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By V. G. Mooradian, John T. Norton

THE diffusion of metal atoms into the crystal lattice of another metal and the assumption of regular positions to form a homogeneous alloy are some of the most fundamental phenomena of structural. metallurgy. The mechanism of this process has been the subject of a great deal of study from many viewpoints, but the picture is still far from complete. It is generally believed that if one metal is to diffuse into another, the first must have some solubility in the second1. This means that the solvent must be able to accommodate the stranger atoms, either on points of its own lattice or in the interstices between, without losing its own crystallographic identity. It is also a general observation that cold-working is a distinct aid in the diffusion process, causing it to take place with greater rapidity at the same temperature or with the same speed at a lower temperature. There is considerable doubt, however, as to the real significance of the deformation in its effect on the diffusion mechanism. Several factors associated with the cold-working. may be responsible for the increased diffusion rate. The plastic deformation causes a distortion of the solvent lattice, which may be an aid in the assimulation of atoms of another kind. There are many references2 in the literature that suggest that some distortion or "loosening" of the lattice is necessary for atomic migration and that diffusion cannot take place in the undis-

Jan 1, 1935

By Henry F. Hebley

In preparing this paper it has been the aim of the writer to keep the problems of both producers and consumers in mind. Until now, no attempt has been made to familiarize each group with the other's practice and limitations. This paper is an effort to acquaint the readers with some of the factors pertaining to the problem and cost of mining and preparing steam coal, and also to the economics of producing steam with such coal. In recent years all lines of endeavor have turned to intensive mechanization in order to lower the unit cost of production. The average fuel consumption in steam electric generating stations has dropped in 20 years from 4.0 lb. to 1.4 lb. per kilowatt-hour; while the modern power station can generate 1 kw-hr. on a fraction under 1 lb., or 13,000 B.t.u. coal. Also, the amount produced per man has in that same period risen from 3.8 to 8.2 tons, owing to the use of modernized equipment below ground for coal cutting, drilling, shooting, loading, hauling and hoisting. Unfortunately, the rapid speed of 5 tons per minute of operation at which the coal is loaded mechanically precludes any appreciable removal of impurities at the coal face, so that the raw coal is hoisted containing a markedly higher percentage of impurities than the hand-loaded coal, which was subjected to the scrutiny of the miner during loading. Also, during the past 20 years, certain seams of coal lying close to the surface have been made economically available by the improved design of electrically operated shovels and draglines for the removal of overburden running as high as 56 ft. This strip coal frequently contains so much ash in the raw state (Table 1) that it would have no sales value. Therefore, coal preparation must be adopted to beneficiate the raw product. Some seams in the United States have a decreasing ash content with decreasing size, owing, in all probability, to the fact that the coal is friable while the impurities are hard, causing a concentration of the low-ash material in the fine sizes. Illinois No. 6 coal being rather hard, naturally the reverse is true.

Jan 1, 1938

By Henry F. Hebley

In preparing this paper it has been the aim of the writer to keep the problems of both producers and consumers in mind. Until now, no attempt has been made to familiarize each group with the other's practice and limitations. This paper is an effort to acquaint the readers with some of the factors pertaining to the problem and cost of mining and preparing steam coal, and also to the economics of producing steam with such coal. In recent years all lines of endeavor have turned to intensive mechanization in order to lower the unit cost of production. The average fuel consumption in steam electric generating stations has dropped in 20 years from 4.0 lb. to 1.4 lb. per kilowatt-hour; while the modern power station can generate 1 kw-hr. on a fraction under 1 lb., or 13,000 B.t.u. coal. Also, the amount produced per man has in that same period risen from 3.8 to 8.2 tons, owing to the use of modernized equipment below ground for coal cutting, drilling, shooting, loading, hauling and hoisting. Unfortunately, the rapid speed of 5 tons per minute of operation at which the coal is loaded mechanically precludes any appreciable removal of impurities at the coal face, so that the raw coal is hoisted containing a markedly higher percentage of impurities than the hand-loaded coal, which was subjected to the scrutiny of the miner during loading. Also, during the past 20 years, certain seams of coal lying close to the surface have been made economically available by the improved design of electrically operated shovels and draglines for the removal of overburden running as high as 56 ft. This strip coal frequently contains so much ash in the raw state (Table 1) that it would have no sales value. Therefore, coal preparation must be adopted to beneficiate the raw product. Some seams in the United States have a decreasing ash content with decreasing size, owing, in all probability, to the fact that the coal is friable while the impurities are hard, causing a concentration of the low-ash material in the fine sizes. Illinois No. 6 coal being rather hard, naturally the reverse is true.

Jan 1, 1938

By C. F. Nagel

This paper is written primarily for those who are familiar with the processes mentioned but who desire a further insight into some of the fundamental principles. It does not give a complete description of the various practices employed in the working of aluminum and its alloys, but presents a few illustrations of the essential respects in which aluminum differs from other common metals, and emphasizes the controlling factors of the processes under consideration. Heat Treating Certain aluminum alloys are capable of having their mechanical properties greatly altered by a heat-treatment process. The degree of this irnprovement may be illustrated by some typical properties of dura-lurnin (Table 1). It is essential that the material be in the wrought condition in order to obtain rnaximum heat-treatment effects. In the case of duralumin, the process consists of heating the metal to a prescribed temperature and then quenching it. Immediately after quenching, the material is relatively soft though not as soft as in the annealed state. If allowed to stand at room temperature, the material changes, increasing in hardness and strength without loss of elongation, but at the expense of the plasticity. This action is very rapid at first, gradually diminishing in intensity and to all practical purposes being completed in about four days. This process of hardening is termed

By A. B. Kinzel, Walter Crafts

Inclusions of nonmetallic matter have long been recognized as objectionable in steel. A complete theory of the effect of inclusions, which is consistent with that held today, was outlined in Howe's early work on the metallurgy of iron and steel. This, by analogy with wrought iron, assumes that the observed difference in properties between specimens with and across the direction of rolling is due to slag enclosures. The fact that wrought iron shatters in ballistic test is taken as an indication of the effect of inclusions on the resistance to'shock. Since that time, the development of the metallurgical microscope has shown the discrete nonmetallic inclusions in the iron matrix. Better resolution has brought out the great number of inclusions, and the availability of good microscopes in steel mills and laboratories has constantly drawn more attention to these inclusions. This recent emphasis on inclusions has resulted in studies as to their nature, mode of formation and methods of elimination, such as the work of Wohrman, Dickenson, Herty and Schenk. In addition to the published works, many investigations which have not been published have been carried out by private laboratories and have resulted in the application of specifications intended to limit inclusions in many qualities of steel. Neverthless, a clear understanding of the quantitative effect of inclusions on the physical properties of steel has been lacking. It is the specific purpose of this study to determine the quantitative effect of inclusions on the physical properties of steel that determine its behavior under dynamic stress. The study has shown that a quantitative relation between counted inclusions and impact strength does exist in normalized steels, but that factors other than readily visible inclusions are equally important. Furthermore, the present commercial rating of inclusions is unreliable with respect to counted inclusions or dynamic tests, and this study indicates that the tensile-impact test is more reliable as a measure of quality. General Scheme The general plan of the study follows: (1) To develop or establish a satisfactory measure of dynamic strength; (2) to develop or establish a

Jan 1, 1931

By Henry Rawdon

Cold-working is generally considered as a process of hardening metals. Diamet-rically opposite statements concerning the applicability of the scratch-hardness method in the testing of cold-worked metals, particularly after severe deformation, which exist in the technical literature led to the study of the results which are summarized in this paper. A series of metals, of which copper, iron and tin are used as illustrations here, were cold rolled to a definite degree without any intermediate annealing and the hardness determined by both the scratch and Brinell methods. The results indicate that the metal hardens rapidly during the initial stages of deformation; however, after a certain stage, which corresponds to a rather definite microstructure, the metal becomes softer and in its final form may be softer than the metal in its initial stage. As part of the study of the scratch-hardness method for metals and alloys in cooperation with one of the technical committees of the American Society for Testing Materials, the authors devoted considerable time to the study of the changes in hardness of metals when cold rolled. Various seemingly contradictory statements in the technical literature concerning the applicability of the scratch-hardness method to such cold-rolled materials were among the principal reasons for the investigation, the results of which are in part presented here. The effect of cold deformation, at least in moderate degrees, on the hardness as measured by the Brinell and other common methods is so well known that further reference is unnecessary. Concerning the scratch hardness of cold-worked metals, Martens and Heyn state' that hardness, whether measured by the ball-pressure method (Kugeldruck) or by the scratch method (Ritzverfahren), will be increased by cold deformation. Jeffries and Archer give a seemingly diametrically opposite view. They state,2 that "the sclerometer (indicating scratch

Jan 1, 1924

By Edgar Bain

THE results are presented of an investigation to discover the fundamental atomic conditions existing in Corson's high-copper alloys hardenable by means of silicide solution and reprecipitation. The study attracted the writer because it offered a very convenient example of the general type of hardenable alloys exemplified by duralumin, Sykes' iron-tungsten and iron-molybdenum alloys and the hardenable lead antimony. SUMMARY OF RESULTS AND CONCLUSIONS In brief, the investigation shows that very perfect crystallinity exists in the solid solutions prepared at high temperature to contain as much dissolved silicide as possible. The lattice parameter of copper is altered very little by the amount of cobalt, nickel or chromium, and silicon dissolved. The hardening by drawing at a temperature to initiate precipitation of excess silicon and metal produces a remarkable change in the atomistics of the solid solution. The old perfection of crystallinity in the solid solution is destroyed and the new atomic spacings are of variable magnitude even in one grain, and a condition in a measure resembling that found in martensite is observed. Were no particles whatever precipitated by the drawing action, still ample causes for hardness would be in evidence in the solid solution alone. The lack of plane continuity in the crystal grains would oppose slip in a very effective manner. Complete annealing restores the crystalline perfection in large measure. In these alloys even the most sensitive methods failed to reveal the characteristic pattern of the silicide precipitated by the anneal, but this was largely to be expected as the amount is relatively small.

Jan 1, 1927

By Arthur B. Cummins

Diatomite is a siliceous rock of sedimentary origin, which may vary in degree of consolidation, but which consists mainly of the fossilized remains of diatoms. These are microscopic algae of the order Bacillaria. Diatomite is a unique form of silica, there being nothing else found in nature or produced by the manufacturing arts, that has its characteristic physical structure. There are numerous sediments which contain some diatom residues, admixed with a substantial amount of other materials-clay, carbonates or silica. While these are classified as diatomaceous silts, shales, or mudstones, they are not properly diatomite, a designation which is restricted to material of such qualities that it is suitable for commercial uses. The terms diatomaceous earth and kieselgur are synonymous with diatomite. The expressions infusorial earth and tripolite are obsolete. Diatomaceous silica is a definition best used to distinguish the basic component of diatomite, that is, the substance of the silica shell itself and is the major constituent of beneficiated diatomite or processed diatomaceous products. Some highly indurated materials, such as cherty shale, porcelanite, and opaline cherts which have resulted from diagenetic changes cannot be considered as diatomite although they may have been derived therefrom. On the other hand, diatomaceous oozes or loose sediments consisting mainly of diatom residues with or without much organic matter are source materials in process of becoming diatomite. Composition and Properties Pure diatomite is composed of opaline or hydrous silica, with small amounts of associated inorganic components-alumina, iron, alkaline earths, alkali metals, and minor constituents, all of which may occur in solid solution or as an essential part of the opal complex. Crude diatomite on the other hand may contain variable amounts of organic matter and soluble salts, and the usual contaminants of sedimentary formations-particles of rockforming minerals, sand, clay, or carbonates. As occurring in nature, diatomite contains an unusual amount of free water, which may vary from 10 to 60 pct or more. Diatomite, in the dry deposits which are characteristic of most of the important world deposits, occurs as a lightweight, comparatively light colored, "chalklike" material. The apparent density (dry basis) in situ varies from 20 to 40 lb per cu ft. The structure may be either massive or finely stratified. The earth is highly porous, usually soft and easily friable. It is nonreactive with acids and may be tentatively identified by the above characterizations. Confirmation is by microscopic examination which readily reveals the nature of the material. In deposits which contain organic matter the appearance of the material is totally different. The color may vary from light tan or gray to brown, greenish or nearly black. There is frequently difficulty in distinguishing it in the field from peatlike materials, but the difference is readily apparent after calcination. Powdered diatomite or diatomite products have an apparent density (loose weight) of 5 to 16 lb per cu ft, wet densities of 10 to 30 lb per cu ft, specific gravities 1.9 to 2.35, index of refraction 1.42 to 1.48. Diatomite is essentially micro-amorphous, but does show some tendency toward orientation in structure after a cristobalite pattern. Amorphous silica has been considered as a random association of cristobalite crystallites, the size of which are only slightly larger than a unit cell.20 The prop-

Jan 1, 1960

By W. R. Kube, W. H. Oppelt

Five low-rank coals, including two lignites, a steam-dried lignite, and two subbituminous coals, were carbonized at 940°F, in a bench-scale carbon-ize~ with a nitrogen and hydrogen atmosphere, or both, using pressures from atmospheric to 1000 psig. Coking characteristics were observed, and yields, composition, and distribution of products from thermal degradation were determined. The influence of pressure on yields from coal carbonization, as well as on modification of coke structure, has long been of interest. One of the first attempts at pressure carbonization was that of Capps and Hulett1 who in 1917 investigated the effects of pressure ranging from 1 to 20 atm on yields at 600° C for bituminous and subbituminous coals. High-pressure carbonization has not been used commercially for coke production. More recently, carbonization at relatively high pressure in the presence of catalysts and hydrogen has been proposed for the production of metallurgical-grade coke from low-rank fuels.' Another approach involves carbonization at high pressure in a hydrogen atmosphere to produce heating gas and a solid residue that is gasified with oxygen and steam to produce the hydrogen required for hydro-genation 3-4 or, alternatively, is burned to raise steam. Recently it has been proposed to carbonize coal under pressure, burn the gas in a gas turbine to produce power, and use the solid residue as fuel in a conventional steam-power plant.5 Our primary interest in pressure carbonization stems from an attempt to determine the influence of pressure on the coking characteristics of lignite to design a high-pressure slagging gasifier using oxygen and steam. At atmospheric pressure, North Dakota lignite is generally considered to be non-coking. However, lignite and subbituminous coals have been reported to show increased agglomeration properties in steam, hydrogen, or carbon-dioxide atmospheres at elevated pressures, although no strong coke was formed at pressures up to 3000 psig.6 If lignite would agglomerate seriously under gasification conditions, proper flow of charge through the gasifier could not be maintained without installing a mechanical stirring device or destroying the caking properties of the coal before gasification. Data on the caking properties of lignite or other gasification fuel, as well as on yields of products under conditions simulating the carbonization process in the pregasification zone, were required in the preliminary design stage of the gasifier. No information was available concerning the influence of pressure and type of atmosphere on North Dakota lignite. To provide this basic data, the U. S. Bureau of Mines investigated the effect of pressure and a hydrogen or nitrogen-rich atmosphere on the yield of products and on coke formation in a bench-scale pressure carbon-izer. SCOPE OF INVESTIGATION Five coals were tested at 940°F in nitrogen and hydrogen atmospheres, at pressures from atmospheric to 1000 psig. Yields and composition of solid, liquid, and gaseous products were determined as a function of the process pressure, and attention was given to the physical appearance of the solid residue. Percentage of carbon converted, sulfur retained in char, and thermal balances were calculated. In this paper, primary consideration is given to carbonization in a nitrogen atmosphere and to data concerning the solid phase. The effect of pressure in hydrogen is presented in detail for only one lignite. More complete information on the response of the other coals in a hydrogen atmosphere will be published in a USBM Report of Investigations. DESCRIPTION OF EQUIPMENT Details of the bench-scale pressure carbonizer are given in Fig. 1. The body of the carbonizer was

Jan 1, 1961

By G. E. Perry, J. F. Bruskotter, D. G. Russell, J. H. Goodrich

The depletion performance of gas wells has been investigated by mathematical simulation techniques. The gas well model which was studied consisted of a single well located in the center of a bounded, cylindrical, homogeneous reservoir. Dependency of gas compressibility and viscosity on pressure was considered in studies of well performance at both constant mass flow rate and constant flowing pressure conditions. To carry out the investigation, the nonlinear, second-order, partial differential equation which describes Darcy flow of a nonideal gas through porous media was solved numerically. Some of the previous investigations of gas well performance have been of limited general use, because assumptions were introduced to simplify either the gas properties or the basic differential equation. Other studies have been rigorous in these respects but have presented a very limited set of calculated results. The present study was attempted to present a rigorous theoretical model and sufficient numerical results to permit meaningful conclusions to be drawn. It was found that all terms must be retained in the partial differential equation to make accurate predictions. The neglect of higher-order terms, e.g., terms of the order of the "gradient squared", leads to serious material balance errors at large times and to conservative estimates of gas well performance. The higher the gas flow rate and/or the lower the permeability-thickness product of the formation, the more pronounced are these deviations. For example, in a well draining 640 acres in a 25-md-ft formation (8,120 MMcf gas in place) at a constant rate of 993 Mcf/D, the rigorous solution predicts a bottom-hole pressure decline from 4,000 to 1,000 psia in 8.7 years. If higher-order terms are neglected in the differential equation, this decline in pressure is predicted to occur in 5.3 years. With the results of the numerical solution of the differential equation as a basis, simple, easy-to-use approximations for predicting gas well performance for Darcy flow conditions have been developed. These simple approximations are based on the familiar equations for flow of a single, slightly compressible fluid. The approximate methods possess a high degree of accuracy and enable the prediction of long-term gas well performance to be made quickly and accurately without the use of a digital computer. Both transient and stable flow period approximations were developed. INTRODUCTION In recent years income from the sale of natural gas and associated products has represented an ever-incre as ing fraction of the industry's total revenue from operations. To meet the surge in demand for natural gas, the industry has depended heavily upon established reserves and has actively pursued development of new reserves. The search has progressively led to reservoirs which yesterday were too tight and/or deep to yield the desired return on invested capital. More than ever before, evaluation accuracy is now required to forecast the criteria upon which engineering recommendations and management decisions are based. Considerable effort has been expended by both research and operations personnel on the development and application of methods for analyzing and predicting the performance of gas wells. Fundamentally, the problem is the familiar one of extracting data during the drilling, testing and early production life of a well and applying these data within an accurate simulation model to predict long-term behavior. During the past 30 or more years a voluminous literature dealing specifically with gas field problems has been generated. A recent book' lists a comprehensive bibliography of published material through 1959. Over 1,200 references are cited. Since then 39 additional articles on natural gas technology have been published in Transactions volumes of the Society of Petroleum Engineers of AIME. Most existing theory for predicting gas well performance requires that one or more idealizations (e.g., steady-state flow, ideal gas of constant viscosity, small and constant compressibility and constant-viscosity fluid) be applied. Although existing theory may apply directly or be adapted by various artifices to describe specific gas well and reservoir behavior, no widely applicable method is available, and existing methods appear to be subject to appreciable error unless better limits of applicability are defined. The objectives of this paper are (1) to present numerical solutions to the partial differential equation describing gas flow under conditions of general interest in gas well performance prediction work, (2) to present solutions which possess a high order of accuracy for both transient and stabilized flow periods of a well producing at constant rate or constant pressure, and (3) to develop and present simplified relationships which can be used as high-order approximations to the exact numerical results for fast and accurate predictions of gas well performance at the operating level. Combined, these objectives are designed gen-

Jan 1, 1967

By C. H. Li, R. J. Stokes, T. L. Johnston

The phenomenon of solid-solution strengthening has previously been studied in a number of binary alloy systems.1-8 There has been, however, very little information published concerning the strengthening effects of specific solutes in magnesium alloys. Schmid and his coworkers9,10 investigated the behavior of aluminum and zinc in binary and ternary magnesium-alloy single crystals, but this work was done before high-purity materials were readily available. Workers at the Dow Chemical companyH reported increases in the critical resolved shear stress upon alloying magnesium single crystals with zinc and indium. Recently, Hardie and parkins* investigated the extent of hardening produced by the addition of various solutes to poly crystalline magnesium. The present work was undertaken to provide data on the strengthening effects of a number of solutes in high-purity magnesium, for the purpose of supplying further experimental information which might be useful in describing a general mechanism for solid-solution strengthening. To simplify interpretation of the results, the mode of deformation was limited to basal slip, through the use of single crystals. EXPERIMENTAL PROCEDURE Magnesium and magnesium binary-alloy single crystals containing indium, cadmium, thallium, aluminum, and zinc were prepared in the form of l/2-in.-diam rods, approximately 8 in. long, using a modified Bridgman technique in which the crystals were slowly cooled from the melt in a steep temperature gradient, in an atmosphere of helium. It was found that a solid-liquid interface travel speed of about 0.7 in. per hr consistently produced single crystals. The poly crystalline starting materials for the preparation of single crystals consisted of 1/2-in.-diam extruded rods, prealloyed to the desired composition. The unalloyed magnesium and magnesium-indium extrusions were furnished by the Dow Chemical Co. The other alloys were prepared at the Rensselaer Polytechnic Institute Metallurgical Laboratories. Some preliminary studies of the strengthening effect of indium were conducted at room temperature using a constant rate of tensile loading of 1040 g per min. Stress was applied to the crystals by means of a simple 5:l lever arm. The lever was loaded by a constant rate of flow of shot into a receptacle suspended from the long arm of the lever. Plastic flow was detected by an electrical resistance strain gage cemented to the surface of the crystal normal to the minor axis of the predicted glide ellipse. The crystals were acid machined to produce tensile specimens with a reduced section between the grip ends, with an additional step in the center of the reduced section to compensate approximately for the slip-retarding effect of the strain gage. The balance of the single crystals were extended in an Instron tensile tester. This machine employs a synchronously driven screw and automatically records applied load as a function of cross-head separation. It became unnecessary therefore, to employ a strain gage to detect deformation or to acid machine a reduced section. Preparation for testing reduced merely to chemical cleaning of the surface, thus minimizing the amount of handling and probability of accidental damage to the crystals. The rate of elongation employed in all the tests was 0.002 in. per min, corresponding to a strain rate of approximately 0.0004 per min. EXPERIMENTAL RESULTS The investigation confirmed the finding of many workers that the yield strength of hexagonal metal crystals is strongly orientation-dependent. This is illustrated in Fig. 1, in which o, the tensile stress required to produce gross plastic flow in eleven unalloyed magnesium crystals stressed at a constant rate of loading is plotted as a function of sin X, cos Ao where X, is the angle between the

Jan 1, 1960

By Worthen Bradley, R. G. Hall

THIS paper will attempt to show how a metallurgical problem at one California quicksilver mine was solved, and how the solution was applied successfully at another mine. The pronouns "we" and "our," as used below, refer to the Bradley Mining Co. of San Francisco. The term "concurrent firing" for the purpose of this paper can be defined as feeding and firing a rotary kiln at the same end-that is, of course, the upper end. This is as opposed to "counter-current firing," the orthodox method, in which a kiln is fed at the upper and fired at the lower end. The terms "quicksilver" and "mercury" are used interchangeably. EARLY REFERENCES The earliest work on nonferrous metallurgy, we believe, was The Pirotechnia of Vannocio Biringuccio,1 its first edition having been printed in Italy in 1540. Quoting from its chapter entitled "Concerning Quicksilver and Its Ore": Quicksilver . . . is one of the gods and has divine strength in itself, and also, to the annoyance of the alchemists, it is winged. Hence, when it sees that it is in gravest danger, it loosens itself from . . . every bond . . . and flies away into the heavens, escaping from the hands of those who crucify it. Almost laughing, it leaves all its adversaries mocked and scorned, with their phials and filters empty . . . How thorough a job, under certain conditions, it can do of mocking its adversaries and leaving their phials and filters empty, was found out four centuries later at the Sulphur Bank mine, on the east shore of Clear Lake, in Lake County, California. The other mine mentioned in the title is the Reed, in Yolo County, California, 35 miles by road southeast of Sulphur Bank. Reed and Sulphur Bank ranked respectively fifth and seventh in U. S. production in 1943. The earliest direct reference we can find to furnacing troubles at these mines was by Thomas Egleston in 1890.2 Speaking of Sulphur Bank, Egleston says: Sometimes there is more sulphur than cinnabar in the ore, which is a detriment to both . . . making the sulphur impure, and rendering the cinnabar difficult to work on account of the soot. In some of the early . . . furnaces the accumulation of soot from the excess of sulphur has been known to penetrate as far as the fan blower at the end of the . . . condensers, and completely prevent its revolution. In order to get rid of the inconvenience of this accumulation . . . , as well as to get a commercial value from the sulphur, it (the sulphur) is now separated by steam and sold. It is claimed that the sulphur alone pays all the expenses of . . . the mine. The mine was first worked for sulphur, and the cinnabar it contained was considered to be an inconvenience, and was carefully picked out and thrown away. as its richness and value were not

Jan 1, 1945

By E. Seidl

THE basic material for testing aluminum, copper and zinc is a cast metal, principally in the form of wire bars (Figs. 1 to 3) and plates for the produc- tion of sheets or strips, (Figs. 4 to 7). Experience has proved that the chemical and crystallographic proper-ties of such cast metal exercise a certain influence when it is being worked, which is usually done while the metal is hot. In a chemical sense the slight impurities, which even the purest industrial metal contains, have a disturbing effect. They settle either along the outside limits of granulation, as in the case of aluminum and copper, or else in the interior of the crystal, as in the case of zinc; but frequently are also found accumulating at certain points (formation of the blowholes and skin) (Fig. 7). The crystallographic character of the metals is either that of uniformly fine granulation, or else there occurs a certain distinct casting texture marked by sharply defined cooling conditions and consisting of crys-tals of a pronounced stalk-like or blade form. Since we generally distinguish between a crystal texture and a crystal structure, the term crystal texture is used here for the arrangement of the crystals relative to each other and their microscopic composition; crystallic structure is used to mean the radioscopically ascertain-able structure of the crystal. The influence of the impurities and of the crystalline character on the working of the metals has been fre-quently pointed out in practice as well as in science.

Jan 11, 1927

By H. D. Kynor

By the term mechanical mining is meant that operation, or series of operations, that replace the hand methods of mining. The first undercutting machine to operate in anthracite was placed in the Butler mine of the Hillside Coal and Iron Co., Dec. 23, 1910, by the Sullivan Machinery Co. The first Jackhamer used in the anthracite field was installed at the Wadesville colliery of the Philadelphia & Reading Coal and Iron Co. in Oct., 1912, by the Ingersoll-Rand Co. The first longwall conveyor was installed at the Dodge mines of the Delaware, Lackawanna, & Western Coal Co. in March, 1912. The first mechanical scraper equipment was installed in the Seneca mines of the Lehigh Valley Coal Co. in January, 1914. The amount of anthracite mechanically mined since the first mining machine was installed in 1910" is as follows: Penna. Coal Co. D. L. & W.. ScRanton Temple Hudson YeaR and Hill- Tons Coal Co., Coal Co., Coal Co., Total, side Coal Tons Tons Tons Tons and Iron. Tons 1920................ 372,737b 367,000d 322,892 74,127 371,878 1,508,634 1919................ 950,786 no record 306,616 81,575 319,356 1,658,333 1918................ 917,778 744,966 24,880 44,756 288,781 2,021,161 1917................ 757,940 838,800 5,050 57,279 164,180 1,823,249 1916................ 286,780 860,663 13,960 114,173 101,475 1,377,051 1915................ 428,819 592,169 8,253 1,029,241 1914................ 219,188 153,896 373,084 1913................ 171,505 1912................ 124,267 124,267 1911................ 40,319 40,319 1910................ 1,184 1,184 a A slightly greater production was obtained than here indicated, as the tonnage from individual operations is not shown. b Decrease due to strike conditions in 1920. c Does not include tonnage of D., L., & W. d D., L., & W. decrease in 1920 due to having fewer mining machines in operation. There are about 150 undercutters in use in the anthracite region, 80 mechanical loaders, and 10 longwall conveyors.

Jan 1, 1922

By J. E. Neal, C. T. Naber, O&apos

Silicon thin films were deposited by electron beam evaporation in an ultrahigh vacuum onto (0001) and (1102) sapphire substrates. Attempts were made to correlate the structural properties of the deposited silicon films with the following: 1) substrate orientation, 2) substrate surface condition, 3) substrate temperature, and 4) deposition rate. The substrate temperatures were varied between 500° and 1000°C and the deposition rates were varied between approximately 50 and 700A per min. The following sapphire surface treatments were investigated: 1) annealing in the ultrahigh vacuum at 1200° C; 2) heating in a hydrogen atmosphere at about 1350°C; and 3) etching with silicon by evaporating silicon onto sapphire substrates heated to 1200° or 1300°C. Twinned silicon films were occasionally formed at substrate temperatures between the 800° and 1000°C on unprocessed mechanically polished substrates; however, the reproducibility and crystallinity of these films were generally poor. Single-crystal and twinned silicon films were formed at substrate temperatures between 700° and 1000°C on substrates which were silicon-etched at 1300°C prior to deposition. Fiber texture films were formed at substrate temperatures between 500° and 700°C. The (111) lattice plane of the silicon single-crystal films was parallel to the (0001) sapphire plane and the (100) silicon plane was parallel to the (1102) sapphire plane. TECHNIQUES are well-established for growing single-crystal silicon thin films on sapphire by chemical methods.'-* Vacuum epitaxial techniques have a number of advantages over chemical epitaxial techniques in the fabrication of thin film microcircuits.5 One of the most significant is that vacuum techniques are compatible with well-established procedures for forming vacuum-deposited thin-film resistors, capacitors, and interconnections. Salatna, Tucker, and young6 recently reported the formation of relatively poor crystalline-quality silicon films on sapphire by electron beam evaporation in a vacuum of about 7 x 10-7 Torr. The purpose of the investigation described here is to determine the relationships between the structural properties of silicon thin films deposited on sapphire substrates by electron beam evaporation in an ultra-high vacuum and the following: 1) substrate orientation; 2) substrate surface condition; 3) substrate temperature; and 4) deposition rate. The substrate temperatures were varied between 500° and 1000° C and the deposition rates were varied between approximately 50 and 700A per min. Two orientations of sapphire were used: (0001) and (1102). The thick-nesses of the films were between 8000 and 16,000A. The morphology and crystallinity of the deposited films and substrate surfaces were investigated by optical microscopy, electron microscopy, and electron diffraction. APPARATUS AND PROCEDURE A cross section of the ultrahigh-vacuum thin-film evaporator is shown in Fig. 1. The bell jar is stainless steel and copper gaskets are utilized at all seals. High vacuum is attained by a 6001iter per sec ion pump and a titanium sublimation pump. Sorption pumps are used to rough the system to a pressure of about 10 µ prior to starting the ion pump. Vacuums in the 10- 10 Torr range were attained after baking the system at about 250°C for 8 hr. Vacuums in the 10-8 to 10-9 Torr range were maintained during silicon evaporation. The silicon charges, which were cut from p-type single-crystal boules which had resistivities between 2000 and 4500 ohm-cm, were placed in the water-cooled copper crucible of a 180 deg bent-beam 5-kw electron beam evaporator. During evaporation, a molten zone was formed in the top center of the silicon charge, and the portion of the silicon charge in contact with the water-cooled crucible remained solid. The substrate heater, which has been described

Jan 1, 1969

By James C. Ray

The age classification of the mineralized veins of the Butte district, as given by Weed and Sales, was tacitly accepted for many years. Weed, whose field work was completed in 1906, divided the copper veins into groups of four ages.' In 1913, Sales modified Weed's classification and assigned all mineralized veins (including the silver-zinc veins of the border or "peripheral" zones) to three periods of fracturing and mineralization. Both writers based their classifications mainly on the relative ages of the observable faulting whereby the veins of a so-called "earlier" system are intersected and offset by those of a "later" system. Nevertheless they possess structural and mineralogical characteristics in common which indicate that they are of the same age. The writer has maintained since 19143 that these vein systems were formed during one general period of mineralization along a network of intersecting fractures of approximately simultaneous origin and that the existing offsets are largely due to postmineral faulting. Leith,* takes cognizance of the accumulating mass of data relative to the simultaneous formation of intersecting fracture systems and says, referring to ~utte: "It now appears that the mineralization accompanying them (individual structure systems into which the veins have been grouped) is substantially of one period, indicating that the successive structural movements took place mainly within the period of mineralization." This paper presents the results of certain structural experiments which suggest a modified interpretation of the published data on the Butte district. The interpretation is substantiated by the writer's observations in the Butte mines and is offered with the hope that it will reconcile the structural with the mineralogical conditions existing in this most interesting district; also, that it will emphasize the importance of a

Jan 1, 1931

By A. Grant Elliot, H. W. Lavendel

qualitative picture has been developed to describe the oxidation behavior of TaSi2-coated tantalum and CbSi2-coated columbium. These systems have a significantly lower inherent oxidation resistance than MoSi2-coated molybdenum does. This stems primarily from the fact that Ta2O5 and Cb2O5 are nearly as stable thermodynamically as SiO2, whereas MoO2 or Moos are not. Further, diffusion of silicon in the Ta- and Cb-Si system is considerably slower than in the Mo-Si system. These ,factors prohibit the mechanism of selective oxidation of- silicon which accounts for the oxidation resistance 01- MoSi2-coated molybdenum. The silicide can be stabilized by adding suitable Modifiers which increase the thermodynamic stability of the silicate formed during oxidation. Modifiers, such as aluminum, can be inroduced into solid solution in the coating. in controlled amounts through proper selection of the source in the pack cementation process of coating fov~rzatiorz. Addition of aluminum to TaSi2, coatings on tantalum was effective in moderately increasing the oxidation resistance. EXTENSIVE experimental work and analysis have established the nature of the oxidation behavior exhibited by MoSi2- and MoSi2 -coated molybdenum-base alloys, and defined the conditions for maximum protection against oxidation of the substrate.'-* The oxidation resistance of MoSi2 in the temperature-pressure range of 1100°C-PO2 > 10-5 atm to 1900°C— PO2 > 10-1 atm is due to the formation at the surface of a continuous film of SiO2 which results from selective oxidation of silicon. Under the prevailing kinetic conditions, this film is stable toward the molybdenum silicide with which it comes in contact. Initially molybdenum oxidizes also, but it forms volatile species. SiO2, however, nucleates and grows as a condensed phase. Once a continuous film of SiO2 has formed, the oxidation rate falls to that observed for the oxidation of pure silicon indicative of diffusion through the oxide film as the rate-controlling mechanism. This oxidation behavior is of course highly dependent upon temperature and oxygen pressure. Bartlett and Gage13 and Bartlett, McCamont, and Gagelb define precisely this dependence in terms of the oxygen partial pressures and silicon diffusivities required to support a stable SiO2 film. At low temperatures (near 500°C—the "pest" region) silicon diffuses too slowly to be selectively oxidized. Hence, molybdenum and silicon oxidize readily in proportion to their stoi- chiometry. At high temperatures and low pressure, SiOz dissociates to form volatile SiO(g), and a protective film cannot be maintained. Application of the MoSiz/Mo system is limited to temperatures below 1900oC, the eutectic between MoSi, and MO5Si3.5 The oxidation behavior of MoSi2-coated molybdenum is essentially the same as that outlined above with the exception that the MoSi2 is not in equilibrium with the molybdenum substrate. At the temperatures under consideration silicon will diffuse rapidly into the molybdenum eventually converting the coating to MosSi3.4 The rate constant for subsequent decomposition of Mo5Si3 into Mo3Si plus silicon, and/or the diffusivity of silicon through Mo3Si then becomes low enough to allow active oxidation of both molybdenum and silicon with subsequent degradation of the specimen. A stable silica film can be formed but at temperatures and/or oxygen partial pressures higher than those required with MoSi2 present as a source of si1icon.l, 4 Because of the similarity between the silicides of molybdenum and those of columbium and tantalum one would expect similar oxidation behavior for coatings in the respective systems. This is not entirely the case, however, as shown by the experimental results reported herein. Regarding tantalum and columbium disilicide coatings on tantalum and columbium substrates, respectively, the oxygen arriving at the surface of the coating partitions itself nearly equally between the metal and the silicon, and a two-phase oxide layer (Me2O5 plus SiO2) is always formed. The diffusion of silicon in the tantalum and columbium silicides is relatively slow, compared to that in the molybdenum silicides, which further enhances this equipartitioning of oxygen. Thickening of the coating during service by inward diffusion of silicon into the substrate is correspondingly slow, and the effective thickness of the coating at the roots of cracks and defects is only slightly changed providing high probability for premature coating failure. Furthermore, the SiO2 glass that is generated is not thermodynamically stable with respect to the coating. The metal silicide tends to reduce the SiO2 liberating either free silicon or SiO. The situation can be improved by suitably modifying the coating such that the stability of the protective glass which is generated during service is increased. Thus, selective oxidation of silicon and the modifying agent will occur, and the silicide coating will not tend to reduce the oxide layer. Modifying agents can be introduced into the coating by the pack cementation process. Using sources containing the modifier at controlled chemical potentials allows control of the coating composition. Partially substituting aluminum for silicon in TaSi2 coatings by forming a Ta(Si,Al)2 solid solution was effective in moderately increasing the oxidation protection.

Jan 1, 1968

By John H. Schemel

Large Zircaloy-2 hammer or press forged bars did not exhibit the uniform excellent corrosion resistance to steam normally expected of the alloy in wrought form. Weight gains of coupons cut from forged bars were 40 to 60 mg per sq dm compared to the 28 mg per sq dm obtained on hot rolled sheet and strip. The mechanism of this corrosion and its relation to microstructure is discussed. After these observations, a solution heat treatment followed by rapid cooling was tried on coupons from eight heats of forged bars. The basket-weave structure resulting from the quench did not show agglomeration of intermetallic compounds. These coupons showed uniformly good corrosion resistance with weight gains very close to the 28 mg per sq dm expected of Zircaloy-2 after the 14-day steam test. A large forging was solution heat-treated and tested for structure, mechanical properties, and corrosion resistance. Corrosion resistance was excellent and uniform throughout the section. The normally anisotropic mechanical properties were changed to completely iso-tropic. Strength levels were raised while there was a small loss in ductility at the service temperature. Tempering of the quenched structure below the ß transus did not improve the ductility at the test temperature of 600°F. ZIRCALOY-2 end caps for nuclear fuel elements Zircaloy-2 is an alloy of 1.5 pct Sn, 0.1 pct Fe, 0.1 pct Cr, and 0.05 pct Ni, balance hafnium-free zirconium patented by Westing-house Electric Co. used in pressurized water reactors are machined from large hammer-finished forged bars. The bars forged for this application range from 3 1/2 in. to 7 1/2 in. squares. One of the tests used to evaluate Zircaloy-2 for this service is a 14-day exposure to very high-purity steam at 75oF and 1500 psi pressure. Normally wrought products will exhibit a black lustrous film of zirconium oxide after the test and show a weight gain of approximately 28 mg per sq dm. Coupons representing the forged bars exhibited a wide variety of corrosion results ranging from acceptable black coupons to some covered with white crystals of zirconium oxide that had weight gains of nearly 100 mg per sq dm. One of the most common effects was a white corrosion product that looked like a stain to some observers and the outline of massive metal grains to others. Very careful specimen preparation prior to the corrosion test did not affect the result and metallographic examination did not reveal a structural feature of a size and shape that would correlate with the corrosion product. In addition to the relatively poor corrosion resistance, the forged product was not as ductile as desired. The problem of obtaining uniform and more acceptable properties in these heavy-forged sections seemed to be a function of the microstructure of the metal and, in particular, the distribution of the intermetallic compounds. None of the four alloying elements however are appreciably soluble in a zirconium and are present as compounds which usually appear scattered randomly throughout the structure. Moudryl showed that the distribution of these intermetallic compounds in Zircaloy could be related to a ostringero corrosion failure. Grozier et al. discussed another structural defect that causes a similar corrosion effect. In this case, an elongated gas-void was determined to be the cause. M. L. Picklesimer held in his discussion of the Grozier paper that at least a part of the observed =stringersn were caused by the distribution of the intermetallic compounds. He proposed a

Jan 1, 1962

MINING, to be precise, ends when the ore is delivered to a bin outside the mine. Usually the next step is concentrating; or, as it is more often called, milling. A few elementary definitions will help make clear the discussion that is to follow. A rock is an aggregate of minerals; copper ore is rock that contains copper-bearing minerals in quantity sufficient to make it profitable to mine and recover the copper in the form of marketable metal. Manifestly, under a literal interpretation, a mass of material might be copper ore one day and merely copper-bearing waste rock a week later, if the price of copper happened to drop in the interim. Emphasis already has been placed on the expansion that took place in the ore reserves of the Porphyry companies as a consequence of the great strides made in the technique of mining and ore treatment. So, even if one inserted a qualifying phrase, "at an average price for the metal," after the word "profitable," the definition would still be open to criticism. Place is another factor. It is evident that a body of excellent ore in Arizona might cease to be ore in the economic sense if it were moved intact to the interior of China. However, it is with ore in its technical and scientific aspect that this chapter is concerned. Speaking in general terms, the ton of Porphyry ore as it arrives at the surface contains 25 to 70 lb. of copper minerals in the form of disseminated particles or thin coats along fracture planes. When subjected to appropriate treatment this ton yields 12 to 40 lb. of metallic copper. These ranges take into account conditions of today and of 25 years ago. Two procedures are available: (1) concentration, followed by smelting of the concentrate, or (2) leaching and precipitation, usually by electrolytic deposition. Smelting and leaching are metallurgic processes in that they involve chemical change; concentration

Jan 1, 1933

By 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 min., for example, would, for many purposes, he 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 and alloys that take place on annealing, and a number of generalizations have been 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 he contradictory to them. According 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, according to ordinary standards, would be classified as coarse or large.

Jan 1, 1938