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By A. Muan

Liquidus data are presented for mixtures in the ternary system FeO-Fe2O3-SiO2 in equilibrium with a gas phase with O2 pressures ranging from 10-10.9 to 1 atm. Data obtained are combined with previously published data to construct lines of equal 02 pressures and lines of equal CO2/H2 mixing ratios along the liquidus surface. Courses of crystallization of selected mixtures under conditions of constant total composition, constant O2 pressures, and constant CO2/H2 mixing ratios are discussed. PHASE equilibrium studies of silicate systems where iron is one component are complicated by the fact that iron readily occurs in three different states of oxidation: Fe3+, Fe2+, and Fe0. Success or failure in work with iron silicate systems is to a large extent dependent on control of the oxidation state of iron and all investigations therefore must be carried out under carefully controlled atmospheric conditions. Silicate systems containing only strongly electropositive metals (like Na+, Ca2+, Mg", etc.) can, for simplicity, be treated as condensed systems, that is, the gas phase can be neglected and the phase relationships discussed in terms of the phase rule written in the well known simplified form P + F = C + 1. In the case of iron silicate systems, however, the composition of the condensed phases varies with the gas composition, and a complete picture of phase relationships can be obtained only by varying the gas composition over a wide range. In order to understand the phase relationships in the more complicated multicomponent silicate systems with iron oxide as one of the constituents, a knowledge of the ternary system FeO-Fe2O3-SiO2 is essential, since it constitutes a bounding portion of all such systems. It was with this in mind that the present study was undertaken. Previous Work A considerable amount of work has been done on various aspects of the chemistry and metallurgy of systems containing silica and iron oxides. The two bounding binary systems FeO-Fe2O3 and FeO-SiO2" The first attempt to obtain information on phase relationships of iron oxide-SiO, mixtures at different 0, pressures was made by Greig.' Darken" determined the melting points of iron oxide on solid silica under various atmospheric conditions. Darken did not determine experimentally the composition of the melts at liquidus temperatures but discussed very ably the principles involved in applying the phase rule to the system. In a recent study Schuhmann, Powell, and Michal8 determined experimentally the liquidus surface of a portion of the ternary system and combined the new information with data in the literature to construct a phase diagram. Their method was briefly as follows: Homogeneous mixtures with various contents of SiO2, FeO, and Fe2O3 were made up by melting together stock mixtures in various proportions. Samples of the homogeneous mixtures, the compositions of which were determined by chemical analysis, were then heated in platinum crucibles in an inert atmosphere until equilibrium among the condensed phases was achieved. The samples were quenched to room temperature and the phases present determined by microscopic examination. Assuming that no change in composition takes place during the equilibration run in inert atmosphere, the liquidus surface can be determined, but no information is obtained regarding the partial pressures of 0, of the gas phase in equilibrium with the condensed phases. The author's method, to be described in the next section, permitted the location of points at the liquidus surface as well as a calculation of the corresponding partial pressures of O2. Experimental Method General Procedure: The standard quenching technique was adapted for a study under controlled variable atmospheric conditions. Premelted mixtures of silica and iron oxides in platinum envelopes were held at constant temperature under chosen atmospheric conditions until equilibrium was reached among solid, liquid, and gas phases. The sample was then quenched to room temperature, the phases present identified, and, for the most significant runs, the composition was determined by chemical analysis. The corresponding partial pressure of 0, was calculated from known equilibrium constants of the gas reactions occuring in the furnace atmosphere. Materials: Starting materials were oxides of commercially highest available purity; cp silicic acid was dehydrated by heating to 1350°C for 6 hr and cp Fe2O3 was dried at 400° C for the same length of time. Samples of 10 g were made up by mixing

Jan 1, 1956

By H. Kenyon Burch

PaQe Introduction.............................................................. 708 Plant Sites................................................................ 709 Type of Construction...................................................... 710 Mine Plant............................................................... 710 Dual Arrangement.................................................... 711 Underground Haulage............................................. 711 Tipples........................................................... 712 Underground Pockets............................................. 712 Automatic Measuring and Loading Devices......................... 712 Shafts ............................................................. 716 Ore and Spillage Skips............................................ 716 Automatic Hoists................................................. 716 Man Elevator..................................................... 717 Crushing Plant....................................................... 718 Storage Bin........................................................... 720 Sampling Plant....................................................... 720 Motors and Other Equipment.......................................... 721 Compressor Equipment................................................ 721 Concentrator............................................................. 722 600-Ton Test Mill..................................................... 722 The 15,OO0-Ton Concentrator...................................... 726 Grinding Section.................................................. 726 Floor Arrangement........................................... 726 Marcy Ball Mills............................................. 729 Performance of Crushing Machines............................ 730 Flotation Section.................................................. 780 . Flow-Sheet with Callow Flotation Cells....................... 731 Flow-Sheet with the Inspiration Flotation hfachines............. 731 Flotation Air Supply.......................................... 733 Concentrates Filter Plant.......................................... 733 Drag Classifiers................................................... 733 Tailing Settling System........................................... 735 200-Ft. Dorr Thickener ...................................... 736 General Equipment and Supplies.......................................... 737 Water Supply......................................................... 737 Power Supply......................................................... 737 Transformer Stations.................................................. 738 Shops and Railroad Facilities.......................................... 739 Conclusion................................................................ 740

Jan 1, 1917

By H. C. Theuerer

GeC14 may be purified by extraction with HCI and chlorine. The process is as effective for the removal of AsCI:, as the more cumbersome distillation methods usually used for this purpose. GERMANIUM for semiconductor use contains impurities at levels no higher than a few parts in ten million. Material of this quality is obtained from highly purified GeC1, by hydrolysis to the oxide and reduction of the oxide in hydrogen. When purifying GeCl,, AsC1, is the most difficult impurity to remove. This is usually accomplished by multiple distillation procedures.1-3 AsC1, may also be removed from GeC1, by extraction with HC1.1-4 Reducing the arsenic to low concentrations is not practicable, however, because of the large number of extractions needed. This paper discusses a new method for the removal of arsenic from GeC1, by extraction with HC1 and chlorine. The method is rapid, leads to little loss of germanium and is at least as efficient as the distillation procedures currently being used. Theory of Extraction Procedures In the simple extraction of GeC1, with HC1, the following reaction occurs ASCl8G8C1 D AsCl3rc1 at equilibrium CA/Cn= K, where K is the distribution coefficient, and C, and C,, are the molar concentrations of AsC13 in HC1 and GeCl,, respectively. The materials balance equation for this reaction is VACA + vncn = VnC,, where V, and Vn are the volumes of HC1 and GeCl4, respectively, and C, is the initial concentration of AsC13 in GeC1,. From this it can be shown that for multiple extractions where C,, is the concentration of AsC13 in GeC14 after n extractions, and r is the ratio of V, to V,,. It is assumed that r is maintained constant, that equilibrium is established during each extraction, and that K is independent of the AsCl3 concentration. By saturating the system with chlorine, the following reaction occurs in the aqueous phase AsCl3 + 4H2O + Cl2 D H5AsO4 + 5HC1 at equilibrium K' = ------------ ai - a4 h2u - aet2 where a is the activity of the various components. The effect of this reaction is to reduce the concentration of the AsC1, in the aqueous layer and, therefore, to promote further extraction of this component from the GeC1, layer. If the arsenic acid remains entirely in the aqueous phase, the net effect of this reaction is to promote the removal of arsenic from the GeC11. The materials balance equation for extraction with HC1 and chlorine with the foregoing reaction is, then, VaCC + VACA + VACn = VnCo where C,. is the molar concentration of H3AsO, in the HC1. With the added assumptions that the activities of AsC13 and H8ASO4 in the aqueous phase are equal to their molar concentrations, it can be shown that for n extractions Cn/Cu = (1/rkK + rK + 1) n where k - K1 a4h2o - acl2/aoncl. It can be seen by comparing Eqs. 1 and 2 that if k is large, the removal of AsC1, by HC1 extraction will be greatly improved by the addition of chlorine. Dilution of the HCI used in the extraction with chlorine would also favor the separation. This, however, would increase the loss of GeCl,, which is undesirable. Experimental Procedure Germanium prepared from oxide of semiconductor purity is n-type with resistivities greater than one ohm-cm. The resistivity is controlled by the donor concentration, which is —lo-: mol pct. Germanium prepared from material with added arsenic will have lower resistivity commensurate with the arsenic concentration. With such material, at arsenic concentrations above 10-1 mol pct the resistivity is controlled by the added arsenic, and effects due to other impurities initially in the oxide are negligible. In this investigation GeO, of semiconductor purity was converted to GeCl,, and -0.01 mol pct As was added. This material was used for the extraction experiments and the purification attained determined by a comparison of the resistivity data for samples of germanium prepared from the initial and purified GeC1,. A method for calculating the arsenic concentration from the resistivity data is discussed later. The details of the experimental procedures used are as follows: Two hundred and thirty cu cm GeC1, were prepared by the solution of GeO, in HC1, followed by

Jan 1, 1957

By Charles H. MacDowell

Up to 1909 the American public had little knowledge of, or interest in, potash. Some remembered that it had to do with soft soap and sore throat,, but further they knew not. In 1909-10, the German-American potash war, and the publicity attending hostilities, brought home to America the knowledge that potash was an important article of commerce; that Germany monopolized its production and distribution, and exercised all the prerogatives attending complete control. The present war, with its transportation embargo, has again directed attention to Germany's strength as a potash producer and her present unfortunate situation as a distributor. As a consequence, the search for potash takes on new life and it again becomes a subject of general interest. My first knowledge of potash came from a study of the German potash exhibit at the World's Fair in 1893. This investigation led to the recommendation that Armour & Co. engage in the manufacture of commercial fertilizers and the fertilizer branch was organized early in 1894. From then to now " potash " has been a live subject. Two and eight-tenths per cent. of the earth's crust consists of potassium oxide. It is an important constituent of feldspar, granite, and other igneous rocks. Potash is valuable commercially in a water-soluble form. In igneous rocks it is locked in so tight that it is of little value and no utilization in a commercial way has been made of these insoluble forms. Potash in water-soluble form is found in large deposits in Germany; in smaller deposits in Austria and Spain; and in brines in some of our Western arid basins. The deposits in Germany, Austria, and Spain are concentrations from sea waters containing potash derived from the decomposition of potash-bearing rocks. It has been found that the amount of potash remaining in decomposed rocks is not the same as that in the original rock. For instance, granite containing originally 5.58 per cent. potash contained only 1.49 per cent, in the decomposed rock. Syenite containing 6 per cent. in the original

Jan 1, 1915

By A. M. Gaudin, J. G. Morrow

FLOTATION requires the existence of a definite contact angle. This contact angle, the surface tension of the solution, and adsorption at the solid-fluid interface are quantitatively related. Adsorption of dodecylammonium acetate on hematite was measured for a wide range of concentrations of reagent in solution. Similar measurements for quartz have already been made. Contact angle measurements were then made on polished surfaces of hematite and of quartz immersed in aqueous dodecylammonium acetate solutions, and a functional relationship was sought between adsorption density at the mineral-solution interface and the contact angle. Finally, the surface tension of the aqueous amine acetate solutions was measured. These data were combined to give an evaluation of the work of adhesion for the three-phase system. Specular hematite was crushed and then ground dry in a laboratory porcelain mill, with flint pebbles, to pass a 200-mesh screen. The ground product was sized in a Haultain infrasizer, and one of the granular sizes (cone No. 3) was used in all adsorption tests. A hand magnet was used to remove magnetite and abraded iron. Quartz was removed in a Frantz isodynamic magnetic separator. The purified hematite was leached in aqua regia, washed with distilled water until the washings appeared free of electrolyte by conductance measurement, dried in a low-temperature oven, and stored in a pyrex container. The specific surface of the closely sized hematite was determined by the krypton gas adsorption method.' Three measurements gave an average value of 1350 sq cm per g. Chemical analysis showed Fe -69.37 pct, insol = 0.72 pct. The quartz used in the flotation tests had been prepared by Chang" for an earlier investigation. Demineralized distilled water was used for all test solutions. Dissolved salt content was of the order of 0.03 ppm, expressed in terms of sodium chloride, as estimated from conductance measurements. Dodecylammonium acetate was obtained from Armour & CO. in two forms, the unmarked compound and a preparation marked by carbon 14 in the hydrocarbon chain of the aminium ion. Specific activity of the active salt was 0.134 millicurie per g. The important physico-chemical constants for the primary amine salt have been reviewed by de Bruyn. The calculated effect of hydrolysis of amine salt on pH of aqueous solutions and the effect of pH on the distribution ratio of the alkylammonium ion to free amine are of particular interest. All other chemicals used in this investigation were of analytical reagent grade. A column method' was used for adsorption work. Attainment of equilibrium distribution in the adsorption column depends on the solid-solution contact time, hence upon the volume of solution passed. It was assumed that contact time required for equilibrium would be a maximum for the lowest reagent concentrations. On this premise it was demonstrated experimentally that the passage of 500 ml of solution through the mineral bed was adequate. An aliquot (1 to 5 cc) of the solution to be analyzed was transferred to a small pyrex cup and allowed to evaporate to dryness at room temperature; 4 or 5 mg of unmarked amine acetate were added to the dried sample and the cup and its contents were transferred to the combustion system for analysis. Evaporation at room temperature must be emphasized, as even slightly elevated temperatures result in loss of reagent. A laboratory model G Beckman pH meter equipped with a glass electrode was used to measure pH of amine acetate solutions. The technique of internal gas counting of radioactive carbon dioxide in a Geiger-Muller counter was used. Developed originally by Brown and Miller,- his method was adapted to the analysis of carbon-14 marked flotation reagents by Chang, de Bruyn, and Bloecher. nalytica1 method and procedures have been described in detail by Bloecher.' Contact angles were measured by the captive-bubble technique." The mineral specimens were carefully selected to avoid cracks and inclusions of other minerals. All specimens were mounted in plastic and polished to produce a smooth surface. The final polishing and contact-angle measuring

Jan 1, 1955

By Thomas Kesler

THE Cartersville mining district, 35 miles northwest of Atlanta, Ga., has been of varying but continuous importance in the southern mineral industry during the past century. Noted chiefly for its production of brown iron ore, manganese oxide ores, barite, sienna, and magnesian limestone, the district and its environs have produced brick and tile clays, slate, gold, bauxite, and graphitic schist. Minor deposits of serpentine, sericite schist, copper ore, and red iron oxide have been prospected. The obvious deposits of brown iron ore, together with some associated specular hematite, were mined out years ago, although a little ore was left in the workings. Moderately steady production of sienna reached a peak about 1930, then declined rapidly. Manganese mining passed through a relatively active period from the World War to 1931, but has subsided to a small but rather constant output for the Birmingham market. How-ever, the White Manganese Corporation has prepared for possible increased production by constructing a new washer capable of handling about 300 tons of ore per day. Principal activity in the district proper has centered for some years in the production of barite and magne-sian limestone.

Jan 1, 1940

By F. Forscher

Pronounced porosity, decreasing with distance from the fracture surface, is found in the necked region of tensile specimens tested at room temperature or liquid nitrogen temperature. A hydrogen solution treatment followed by a quench prevents pore formation in tests at —196°C, but has little effect on tests made at room temperature. Reduction of area values at —196°C are strikingly improved by the same treatment, but show no improvement in room temperature tests. The experimental results support the hypothesis that strain-induced porosity results with hydride initially present or, in material containing less than 50 ppm H, with hydride precipitated by strain aging. ZIRCONIUM'S advent as an engineering material in nuclear reactor construction has brought forth many investigations concerned with the properties of this metal and its alloys. Some attention has been given to the ductility of the metal.1, 2 Particularly, the effect of hydrogen on the impact strength was noted," indicating a pronounced dependence of ductility on the hydrogen content and its distribution in the metal. Micro graphic:' and X-ray diffraction studies' have shown that a precipitated hydride phase causes embrittlement in zirconium,' which implies a distinctly different mechanism from that causing hydrogen embrittlement in steels."-' In the latter case, it is assumed that atomic hydrogen diffuses to rifts, where it forms molecular hydrogen under such internal pressures that it causes the rifts to enlarge, leading to fracture. Thermo-dynamic studies of the Zr-H system8, 9 also indicate that the internal pressure of molecular hydrogen would be too low to cause any damage to the zirconium at room temperature, and the formation of a zirconium hydride (d phase) is favored." It is noteworthy that this phase has a face-centered-cubic structure and nearly 18 pet larger molar volume than close-packed-hexagonal a-zlrconlum' Other features of the ductility of zirconium are the absence of a typical cup-cone failure upon tensile testing, a pronounced strain-induced porosity in the necked region of a tensile bar, Fig 1, and the associated spongy appearance of the fracture surface A tremendous improvement in ductility at liquid nitrogen temperature can be observed following a heat treatment that retains the commonly present quan- tities (10 to 50 ppm) of hydrogen in solution. Such tests show a typical cup-cone failure and the absence of strain-induced porosity, Fig. 2. The present paper reports results of an investigation into the causes of strain-induced porosity in zirconium. Room temperature tensile fractures of mild steel, aluminum, and titanium have also been examined for strain-induced porosity. In each case porosity could be detected, but the amount was orders of magnitude less than was found in zirconium. Of the three metals, titanium showed the strongest effect. Material, Specimens, and Preparation The greater part of this investigation was done on Westinghouse crystal bar zirconium, are-melted, forged, and hot-rolled. Chemical analyses of the hot-rolled plates are given in Table I, along with those of the Foote crystal bar zirconium used in this work. The specimens were machined from the hot-rolled plate (1550°F) of 1/2 in. thickness and subsequently heat-treated according to one of the treatments shown in Table IS. All specimens were machined round, the longitudinal axis in the rolling direction, with a gage

Jan 1, 1957

By George A. Colligan, John M. Lo

Electrical resistivity as a function of temperature was investigated in undercooled gallium and under-cooled Ga-In alloy of eutectic compositian to examine structural changes in undercooled melts. A continuous linear extension of the resistivity was determined for 99.999 pct pure gallium when undercooled below the stable Ga(l)-liquid, and the metastable Gafl)-liquid equilibria. In icndercooled Ga-In, a significant continuous negative departure from linear resistivity behavior was observed below the eutectic temperature. All resistivity measurements were made by the four-point probe technique. ThE temperature range for investigations into the physical properties of liquids before freezing has been greatly extended with the undercooling of massive melts of pure metals and alloys. Experimental determinations of thermal and transport properties and diffraction patterns in undercooled systems should throw further light on the structural behavior of liquids. Many measurements showing prefreezing anomalies in viscosity1'5 have been regarded677 as evidence for structural groupings in the liquid state. However, the majority of viscosity results,~)~-~~ conforming to the law 17 =A exp(~/RT), do not support theories of atomic aggregation. For the system Cd-Sb, which exhibits a metastable solid phase, Fisher and Phillipsg reported that, in undercooled alloys, the activation energies for viscous flow below the stable liquidus are much higher than those above it. Similarly, Miller et a1." observed a doubling of the activation energies for electrical conductivity in undercooled Cd-ib alloys. These effects were suggested as indicative of atomic association and clustering in the liquids at lower temperatures. With the recent establishment of metastable phases in pure gallium22 and its alloys,23 attempts were made during this investigation to undercool bulk samples and to determine the temperature dependence of electrical resistivitv. Pure gallium, when undercooled below -17°C at atmospheric pressure, can crystallize to either a stable Ga(1) phase (mp, 29.78"C) or a metastable phase identi-

Jan 1, 1967

By Waldemar Lindgren

THE purpose of this paper is to present certain facts relating to Cordilleran differentiation and metallization. Theoretical discussions concerning the exact modus operandi of differentiation, the causes that led up to it, and the original distribution of the magmas have been omitted because the author feels that his knowledge is deficient. These subjects have been adequately treated in the admirable works of Iddings, Daly, Harker, Tyrrell, Shand, and Wolff. The facts here set forth seem to indicate that differentiation and metallization form one continuous process during the eastward movement of the magmas, culminating in the alkaline province of the eastern border of the Cordilleran Ranges.

Jan 1, 1933

By John B. Baker, Bernard B. Betty, H. F. Moore

For several years there has been in progress in the Materials Testing Laboratory of the University of Illinois an investigation of creep and fracture of lead and lead alloys. In the course of this investigation it has been shown that the phenomenon of creep occurs in part at the grain boundaries of lead and lead alloys. To study the occurrence of creep and the development of fracture within crystalline grains, two series of tests of single crystals of lead have been carried out. The first of these, a preliminary series, by Mr. Betty, has been described.l,2 The second, pursued by Mr. Baker for his doctoral dissertation, was carried out under the direction of Professor Moore, with the assistance of Prof. G. L. Clark in the X-ray work, and the cooperation and advice of Mr. Betty. This paper is based on the test data obtained in this second series. Single crystals of a very pure commercial lead have been prepared, some of them tested to measure creep, others tested to fracture under long-continued steady load, and still others tested under cycles of repeated tension. An interpretation of the test data of these single-crystal tests is offered, which is a combination of parts of several well-known theories. Specimens The single-crystal specimens were made from a piece of very pure commercial lead sheathing. A spectroscopic analysis of one of the single crystals showed the presence of 0.005 per cent Bi, 0.0001 per cent Cu and 0.0003 per cent Ag. Preparation.—The Bridgman method of casting single-crystal specimens was used.3 The specimens were cast to the shape and size shown in Fig. 1 (dimensions in Fig. 4c) in a duralumin mold. Molten lead does not stick to duralumin. Fig. 1 shows the mold and the blast flames for heating. After the mold had been heated to the temperature of molten

Jan 1, 1938

By John B. Baker, Bernard B. Betty, H. F. Moore

For several years there has been in progress in the Materials Testing Laboratory of the University of Illinois an investigation of creep and fracture of lead and lead alloys. In the course of this investigation it has been shown that the phenomenon of creep occurs in part at the grain boundaries of lead and lead alloys. To study the occurrence of creep and the development of fracture within crystalline grains, two series of tests of single crystals of lead have been carried out. The first of these, a preliminary series, by Mr. Betty, has been described.l,2 The second, pursued by Mr. Baker for his doctoral dissertation, was carried out under the direction of Professor Moore, with the assistance of Prof. G. L. Clark in the X-ray work, and the cooperation and advice of Mr. Betty. This paper is based on the test data obtained in this second series. Single crystals of a very pure commercial lead have been prepared, some of them tested to measure creep, others tested to fracture under long-continued steady load, and still others tested under cycles of repeated tension. An interpretation of the test data of these single-crystal tests is offered, which is a combination of parts of several well-known theories. Specimens The single-crystal specimens were made from a piece of very pure commercial lead sheathing. A spectroscopic analysis of one of the single crystals showed the presence of 0.005 per cent Bi, 0.0001 per cent Cu and 0.0003 per cent Ag. Preparation.—The Bridgman method of casting single-crystal specimens was used.3 The specimens were cast to the shape and size shown in Fig. 1 (dimensions in Fig. 4c) in a duralumin mold. Molten lead does not stick to duralumin. Fig. 1 shows the mold and the blast flames for heating. After the mold had been heated to the temperature of molten

Jan 1, 1938

By Frederic E. Carter

There have been many attempts to prove that platinum was known to the ancients, but since no traces of the metal have been found in the relics of early times, it must be concluded that it was not known to them. As far as records go, it was actually first discovered in the 16th century in a Spanish mine on the Pinto River in South America; from which source it received its name of Platina del Pinto (little silver from the Pinto). It was more or less of a rarity and was a subject of interest to a few chemists only, until the year 1822 when the metal was first discovered in Russia. In 1819 there were noticed in the washings of the gold sands of the southern part of the Ural Mountains, grains of a heavy white substance, but it was not until three years later that this substance was found to contain platinum. While at first the amounts of platinum brought from the Urals were meager, prospecting soon disclosed rich deposits extending over a considerable area, and nuggets from 10 to 20 lb. were by no means rare. This discovery assured to chemists an ample supply of platinum for their crucibles, etc. The ore is now found in various parts of the world but the richest deposits are still found in the Ural Mountains. The platinum of commerce is obtained entirely from alluvial deposits at depths varying from 6 to 40 ft. The sand and gravel of former river beds are subjected to a series of screenings and washings to effect the separation of the ore. Actually, probably all gold-bearing gravel beds of the world contain platinum, and it is more than likely that large quantities of platinum ore have been thrown away with the black sand washings from gold placer deposits. This is especially true of the alluvial deposits of the Pacific Coast in California and Oregon. Platinum ore is usually found in the form of rounded or flattened grains of "sand," and occasionally in irregular lumps of the size of peas. Large nuggets are very rare. The ore has a metallic luster and is distinguished by its steel gray color, but shows light gray streak when rubbed on a hard white surface; it has a high specific gravity, 16 to 19; is infusible in the hottest blast furnaces, and insoluble in any single acid. Platinum ore is a complex body consisting of the metal in combination with varying proportions of the other members of the platinum group; iridium,

By C. H. Mathewson, H. M. Day

The constitution of the system silver-mercury has attracted the attention of many investigators during the last two decades, but since their results are for the most part in poor agreement, there is little need for a review of their individual contributions. It remained for the very careful thermal and microscopic investigation of Murphy1 in 1931 to give the constitutional diagram in its present and unquestioned form, which is shown in Fig. 1. He devised methods for taking cooling curves on alloys under high pressures and for the microscopic observation of alloys which contained liquid mercury as a structural constituent at ordinary temperatures. The compositions of the intermediate phases were confirmed and supplemented through X-ray analyses by Preston2 and Stenbeck.3 According to Murphy, at 2760 C. silver is able to dissolve 44 to 45 weight per cent of mercury, which may increase at lower temperatures to about 50 per cent. Preston concluded that the saturation boundary occurred at 46 ± 2 per cent at 100° C. From the values reported in the literature, these are the only ones that may be accepted as lying even in the right region. Preparation of Alloys The silver used in the present investigation was supplied by the United States Metals Refining Co. through the courtesy of the Committee on Industrial Uses of Silver and, since a complete spectrographic and chemical analysis was furnished, no attempt was made to purify it or to further establish the impurities present. The analyses reported by the company are shown in Table 1. Milligan4 has found that the magnesium content is probably less than 0.0005 per cent.

Jan 1, 1938

By H. M. Day, C. H. Mathewson

The constitution of the system silver-mercury has attracted the attention of many investigators during the last two decades, but since their results are for the most part in poor agreement, there is little need for a review of their individual contributions. It remained for the very careful thermal and microscopic investigation of Murphy1 in 1931 to give the constitutional diagram in its present and unquestioned form, which is shown in Fig. 1. He devised methods for taking cooling curves on alloys under high pressures and for the microscopic observation of alloys which contained liquid mercury as a structural constituent at ordinary temperatures. The compositions of the intermediate phases were confirmed and supplemented through X-ray analyses by Preston2 and Stenbeck.3 According to Murphy, at 2760 C. silver is able to dissolve 44 to 45 weight per cent of mercury, which may increase at lower temperatures to about 50 per cent. Preston concluded that the saturation boundary occurred at 46 ± 2 per cent at 100° C. From the values reported in the literature, these are the only ones that may be accepted as lying even in the right region. Preparation of Alloys The silver used in the present investigation was supplied by the United States Metals Refining Co. through the courtesy of the Committee on Industrial Uses of Silver and, since a complete spectrographic and chemical analysis was furnished, no attempt was made to purify it or to further establish the impurities present. The analyses reported by the company are shown in Table 1. Milligan4 has found that the magnesium content is probably less than 0.0005 per cent.

Jan 1, 1938

By T. S. Lovering

The Moffat tunnel passes through the continental divide about 50 miles west of Denver, Colo., on the Denver & Salt Lake R. R.: It is 16 ft. wide, 24 ft. high, and 32,383 ft. long, a distance of a little more than 6 miles. The advantages accruing from its construction may be briefly summarized as follows: The tunnel eliminates 27 miles of grade averaging more than 3.5 per cent. and actually running well over 4 per cent. in many places, and changes the steepest grade from 4.5 to 2 per cent. It reduced the peak of the railroad from 11,660 to 9249 ft. which enables one engine to pull four times as much freight as it could before the tunnel was built. If the Denver & Salt Lake R. R. completes its line, this road will shorten the distance between Denver and Salt Lake City by 200 miles and will have no steeper grades than the lines now connecting the two cities. The proposal to drive the tunnel through the divide dates back about 25 years and D. H. Moffat, who was the leading spirit in the organization of the Denver & Salt Lake R. R. spent much of his time and energy in efforts to raise money for the tunnel that bears his name. He was unsuccessful and died before the work was started. In 1920 an effort was made to obtain state legislation favoring a bond issue to finance three important railroad tunnels in Colorado but the measure was defeated, largely through the efforts of the citizens of the region near Pueblo. A few years later devastating floods caused the Pueblo voters to seek relief from the state and at this time they withdrew their objection to the tunnel bond issue. As a result, a $6,720,000 bond was issued to finance the Moffat tunnel. Construction bids were so high that the work was finally allotted on a scheme analogous to a cost-plus basis. The contract was awarded to Hitchcock and Tinckler, who are paid a fee of $140,000 for driving the tunnel. All bills are paid by the Moffat Tunnel Commission. The contract was let Sept. 19, 1923, and Hitchcock and Tinckler agreed to complete the work by July 19, 1927. In the event of finishing before this date they were to be given a bonus of $1000 a day and

Jan 1, 1928

By I. H. Pratt

The results of a study on the preparation of thin-film capacitor structures are discussed. The dietectric source material was quartz which was sputtered and deposited onto aluminum electrodes and counter-electroded to complete the metal-oxide-metal structures. This configuration was utilized to evaluate the dielectric, the device characteristics, and related process parameters. The effect of gas sputtering pressure, magnetic field strength, source-to-substrate distance, and power density on the rate of deposition is shown. Increased film thickness uniformity over a 3 by 3 in. area by optimum substrate positioning is indicated. Dielectric constant, dissipation factor, dielectric breakdown strength, insulation resistance, heat treatment, capacitance, and dissipation over the range 400 Hz to 5 MHz are reported. In the fabrication of silicon-integrated circuits, silicon dioxide has found use as a material suitable as a diffusion mask, for surface passivation of the silicon, and for protection of conductive films used for interconnections. Its use as a dielectric for thin-film capacitors in film hybrid circuits has been limited, to a degree, for lack of a compatible processing technique and because of its relatively low dielectric constant. With the recent advent of practical metal-oxide-semiconductor (MOS) field effect devices, the material is now being used to insulate the gate electrode from the conducting channel in the silicon. In this latter application, more stringent requirements have been imposed on .the oxide. A comprehensive resume of the use of silicon dioxide in integrated silicon device technology has been compiled including oxide film and bulk properties, method of oxide formations, and their applications.' A relatively new process to deposit SiO, and other dieIectrics is by rf sputtering, and the purpose of this paper is to describe the behavior of capacitors fabricated with a dielectric which has been sputtered from a quartz target and to indicate the relative effect of several of the process parameters on the film deposition. Work on rf sputtering of SiO2 and other dielectrics has been reported utilizing a triode type of sputtering system as described herein or a diode self-sustained glow discharge system. 2-8 SPUTTERING The process occurs during an electrical discharge in a gas plasma which provides the ions for acceleration to the target to produce the desired sputtering. The necessary plasma can be generated by a dc glow discharge through application of a high potential between two electrodes at approximately 2 to 10 x 10-2

Jan 1, 1969

By J. M. Cases

Study of the normal interaction between flotation collectors and the silicates through measurement of the electrokinetic potential carried out by the streaming potential and flotation recovery methods indicates that the interaction is wholly 07 partly of electrostatic origin. In some cases, it partly consists of the chemical affinity of the polar head of the collector for the active surface sites. Reagents composed of a polar head and a paraffinic chain and forming micelles in solution were used as flotation collectors. They are sodium dodecylsulfate (anionic collector) and dode-cylammonium chloride (cationic collector). The adsorption isotherms on biotite of alkylamine chloride having 10 to 18 carbon atoms in their chain all show a sharp change in slope relevant to the condensation of alkylammonium ions into bidimensional phase.1-1 Condensation is possible because of the relative homogeneity of the adsorbing surface and of the very strong lateral binding forces through Van der Waals type bonds in the adsorption layer. The different isotherms are seen to coincide when, instead of the equilibrium concentration, the under-saturation ?µ = kT In C/C, is plotted in abscissa, C representing the concentration of the solution with which the adsorbed layer is in equilibrium and C, the saturation concentration of micelles in solution or. critical micellar concentration. More particularly, the undersaturation ?,u1*, corresponding to a surface coverage 6 of 0.5, is equal to Since silicates immersed in aqueous solutions show a surface charge which is a function of pH, it is of primary importance to study the influence of this parameter on the adsorption of collector ions acting as Strong electrolytes in the pH range where they are utilized. The aim of this present paper is to determine by studying electrokinetic phenomena and recovery curves effectuated with a cationic collector and a anionic collector, the nature of the normal adsorbate-adsorbent interaction. Tables 1 and 2 sum up part of the results previously obtained'H11 for the determination of the point of zero charge of the silicate studied by the streaming potential method. Throughout the remainder of this paper, the surface charge will be considered positive for all values of pH below the point

Jan 1, 1971

By W. J. Moore, E. M. Swiggard, H. Shenker

Beryllium is the most soluble of the double-acceptor impurities in germanium; the solubility is at least 1 x 10 19 atoms cm3. Photoconductive, optical, and electrical measurements were made on a set of Ge:Be samples grown without other intentionally added imp~ivities. The excited-states spectrum of beryllium in germanium was determined both in zero field and in magnetic fields up to 30 kc. It was found that the absorption 0-f lines in the vicinity of the G line increased markedly with increasing magnetic field. The ioniza-tion energy of neutral beryllium in germanium was determined to be 24.3 * 0.1 mez: using the excited-states spectrum. An infrared detector using a Ge:Be element was found to have a normalized detectivity D* (50 p, 1000 cps, 1 cps) of 9 X ldO cm-~ps"~-w-'. The Ge:Be sambles exhibited low-field breakdown and inibzirity band conduction effects at low temperatures. WHILE the properties of most dopants in germanium have been thoroughly investigated, the properties of beryllium in germanium have had relatively little attention. Much of the work that has been done' has been concerned with the properties of singly ionized beryllium in germanium. The purpose of the present work was to determine the photoconductive and electrical properties of beryllium-doped germanium (Ge:~e) with a small concentration of other electrically active impurities. Ge:Be is of special interest since beryllium is the most soluble of the known double-acceptor impurities in germanium. MATERIALS PREPARATION A set of &:Be crystals with beryllium concentrations between 5 x 1013 and 1x 10'' cmm3 and without other intentionally added impurities was grown in a hydrogen atmosphere by the horizontal zone-refining techniques described by Swiggard and Shenker.2 The segregation coefficient of beryllium in germanium was found to be about 0.07 and its maximum solubility was found to be greater than 1 x 10'' atoms cm-3 which is in agreement with previous results.' Most of the crystals were found to have a small net concentration of shallow acceptors; for example, a crystal having a beryllium concentration of 1.1 X 1016 cm-3 was found to have a net concentration of shallow acceptors of less than 1.5 X 1013 cm-3. Ingots designed to have a beryllium concentration of 1 x 1017 cm-3 or less exhibited a loss of electrically active beryllium. That is, the beryllium concentration was lower than expected and the decrease of the beryllium concentration along the length of the ingot was much larger than expected. It is hypothesized that this effect is due to the oxidation of the beryllium by the residual oxygen in the system. This effect is similar to but not as severe as the effect observed with boron in germani~m.3, 4 OPTICAL ABSORPTION SPECTRUM The excited-states spectrum of neutral beryllium atoms in germanium was studied by measuring the infrared optical absorption spectrum. A typical spectrum is shown in Fig. 1; the labeling of the absorption lines follows that of Fisher and Fan.* The spacings between the observed lines and the D line are nearly equal to the corresponding spacings for the other ac -ceptors in germanium.5-7 By the use of the theoretical result67' that the neutral impurity ionization energy is 2.53 mev larger than the energy of the D line, the ionization energy of neutral beryllium in germanium was determined to be 24.3 * 0.1 mev at 4.2"K. This method yields a more precise value of the impurity ionization energy than the usual Hall effect method.' The absorption spectrum of Ge:Be was also measured as a function of magnetic field using a magnetic field parallel to the incident radiation and using unpolarized radiation. A typical spectrum taken at 30 kG is shown in Fig. 2. An unexpected observation is that the absorption of the lines in the vicinity of the G line (there is a strong possibility that some of these lines may be associated with lines other than the G line) increases with magnetic field. RESISTIVITY AND HALL DATA Measurements of Hall voltage vs temperature were made on several of the samples. The thermal activa-

Jan 1, 1968

By Fred E. Wright

In a recent paper1 a detailed discussion is given of the possibilities of using polarized light in the examination of opaque substances. The factors underlying the problem are there treated from the viewpoint of the electromagnetic theory of light and the presentation is necessarily mathematical in form. The practical methods resulting from the discussion are, however, relatively simple and promise to be of value in the determination of certain ores and metals when studied in reflected light under the microscope. The results of the theoretical investigation referred to may be summarized by stating that in general the optical constants, such as refractive indices and absorption indices, cannot be satisfactorily ascertained on small, random, polished sections; that the use of polarized light enables the observer ordinarily to determine whether the crystal plate is iso-tropic or anisotropic, and also to ascertain the degree of anisotropism; that for this purpose methods based either on the contrast in intensity between the two reflected components of non-polarized light, or on the amount of rotation of the plane of polarization, on reflection, of vertically incident, plane-polarized light, may be employed; that methods based on the phase difference between the two reflected components are in general of little value because of the small differences in phase which ordinarily result for a relatively large change in birefringence or biabsorption. The measurement of the optical properties of transparent minerals, even in minute irregular grains, is a simple task with modern petrographic microscope methods and is accomplished by petrologists as part of their ordinary routine work. But the determination of the optical constants of opaque substances is difficult and is rarely attempted; all observations are necessarily made in reflected light and are restricted commonly to the determination of color, of hardness, of the character of crystallization, and of the behavior of the mineral or metal plate toward reagents and abrasives. With practice, the observer becomes expert in recognizing details of this kind and determines with a high degree of certainty the different

Jan 1, 1920

By S. J. Page

Introduction Dust from cutter machines and face drills is controlled in most mines by water. However, the large quantities of water used in metal and coal mines for dust control and suppression pose serious operational problems in water soluble ores, such as salt, trona, or gypsum. This paper reviews the strategies to suppress and collect dust on cutter machines and face drills where water usage must be restricted to very low flow rates - typically 3.78 L/min (1 gpm) or less.

Jan 1, 1985