauer, Utah. The modern mill at Pioche was completed in 1941. The operations are medium sized in the nonferrous field, employing an average of 350 men in the mine, mill, and related works. The complex lead-zinc ore is mined from replacement deposits in a comparatively flat, extensively faulted, limestone horizon. Mining methods vary from stull-supported open stopes to filled square-set stopes. The thin bedded limestone and shale overlying the ore is allowed to cave as areas are mined out and caving frequently follows closely upon ore extraction. The relatively heavy ground and the numerous faults add to the problems of safe mining. The mine is well mechanized and the mill and surface plant are modern and well equipped. Labor is organized in a C.I.O. union and labor-management relations have been unusually harmonious. During most of the period since 1923 a competent supervisory staff worked to reduce safety hazards but the primary responsibility for safety rested on the individual workman. Accidents happened and all too frequently they were regarded by all concerned as unavoidable. In October 1939, the late Robert L. Dean became superintendent at Pioche. Most of his previous experience had been in the fields of iron and coal mining and from that experience he brought the concept that no accident is unavoidable. Many of the features of our present health and safety programs were initiated by Mr. Dean during his term as superintendent. Health Program: Our health program centers in Dr. Q. E. Fortier and his new, well-equipped, and well-staffed, modern hospital in Pioche. The program starts with a thorough pre-employment physical examination and is followed by yearly re-examinations at the expense of the company. The Pioche Mutual Benefit Association, to which all Pioche mine operators and employees belong, pays benefits covering hospitalization and surgery expense incurred by employee members and their families. The Association is governed by a board of directors elected by its members. The mine operators of the district donated the original capital and pay the monthly dues of the employee members. The employees pay the dues covering members of their families. Though not strictly a part of the

Jan 1, 1951

By Ian Campbell, G. Austin Schroter

Although there is now an extensive literature on the bleaching clays, not a great deal of material is to be found concerning the geological features of these deposits and their bearing on problems of exploration and development. At the same time, chemical and crystallographic research on the clay minerals during the past few years has laid a suitable foundation upon which to base conclusions of economic value drawn from field observations. All of the criteria and deductions herein presented are based upon extensive field work by the senior author, both in the United States and Canada, and when .subjected to the ultimate tests of development and exploitation they have held up remarkably well, despite the fact that many of these conclusions apparently have not been reviewed in the literature heretofore. The nomencelature of the bleaching clays is rather confusing in the light of present-day commercial standards and has even led to litigation.'" The old term "fuller's earth" is largely based upon trade usage and the definition of the term therefor? is dependent upon the changing standards of commerce. For statistical purposes the Bureau of Mines8' classes as "fuller's earth" all natural bleaching or filtering claylike materials that possess high adsorptive capacity without previous chemical treatment or activation. Conversely, the so-called activated or acid activated clays are now generally recognized as any clay mineral or mixture of the clay minerals whose adsorptive capacity has been developed to commercial standards by chemical or physical treatment. Therefore, without attempting to propose any additions to the nomenclaturc: of bleaching clays, this paper will refer to naturally adsorptive clays and activable clays, respecbively, for the two types indicated.

Jan 1, 1942

By Robert A. Colten, Frederick C. Hull, Robert F. Mehl

It is known that pearlite forms from austenite by a process of nucleation and growth, and that the rate of formation of pearlite may be described by a rate of nucleation and a rate of growth.l,2 The manner in which these two quantities operate to produce the observed isothermal reaction curve has been analyzed in a paper published in I939.3 Two types of process were described: (I) that in which nucleation occurs at the grain boundaries of the parent phase, with the nodules growing toward the centers of the grains, initially as hemispheres and then after impingement as roughly radial-columnar structures; and (2) that in which nucleation occurs generally, with the nodules growing to full spheres until impingement with other growing nodules restricts growth. Both cases are met in the formation of pearlite from austenite (Fig. I);2,4 the former, occurring near the knee of the S-curve, has been named "grain-boundary transformation," and the latter, occurring at temperatures near Ael, has been named "group-nodule transformation." In developing our knowledge of the factors that determine the rate of formation of pearlite from austenite, it is important1,2 to obtain data on the rate of nucleation and the rate of growth of pearlite. Such data, when obtained near the knee of the S-curve, will furnish information of use in understanding the factors that affect hardenabil-ity; when obtained at higher temperatures, such data will be useful in understanding the behavior of steels that during heat-treatment react to pearlite.2 It is the purpose of this paper to present data on the rate of nucleation and the rate of growth of pearlite in dependence upon composition, grain size, temperature, and the degree of homogeneity of the parent austenite. The studies are restricted chiefly to plain carbon commercial steels." Previous Data on Rate of nucleation and rate of Growth Data on the rate of nucleation and the rate of growth of pearlite have been published by Scheil and Lange-Weise,5 by Mirkin and Blanter,6,7 by Meh1,l and by Dorn, De Garmo and Flanigan.2, It is difficult to interpret the data, for in most cases too little information is given on austenitizing temperatures and times, the state of homogeneity of the austenite (presence or absence of carbide, etc.), austenite grain size, and mode of formation of pearlite at the temperatures given. Except for the approximations of Mehl and the work of Dorn, austenite grain size was disregarded, though it is well known

Jan 1, 1942

By Robert F. Mehl, Gerhard Derge

The gamma-alpha transformation in iron and iron-rich alloys is of such practical and theoretical importance that many papers have been published upon the subject relating to critical temperatures, transformation rates and accompanying property changes. Although crystallo-graphic studies are of less immediate practical usefulness, the opportunities which these offer to furnish data on the basic atomic movements which characterize the transformation are not to be neglected1. The early work on the crystallography of this transformation has been reviewed in the fourth paper of this series2; since then several important papers have appeared. Our present knowledge may be briefly summarized as follows. Kurdjumow and Sachs, working with a 1.4 per cent carbon steel3, established the orientation relationships subsisting between the face-centered gamma and the metastable tetragonal lattices in freshly quenched martensite, and between the face-centered gamma and the body-centered alpha lattices in tempered martensite. The orientation relationship observed in the latter case may be stated in terms of planes and directions observed to lie parallel in the two lattices: {111} ?//{110}a [110] ?// [111]a (This notation is used throughout as the most descriptive means of expressing the fact that any (111) plane of the gamma phase may be parallel to any (110) plane of the alpha phase, and that a [110] direction in a particular (111)? plane is parallel to a [Ill] direction in the corresponding (110)a plane.) From these relationships the atomic movements that transform the gamma lattice into the alpha may be inferred. In the present experiment these may be considered as consisting primarily in a shear of the atoms parallel to the {111} planes in [110]? Directions

Jan 1, 1937

By H. C. Casey, M. B. Panish

The roles of the phase diagram and the diffusion and solubility analyses in the selection of sources for the diffusion of zinc into GaAs are discussed. Isothermal sections of- the phase diagram are described at 1000°, 775°, 744°, and 700°. Below 744° the three solid phases, Zn3As2, GaAs, and ZnAsz, may be in equilibrium. In the composition regions where the three solid phases are in equilibrium, the partial pressures of the components do not vary with composition and there is no liquid phase. A diffusion source composition within that region containing 5, 50, and 45 at. pct Ga, As, and Zn was selected to yield reproducible diffusion profiles without surface damage. The 5/50/45 ternary source Provides a significant improvement in the reproducibility and planarity of- the zinc diffusion as compared with other zinc diffusion sources that result from starting with elemental zinc, dilute solutions of zinc in gallium, or various combinations of zinc and arsenic. Several experimental diffision profiles for the 5/50/45 diffusion source have been determined. The profiles are very steep in the region of the junction and produce devices that exhibit step junction behavior. The junction depth varies as the square root of time. Diffusion at 700°C for 4 hr gives a 5-µ junction depth and a surface concentration of 2.4 x1020 cm-3. The surface concentration is enhanced by a factor of three and the junction depth decreased by a factor of ten as compared with diffusion with a starting source 01- elemental zinc. The differences in dijyusion behavior with these two sources are due primarily to the approximately 10' greater equilibrium As4 partial pressure for the 5/50/45 source. ThE most common technique for the preparation of GaAs p-n junctions for diverse applications ranging from switching diodes to injection lasers has been to diffuse zinc into the solid from the vapor phase. The zinc impurity has generally been provided by introducing into a diffusion ampoule elemental zinc, dilute solutions of zinc in gallium, or various combinations of zinc and arsenic. For the purpose of eliminating surface deterioration, zinc has been diffused into GaAs through SiO2 films1 and from zinc-doped SiO2 films.2 During a study of the injection and recombination mechanisms in GaAs junctions, we found that these diffusion techniques either resulted in nonreproducible diffusion profiles and nonplanar junction interfaces or were extremely inconvenient to use. An unpublished report by Allen and pearson3 emphasized that an understanding of diffusion requires relating the diffusion conditions and system compositions to the ternary phase diagram. Recent studies have made it possible to relate the effect of starting source composition on the GaAs sample surface and diffusion profile reproducibility and, in addition, to estimate the expected surface concentration and zinc diffusivity. These studies include the Ga-As-Zn phase diagram,415 the determination of the incorporation reaction for zinc as a substitutional impurity,6 and the analysis of the concentration dependence of the diffusion coefficient.' In this paper the role of the phase diagram in the selection of the starting diffusion source composition is illustrated, and an application of the diffusion and solubility analyses is used to demonstrate their utility in the estimation of surface concentration and diffusivity for various starting source compositions. Consideration of the isothermal sections of the ternary phase diagram shows that below about 744° C a composition region exists where the three solid phases Zn3As2, GaAs, and ZnAs2 are in equilibrium without a liquid phase. In this region the partial pressures of the components do not vary with composition, and thus the surface concentration and diffusivity depend only on temperature. A diffusion source composition within that region containing 5, 50, and 45 at. pct Ga, As, and Zn was selected. As will be described in detail, this diffusion source yields reproducible diffusion profiles without surface damage, planar junction interfaces, and steep profiles that result in devices with step junction behavior. Only closed diffusion systems are considered. Open or flowing vapor systems require the maintaining of constant vapor pressures in the flowing gas and represent control problems outside the scope of this discussion.

Jan 1, 1969

By G. R. St. Pierre, S. W. Gilby

The equilibrium vapors established over Fe-Cr-Ni alloys containing up to 50 pct Cr at 1600°C were determined by collecting the effusate from thoria Knud-sen cells. From these data, the activities of iron and nickel in the ternary alloys have been calculated. In a separate set of measurements, a mass spectrometer was used to determine the activities of the three components in a series of Fe-Cr-Ni alloys. In binary Ni-Cr melts, the activity coefficient of chromium referred to pure solid chromium as standard state is less than one at low chromium contents but is greater than one for melts containing more than 30 at. pct Cr. For Ni-Cr melts containing less than 10 at. pct Cr, In ?Cr = 0.15-0.92 N2. Ternary activity diagrams for Fe-Cr-Ni alloys are presented. In iron-rich alloys, the interactions between the three components are negligible; however, in nickel-rich alloys, the three principal interactions have significant positive values. THE activities of components in binary Fe-Ni alloys have been measured both in the solid solution1-3 and liquid solution4-6 temperature ranges. The determination for Fe-Ni melts have been made by three different methods: transpiration,4 Knudsen-cell effusion with analysis of an accumulated condensate,' and Knudsen-cell effusion with direct measurements of relative component intensities by mass spectrometric methods.6 The results obtained by the three different methods in three different laboratories are in excellent agreement and considerable confidence is placed in the activity coefficients for Fe-Ni melts. At 1600°C, the activity coefficients in dilute solution are ?°Ni = 0.66 and ?oFe = 0.40 for the pure liquid components as standard states. Measurements made on solid solution Fe-Cr alloys7-10 indicate that the component activities are slightly greater than ideal. The measured activities in iron-rich Fe-Cr liquid alloy11-16 indicate almost ideal behavior for this system. The recommended activity coefficient of chromium in dilute solution in liquid iron at 1600o C, ?oCr, is 1.18 when referred to pure solid chromium as standard state and 1.04 when referred to pure undercooled liquid chromium as standard state." The conversion factor of 1.14 is based on a melting point of 1857°C and an enthalpy of melting of 4047 cal per g at. for chromium.21,37 The activity coefficient of iron in dilute solution in liquid chromium has not been measured. Activity measurements on solid Ni-Cr alloys have been made by several investigators.17-20 During the review of this manuscript, Fruehan12 published the results of a study on liquid Ni-Cr alloys at 1600°C. He used galvanic cells22 with ZrO2(CaO) as the electrolyte and Cr/Cr2O3 for the reference electrode. His results indicate that ?oCr in nickel at 1600°C is about 1.01 when referred to pure solid chromium and about 0.89 when referred to pure undercooled liquid chromium as standard state. The activity coefficient of nickel in liquid chromium is unknown. The compositions of vapors freely evaporating from some molten Fe-Cr-Ni alloys have been measured by Lyubimov, Granovskaya, and Berenstein.23 Their results, combined with known vapor pressures, indicate strong positive deviation for chromium in iron-rich alloys and strong negative deviation for chromium in nickel-rich alloys. EXPERIMENTAL PROCEDURES This research was undertaken to determine the activities of components in ternary Fe-Cr-Ni melts containing up to 50 at. pct Cr. At the initiation of the research, we decided to use a Knudsen-cell method wherein a portion of the effusing vapor is condensed on a cold plate.' The composition of the equilibrium vapor for each alloy composition is determined in this method by holding the system under constant conditions for a period of time sufficient to collect enough condensate on the cold plate for chemical analysis. The activities of components in ternary alloys can be calculated from such vapor composition determinations by Eq. [1].24

Jan 1, 1970

By N. A. Gokcen, J. Chipman

A revised treatment of the authors' published data eliminates the complex relation previously proposed between concentration of silicon and activity coefficient of oxygen in liquid iron. Revised values of the thermodynamic properties of the liquid solution are presented. IN a recent experimental study of the reaction SiO2 (s) = Si+ 2O; Kf, = [% Si] [% O]² [1] the authors' found a substantially constant equilibrium product in liquid iron at 1600°C of 2.8x10-5 They also reported extensive data on the reactions: SiO2 (s) + 2H2 (8) = Si- + 2H2O (g); K'2= [% Si] (H2O/H2 [2] and H, (g) + 0 = H2O (g); K'3 =( H2 O [31 (H2) [%O] From the results on reaction 3 and earlier data of Dastur² on this same reaction in the absence of silicon, they determined the activity coefficient of oxygen, f0, on the basis of the definition K3 = (H2O)/ (H2)f0 [% 0] where K, is the equilibrium constant and f0, is taken as unity in the pure Fe-0 system. Similarly values of fsi were deduced from results on reaction 2. In a more recent study" of analogous reactions in the system Fe-A1-0, it was found impossible to reconcile the results on reaction 3 with Dastur's data; accordingly the latter were ignored and the equilibrium results were extrapolated to find a value of K, at zero concentration of aluminum. This procedure failed to locate the cause of the discrepancy but it did yield reasonable values of activity coefficients. It also avoided introduction of the complex empirical relation between the oxygen activity coefficient and the concentration of the added element. The same type of discrepancy exists for system Fe-Si-0.' In the earlier paper an attempt was made to fit both sets of data by a single curved line (Fig. 6 of ref. l), the form of which is contrary to the theoretical requirement of a finite slope at infinite dilution. In the light of experience on the Fe-A1-0 system the discrepancy must be recognized as one which can be resolved only by more refined measurements. Accordingly Figs. 6 and 10 are retracted. It is pointed out also that until the discrepancy is resolved Figs. 7, 8, and 11 are subject to some uncertainty. Qualitatively the following conclusions still appear valid: 1—The activity coefficient of oxygen is reduced by addition of silicon. 2—In dilute solutions the activity coefficient of silicon increases with its concentration. 3—With respect to equilibrium in reaction 1, the above effects are approximately compensating. The discussion of K'1 in the previous paper requires no revision. It was pointed out that the constancy of the product [% Si] [% 0]² ndicated a compensating effect of the activity coefficients of silicon and oxygen. Therefore, as a very good approximation, K1 = K'1 and the following average values are suggested both for K, and K', at the temperatures 1550°, 1600°, and 1650", respectively, 1.0x10-", 2.8~10-" and 5.5 ~lo-'. Revision of the thermodynamic treatment is necessitated by the recent appearance of new data, based on a combination of combustion and solution calorimetry,' which yields for the heat of formation of low-cristobalite from the elements, the value —209,330 ±250 cal per mol at 25°C. This is about 4000 cal larger than the value previously accepted. The new value for cristobalite is used, together with Kelley's tables of high-temperature heat contents" and entropies and with Korber and Oelsen's' heat of fusion of silicon to obtain the following equation for the standard free energy of cristobalite in the temperature range 1700" to 2000°K: Si (1) + 02 (g) = Si02 (crist.); ?F° = -217,700 + 47.OT [4] The free energy of solution of 0, in liquid iron is:8 O2 (g) = 20 (in Fe); AF° = -55,860 - 1.14T [5] and these two equations are combined to give: Si (1) + 20 = SiO, (crist.); AF° = -161,840 + 48.14T [6] ?F°1873 = -71,700 cal. From the experimental value of K, = 2.8x10-5, Si + 20 = SiO2 (crist.); ?F°1873 = -39,000 cal. [7] The combination of Eqs. 6 and 7 yields the free energy change when liquid silicon dissolves in iron to form the dilute solution of unit activity (1 pct). Si (1) = Si; ?F°1873 = -32,700 cal. [8] The heat effect in this process according to Korber and Oelsen' is an evolution of 28,500 cal per gram

Jan 1, 1954

By L. O. Bieber, L. H. Martin

DIFFERENT MELTS OF THE same type of nickel and high-nickel alloys, while having almost identical mechanical properties at room temperature, may have widely varying hot malleability. Either the upper limit or burning temperature may vary or a variation in malleability may occur within the temperature limits normally encountered during hot working. Melts which have reduced hot malleability of the latter type, are said to have a "hot short" range. Examination of melting records and chemical analysis of these heats fails in most cases to show the reasons for these variations. In May, 1930, an investigation was started to determine if a quick and accurate method of hot-malleability testing could be developed which would predict the ability of the metal to withstand hot forging and hot rolling by standard mill practices. The results obtained were so satisfactory that from that time on, all melts of nickel and high-nickel alloys produced in the International Nickel Company's Huntington, W. Va. Works have been tested when hot malleabilty was an important factor. To date, over 63,000 commercial melts of Monelt † nickel, Inconel† and other high-nickel alloys have been tested and the test data compared with processing results. As the result of experience gained in over sixteen years, two standard methods of hot malleability testing have been adopted.

Jan 1, 1948

By Donald D. Carr, Lawrence F. Rooney

Perhaps no other mineral commodity in this volume has as many uses as limestone and dolomite. These carbonate rocks are the basic building blocks of the construction industry, the material from which aggregate, cement, lime, and building stone are made. Carbonate rocks, and their derived products, are used as fluxes, glass raw material, refractories, fillers, abrasives, soil conditioners, ingredients in a host of chemical processes, and much more. Although the use of limestone and dolomite goes back before recorded history, new uses and products are continually being found. Carbonate rocks form about 15% of the earth's sedimentary crust and are widely available for exploitation. Found extensively on all continents, they are quarried and mined from formations that range in age from Precambrian to Recent. Reserves of carbonate rock are large and will last indefinitely, although high-purity deposits may be absent or have limited avail- ability in certain areas. Limestone and dolomite are so useful and so abundant that in 1972 more than 690 million tons were produced in the United States. In fact, about 75% of all stone quarried or mined in the United States was carbonate rock. Sand and gravel was the only mineral commodity produced in greater quantity. In this chapter we have sought to provide the general reader an overview of carbonate rocks, their composition, distribution, production, and uses, with emphasis on developments since 1960. In doing so we borrowed extensively from our recent report on the applied geology of limestone and dolomite (Rooney and Carr, 1971). The literature on the limestone and dolomite resources of the United States and Canada is so vast and diverse that one can easily become mired down in print. We tried to list those references that are easily accessible and that provide the economic geologist with a starting point for more intensive study. The table listing selected references on limestone and dolomite resources in Canada and the United States reflects our attempt to be selective rather than exhaustive and to direct the reader to the best sources of detailed information.

Jan 1, 1975

By F. F. Skiba, J. E. Warren

An idealized miscible displacement process in a three-dimensional, heterogeneous porous medium has been studied via experimental computation based on a "Monte Carlo"' model. The macroscopic dispersion which results solely from variations in the permeability of the porous system is related to the scale of the heterogeneity as well as the distribution function for the permeabilities. The interpretation of laboratory data is often subjective and may bt? misleading since ambiguities are not always recognized. Furthermore, an experiment performed on a conventional oil-field core does not yield a valid measure of Macroscopic dispersion for reservoir engineering purposes since the scale of heterogeneity that is significant in the laboratory is not significant in the reservoir. The analysis of field-performance data is discussed and it is shown that a unique characterization of the reservoir can not be obtained from this information alone. A possible method based on a minimum of data, for estimating the spatial distribution of permeabilities in a reservoir is postulated INTRODUCTION Many studies concerned with diffusion and dispersion in porous media have been undertaken because of the potential importance of miscible displacement processes for increasing the recovery of oil. The results from a large number of these studies have been published; in a recent paper Perkins and Johnstonl presented a comprehensive survey of the pertinent literature and excellent appraisal of the "state of the art". In this investigation, dispersion resulting from macroscopic variations in the properties of the porous medium is of primary interest. Dispersion, in this sense, is caused by fluctuations in the velocities of the individual fluid elements as they move through the porous system. This phenomenon is the result of inhomogeneities in the permeability and/or porosity, but it can be amplified by differences in the characteristics of the fluids involved. The objectives of this study are the following: (1) to determine the qualitative manner in which macroscopic rock properties affect the observed dispersion coefficient; (2) to evaluate the possible influence of macroscopic dispersion on laboratory experiments; and (3) to appraise the significance of macroscopic dispersion with regard to reservoir performance. Investigations of this type are essential since many miscible displacement processes, while seemingly understood from a mechanistic point of view, do not behave in a predictable manner under field conditions. Although a plausible explanation is that the process is dominated by the environment, little serious effort has been devoted either to describing the reservoir itself or to determining the probable effect of the reservoir properties on the process. This study is intended to be exploratory in nature; however, it is hoped that it will provide additional insight into the physical problem and that it will suggest areas suitable for further investigation. EXPERIMENTAL COMPUTATION MODEL To limit the observed dispersion to that which results solely from variations in the properties of the porous medium, an idealized process in which one incompressible fluid displaces another identical fluid is simulated. This simulation is achieved by means of a modified Monte Carlo method — by tracking a number of mathematical particles (tracer) through the system according to the steady-state, single-phase velocity distribution. Then the system is characterized by the distribution of the residence times of the particles. Since any number of particles can be injected simultaneously (a true delta-function distribution) and only pressure conditions are imposed on the boundaries, the model is completely determinate. Furthermore molecular diffusion, microscopic dispersion, adsorption and/or reaction are automatically precluded from the model. The heterogeneous medium is represented by a rectangular, three-dimensional array of uniform, homogeneous porous blocks which are randomly arranged; it is assumed that any two opposing faces of the system are held at fixed potentials

Jan 1, 1965