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By J. F. Kemp

PAGE Introduction,............170 I. The Competence oF the Igneous Rocks to Supply the Materi als oF Veins,...........171 The Demonstrated Presence of the Metals in the Igneous Rocks,. . 171 The Presence of the Metals in the Sedimentary and Metamorphic Rocks, 173 Conclusions,...........175 The Abundance in Igneous Racks of Vapors or Dissociated Gases which will Yield Water on Emission and Cooling,. 175 The Sequence of Eruptions,. .. . 1 . • .. 78 The Sequence of Vein-Formations,.......1 79 Contact-Metamorphism,.........180 Pegmatites,............181 Frequency of Pneumatolitic Minerals in Veins,.. 183 Surface-Flows of Igneous Rock Unfavorable to Vein-Formation,. . 183

Jan 1, 1902

By U. C. Tainton

THE world-wide continuation of low prices for zinc in 1934 has militated against any striking changes in the position of the metal. The price of zinc in London at the end of the year, about £11 5/8 per long ton, or 2.5c per pound at the existing rate of exchange, is more than 25 per cent below the average price for last year. In these circumstances probably the most significant event of the year was the putting into operation of the new electrolytic plant of the Giesches company at Magdeburg, Germany. This plant is designed to have an initial capacity of 20,000 long tons per year, and it is planned to increase this to 40,000 tons annually. This development is significant not only as indicating a continued swing of zinc metallurgy towards electrolytic methods, but also because it will make Germany virtually independent of foreign sources of zinc. This will mean that the zinc tonnage normally exported to Germany from Belgium and Poland will. become available for other markets, and it is feared may lead to lower prices unless the production of Bel-

Jan 1, 1935

By Herbert Hoover

This paper is in the nature of a rough preliminary report on the progress that has been made in the application of the mass spectrometer to various problems arising in the petroleum industry. A few years ago the authors considered a number of the problems that were arising in the qualitative and quantitative measurement of small amounts of hydrocarbons. The methods available of making analyses by chemical techniques appeared to leave much room for improvement. Without going into the reasons at this point, attention was turned to the possibility of employing physical instead of chemical methods of accomplish-ing the desired results. A preliminary investigation disclosed that the mass spectrometer presented a possibility of solving many problems which could not easily be accomplished by other methods. Work was begun in developing the necessary apparatus and technique. A great deal of encouragement and many valuable suggestions were received from Dr. Robert A. Millikan, Dr. W. R. Smythe, and Dr. W. N. Lacey, of the California Institute of Technology, and from Dr. E. 0. Lawrence, who recently received the Nobel Prize, of the University of California. The authors particularly wish to acknowl-edge the very great willingness of these out-standing scientists to be helpful in solving many of the problems that were involved. So far as the authors are aware, this was the first application of the mass spectrometer to commercial work. The results were considerably better than had at first been anticipated. Briefly, it is pos-sible to run a qualitative and quantitative analysis of an unknown mixture of hydro-carbon gases, with an accuracy of better than plus or minus 5 per cent of each of the various constituents. An exceedingly high degree of sensitivity has been obtained, and a relatively short time is required to com-plete an analysis. Furthermore, it is un-necessary to separate a mixture of gases into its various components in order to complete the analysis.

Jan 1, 1940

By M. G. Taverner

Research was conducted into cold briquetting dross arisings and metallurgical coke fines from an Imperial Smelting Furnace (I.S.F.) as an economic means of agglomerating fine materials for smelting in a blast furnace. A mechanism was postulated whereby strong bonds were developed within the briquettes; laboratory scale smelting trials and full scale plant trials are included in the paper with a description of a two tonne/hour briquetting pilot plant. Benefits from smelting briquettes in an I.S.F. were measured directly in metallurgical coke savings and, indirectly, by a significant improvement in sinter plant productivity.

Jan 1, 1977

By E. J. Duggan

THE mine and mill of the Climax Molybdenum Co. are at Climax, Colorado. Climax is on Fremont pass directly on the Continental Divide, at an elevation of 11,400 feet. DESCRIPTION OF ORE The Climax ore-bearing rock is essentially an altered and highly silicified granite, fully half of the gangue being quartz. Molybdenite is the only mineral of economic consequence and most of it is intimately associated with quartz in the form of fine veinlets and stringers. Other minerals are molybdite, pyrite, and chalcopyrite. While the molybdite may be readily extracted by hydrometallurgical methods, its content is too low to make such operations profitable. The pyrite content ranges from 2 to 5 per cent and that of the chalcopyrite from 0.03 to 0.05 per cent. There is not enough copper to make its recovery attractive and one of the metallurgical problems is the elimination of it and the pyrite from the product. On account of the close association of the molybdenite with the quartz and the necessity of eliminating the pyrite and chalcopyrite from the final product, fine grinding followed by flotation is the only feasible method of concentration. HISTORY Construction of the first milling unit was started in 1017 and it was operated during parts of 1918 and 1910. In the postwar years, there was almost no demand for the product and production was at a standstill until 1024. The Company's research campaign to develop the use of the metal began to show results in that year. From 1926 to 1932 production ranged from 500 to 1200 tons per day. In 1931 an additional mill section was built and production was gradually increased until in 1934 and 1935 about 3000 to 4000 tons was milled per day. This tonnage overtaxed the milling facilities, and as the demand for molybdenum was growing constantly, additional milling equipment was needed. In 1936 and 1937 another crushing plant, six additional mill sections and the necessary auxiliary plants were constructed and brought into operation. This plant was designed to mill I0,000 tons per day, but it was not long before 12,500 tons was being treated during periods of peak demands. During the summer of 1941, to meet defense needs, the mill has been required to treat 15,500 tons per day. This has been accomplished with little plant expansion and at no loss in recovery, as will be described later. To increase capacity still further, one more primary section is now being built. This will bring capacity to 18,000 tons per day, which can be stretched to 20,000 tons at a small sacrifice in recovery. CRUSHING There are two crushing plants: No. I, of 5000 tons capacity (flowsheet in Fig. I) and No. 2, of 15,000 tons capacity (Fig. 2).

Jan 1, 1942

By C. Richard Tinsley

Mineral economists debate whether to call the deep-ocean nodules "manganese nodules," "nickel nodules," "polymetallic nodules," or even "ferro-manganese nodules." It is nickel and copper that are generally regarded as the main targets in the nodules. Processing considerations are thought to virtually dictate that Deepsea Ventures will produce high-purity manganese metal (at least if it follows a hydrogen chloride leach), whereas other groups have been focusing on the selective extraction of copper, nickel, cobalt, zinc, and molybdenum, while rejecting manganese to tails. Solvent extraction appears to be the primary multimetal extraction technique (except for manganese). These processing considerations indicate that metal production f, or Deepsea Ventures is essentially a co- product system (manganese recovery is necessary to recycle chloride ions) while the other groups can more easily approach the metals as selective co-products (e.g. recovering nickel and copper, and rejecting cobalt). Some zinc may be produced as a co-product, as it may have to be removed in the solvent extraction process.

Jan 4, 1975

[A session of the Institute of Metals held during the February, 1926, meeting of the Institute, was devoted to a symposium on ''gas" in copper. S. Skowronski, Perth Amboy, N. J., was chairman. On the program were papers by T. S. Fuller; W. H. Bassett and J. C. Bradley; Susan B. Leiter, and W. H. Bassett and H. A. Redworth. These papers follow the chairman's introductory discussion.] S. Skowronski, Perth Amboy, N. J.—There are today two groups of metallurgists, one group who believe in oxygen-free copper and another group who believe that oxygen is absolutely essential in copper; not that the two groups disagree, but that a certain grade of work calls for oxygen-free copper, while another grade of work does not. I can sum up the problem by reading the abstract of an article by Frederick Johnson of Great Britain in The Metal Industry of Sept. 4, 1925. Few, who have watched the trend of things during the last two decades, can have failed to notice the steady growth of opposition to the prevalent use of copper in the "tough-pitch" condition, which for many ages enjoyed an unchallenged supremacy. Broadly speaking, there are two schools of thought in the metallurgical world, one holding the view that copper containing a small proportion of oxygen is an eminently suitable material for users, the other expressing its preference, in no hesitating or uncertain manner, for copper from which oxygen has been removed by means of a deoxidizer. In the old days, before the advent of the converter and the electrolytic refining process, the copper of commerce was so impure that the presence of oxygen was imperative in order to neutralize the influence of impurities which militated against the hot-working properties of the metal. For electrical purposes, oxygen must be present, because sound bars and billets cannot be produced without it, except at the expense of electrical conductivity. For most engineering purposes, however, electro-deposited copper may be used either by itself or with the addition of alloying elements, e. g., arsenic and nickel, which experience has proved to be beneficial, such copper being freed from oxygen by the aid of a deoxidizer, e. g., phosphorus. Such material has positive advantages over "tough-pitch" copper as at present produced from refinery furnaces. It has greater toughness and malleability, and is immune from the action of reducing gases at high temperatures, the destructive action of which, in the case of "tough-pitch" copper, is well known. The reasons why there has been no wholesale replacement of "tough-pitch" copper by deoxidized copper are commercial in nature; copper can be more economically melted in large-capacity furnaces which lend themselves to the poling process and are not so suitable for control of uniformity of action of deoxidizers as the smaller electric or crucible furnaces, whilst they are also more convenient for the production of very large castings. Moreover, the equipment of most large copper manufacturing plants is designed for casting "tough-pitch " copper in open moulds, e. g., wire bars and cakes, and these could not be used for deoxidized copper, which must be cast in vertical moulds as in brass-shop practice. Further, there are still certain impure brands and

Jan 1, 1926

By AIME AIME

Council.* PRESIDENT OF THE COUNCIL. JOHN HAYS HAMMOND* New York, N. Y. (Term expires February, 1909.) VICE-PRESIDENTS OF THE COUNCIL. SAMUEL B. CHRISTY BERKELEY, CAL. JOHN A. CHURCH NEW YORK, N. Y. PERSIFOR FRAZER PHILADELPHIA, PA. (Term expires February, 1909.) J. PARKE CHANNING NEW YORK, N. Y. FREDERICK 1V. DENTON PAINESDALE, MICH. JOHN B. FARISH DENVER, COLO. (Term expires February, 1910.)

Mar 1, 1908

By O. L. Culberson, J. J. McKetta

Experimental and smoothed data are presented for the solubility of methane in water for temperatures of 77, 100, 160. 220. 280, and 340°F at prejsures to 10.000 psia. The minimum solubility phenomenon exists within this temperature range to pressures of 10.000 psia. INTRODUCTION The study of hydrocarhon-water systems has been extended to the determination of the solubility of methane in water at pressures to 10.000 psia. The experimental apparatus, and the technique. are the same as that previously reported.' - In the determination of the solubility of methane in water, only two phases were present at temperatures between 100 and 340°F. these being the vapor phase and the water-rich. liquid phase. The determinations involved the agitation of methane and water in an equilibrium cell. withdrawal of a sample from the liquid phase, and the analysis of the sample. The experimental value; determined in this manner are pre9ented in Table I and in Fig. 1. Since experimental and analytical techniques have improved since the initial experiments with this equipment, it was decided to repeat the 77°F isotherm determinations.' Fig. I shows that the individual results for this isotherm are much

Jan 1, 1951

By J. J. McKetta, O. L. Culberson

Experimental and smoothed data are presented for the solubility of methane in water for temperatures of 77, 100, 160. 220. 280, and 340°F at prejsures to 10.000 psia. The minimum solubility phenomenon exists within this temperature range to pressures of 10.000 psia. INTRODUCTION The study of hydrocarhon-water systems has been extended to the determination of the solubility of methane in water at pressures to 10.000 psia. The experimental apparatus, and the technique. are the same as that previously reported.' - In the determination of the solubility of methane in water, only two phases were present at temperatures between 100 and 340°F. these being the vapor phase and the water-rich. liquid phase. The determinations involved the agitation of methane and water in an equilibrium cell. withdrawal of a sample from the liquid phase, and the analysis of the sample. The experimental value; determined in this manner are pre9ented in Table I and in Fig. 1. Since experimental and analytical techniques have improved since the initial experiments with this equipment, it was decided to repeat the 77°F isotherm determinations.' Fig. I shows that the individual results for this isotherm are much

Jan 1, 1951

COLORADO SCHOOL OF MINES On February 21, 1918, the students of the Colorado School of Mines who are members or have applied for membership in the Institute re-organized the "Scientific Society of The Colorado School of Mines,? which has for its .purpose the study and discussion of mining problems. Its meetings will be held on the first and third Wednesdays of each month, in Guggenheim Hall. Following are the officers R. W. GIBSON, President, W. A. CONLEY, Vice-president, F. L. SERVISS, Sec'y.-Treas. At present there are 62 members, seven of whom are Faculty members. F. L. SERVISS, Secretary.

Jan 5, 1918

By Arnulf Muan, R. W. Taylor

Activities of iron in Fe-Pt alloys have been dctermined by equilibrating mixtures of platinum metal and iron oxide at known oxygen Pressures in a thermobalance at 1300°C. Conzpositions and iron activities of the oxide phase at equilibrium are known from previous work, and compositions of the Fe-Pt alloy phase formed at equilibrium were detcvt?zined from the observed weight changes of the samples. The activity curve obtained shows a strow negative deviation from Raoult's law. THE present investigation was undertaken as part of a research program dealing with phase equilibrium relations existing among the oxides of iron and titanium at 1300°C. At low oxygen pressures of the gas phase in equilibrium with these oxides, the iron activity of the system is high, and considerable alloying of iron with the platinum used as a container material takes place. Thermodynamic data for Fe-Pt alloys at 1300°C are needed in order to evaluate quantitatively the extent of such reactions. Larson and chipmanlhave determined activities of iron in Fe-Pt alloys at 1550°C by equilibrating platinum metal with CaO-iron oxide-SiOzmelts in which the iron activities were known. Compositions of the resulting Fe-Pt alloys were determined by chemical analysis. Mundiath and Gerassimov2 have studied thermodynamic properties of Fe-Pt alloys by electromotive force measurements in the temperature range 550" to 1000°C. The experimental method used in the present investigation is a slight modification of that used by Grube and Ratsch3 in studies of NiCr-alloys. 1) EXPERIMENTAL METHOD 1) General. Mixtures of platinum metal and iron oxide were equilibrated at 1300°C in atmospheres of known oxygzn przssures, and the course of the reactions was followed by measuring the weight changes of the mixtures. The principles involved in the derivation of composition-activity relations from these measurements are illustrated by the composition triangle for the system Fe-FeZO3-Pt shown in Fig. 1. Take as an example a mixture of FeZO3 (hematite) and platinum such that the total composition is represented by point T. If this mixture is heated to 1300c in air (poz = 0.21 atm) and the oxygen pressure is then reduced gradually, the oxygen content of the oxide phase decreases and increasing amounts of iron enter the metal phase. As the oxide phase and the metal phase for all practical purposes are insoluble in each other, their compositions are represented by points moving toward Fe along the joins Fe-Fe,03 and Fe-Pt, respectively. The total composition of the mixture during this process also changes, but only with respect to oxygen content, because the vapor pressures of iron and platinum are negligible at 1300°C. Hence the change in total composition is described by a straight line (constant Fe/Pt ratio) radiating from the 0 apex of the composition triangle Fe-Pt-0, of which the triangle in Fig. 1 is a part. Only one such line ("oxygen reaction line", T-T",) is shown in Fig. 1. The total composition of the alloy-iron oxide mixture at any instant must, in addition, be located on the straight line (conjugation line) connecting the two points representing the compositions of the two coexisting phases. It therefore follows that the total composition of the mixture at any instant is represented by the point of intersection between the conjugation line and the oxygen reaction line. An example of the situation prevailing at a chosen oxygen pressure, po2, is shown in Fig. 1 by points a' (alloy composition), b' (oxide composition) and T' (total composition). Point b' is known from the work of Darken and Gurry,4 and point T' is experimentally determined by the observed weight change of the mixture (distance T-T). Hence, point a', the composition of the alloy, is determined from the above data as the intersection between the join Pt-Fe and the extension of the straight line bl-7'. The activity of iron in the alloy at equilibrium is identical to that of the iron oxide phase, if the same

Jan 1, 1962

PRESIDENT OF THE COUNCIL. JOHN HAYS HAMMOND NEW YORK, N. Y. (Term expires February, 1909 ) VICE-PRESIDENTS OF THE COUNCIL SAMUEL B. CHRISTY BERKELEY, CAL. JOHN A. CHURCH NEW YORK, N.Y. PERSIFOR FRAZER PHILADELPHIA, PA. (Term expires February, 1909 ) J. PARKE CHANNING NEW YORK, N. Y. FREDERICK W. DENTON PAINESDALE, MICH. JOHN B. FARISH New York, N. Y. (Term expires February, 1910)

Jan 1, 1910

By T. E. Schmieman, J. E. Miller, M. L. Rizzone

Both centrifugal and reciprocating-type pumps have been widely used in the transport of slurries. Although with some limitations, centrifugal pumps may be used, especially for short-haul systems, however, for the long pipelines the reciprocating pumps are better suited. A state-of-the-art review is presented in which a discussion of applications is made and some of the problems associated with meeting the proper design conditions for satisfactory service are discussed. Several developments underway give considerable promise of better pumps in the future, although the current level of development provides for an economical means to move slurries. The movement of liquids in pipelines necessarily occasions the use of pumps. The petroleum industry is familiar with the transport of solids through mud pumps and cementing and fracturing pumps where the movement of slurries is an everyday matter. In the drilling of an oil well, the circulating fluid utilized to remove drill cuttings is called drilling mud. This substance is usually a fairly sophisticated material designed to develop certain characteristics desirable in the drilling process. The cuttings are suspended in a moving column of this fluid and brought to the surface. The separation of the cuttings from the drilling fluids is accomplished by the use of shaker screens and settling pits; however, it is impractical to remove the cuttings completely and as a result they are pumped through the mud pumps back into the circulating stream. Over the years, mud pumps have been improved so that rather long life can be obtained from liquid end parts subject to the attritional effects of the abrasive-laden fluid. It is from this background that reciprocating-type slurry pumps have been developed. Centrifugal Pumps Centrifugal pumps have also been used to transport solids, where low heads are required, typically up to 200 ft or so, and for short hauls. The centrifugal pump is a hydrokinetic device wherein the increase in velocity of a fluid stream is converted to head, and to achieve high heads a large change in velocity is necessary. Abrasive laden fluids cause wear on impellers and casings as a result of erosion by the fluid and the suspended particles. Centrifugal pumps, therefore, can only be used where the internal velocity of flow is rela- tively low. The advantage of centrifugal pumps is their high capacity at relatively low capital cost and usually relatively small space requirement. One of the disadvantages of the centrifugal pump when used in slurry pipelining can be seen in its typical pressure-volume performance relationship, which tends to work against the application (see Fig. I). If an increase in pressure (head) is occasioned by flow restrictions in the pipeline, say by the dropping out of solids, a desirable characteristic of a slurry pump would be that it develop increased pressure to overcome the restriction. The centrifugal pump provides the increased pressure only at the expense of considerably reduced volume which then results in a lower flow velocity. With the reduced flow rate, adequate velocity to hold the material in suspension and keep it flowing in the line might not be achieved. If centrifugal pumps are considerd for the movement of solids in a long line, a series of pumps must be staged in order to provide the necessary motivating force. A large number of pumps in the line would be required, since each of the pumps could provide only a small pressure increment. An equal number of standby pumps

Jan 1, 1971

Coal Division Industrial Minerals Division Minerals Beneficiation Division Mining, Geology and Geophysics Division Elmer A Jones, President President-elect Will Mitchell, Jr, Past President J B Morrow, Eastern Regional Vice-President G Donald Emigh, Central Regional Vice-President J D Forrester, Western Regional Vice-President R B Ladoo, Treasurer John Cameron Fox, Secretary AIME 29 West 39 St, New York 18, N Y

Jan 1, 1957

By H. I. Smith

CONTENTS [PAGE Problems of Mining and Processing Mineral Aggregates (TP 1649, by NATHAN C. ROCKWOOD, Min. Tech., Nov. 1943. Discussion by H. I. SMITH, IRVING WARNER and the author) t Mica in War (TP 1749, by RUSSELL G. WAYLAND, Min. Tech., July 1944. Discussion by H. S. SPENCE) 3 Three Roofing-granule Plants in Pennsylvania (TP 1787, by RICHARD M. FOOSE, Min. Tech., Jan. 1945. Discussion by H. I. SMITH)5 Methods of Prospecting and Mining Optical Calcite in Montana (TP 1896, by E. W. NEWMAN, Min. Tech., Nov. 1945. Discussion by W. C. STOLL and FRANK C. ARMSTRONG, and the Glass Sand and a Glass Industry in Puerto Rico (TP 1939, by HOWARD A. MEYERHOFF and J. EARL FRAZIER, Min. Tech., Nov. 1945. Discussion by A. M. SHORT, the author and PHILIP The "Bonanza" Mica Operation of Purdy Mica Mines, Limited, Mattawsn Township, Ontario (TP 2154, by HUGH S. SPENCE, Min. Tech., March 1947. Author's supplement and discussion by JOHN A. BAKER, E. J. LINTNER, and the author) 7 Process for Manufacture of Dead-burned Magnesite and Precipitated Calcium Carbonate from Dolomite (TP 2155, by ROBERT D. PIKE, Min. Tech., March 1947. Discussion by 0. C. RALSTON and the author) 9] Problems of Mining and Processing Mineral Aggregates H. I. SMITH*-Mr. Rockwood has presented a very interesting paper on problems of the mineral aggregate industry in meeting specification requirements, which apparently are ever decreasing in tolerance. May I call attention to a method of mineral separation that may be of value in separating the flat aggregate particles from the more angular ones and possibly the soft particles from the hard. The method is the old Pardee spiral coal separator, extensively used many years ago in the anthracite region for separating rock and bone from anthracite coal.1 The success of the process depends on the relative coefficient of friction of the aggregate particles to be separated rather than on their relative specific gravity. The flat and the soft particles normally will slide more slowly and stay on the inner spiral until they reach the delivery spout at the bottom whereas the round and the angular pieces will work to the outer edge and fall off into a spiral of larger diameter. The capacity of the separator is increased materially by having three inner spirals, with a separate feed for each, on which the particles travel more slowly, and one outer spiral from which the more rapidly traveling pieces slide to the bottom. IRVING WARNER*-I have long been convinced that much of the equipment and methods developed for mineral dressing might be advantageously employed in the mineral aggregates industry, and more particularly in the production of sand and gravel. The two industries are not well acquainted with each other or their problems. They have separate trade publications. The difficulty with the situation is that there are few large sand and gravel plants and few provided with technical services in their own organization or by retainer. This does not refer to engineering organizations but rather to improvement of plant technic in processing.

Jan 1, 1947

By William F. List, Marvin A. Schuster

Monolithic electrooptical mosaics of 2500 photo-transistor elements with internal row and surface column interconnections have been fabricated by epitaxial-planar diffsion techniques. Unique access to any elemed of the mosaic is provided through one of the fifty X and one of the fifty Y external leads. The sensor mosaic can be used for imaging applications and has a 1:1 aspect ratio, a resolution of 100 lines per in., a dynamic range in excess of lo3, a sensitivity of 0.5 per pw, element response within a 2:l range over 75 pct of the mosaic, and a minimum detectable signal of the order of 10-' w. Design considerations which ilnpose particclar fabrication yequirements are disctussed along with some of the problems peculiar to the epitaxial and planar-dijfision techniqes by which this device is fabricated. The solid-state silicon monolith has an imaging area of 0.5 by 0.5 in. and an element center -to- center spacing of 0.010 in. J monolithic solid-state electrooptical device has been developed as the photon-sensing mosaic for use in an image-converter system.' This system is the solid-state equivalent of the vidicon and can image radiation in the visible and near-infrared regions of the spectrum. The electrooptical image converter has the desirable size, weight, reliability, and low-power characteristics inherent in solid-state devices. It is read out by direct-wire means rather than by beam-scan techniques. The packaged unit is shown in Fig. 1. A selection of material for the sensor was based on considerations of both reliable fabrication techniques and material spectral response. Silicon was selected both for its response from the lower end of :he visible to the long-wavelength cut-off above 11,000A and for its well-developed epitaxial planar-diffused technology. The electrical image is composed of M x N discrete information bits with each bit emanating from one of the individual phototransistor sensors. The interconnected mosaic concept was introduced to provide a structure which is both manageable in its number of leads and compatible with conventional viewing systems which accept XY data. Interconnections along the Y direction are provided by internally diffused strips, while interconnections along the X direction are formed by vacuum-deposited metal surface bars. Unique access to any individual element of the M x N mosaic is available through one of the M and one of the N external leads. PHOTOTRANSISTOR DESIGN A phototransistor structure2 was selected for the discrete photon detectors of which the mosaic is com- posed. Basically, the mode of phototransistor operation is such that incident quanta are absorbed in the base area of the element where they generate electron-hole pairs. If the electrons are liberated within a diffusion length of the depletion region around the collector junction, they will diffuse to this depletion region and be swept across the junction where they account for a small component of the photocurrent. Similarly, the holes which are created within a diffusion length of the emitter junction will diffuse to this region where they forward bias the emitter and so induce injection of minority carriers into the base. This accounts for the substantial transistor photocurrent. This mechanism of operation implies several design and fabrication goals for the individual sensor elements: high electrooptical conversion efficiency, sufficient carrier lifetime in the base regions, and a maximum volume in which photons can be absorbed within a diffusion length from the depletion layer about the junction. Moderately high transistor gain is desirable to permit readout at low light levels; however, very high gain has a deleterious effect on mosaic dynamic range. The mosaic must also be characterized by good uniformity of element response as well as by good isolation between elements. The above set of conditions imply that junction depths must be optimized with respect to photon ab-

Jan 1, 1967

By C. Law McCabe, R. G. Hudson

The Knudsen cell has been employed to determine the free energy of formation of Mn7Cs in the temperature range 800" to 950°C. A value of 66,440 cal was found for hH°o for a-manganese. Measurements of the pressure of manganese over a mixed carbide, (Fe,Mn),C, points to a power relationship between aun7cs and N.4,. RECENTLY Kuo and Perssonl have reported that the carbide of manganese which is in equilibrium with graphite at temperatures up to 1100° C is Mn7Ca. There are no published data on the thermo-dynamic properties of this compound. In order to determine the stability of Mn7Ca, it appeared that, by obtaining the pressure of manganese above 8-manganese and also above Mn,C, in equilibrium with graphite, the free energy of formation of Mn7Ca from 8-manganese and graphite could be obtained. In addition, the vapor pressure of manganese, reported by Kelley From data of Bauer and Brunner,' is subject to some uncertainty and further determinations of the vapor pressure of manganese seemed warranted. In this investigation of the pressure of manganese vapor above pure manganese and also above the carbide of manganese in equilibrium with graphite the apparatus used is the Knudsen orifice cell. The same apparatus, experimental procedure, and method of calculating the pressure was used in this investigation as in one previously reported.~ Care was taken to insure that the cells were at constant weight before using them in a run. The manganese charged in the cell was CP grade powder, carbon free, obtained from the Fisher Scientific Co. A spectroscopic analysis of the manganese after appreciable amounts of it had vaporized from the Knudsen cell showed that no element was present in sufficient quantities to contribute to a weighable weight loss or to decrease the vapor pressure of manganese to any appreciable extent. The spectro-graphic analysis was 0.002 pct Cu, 0.05 pct Fe, 0.002 pct Pb, and 0.002 pct Ni. 8-manganesea is the allo-tropic form of manganese which was present in the cell at temperatures used in this investigation. The manganese carbide, Mn,Ca, was made in the following way: In a closed graphite cell manganese powder was added to graphite powder, which was made from graphite rods for spectrographic use. The manganese powder was the same as that described previously; 5 pct excess graphite was added over that required for the formation of Mn7C,. The mixture was heated in a closed graphite cell for approximately 20 hr at 1350°K under vacuum. X-ray analysis revealed that there was no manganese present after this treatment, but that the lines due to Mn,C, were present. In order to prove that there was no volatile carbide of manganese which was effusing out of the cell, the following experiment was performed: A graphite effusion cell containing graphite power, in excess of that to form Mn,C, of a desired amount, was brought to constant weight on heating at 1228°K. The required amount of manganese was accurately weighed and then added to the graphite effusion cell. The cell was placed in a vacuum at 1228°K for one week, which was the time calculated for the manganese to have effused completely, assuming instantaneous formation of Mn,C8. The cell was then weighed again. This experiment was carried out on two different occasions and both times the weight loss of the cell came within 1 pct of the weight of manganese originally charged minus the weight of manganese left in the cell, as determined by chemical analysis. These data are summarized in Table I. This agreement is considered to be within experimental error and is taken as proof that no carbide of manganese is volatile in this temperature range. It was established, by X-ray analysis, that Mn,C, formed before appreciable amounts of manganese vaporized from the metal powder which was charged. The identification of the carbide of manganese which was present in the Knudsen cell in equilibrium with graphite and manganese vapor was carried out by Kehsin Kuo at the University of Uppsala. He established that the authors' sample, which was submitted to him for analysis, contained the phase

Jan 1, 1958

[*E. O'C. Acker '86 Jinzoc Adachl '88 T. H. Aldrich '96 *Truman H. Aldrich '78 Walter H. Aldridge '89 *Anson W. Allen '87 John H. Allen '84 *Thomas Andrews '94 *William R. Analeby '90]

Jan 1, 1946

By G. W. Healy, J. C. Schottmiller

Molten silicates were found to exist in the Cr-Si-0 system at temperatures above 1450°C. one atom of oxygen is readily removed from CrzOs in the presence of Si02 at 1700°C, forming a silicate melt. Steam-hydrogen ratio measurements made at this temperature indicate that the free energy of the reaction: Cr20s(c) + Hz = 2CrO (in Si02 -saturated melt) + H20 is approximately 5600 * 1500 cal. A deep-blue chromous silicate, probably Cr2Si04, forms from these melts at about 1400" to 1500°C, and is characterized by.its distinctive X-ray diffraction pattern and optical properties—distinct pleochroism and high refractive indices. THE question of the state of oxidation of chromium in slags has vexed metallurgists for many years The experiments of Koerber and Oelsenl suggested the probable presence of divalent chromium in silica-saturated slags equilibrated with high-chromium melts. Hilty and coworkers2 had also found chromium at lower valency, as Cr304, in inclusions formed from oxygen-saturated Fe-Cr melts with as little as 10 pct Cr. In both cases, disproportiona-tion of the lower oxide to CraO3 and chromium was found to occur to a greater or lesser extent, depending upon the rate of cooling from the high temperature. The work on Cr304 was sufficiently detailed for chipmans to derive its thermodynamic properties, but Oelsen's experiments in the silicate system were not extensive enough since most of his runs were made with slags containing large amounts of manganese oxide in addition to iron and chrome oxide and silica. The present study describes experiments carried out to map out an approximate liquidus diagram in the CrzOs, "CrO", SiOa portion of the Cr-Si-0 system, and to measure the partial free energy of solution of oxygen in the system. EXPERIMENTAL 1) Approximate Melting-Point Determinations. Preliminary trials showed that when an equimolar mixture of Cr20s and SiOa was treated with hydrogen in the temperature range 1500" to 1600°C, copious amounts of steam were evolved, and a low-melting liquid formed which could be quenched to a blue, crystalline, material having a distinctive X-ray diffraction pattern. It was found that the identical material could be produced by heating intimately mixed, finely divided Cra03, Cr, and SiOa, held in a tungsten crucible, under purified argon. Thus, it was possible to prepare mixtures containing any desired proportions of chromium, silicon, and oxygen, pel-letize them, heat to temperature in the furnace shown in Fig. 1, and observe, after cooling, whether the pellet remained unchanged or showed signs of incipient, partial, or complete melting. 2) Free Energy of Solution of Oxygen. This was studied by measurement of steam-hydrogen ratios for the reaction: H20 (gas) + O (dissolved in charge) + Ha (gas) The experimental method chosen was to prepare a

Jan 1, 1964