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By Albert A. Smith

The creep properties of metals have assumed increasing importance in recent years and many investigations have been made on various phases of the problem. In the past year the annual lectures of the Institute of Metals Division1 and the Iron and Steel Division2 were concerned with this subject, and are excellent reviews. For many years the creep properties of lead and lead alloys have been investigated at the Central Research Laboratories of the American Smelting and Refining Co., and it is hoped that the present paper will contribute knowledge of some of the factors that influence creep. Lead, being a metal that recrys-tallizes readily at room temperature, is an excellent material upon which to investigate creep phenomena because of the simplicity of the apparatus needed, and it might be expected that results would apply to some extent to elevated-temperature tests of other metals. Material The creep tests of this investigation were all made on high-purity lead (99.9998+ Pb) in which the only impurity that could be detected by spectrographic and chemical means was approximately 0.0001 per cent Fe. Flat strips, 0.750 in. wide by 0. 100 in. thick, were prepared by extruding 2-in. dia. cast billets at a temperature of 250°C. This gave a material of 2 to 3 mm. average grain size with a tensile strength of j.400 lb. per sq. in. when tested at a straining rate of 5 per cent per minute. With this extremely soft material, great care was necessary in handling the specimens, to avoid distortion and subsequent recrystallization. The creep tests at 30°C. were conducted in a constant-temperature room, specially built for the purpose in the basement of an office building in which there was no moving machinery, and no vibration was detectable under the most severe conditions of shock in the adjacent surroundings. The room was well insulated and heated electrically, control being by means of a de Khotinsky regulator operating a relay. Maximum temperature variation over a period of several years has been ± 1/2°C. Specimens of the extruded strip, 16 in. long, were used for test purposes with no reduced gauge section, thus eliminating any distortion due to machining. The method of clamping and supporting the specimens is shown diagrammatically in Fig. 1. The gauge marker for the measurement of extension consisted of an aluminum strip, 0.050 in. thick by 0.75 in. wide, one end of which was ground and sanded to a precise knife-edge and fastened to the specimen by suitable pins. After the strip was fastened in place a fine scratch was inscribed just below the knife-edge by means of a sharp teasing needle. Just below this gauge scratch a short vertical mark was made so that the same point could be located and read each time. Several hundred specimens have been prepared by this method, and it was found that with experi-

Jan 1, 1941

By R. Schuhmann

Available thermodynamic data applicable to copper smelting systems are collected and tabulated, and the important gaps are pointed out. A few examples are given of estimations which can be made from the available data. An experimental research program is proposed to supply the thermodynamic data that appear most essential to better quantitative understanding of the chemistry of copper smelting. The proposed program is designed also to shed specific light on the practical problems of slag losses and magnetite behavior. OPPER smelting, from flotation concentrates to V-/ blister copper, is conspicuous among the large scale chemical processes which are conducted with only relatively incomplete knowledge of the physical chemistry involved. For example, no common metallurgy text explains adequately why copper enters the matte phase while iron enters only to the extent that sulphur is left over after satisfying the copper. Explaining this important phenomenon as a manifestation of the greater affinity of sulphur for copper than for iron is unsound because the affinities of copper and iron for sulphur are about the same at smelting temperatures. As will be shown, other affinities are really decisive in the relatively clear-cut separation of copper in the matte. In contrast, thermodynamic studies have contributed much to our understanding of copper refining, zinc oxide reduction, magnesium production, steelmaking, etc. For each of these processes, the important reactions are clearly recognized, and fair to good quantitative values of the free-energy changes and equilibrium constants are available. Such data have proved to be of constantly increasing practical value in process development and improvement. Work in other fields has furnished much thermodynamic data applicable to copper smelting systems. In fact, several promising starts have been made in applying such data to specific smelting problems. Kelleyl made an appraisal of the possibilities of recovering elementary sulphur from low grade matte. His calculations and compilations of thermodynamic data have represented the starting point for much of the work in this field, including the present survey. Huang and Hayward2 nd Aksoy3 used thermodynamic methods in the study of copper losses in reverberatory slags. Peretti4 used thermodynamic data in explaining the chemistry of converting. The recent publications of Darken and Gurry"." and of Darken,' dealing with the iron-oxygen and iron-silicon-oxygen systems, respectively, present equilibrium data that are applicable to copper smelting systems. Also additional data were reported recently on the affinity of sulphur for copper, manganese, and iron8 and on the sulphur pressures of iron-sulphur melts." The survey presented in this paper was made as the basis for planning an experimental program on the thermodynamics of copper smelting. Few researches on the chemistry of copper smelting have been reported in recent years, so that a reappraisal and coordination of old and new data are essential if further work is to take the directions of maximum value. The experimental program is now in progress, and the plan of attack is outlined at the end of this paper. Progressive Oxidation and Desulphurization of Copper-bearing Liquid Phases: The chemical activities of sulphur and oxygen are two of the most important thermodynamic yardsticks to be applied to copper smelting processes. Virtually the entire smelting and refining sequence involves a series of systems characterized by decreasing sulphur activity and increasing oxygen activity. In this section, therefore, an attempt is made to define and explain these activities in terms of equilibrium partial pressures of SO2, s2, and O,. Also, estimates of these quantities are presented, the estimates being based largely on calculations presented in a later section of this paper. The sequence of steps from raw flotation concentrate to fully oxidized copper ready for poling involves progressive and controlled oxidation. Iron is oxidized and enters the slag. Sulphur is oxidized and leaves in the gas. Table I summarizes several important features of this oxidation and desulphurization sequence, starting at the beginning of the matte blow in the converter. The top line gives in order the principal smelting and refining stages up to fully oxidized copper, plus the additional step, not used commercially, of oxidizing all the way to Cu,O. In the second line are shown the principal copper-bearing liquid phases which characterize the process. Through most of the sequence the copper

Jan 1, 1951

By A. R. Kaufman, P. Gordon

THE large-scale manufacture and use of uranium in conjunction with the atomic energy development during the war led to a need for knowing the equilibrium diagrams of uranium with various other metals. The alloys of uranium with aluminum and with iron were among the first that were studied for this purpose. Much of the work was done in the manner of a survey since it was necessary to determine the important features of the phase diagrams rather than to obtain completely detailed results. For this reason no attempt was made to locate exactly such features as liquidus lines, solid solubility limits and compound and eutectic compositions. It is believed, however, that there are no great inaccuracies in the diagrams reported here and that no important points were overlooked. Earlier work on alloys of uranium with aluminum and iron is almost nonexistent and in each case is considered to have been of little value by M. Hansen. It is interesting to note, however, that the compound UAl3 was first reported in 1902 by L. Guillet. Experimental Procedure Materials: The uranium used for making most of the aluminum alloys was obtained from material prepared by Metal Hydrides, Inc., and melted in vacuum at M.I.T. Because of the lack of an adequate supply of metal, it was necessary to use material from several different batches and hence it is impossible to state an exact analysis. However, a few results indicated about 0.01 to 0.03 pct iron and probably about 0.03 to 0.05 pct carbon. Toward the end of the work a small amount of metal was obtained from Brown University and from Iowa State College and this was used in determining the transformations in pure metal and in some dilute alloys. All of the aluminum used in this investigation came from a supply of high purity metal (greater than 99.9 pct aluminum) which was obtained through the courtesy of Dr. Mehl of the Carnegie Institute of Technology. The uranium used for making the alloys with iron was produced by the bomb reduction process which has been described by J. Chipman.² This metal, after vacuum melting, contained about 99.9 pct uranium by weight with carbon and iron as the chief impurities. Electrolytic iron containing about 0.012 pct carbon, 0.020 pct nickel and 0.009 pct copper was used in making the melts. Melting Equipment: The melting of the alloys went through a stage of development which culminated in the use of beryllia or beryllia-lined crucibles and in the use of high frequency heating in either vacuum or in an atmosphere of argon. It was found that uranium at a few hundred degrees above its melting point would pick up aluminum and to a lesser extent silicon from an alundum thimble while aluminum above 1000°C would extract silicon from the impure alundum. No reaction of either metal with beryllia was noted at temperatures as high as 1800°C. The distillation of aluminum from the aluminum-rich alloys was quite troublesome at temperatures above about 1300°C and was only partially avoided by the use of argon instead of vacuum. Melting in resistance furnaces,

Jan 1, 1951

By F. George, W. Tice, M. Salkind

It was found that Al-A13Ni could be readily cold rolled perpendicular to but not parallel to the whiskers. Reductions of more than 98 pct were achieved without cracking by rolling perpendicular to the whiskers, whereas extensive edge cracking was noted after only 15 pct reduction when rolling parallel to the whiskers. The longitudinal and transverse tensile strengths were nearly doubled, and the longitudinal yield strength more than tripled by cold rolling 50 pct in a direction perpendicular to the whiskers. The whiskers exhibited some waviness (elastic bending) as a result of cold rolling, but at very high reductions (greater than 75 pct) whisker fracture and misalignment became significant. A fine dislocation substructure in the matrix consisting of cells attached to the whiskers was pro -duced by cold rolling. Most of- the substructure was readily removed by a 1-hr anneal at 500°C. Cold rolling was found to substantially reduce the thermal stability of the microstructure at 610°C but did not affect the stability at 500°C. FIBER and whisker reinforced composite materials promise significant improvements in properties over conventional materials. Before they find wide use, however, it will be necessary to understand the response of these highly anisotropic materials to common metalworking processes. Most of the nonmetal-lic fiber reinforced materials have very low elongations (a few pct or less) in the direction of fiber alignment. Thus, metalworking techniques such as rolling and forging would not be as broadly applicable to these materials. This investigation was initiated to determine how a composite system consisting of Al3Ni whisker reinforced aluminum responded to rolling, what changes in the microstructure occurred, and the effect of deformation on the mechanical properties. The composite material studied was produced by unidirectional solidification of the A1-Al3Ni eutectic alloy'-7 and consisted of 10 pct by volume of aligned whiskers of Alai in a matrix of aluminum. It should be pointed out that this system is not representative of all composite materials, and the results will therefore not be universally applicable. The A1-Al3Ni system is characterized by: 1) A strong fiber-matrix interfacial bond 2) A ductile matrix 3) A sufficiently low fiber content to allow significant plastic flow between fibers 4) Strong, completely elastic whiskers (tensile strength 400,000 psi, elastic modulus = 20 X 106 psi.1 These factors allow the material to be readily rolled perpendicular to the fibers. If the fiber-matrix bond were not strong, such a weak interface could fail during rolling. A measure of the ability of a composite to be rolled in the transverse direction can be obtained from noting the transverse tensile behavior. In the case of Al-Al3Ni,2 there is considerable ductility (15 to 30 pct). In the case of boron filament reinforced aluminum, for example, the transverse elongation is less than 1 pct,8 and the material could probably not be cold rolled as readily in that direction. EXPERIMENTAL PROCEDURE 3-in. diam ingots of A1-A13Ni eutectic were unidi-rectionally solidified in graphite crucibles. The starting materials consisted of 99.99+ pct pure nickel and aluminum, and the pure eutectic ingots were made with 6.2 wt pct Ni. The unidirectional solidification process (described in detail elsewhere1-3) consists of preparing a master heat of eutectic composition, remelting, and withdrawing the ingot vertically downward through the heat source at a controlled rate so that plane front solidification proceeds upward at a constant velocity. The resulting microstructure consists of 10 pct by volume of whiskers of very high aspect (length to diameter) ratio. The fiber lengths have not been measured because of the difficulty of detecting fiber ends9 but exceeds 104. There is some possibility that the fibers may be continuous within one grain. Flat sheet specimens 2¾ in. sq and approximately 0.2 in. thick containing whiskers parallel to the plane of the sheet and to one edge were used for this study. A1-A13Ni exhibits either a rod-like (high solidification rates) or a blade-like (low solidification rates) whisker morphology,1,3 and both types were studied. Rolling was accomplished using a two-high rolling mill at a speed of approximately 10 fpm. The rolling direction was either parallel to or perpendicular to the direction of growth (direction of whisker alignment). Reductions of from 0.002 to 0.03 in. per pass were used with the most common value being 0.005 in. per pass. Cold rolling of Al-Al3Ni to more than 98 pct reduction in thickness was accomplished with no intermediate anneals. In addition. a series of speci-mens was cold rolled 97 pct with a 1-hr, 500°C anneal in air after each 50 pet reduction. Tensile testing was accomplished using a Tinius-lsen four screw testing machine. Flat sheet specimens + in. wide and between 2 and 2; in. long with the thickness dependent upon rolling reduction, were used. The gage section was in. wide and 1 in. long. Strain was measured using a clip-on LVDT extensome-

Jan 1, 1970

By C. M. Schwartz, A. E. Austin, W. B. Wilson

High-temperature X-ray diffraction studies were conducted with Th-U alloys with up to 10 wt pet U. The solid solubility of uranium in thorium as a function of temperature was determined by the method of lattice parameters. Thorium will dissolve up to 2.5 wt pet U at 950°, 4.5 wt pet U at 1150°, and 7.5 wt pet U at 1250°C. Determinations were made of the temperature of the transition of thorium and of the effect of uranium upon the transition. The a to ß transition for thorium was observed to occur at 1330' ±20°C. Mean coefficients of expansion were calculated for thorium and two alloys, and for ThO2 in contact with the thorium, using X-ray lattice-parameter data. Values obtained at 950° C for thorium and Tho2 were 12.1 and 9.40 X 10-6 per OC, respectively. Impurities obtained during the X-ray exposure were identified by diffraction and were essentially Tho2 and ThC, with two additional unknown phases being detected. The effect of the impurities upon the results is discussed. DIRECT investigation (i.e., high-temperature X-ray diffraction studies) of the phase diagram of thorium-rich uranium alloys has been shown to be necessary since recent work1 - has disclosed the presence of an allotropic transformation near 1400°C in pure thorium with the room temperature face-centered-cubic phase transforming to a body-cen-tered-cubic structure at the elevated temperature. The effect upon the transition of the addition of uranium to thorium and of the solubility of uranium in thorium at high temperatures remained unknown, yet was of interest in understanding fabrication procedures and elevated temperature use. The present work was undertaken to provide information in this area by determining the transition temperature, the effect of uranium on the transition temperature, and the solubility of uranium in thorium as a function of temperature. Experimental Work The high-temperature diffraction data were obtained using a camera especially designed for the purpose3 and capable of reaching temperatures in excess of 2000°C at pressures as low as 1 x 10." mm Hg. Temperature regulation was provided by regulating the power input to ±0.1 pet variation, and by regulating the water flow through the camera jacket to provide a constant thermal load. The X-ray sample was a rod nominally 80 mil diam, which was further turned down to 20 mil and then etched to 18 mil over 1/2 in. of one end. This was placed in the sample holder and mounted on the camera so that the smaller part was surrounded by a cylindrical tantalum-sheet radiation-type heating element. Diffraction from the sample was recorded on film after passing through a slot in the heating element and radiation-baffle shield and through beryllium vacuum windows. The X-ray film mounting was of the Straumanis type4 with a camera diameter of 114.59 mm. Since previous work of Chiotti' indicated that impurities considerably alter the transition temperature, chemical analysis of the arc melted iodide crystal-bar thorium samples was obtained prior to testing. The analysis disclosed the material to contain as low as 0.001 ±0,0002 wt pet H and 0.007 ±0.001 wt pet 0. Carbon was 0.003 wt pet and nitrogen less than 0.002 wt pet. This material was sealed in mild steel in an inert atmosphere and subsequently hot rolled to 3/8-in. diam rods at a temperature of 732°C. Following removal of the jacket, the material was pickled and cold swaged to 1/8-in. rods, from which the diffraction samples were prepared. The alloys were similarly prepared, with the uranium being added during arc melting. The uranium analyses of the alloys prepared appear in Table I. The experimental procedure for diffraction examination of the three samples of high-purity thorium differed from those of the Th-U alloys. The original practice, later modified, consisted of pumping down the camera with the diffusion pump on and then admitting liquid nitrogen to the cold trap of the system. This was modified for the Th-U alloys by maintaining liquid nitrogen in the cold trap at all times before and while the diffusion pump was heated. This minor change produced a reduction in the amount of carbon pickup by the sample during exposure to the diffusion-pump vapors. The sample was brought to the desired test temperature and exposed for 21/2 hr at pressures which were usually 2 x 10-6 mm Hg, or lower. Exposures were made at

Jan 1, 1959

By C. H. Brehaut, W. N. Taylor, R. S. Douglas, H. A. Shannon

THE name for this new method of mining is derived from a composition of Horizontal, Radial, Diamond, and the drilling is from raises. This method, worked out at Copper Mountain, B.C., is believed to be distinct in many features from other known methods. GEOLOGY The ore deposits of Copper Mountain are related to the Copper Mountain stock, which is an ideal example of the magmatic differentiation in that it grades from a basic gabbro at the border to an almost pure orthoclase-pegmatite core. The "contact" ore bodies lie along the contact of the gabbro and an older complex of volcanics and sediment termed the "Wolfe Creek" formation. These older rocks, collectively referred to as greenstone, had been fractured prior to the intrusion of the stock and were highly metamorphosed during the intrusion. The "outlying" ore bodies are somewhat different in character, though a similar structural pattern prevails. It is believed that a deep-seated magma of which the Copper Mountain stock is a part has given off solutions that caused a partial granitization of some of the volcanics. Mining problems are caused further by the presence of a series of soft barren dikes intersecting a great many of the ore bodies, which are about 30 ft. wide, strike north-south, and dip at a high angle to the east; and are further increased by the presence of four major faults, with a great many minor faults running at acute angles from them. Fault zones average 8 ft. in width, and consist of gouge and breccia. They strike northeast and dip steeply to the northwest. The faults cut through the ore zones and the dikes, and continue on into the gabbro. The general mine structure with two types of ore bodies, bounded by weak walls and intersected by several series of soft barren dikes and major faults, indicated that a method of mining should be devised that would remove the ore at low cost with the least disturbance of the waste walls and dikes. THEORETICAL ESTIMATE OF STOPING WITH THE DIAMOND DRILL After consideration of various methods, the most suitable one appeared to be horizontal drilling to break the ore in a manner similar to shrinkage stoping. Drilling vertical holes or rings from a bench and breaking to an open slot was eliminated because the weak walls of ore, dike or waste would not permit this type of opening. It was then decided to drill either horizontal radial holes from a raise or parallel holes from a slot cut across the ore body. After discussion, the latter method was believed unsuitable, for the following reasons:

Jan 1, 1945

By Frederic Becket

IN a recent article,1 which described the softening effect of columbium in plain high-chromium steels, the authors stated that their investi-gations had shown columbium to be also a particularly valuable inhibitor of intergranular corrosion in steels of the 18 per cent chromium, 8 per cent nickel type. It is the purpose of the present paper to record some of the results obtained through the introduction of columbium to the austenitic chromium-nickel steels. The damaging effects of this type of corrosion have become so widely known as to restrict considerably the applications of the steels under consideration, and therefore there is little question of the importance of the goal to be attained. Numerous contributions concerning the susceptibility of the aus-tenitic chromium-nickel steels to intergranular corrosion have appeared during the past few years, and among others who have dealt construc-tively with the subject are such well-known authors as Strauss and Houdremont of Germany, Hatfield of England, and Bain in the United States. Different theories have been propounded as to the cause of intergranular corrosion, and various remedial measures have been proposed, the majority of which involve the use of addition agents. Titanium is the addition agent at present most generally employed, as suggested by Houdremont and modified as described by Bain, Aborn and Rutherford.2 Little has been published on the effects of holding these steels for long periods at the relatively lower temperatures in the presence of

Jan 1, 1934

By A. Taylor

NICKEL-RICH alloys hardened with small additions of titanium and aluminum and centered around that region of face-centered-cubic primary solid solution, 7, where the atomic ratio of nickel chromium is about 3 to 1, form an important series of high temperature materials because of their resistance to oxidation, high temperature strength, and excellent creep characteristics at elevated temperatures.' With suitable heat treatment it is possible to precipitate a phase based on the ordered face-centered-cubic y' phase, Ni,,Al, from the randomly ordered nickel-rich y face-centered-cubic primary solid solution. By adjusting the ratio of aluminum to titanium the precipitation of needles of the hexagonal intermetallic compound n-NiaTi may be effected. In the present investigation, the main interest was focused on the interrelationships among the y, y, and 7 phases. By using alloying elements of high purity and a suitable melting technique the presence of carbides and nitrides could be completely obviated, although it is realized that their presence is probably essential in alloys of commercial importance. As a preliminary to the study of the Ni-Cr-Ti-A1 system, it was necessary to establish the constitutional diagrams of the three contiguous systems, Ni-Cr-Al, Ni-Ti-Al, and Ni-Cr-Ti, which together form the nickel-rich corner of the Ni-Cr-Ti-A1 quaternary tetrahedron. Accounts of this work on the ternary systems have already been published by the author. A preliminary disclosure of the author's investigations on the ternary and quaternary systems has been made by Hignett2 and has since stimulated work in the same field by Nordheim and Grant." Before the detailed account of the quaternary system, a brief description will be given of the three contiguous ternary diagrams on which it is ultimately founded. Ni-Cr-Ti System The 750° and 1000°C temperature isothermals of the Ni-Cr-Ti system as determined by Taylor and Floyd' are shown in Figs. 1 and 2. The single phase fields of greatest interest are occupied by the extensive face-centered-cubic y primary solid solution of chromium and titanium in nickel, and the close-packed-hexagonal Daltonide, n-Ni3Ti, from which tie-lines radiate across the very wide y+n two-phase field. The chromium-rich primary solid solution is represented by a. As may be seen from the diagrams, the extent of the y phase field increases quite appreciably as the temperature is raised from 750" to 1000°C. Isoparametric lines for the y phase are shown in Fig. 1. They are interesting in that they are almost parallel to the y/r+n boundary. Thus the determination of the tie-line directions is entirely dependent on the exact stoichiometry of composition of the 7 phase. Ni-Ti-Al System The 750°C isothermal section of the nickel-rich portion of the system Ni-Ti-A1 as determined by Taylor and Floyd is shown in Fig. 3.' The regions of greatest interest are the extensive y primary solid solution of titanium and aluminum in nickel, the y' Berthollide phase field based on the ordered face-centered-cubic structure of Ni3Al, and the hexagonal Daltonide phase, n-Ni3Ti. As may be seen from Figs. 3 and 4 the area occupied by the y phase is substantially the same at 750°C as at 1000°C, but the area of the 7 phase is considerably greater at the higher temperature. The tie-lines radiate from n-Ni3Ti across the y+v and y' + v two-phase fields and are evenly distributed

Jan 1, 1957

By B. R. Queneau

[ ] B. R. QUENEAU-One of the difficulties in metallurgy has always been a lack of precision in measurement, and I think the authors are to be congratulated on developing a method which will give us an accurate and dependable quantitative estimate of the amount of retained austenite. O. ZMESKAL*-As Chairman Queneau said, this is indeed an ingenious and needed determination. We have seen figures presented of 1/2 pct retained austenite determined, and I would like to ask the authors the lower limits of this method. How far down do they feel they can go in improving the technique still more?

Jan 1, 1948

By Milton E. Wadsworth, John N. Ong, W. Martin Fassell

The temperature and oxygen concentration dependence on the reaction of sphalerite in oxygen at pressures from 6 to 640 mm Hg have been investigated in the temperature range 700° to 870°C. Sphalerite has been found to oxidize linearly over this entire temperature and pressure range. At higher rates, considerable self-heating was observed. The dependence of the oxidation rate on the oxygen concentration may be expressed by: Rate = k' where k' is the specific rate constant and 0 = K1[O2]/(1 + KI[O2]), where K1 is the equilibrium rate constant for the adsorption of oxygen on sphalerite. Values of the activation energy and the enthalpy of adsorption were found to be 60.3 and —59.6 kcal per mol, respectively. Data have been presented that indicate conditions under which either a sulphatizing or an oxidizing roast may be obtained. ROASTING processes have been employed in the metallurgy of a great number of basic metals in use today. Until recently, however, little attempt has been made to deduce the fundamental mechanism by which oxidation takes place. Structural changes upon oxidation have been investigated1 = and thorough work has been performed with regard to the reaction products and the thermodynamics of the oxidation reactions. The objective of this investigation was to determine the rate of oxidation of sphalerite and to apply the absolute reaction rate theory in the theoretilcal interpretation of the experimental results." "O Description of Apparatus The apparatus contains the following features: 1—a furnace with gas system, 2—an autographic weighing system, and 3—a temperature control system. Furnace With Gas System—The furnace was mounted by a yoke on each end and was free to travel up and down on steel guide rods, permitting the introduction and removal of samples from the apparatus with minimum difficulty. The furnace was heated by three sections of Kanthal wire wound externally on a zirconia tube and insulated with Fiber-frax. Pure gases or mixtures of gases were introduced into the lower end of the furnace through two flowmeters, a mixing chamber, and a gas-tight sparger, Fig. 1. The gaseous products of the reaction and the unused gases were prevented from escaping to the atmosphere by maintaining a small negative pressure on the system. This procedure permitted air from the outside to enter through the small an-nulus around the quartz suspension fiber and prevented the escape of the internal gases. Autographic Weighing System—The autographic weighing system consisted of an adapted gold balance, a photoelectric circuit, and a weight recorder, Fig. 2. The sample was suspended from one end of the balance beam by means of a platinum chain outside the furnace and a long thin quartz fiber on the inside of the furnace. On the other end of the balance beam, the necessary weights were added to counterbalance the sample. In addition, a calibrated chain was added to the balance which was linked directly to the weight recording unit. Control was effected by means of a photoelectric circuit." A parallel beam of light from a strong source was directed onto a small front-surfaced aluminum mirror mounted in the middle of the balance beam and then to a front-surfaced mirror mounted on the ceiling of the room. The beam was then reflected onto a front-surfaced right prism at a distance of 9 ft from the balance

Jan 1, 1957

INCREASING realization that pouring and ingot-mold practices involve many factors of fundamental importance to ingot quality and general steel-mill operations has caused these phases of steelmaking to become major concerns of operators and metallurgists engaged in control of quality and costs. Methods of pouring steel from the ladle into the ingot molds have some direct effects on ingot quality. The mold itself governs solidification and dimensions of the ingot and in so doing exerts some very tangible influences not only on ingot quality but also on product yields and general steel-mill processing. In addition, practices are employed in the handling of molds during daily open-hearth operations that are important to quality and production costs. Therefore, pouring and mold practices must be considered highly specialized and important steps in steel-mill operations. MOLD DESIGN Mold design is difficult to discuss in a precise manner because it varies greatly throughout the industry, both in theoretical concepts and practical application, and few well developed data are available. Most ingot molds are designed to meet conditions peculiar to a given plant wherein quality standards are dictated by end-use requirements, which may differ considerably even for the same grade of steel. The mold designer must also consider the equipment available to process ingots and the product obtained from them. Such equipment, used for stripping, heating, blooming and finishing operations, is seldom, if ever, exactly the same in any two steel plants. Thus, pronounced contrasts in mold designs can be expected to continue, even among plants making strictly comparable types of product, particularly because some producers are just beginning to realize the benefits possible from specialized designs. Certain fundamentals are used in mold design but even these

Jan 1, 1964

By Virgil R. D. Kirkham

NoRth America has for many years led the world in phosphate production, but with development of African deposits and their marketing conditions with respect to European countries, this leadership will shortly pass to Africa. Algeria, Egypt, Tunis, and Morocco have large phosphate reserves and a correspondingly large production because of easy mining and a ready European market, which was developed during the war. An increase in home consumption is destined to develop for the eastern American fields, and the countries of the Pacific will provide a market for the western producers. New processes indicate a decrease in fertilizer costs, which will encourage a more widespread domestic use and assure better marketing conditions. The African deposits, although benefited by a water haul, have the disadvantage of being isolated from a source of acid so that the crude rock is shipped from Africa to its destination, whereas in the United States the chief product shipped is acidulated rock or various types of superphosphatic fertilizers, The principal types of phosphate deposits used in the manufacture of fertilizers are guanos, apatite, phosphatic marl, phosphatic limestone, phosphatic shale, and phosphate rock which is also known as phosphorite. Some of these deposits are found on each of the continents; Table 1 gives their occurrence, age, location, character, extent, etc. Most of the information found in this table represents a compilation of information published elsewhere in a different form and widely scattered.

Jan 1, 1925

By L. T. Leyson, U. C. Tainton

Some time ago, at ameeting of the Institute Prof. J. W. Richards1 said, "I take exception to the statement that all the factors in the production of electrolytic zinc were known long ago.... There is possible in my opinion an improvement of perhaps 50 per cent. in the new electrolytic processes." An examination of the literature of the subject will show the justness of Professor Richards' contention. The work of the earlier investigators was carried on in the shadow of difficulties that, today, are hardly more than memories. We seldom hear now of zinc sponge, that bête noir of the electrolytic-zinc pioneers. Zinc sponge was the name given to a peculiar, soft, black, non-adherent form of zinc deposit that was utterly useless for melting into ingot form. At the big plant at Cockle Creek, New South Wales, in 1897, Edgar Ashcroft2 said that the solution in the plant would suddenly, and without ascertainable cause, go' "bad" and begin to deposit spongy zinc. The most delicate, even spectroscopic, methods of analysis were unable to detect any difference between "good" solution and "bad" solution; either form might change to the other on being kept for a while. When it is added that an outbreak of this insidious disease (which appeared to be infectious, or at least contagious) could be dealt with only by discarding the solution and washing out all tanks and pipe lines, some idea may be gathered of the troubles of the zinc electrometallurgist in what may be spoken of as the "sponge age" of electrolytic zinc. Thanks to the efforts of a number of investigators, we are today able to diagnose with considerable certitude the nature of the malady that puzzled Ashcroft and his co-workers. The researches of Mylius and

Jan 1, 1924

By Edward B. Durham

The refinery at the San Francisco Mint takes the bullion purchased by the receiving department, and carrying Illore than 200 parts of precious metals in 1,000, or, in mint parlance, over 200 fine, and separates and refines the various metals contained therein, using electrolytic processes exclusively. Bullion containing silver is treated in cells charged with a nitric electrolyte. These cells produce fine silver and leave a residue rich in gold. The residue from the silver-cells, together with crude gold-bullion, is treated in cells having a chloride electrolyte. These produce fine gold and leave a residue containing silver chloride. The latter is reduced to the metallic state with zinc and is then treated in the silver-cells. The various waste solutions and the wash-waters, after being freed from the bulk of their precious metals, still contain copper and other metals. These are removed by scrap-iron, and are then treated in the copper-cells, having a sulphate electrolyte. These cells produce pure copper, and collect a residue containing lead, some gold and silver, and all the metals of the platinum gronp that were in the bullion. This residue is relatively small, and is melted into bars and stored until suEcient accumulates to warrant treating it for platinum, etc. The refinery occupies three large and three small rooms. The large ones are, a melting-room, 30 by 34 ft.; a cell-room, 39 by 46 ft.; and a wash-room, 30 by 33 ft. The small rooms are used as foreman's osce, laboratory, and , re- spectively. The methods here described are those in use in December, 1909, when notes for the present paper were taken.

Jan 1, 1912

By Oliver Smalley

Except for the work of Guillet, who conducted a systematic investigation on the zinc-replacing value of nickel in brass, and extended his investigation with a view to developing commercial high zinc content nickel brasses, the author does not know of any other systematic research on the subject. The most promising commercial alloys and their physical properties obtained by Guillet are given below: These test results scarcely justify the use of such quantities of so expensive a metal, and could have been obtained from ordinary commercial brass. For purposes of comparison, the physical properties of ordinary brasses, ranging from 70 per cent. to 50.1 per cent. Cu in both the cast and normalized1 conditions are included in 'Table 1. These incidentally furnish a useful standard of the properties of castings and of rolled, extruded and forged brass when correctly annealed. A close study of some of the well-known special brasses containing nickel reveals a series of alloys which bewilder by their complexity, and me can only hazard a guess at the function and commercial value of each of the many elements used.

Jan 1, 1926

By Albert Sauveur

IT WAS in June, 1889, that I was first admitted to the society of educated men. The admission ticket had been signed, on the recommendation of my old and beloved teacher, Bobby Richards, by General Francis A. Walker at the time President of the Massachusetts Institute of Technology, an institution familiarly known as M. I. T. I immediately proceeded to take advantage of that privilege by departing for Steelton, Pennsylvania, where I understood I was eagerly awaited by the educated officials of the Pennsylvania Steel Company. I was some. what disappointed at the casualness of my reception and at being tucked away in that preserve closet of steel works known as the chemical laboratory. At Steelton I met Major Bent who was president of the company. When I say "met," that is a figure of speech as my acquaintance with him was confined to my being shown

Jan 1, 1937

By M. W. Ditto

THe conversion of the beehive coke plants, in this country, to byproduct plants has been slow, because the coal supplies were near the centers of the steel industry. With the growth of this industry, especially with its development around Chicago, it became necessary to transport large tonnages of coal from the eastern districts and then convert it into coke. The losses due to transportation costs were partly offset by the value of the byproducts recovered. To save the transportation costs, it was desirable that the coal deposits of Indiana and Illinois be utilized. This coal had always been classified as non-coking; it was also considered unsuitable for the metallurgical field because of the high ash and sulfur contents. The conditions, however, were promising enough to start experimental and development work, which crystallized in the design of the Roberts coke oven. The fundamental features of most coke ovens, with respect to the application of heating gas and the recovery of byproducts, are the same and, in the last few years, the tendency has been toward the better application of heating to the walls, higher thermal efficiency, and, by the control of heating conditions, the increase of byproduct yields. Structural features also have been improved and the use of high-grade refractory material has allowed the use of higher temperatures with the resulting higher rated capacity per oven per day. Great improvements have been made in both recuperators and regenerators, particularly with reference to the individualizing of each oven with respect to its adjacent oven, so that each can be operated as a unit if desired. The highest development of the flue type of oven has been applying individual regenerators for the recovery of waste heat. After some research work, it was found that the high-volatile Illinois coals could be utilized for coke by obtaining the better application and control of the heating conditions in the oven. Most of this high-volatile coal that had been used gave a good coke structure under certain conditions. The fact that coke was occasionally made from this coal, demonstrated the possibiity of making coke from it at all times pro-

Jan 1, 1923

By Guillermo Zuloaga

The iron deposits of the Imataca Range of Venezuela, which occur along the Orinoco River, in the northern border of the Guayana Highlands, have lately attracted attention on account of their economic possibilities. Many deposits occur in this area; some of slight economic importance and others that may rank with the largest masses of high-grade iron ore of the world. The geology and the character of the ores seem to be remarkably similar to those of the large iron deposits of Brazil. In the investigation of the Venezuelan deposits a definite relationship has been found between the mineralization of the large orebodies and igneous intrusions, especially norites and granites. The following paper is the result of a field and laboratory investigation of the ore deposits. The field work was done during the months of February and March of the year 1929, partly in the company of Prof. W. H. Newhouse. The laboratory studies have been made in the Massachusetts Institute of Technology, under the supervision of Professor Lindgren and Professor Newhouse. GENERAL GEOLOGY OF GUAYANA HIGHLANDS General Geography and Physiography The Sierra de Imataca proper occupies a narrow belt along the south bank of the Orinoco River, in the northeastern part of the State of Bolivar and in the western part of the Delta Amacuro Territory of Venezuela. The State of Bolivar is generally known as the Venezuelan Guayana, as it forms part of the same physiographic province of the Guianas and northeast Brazil. In general the Venezuelan Guayana is an extensive plateau, sloping gently towards the Orinoco River to the north and towards the Atlantic Ocean to the east. In the northern part mountains are rare, and consist mainly of elongated low hills. Towards the British Guiana-Brazil boundary, table mountains with vertical cliffs are found forming the ranges of Parima, Roraima and Pacaraima. General Geology The Guayana Highlands are the northern extension of the Brazilian Archean shield. Only a few scattered masses of sediments remain on its

Jan 1, 1935

By Daniel Hanson

FoR most of their practical applications metals are required to withstand stresses of appreciable magnitude: indeed, it id because they possess the quality of resisting stress without becoming permanently deformed that they find such extensive use in the service of man. Metals and alloys must, in service, usually behave as elastic substances—or nearly so. It is not difficult to satisfy this condition at ordinary temperatures. Iron and its alloys, especially the steels, are at normal temperatures excellent elastic bodies, capable of satisfying most of the mechanical requirements of the engineer: where electrical, chemical or other properties are impor-tant, which cannot be met by steels, it is usually possible to find a non-ferrous alloy such as nickel, copper or aluminum, which will prove satisfactory. When the metals or alloys are not inherently sufficiently elastic, cold-working or heat-treatment may develop elastic properties to a sufficient extent for practical needs. By means of relatively simple, rapid tests we can measure such properties as elastic modulus, limit of proportionality and proof stress, upon which design can be based with confidence. The case of the soft metals, such as lead and tin, is well known to be exceptional. They possess no definite limit of elasticity, and the value of proof stress or tensile strength depends to a great extent on the speed with which the test is carried out. Design here must be based on other considerations than a well-established theory of the proportionality of stress and strain. It is now generally recognized that steels and non-ferrous alloys possess at temperatures not greatly exceeding that of the atmosphere, characteristics quite different from those existing at ordinary temperatures, and that they assume qualities similar to those of the soft metals. Not only have they no limit of elasticity, but the proof stress and the ultimate stress depend on the time of application of the load. Flow under load may persist for long periods of time, possibly indefinitely, and the determination of a true maximum stress becomes a matter of great difficulty.

Jan 1, 1939

By F. N. Rhines, A. H. Grobe

At elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing. When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible1 and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver. Norbury2 and Leroux and Raub3 have reported internal oxidation (subscaleiormation) in alloys of silver with 2, 7.5, and 30 per cent of copper. The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver.4 Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation. Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detai1.5,6 The present research confirms this anticipation. The oxidation of a series of 20 dilute alloys of silver has been studied metallographically; some types of subscale not encountered among the copper alloys have been found. Instances of internal oxidation in alloys of most of the metals of the 1-6 and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking. A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation; i.e., they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them. In a study of 40 alloys of these white metals only a few cases of internal oxidation have been found. The probable reasons for this difference in behavior will be discussed presently. Experimental Procedure Silver.—The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99.993 per cent Ag)* and the purest avail-

Jan 1, 1942