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By D. W. Breck

Zeolites were first recognized as a new group of minerals by Cronstedt with the discovery of stilbite in 1756. The word zeolite was coined from the two Greek words meaning "to boil" and "a stone" because of the loss of water when heated in the mineralogist's blowpipe (Breck, 1974). In 1845 it was discovered that certain soils lave the power of retaining ammonium salts Way, 1850). These were the first ion exchange experiments. Later it was discovered that it was the hydrated silicates in the soil that produced this phenomenon. Several years later a paper was published dealing with the action of dilute salt solutions on silicates which showed that this base-exchange principle, which we now call cation exchange, is reversible. The quantitative cation exchange behavior of zeolite minerals, such as chabazite, was studied. As a result any aluminosilicate which exhibited the property of ion exchange was referred to as a "zeolite," even today the term has been applied to clay minerals as well as synthetic organic ion exchange resins.

Jan 1, 1975

By M. C. Udy, C. H. Lorig

THROUGH the years much interest has been centered in attempting to develop a direct method of iron-ore reduction, to replace or supplement the present indirect blast-furnace process. It would not be difficult to produce a list of more than 500 patents dealing with the direct production of iron and steel, but the few of this type of process that have proved successful do not produce in competition with the blast furnace; they produce special products. A survey of the literature reveals that the equilibrium conditions for the reduction reactions (iron oxides with carbon monoxide and with hydrogen) have been fairly well established but that data on the rate of reaction are discordant, although the general effects of the variables are known. This dissertation deals with the rate of reduction of a magnetite concentrate with hydrogen. The following variables have been studied: bed depth, gas velocity, particle size and temperature. The behavior of a single particle was also studied. LITERATURE Two general factors should be considered in a study of reduction of iron oxide: (I) equilibrium relations, and (2) rate of reaction. The first factor, equilibrium, has received the attention of many investigators and the equilibria Fe304-FeO-H2-H20, Fe3O4-FeO-CO-CO2, FeO-Fe-H2-H20, FeO¬Fe-CO-C02 are fairly well established. Of the second factor, the rate of reaction, much less is known. Data are comparatively scarce and there is very little concordance. The discordance probably results from the large number of variables influencing the reactions. However, the general effect of the variables is known. Among these variables are temperature, gas velocity, particle size, porosity, gas composition (distance from equilibrium), presence of impurities, greater or less prevalence of side reactions, and even design of the apparatus itself. Wetherill and Furnas1 published an excellent paper in 1934. They point out that any one or more of five processes (the chemical reaction, diffusion of the reactant through the gas film, diffusion of the reactant through the solid phase, diffusion of the reaction product through the solid phase, or diffusion of the reaction product through the gas film) may be the slow process, and thus the rate-controlling process. It is regretted that the work of these authors was limited to experiments at one temperature, and that the range of gas compositions was limited. Langmuir2 has shown that heterogeneous reactions take place at phase boundaries.

Jan 1, 1942

By Robert M. Grogan, Gill Montgomery

Fluorspar, the commercial name for fluorite, is a mineral composed of calcium fluoride, CaF,. Its valuable properties are due to its content of fluorine, and it is the principal commercial source of that element. The name is derived from the Latin word "fluere," to flow, because the mineral has a low melting point and is used in metallurgy as a flux. Cryolite is a sodium aluminum fluoride, Na,AlF,. It is a rare mineral which has been found in commercial quantities in only one place in the world, Greenland. Small amounts of it are shipped from stock in that country, and its place in industry has been taken over almost completely by synthetic cryolite. Because of the relative unimportance of cryolite, discussion of it has been relegated to a short section at the end of this chapter, which is principally concerned with fluorspar. History Fluorspar was used for ornamental purposes by the Greeks and Romans, who fashioned such things as vases, drinking cups, and table tops from it. Various peoples including the Chinese and the American Indians carved ornaments and figurines from large crystals. Its usefulness as a flux was known to Agricola (1564), who wrote about it in 1546. Mining began in England about 1775 and at various places in the United States during the period 1820 to 1840. Production became substantial following the development and widespread adoption of the basic open hearth method of making steel, in which fluorspar is used as a flux. After that, production and usage were stimulated by growth in the steel, aluminum, chemical, and ceramic industries and were accelerated by World Wars I and II. Fluorocarbons entered the picture in 193 1 and the use of anhydrous hydrogen fluoride (HF) as a catalyst in the manufacture of alkylate for high octane fuel blends began in 1942. The development of the froth flotation process in the late 1920s, a differential flotation scheme for separating fluorspar from galena, sphalerite, and common gangue minerals in the 1930s, and the application of heavy-media concentrating methods to the treatment of low grade ores in the 1940s were outstanding technological contributions that enabled increased production of fluorspar concentrates. In recent years the development of pelletizing and briquetting processes for making flotation concentrates into gravel-size particles for use in steel furnaces and the development of more efficient and selective flotation schemes for treating crude ores containing abundant dolomite and barite have been major improvements in the industry.

Jan 1, 1975

By Archer E., Wheeler

Producing copper companies were active during 1941 owing to the national defense program the United States and the requirements of the friendly belligerent nation. This activity extended to the American owned properties in South America, the major part of whose product was taken by the Metals Reserve Co., a U.S. Government agency. Anaconda Copper Mining Co. is building a new converter plant at Anaconda, with four units of the Peirce-Smith type. The addition is being built adjacent to the reverberatory plant so as to avoid the necessity of hauling matte and slag. It is expected to be completed this year.

Jan 1, 1942

By Roscoe C. Clark

In a previous technical note' by Walter Rose, evidence is offered in support of the contention that "the possibility of describing oil recovery features in terms of capillary pressure phenomena has not been established entirely." It is not the purpose of this note to present further discussion of this possibility but rather to point out that the argument presented there does not appear to be generally valid. In the cited note' reference is made to the experiments of Welge2 wherein it was shown that when water was displaced by oil from a core the pressure in the water phase was less than in the oil phase but that when this oil was then produced by water drive the pressure in the water phase was greater than in the oil phase. Rose has concluded from these observations that conditions of static equilibrium did not obtain since the fluid saturations were such that phase discontinuities seemed unlikely. The argument from which this conclusion was drawn is based on the contention that "the pressure is always greatest in the non-wetting phase at each static interstitial interface of contact with the wetting phase." This premise appears to have been reached from a consideration of capillary phenomena in cylindrical tubes, although it may a1so hold for other types of pore geometry, hut as will be shown below it does not hold for all pore shapes and hence is not generally applicable. Since the pore structure of porous media such as reservoir rocks i- in general so complex as to defy exact description. it is undoubtedly of great value to establish a model in terms of pore shapes of known geometry, provided of course that the limitations of the model are recognized. That the limitations of the capillary. or cylindrical, tube model have not always been fully recognized will be evident from the following discussion of a pore of different shape hut one which may a. logically he considered a.; the capillary tube. The pore space to be considered is that shown in Fig. 1, which may be thought of as the "hole in a doughnut."* Consider the interface, A-B-A', between two immiscible fluids, P, and P2, which interface meets the solid alone a line, A-C.A'-C'. The interface A-B-A' is the surface of a spherical segmen† while the line of mutual contact be-

Jan 1, 1950

By G. L. F. Powell, L. M. Hogan

Samples of silver and Ag-O alloy, 0.12 wl pet, have been undercooled to a maximum of 250°C by melting in a slag of commercial soda-lime glass. Grain refinement occurred in undercooled silver samples whet the degree of undercooling exceeded a critical value which varied from 153° to 175°C, depending on the melting conditions. In under cooled Ag-0 samples, the grain structure was fine and equiaxed at degrees of undercooling larger than 50oC. The grain refinement in both silver and Ag-0 alloy samples was the result of recrystallization during or immediately following freezing. When the oxygen content was increased, the degree of undercooling at which recrys-tallization occurred decreased. INVESTIGATIONS of the grain structure of strongly undercooled melts of nickel and cobalt1-4 have revealed a change in room-temperature grain size as a function of undercooling. At large degrees of undercooling the grain size was fine, but samples undercooled by smaller amounts exhibited a much coarser grain structure. The reported undercooling at which this grain size transition occurred in nickel varied between 140° and 175'C undercooling. Walker1 attributed this grain size change to an enhanced nuclea-tion rate. Cavitation at a melt-solid interface was con sidered to generate a high-pressure wave. This, in turn, produced nucleation in the liquid as a result of an elevated freezing point increasing the undercooling in the melt. A similar grain size transition was observed in undercooled silver between 133° and 153°C undercooling.5 The grain size transition in undercooled silver was found to be dependent on oxygen con tent. More recently, the authors5 showed that a simila transition occurred in an undercooled Cu-O alloy, =0.08 pet, but not in oxygen-free copper undercooled more than 200°C. The transition was attributed to recrystallization of the solidified grains after freezing; the greater the degree of undercooling, the more complete the recrystallization. In view of this effect of oxygen content on grain size transition, additional undercooling experiments were carried out with silver. This paper reports the results of these studies on silver and Ag-O alloys undercooled more than 50°C EXPERIMENTAL 1) Materials. The silver was supplied by Matthey Garrett Pty., Ltd., as fine granulate, silver mini' mum 99.9 pet, and contained the trace impurities shown in Table I. The silver originated from two different refineries resulting in the difference in impurity content shown in Table I. However, the variation in composition had no discernible effect on the undercooling behavior. Samples of the silver were melted in an open-ended, vertical, cylindrical resistance furnace, wound with Kantha] wire, the temperature of which was adjusted by means of a variable transformer, 2) Melting and Undercooling. Bulk samples of silver were undercooled by preoxidation and removal of oxidized impurities in a glass slag, as previously described,5 but special precautions were necessary to allow comparison between oxygen-free silver and a Ag-O alloy. Samples free of oxygen were prepared by first melting weights of granulate varying from 200 to 400 g in clean vitreous silica crucibles in air for approximately 15 min. A sample was frozen and a complete glass cover formed over the top surface by adding granulated glass rod. The sample was then melted and frozen several times until no oxygen bubbles appeared in the glass slag. Subsequent thermal analysis indicated that the oxygen content was negligible. The glass acted as an efficient barrier to absorption of oxygen from the air. Ag-O alloys were prepared by melting silver in silica crucibles with only a partial cover of glass, so that the top surface of the melt was in contact with air. The silver was held molten in air for several hours at 1000° to 1050°C, in the expectation that the oxygen in solution would reach equilibrium with atmospheric oxygen. At T - 1000°C the equilibrium oxygen content was calculated as 0.12 wt pet O, using Sieverts law and Eq, [l], derived by Mizikar et a!.7 from the data of Sieverts and Hagenacker8 for 1 atm of oxygen:

Jan 1, 1970

By Sidney A. Swensrud

About a year ago, I attempted in a general way to trace the origin and development of some of the marketing problems of the petroleum industry, and to describe certain trends which it then seemed possible to foresee. To summarize briefly, it was pointed out that the consumption of gasoline, after increasing for more than a decade at an almost unbelievable rate, was slowing down, but that the two factors which determine the supply of gasoline —-namely, the production of crude oil and the percentage of gasoline derived therefrom—were tending steadily to mount. It was suggested that, while the increase in gasoline outlets began with and probably was justified at the start by the rapidly increasing demand, long after all reasonable requirements as to number of outlets had been met the number continued to increase—if anything, at a still more rapid rate—because by that time the overproduction of crude had begun to exert an impelling urge upon the owners of that crude to seek assured outlets for it in the form of gasoline. As more and more companies became integrated all the way from crude oil to marketing, there took place an ever-increasing competition among them, not only for the existing outlets but for new ones. The wide margin between wholesale cost and retail price, which is characteristic of the early stages of most new industries, persisted in the oil industry longer than in most industries, for various reasons. The existence of that wide margin provided in large measure the means of attracting new outlets, for as the gallonage per outlet declined with the increasing number of outlets, competing companies simply offered the dealers a larger part of the total margin. The very nature of competition suggests that such a process would continue until practically all of the available margin was thus given away, and such was clearly the tendency. It was a system that in turn produced increasing marketing expense per gallon on account of the diluted gallonage per outlet; this increased expense might seem to have provided a justification for continuing wide margins. Economics, like its parent, nature, however, progresses by mutations and so began to throw out new types of marketers, in the form of tank-car service stations, cut-price jobbers, and the like—heretics or

Jan 1, 1932

By H. S. George

On one occasion when it seemed desirable to reveal under the microscope not only the metallic structure of an alloy, but certain small non-metallic inclusions that are ordinarily obliterated by etching, it was discovered that, by partly eclipsing the illuminating pencil of light rays, the residual light was thrown on the object from one side and the structure was brought out in relief. At the same time, the non-metallic inclusions were retained in clear view. In this first demonstration of lighting obliquely through the objective a card was thrust part way into the light beam between the arc iris and the light filter; the shadow of the card on the filter served to locate its position. Next several stiff-paper disks of various diameters were mounted on flexible wires; some plasticine on the other end of the wires made it easy to adjust and maintain a disk at any desired position in the light beam. To facilitate manipulation, an assortment of disks was mounted on a wheel, as shown in Fig. 1. The purpose of partly eclipsing the light beam was discussed in an earlier paper.' There it was pointed out that the usual methods of illuminating opaque objects for microscopic examination lend an unnatural appearance to the view, while the new method, which has been termed conical illumination, revels the true relationship of constituents by simulating natural lighting. In nature, all objects are lighted diffusely, or by light predominating from one direction, or by a combination of diffuse and directed light. Under these conditions, objects appear to have three dimensions—they possess relief. The kind of illumination known to metallographists as vertical or axial results in an unnatural appearance, as a large proportion of the illuminating rays are parallel to the line connecting the eye with the object, a condition almost never met in nature. Microconstituents

Jan 1, 1924

By J. R. Thompson

It is common practice, and certainly good business as all of us know, to take care of plant operating equipment. Machinery of any type requires periodic inspection and planned maintenance. With this thought in mind a plant operator should at the end of every shutdown period make regular belt inspections and plan for later appropriate care and maintenance. The points mentioned below are understood well by all of us but are sometimes forgotten because belt conveyors are comparatively easy to operate. Maintenance of any conveyor belt is dependent upon the fundamental characteristics of the two component parts-cover and carcass.

Jan 6, 1950

By E. S. Davenport

IT is indeed an honor and a responsibility to have been selected to present the thirty-fourth in this series of Henry Marion Howe lectures, established to perpetuate the memory of a great teacher and one of America's outstanding scientists. Previous Howe lecturers have established high standards for this annual AIME event. It has been my good fortune to have enjoyed close association with five of these former lecturers; namely, Bain, Grossmann, Johnston, Sosman, and Vilella, all of whom have been prominently identified with the research activities of the organization with which I am connected. Some years ago I had an opportunity to examine a letter written by Professor Howe in 1904. This document was particularly interesting to me since I never had the privilege of personal acquaintance with Professor Howe and do not recall even having seen him during his long and active career. In view of the fact that the letter dealt, to some extent, with matters related to the subject of today's lecture, I would like to quote briefly from it. The letter is datelined, "Bad Kissingen, June 11, 1904." The salutation reads, "Dear Bradley," which suggests that it was probably addressed to Bradley Stoughton, who, I believe, was working with Howe at Columbia University at that time. The letter reads, in part, as follows: "Austenite and Martensite. I have not examined what Osmond says in his new book. His former remarks about austenite I found very confusing, indeed unintelligible. I think we can reconcile matters well enough for the present by assuming that martensite is a transition step between austenite at one end and ferrite and cementite at the other. Above critical range for steel of 0 to 1.80 carbon, austenite is normal state; below Ar1, ferrite and cementite are normal." The letter then continues with a discussion of Osmond's ideas on metallographic nomenclature, particularly his use of the terms martensite, troostite, and sorbite, including the following pointed comment: "For common purposes it seems to me unwise to drag them in, and much simpler to confine ourselves to the end stages Austenite Ferrite plus Cementite Osmond does not really know his own mind— or does not clarify his ideas to others—as to nomenclature." Thus we see that, as far back as 1904, the transformation of austenite, and the products of that

Jan 1, 1958

By John S. Johnson

THE purpose of this article is to describe several types of borehole lining in common use, and especially to offer a relatively new means of reducing the expense of maintaining boreholes where they are subjected to corrosive action of water flowing either inside or outside of their casing. In the Anthracite region of Pennsylvania, boreholes are used for many purposes, the principal ones being: openings between the surface and underground workings through which are passed steam, water and compressed-air lines, ropeways from surface hoists to underground rope haulages, conduits for electric power and signal lines, water-discharge lines from underground pumping stations, and inlets to mine workings for flushing material. LININGS FOR BOREHOLES The inadequacy of steel pipe for use in boreholes has long been recognized. Various substitute materials have been tried, including screw-joint cast-iron pipe (Fig. I). Cast-iron pipe, while very effective as a discharge line for acid water (mine water) being pumped to the surface, is not so effective when serving as a conduit for silt and crushed rock being flushed underground for filling mine voids. Terra cotta pipe (Fig. 2) has been used in boreholes, and lasts a long time if the glazed inner surface of the pipe remains intact. Its installation in a borehole is very difficult and is recommended only where it is certain that there will be no subsidence of the surrounding territory. Accessibility in order properly to join each section of the pipe is essential to a satisfactory job. In large water holes, where it is possible to lower a man into the hole for sealing the joints of the pipe, glazed terra cotta pipe has been used successfully for delivering mine water from pumps in the mines. For large holes used for flushing refuse into mine workings where the surface wash is shallow, standard paving brick have been used to form a tube through the wash to the bedrock. These brick are laid radially, backed by common brick and cobbles laid in cement. It is obvious that the shaft through the wash must be large enough to permit a man to work in it. The flushing material is carried through bare rock from the juncture at bedrock to the openings underground. This plan has been used, particularly where a cast-iron surface line is laid upon the surface to carry the flushing material from the breaker to the hole, and down the hole continuously, with no opening to the air at the top of the hole, thereby eliminating the necessity of an attendant at this point (Fig. 3). Another similar type of borehole lining is constructed of hexagonal pieces of vitrified brick (Fig. 4). This type requires a steel drive pipe through the surface wash large enough to provide a finished tube of the desired size surrounded by a brick wall about 4 in. thick. The special bricks are laid in cement, six to a circle, around a lubricated pipe used as a form, and lowered in sections inside the large drive pipe; the bottom section is seated in a socket drilled in the solid rock, having the same inside

Jan 1, 1941

By William H. Grady

FactoRs entering into the market value of coal are its grade, and the cost of labor, material, and capital. Reduction in these costs cannot be expected in the future, and it therefore follows that greater economy in their use must be accomplished if it is desired to hold the present markets; more tons of product per unit must be obtained in a given time from both men and material, and means devised for increasing the percentage of lump and domestic sizes. This paper is presented for the purpose of inviting discussion and stimulating thought in regard to the influence of methods of procedure and plans of mining, upon the quality of coal, the economical use of labor, material, and capital, and the cost of production. Even the better methods of the present day leave much to be desired, and a review of the reasons and necessities for their use may be of value in pointing the way to more economical mining. The writer does not attempt to discuss untried methods of mining, but rather to state clearly and concisely a summary of the results obtained under the several methods of procedure that have been adopted. In some instances a high degree of concentration has been effected, and comparisons of the results obtained with the results of lesser degrees of concentration form an interesting study. It is believed that much may be accomplished in improving the quality, and in the more economical use of labor, material, and capital, by concentration, and it is to concentration in particular that your study is invited. The writer, who has occasion to visit many mines, most of which are under different management, has been inclined to the opinion that improvement has been retarded in many ways and that mining has not as yet been entirely freed from the early-day practices which were forced upon it. Practices resulting in lack of concentration, to which reference will be made, are: The absence of robbing, necessitating the frequent interposition of barrier pillars; lack of system and of proper supervision, resulting in losses of life and coal. These practices could not well be

Jan 1, 1915

By Arthur Taggart

THE major portion of the work described in this paper was performed by R. W. Young,+ a graduate student in the department of Mining and Metallurgy, Sheffield Scientific School, Yale University, working under a cooperative agreement between the Hardinge Conical Mill Co., the Sheffield Scientific School, and himself. Since this cooperative scheme is at present in effect in the case of a considerable number of other students in the department and since it is the hope of the school that the privilege thus extended may be utilized even more freely in the future by mining and manufacturing companies, it may not be amiss at this point to give a summary of the general plan. Briefly it is as follows: A graduate student, whose undergraduate work in this or other universities shows promise of ability to handle research work, is chosen by conference between the company and instructor involved. The aim of the company in the agreement then entered into is to obtain the solution of one or more of the technical problems with which it may be confronted, or, at the end of 1 or 2 years, to obtain as an employee a man especially trained in its work. As. a means to accomplish one or both of these ends, the company furnishes the machine, apparatus, or material to be tested and pays the student during his graduate work a small salary, usually just sufficient to cover his living expenses, tuition and fees. The aim of the student is special training along a line in which he is particularly interested, the attainment of his advanced degree, and the chance to show to his future employer ability to handle such problems as may be presented to him. In return for the financial aid which he receives he agrees to devote at least half of his working time to the special problem submitted by his company. The other half is devoted to study of the collateral subjects required by the department for the granting of the degree which the student seeks. The student further agrees to enter the employ of the company in question at a wage not greater than that paid in like positions to recent graduates not specially trained and to remain with his employer at such wage for at least 1 year. If the student is to obtain a degree, the special work forming the basis of his investigation must be such as will involve real research and not mere routine manipulation. The subject is chosen by conference between the three parties to the agreement. The work is carried on under the direct supervision of the instructor involved. The school furnishes the general laboratory and library equipment essential to the pursuit of any extended investigation, In

Jan 4, 1917

By F. V. Shallcross

Physical properties of thin films of CdS and CdSe formed by vacuum deposition onto glass sibstrates have been studied as a function of deposition and processing conditions. The crystallinity and surface features of CdS films were examined using electron microscopy and electron and X-ray diffraction techniques. The films were poly crystalline; the preferred orientation and crystallite size increased with film thickness, substrate temperature, and deposition time. The CdS films consisted primarily of hexagonal-phase material, in contrast to similarly prepared CdSe films which have previously been observed to contain mixtures of cubic and hexagonal phases. As-deposited CdS films showed no major dependence of Hall mobility on crystallite size or degree of preferred orientation. Hall mobility and carrier concentration in CdS and CdSe .films were measured at various temperatures; both parameters increased with temperature and yielded activation energies which depended on fabrication conditions. Surface-desorption phenomena and overcoating of the semiconductor with SiO affected the observed electrical properties significantly. THIN films of cadmium sulfide1,2 and cadmium sele-nide3,4 have been employed by various workers as semiconductors in the insulated-gate thin-film field-effect transistor, known as the TFT. These devices are most commonly made by vacuum deposition of all materials onto an amorphous substrate such as glass. A knowledge of the microstructure and electrical properties of semiconductor layers used in the thin-film transistor is essential in order to form a realistic model for the device and to improve its performance, reproducibility, and reliability. This paper will describe studies of the physical properties of vacuum-deposited CdS and CdSe films prepared under various conditions. Structural characteristics examined in- cluded phases present, crystallite size, nature of preferred orientation of crystallites, surface roughness, and structural homogeneity throughout the film thickness. Electrical properties measured were Hall mobility and conductivity and their dependence on temperature and ambient. Thin-film properties are affected by many fabrication parameters including purity and physical form of evaporant, deposition rate, film thickness, design and temperature of the evaporation crucible, geometry of the deposition chamber, nature of the residual atmosphere, composition and temperature of the substrate, and details of postdeposition processing. PREPARATION OF FILMS In this work the semiconductor films were deposited in a conventional oil-diffusion-pumped system with pressures in the 10-8 torr range. The CdS evaporant was obtained from the Eagle-Picher Co. as a high-purity coarse-grained crystalline powder; the CdSe was a high-purity sintered powder supplied by the Harshaw Chemical Co. The evaporation crucible was a resistance-heated molybdenum-wire basket coated with aluminum oxide and filled with a quartz wool plug at the top. The source to substrate distance was usually 10 cm. This region was enclosed by a Pyrex inner cylinder. The substrate was heated with an overlying Pyrex plate coated with tin oxide. The substrate temperature was controlled using a thermocouple attached to the lower side of the heater. This thermocouple was calibrated against another thermocouple attached to a dummy substrate and by observation of melting points of various metal films deposited in the system. The substrates were polished borosilicate glass plates and conventional glass microscope slides. Substrate preparation included cleaning with an ultrasonically agitated detergent bath followed by isopropanol-vapor de-greasing. Film thickness was measured interferomet-rically during and after deposition. STRUCTURE OF CdS FILMS Structural studies were performed on CdS films using electron diffraction, electron microscopy, and

Jan 1, 1967

By G. W. Healy, W. D. Forgeng, N. R. Griffing

The liquidus surface of the C-Cr-Fe system to 1900°C has been mapped from carbon solubility and freezing point measurements, metallographic observations, and published data. In the graphite field, the surface drops precipitously to meet a slope descending from the Cr3C2-C join through the mixed carbide fields to a meandering eutectic valley; this flows from the Cr-C to the Fe-C edge. On the low-cavbon side of the valley, the surface rises to the chromium corner. 1 HE purpose of this inquiry was to gain a more complete knowledge of the C-Cr-Fe liquidus surface. This required an extensive study of carbon and chromium-rich alloys which, in the past, have received the least attention. Sanbongi el al.1 measured the solubility of carbon in liquid alloys containing up to 25 wt pct Cr at temperatures of 1460" and 1545°C and found that it increased with chromium content and temperature. Lucas and wentrup2 also made solubility experiments in graphite crucibles, but at higher chromium contents in the range of 38 to 80 pct and at temperatures of 1550" to 1700°C; however, their experiments were relatively few, and the effect of temperature was not consistent. The present investigation included compsitions ranging from 0 to 94 pct Cr and 1.4 to 11.7 pct C at temperatures up to 1800°C. Saturation experiments in graphite crucibles, thermal analyses during freezing, and metallographic and X-ray diffraction studies were employed to obtain desired information which, together with published data from other investigations about the binary edges and the ternary system at lower carbon levels, made possible the construction of a comprehensive C-Cr-Fe liquidus surface. C-CR-FE LIQUIDUS SURFACE The derived ternary liquidus surface is shown in Fig. 1 where the solid curves are liquidus isotherms. The dashed curves and the binary edges are the liquidus field boundaries of the primary crystals, the arrows along these boundaries indicating their direction with decreasing temperature. Each intersection of three internal boundaries is the composition of liquid involved in four-phase isothermal equilibrium with the three primary crystals whose liquidus fields touch there. It may be observed that a total of six four-phase equilibria occur at melt temperatures. The general topography of the liquidus surface consists of a eutectic valley sloping down from the Cr-C edge at 3.2 pct C to the Fe-C edge at 4.25 pct C. The liquidus surface rises in two directions from the valley, one hillside terminating at the Cr-Fe edge while the opposing hillside rises toward the carbon corner out beyond the top edge of Fig. 1. Both hillsides are interrupted by intersections of surfaces or joints representing the liquid colmpositions of various three-phase equilibria. Seven primary crystals occur, namely a(bcc), ?(fcc), graphite, (Fe, Cr)3C capable of dissolving as much as 15 pct Cr, and three different chromium carbides in which iron is partially soluble by substitution for chromium. The composition ranges of the primary l~hases at melt temperatures are shown

Jan 1, 1962

By J. W. Hickman, E. A. Gulbransen

One of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film. A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film. A comprehensive program has been undertaken to study these phenomena. This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C. Before the introduction of the electron diffraction technique, it was necessary to use either direct chemical analyses or X-rav diffraction analyses to determine the nature of the oxide film formed on the metal or alloy. Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry. In special cases the information obtained may be identical, but in general both viewpoints are necessary. Much of the early work was carried out on the oxidation of bulk samples where thick films were obtained. The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses. Although much useful information has been obtained in this manner. little could be learned about the character of the protective oxides during the period when the films were actually protective. Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique. In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective. Literature The oxidation of iron has been extensively investigated by X-ray and electron diffraction. Jackson and Quarrelll found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature. The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe³O4; between 515° and 900°C. the stable film was FeO. Above the upper change point of iron the oxide was found to be Fe³O4. From 400' to 515°C., FeO, Fe³O4 or a mixture of the two oxides was found. Recrystallization of the air-formed film below 400' and above 900°C. led to the formation of Fe3O4. In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described.

Jan 1, 1947

By E. A. Gulbransen, J. W. Hickman

One of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film. A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film. A comprehensive program has been undertaken to study these phenomena. This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C. Before the introduction of the electron diffraction technique, it was necessary to use either direct chemical analyses or X-rav diffraction analyses to determine the nature of the oxide film formed on the metal or alloy. Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry. In special cases the information obtained may be identical, but in general both viewpoints are necessary. Much of the early work was carried out on the oxidation of bulk samples where thick films were obtained. The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses. Although much useful information has been obtained in this manner. little could be learned about the character of the protective oxides during the period when the films were actually protective. Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique. In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective. Literature The oxidation of iron has been extensively investigated by X-ray and electron diffraction. Jackson and Quarrelll found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature. The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe³O4; between 515° and 900°C. the stable film was FeO. Above the upper change point of iron the oxide was found to be Fe³O4. From 400' to 515°C., FeO, Fe³O4 or a mixture of the two oxides was found. Recrystallization of the air-formed film below 400' and above 900°C. led to the formation of Fe3O4. In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described.

Jan 1, 1947

By E. J. Eisenach, Edward Matsen

AT the present time the Climax Molybdenum Co. is the largest molybdenum producer in the world and the operator of the largest underground mine in North America. It has grown steadily and rapidly since its beginning in 1917. Only 250,000 lb of MoS2 were produced during the first year from 1917 to 1918 when the company was formed. Operations were suspended shortly thereafter because of the lack of a market and knowledge of the uses of molybdenum. During World War I it was used as a substitute for some rare metals and for minor chemical purposes. After 5 years of intensive research and sales promotion, Climax metallurgists succeeded in finding proper applications for the newly discovered metal and the mine was reopened in 1924. Demand for molybdenum increased gradually and in 1930, 3.5 million lb of MoS2 were produced. In the meantime, research work for additional uses of molybdenum continued until it had established itself as one of the most important alloying elements in producing high quality steels. After the start of World War 11, from January 1942 to October 1953, 43 million tons of molybdenum ore were mined and 484 million lb of MoS2 were produced. Climax mine is located in Colorado, 100 miles southwest of Denver and 12 miles northeast of Leadville on the Continental Divide of the Rocky Mountains. The principal mine workings range from 11,170 to 12,000 ft in elevation. Topographically, it lies in the base of a large cirque that is surrounded by Mt. Bartlett to the north, Clinton Peak and McNamee Peak to the east and Ceresco Ridge to the south. This cirque opens to the west and to the Ten Mile Valley.

Jan 3, 1954

It is not often that a mining district is discovered, opened up, exploited and developed into a rich producer within the space of three or four years. Not until the year 1903 was the existence of the rich cobalt-nickel arsenides and silver of Northern Ontario even suspected by the mining public. But it is worthy of record that Dr. W. G. Miller, the man who has done so much to develop sanely and honestly the mineral resources of Ontario, pointed out [ ] the possibilities of this region at least two years before the first discovery was made. . Dr. Miller, then Professor of Geology at the School of Mining, Kingston, Ont., referred in these words to the district: "It will be seen from what has been stated on preceding pages that the district examined contains as great a variety of rocks as probably any part of the Province of equal area . . . Although few discoveries of economic minerals have been made in this territory, it may reasonably be expected that deposits of value will be found when

Jan 1, 1907

By Francis L. Vinton

THE eccentric theodolite I exhibit is one constructed by the Stack-poles of New York, from drawings, considerably modified, of Combes's theodolite. The telescope is on one side of the horizontal limb, and the vertical circle is opposite to the telescope; thus they nearly balance each other, making already the construction lighter than in the instrument of Combes, where the telescope and vertical circle are together on the same side, and are both balanced by a considerable weight. The instrument stands upon three levelling screws or feet, an improvement upon the old or general style of mounting a transit on four feet-for indeed the instrument is easier levelled, and, more-over, stands more stable on three than on four points of support. The general advantage of an eccentric theodolite is evident, namely, that it can measure any and all vertical angles, from 0 to 360, without being interfered with by the horizontal limb as is the transit; besides this advantage, it needs no preparatory adjustment or correction for eccentricity ; on the other hand, however, that correction

Jan 1, 1873