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By W. J. Millard

IT is well known that the excellent mica from Brazil played a most vital role in World War II. Increased production from Brazil was necessary and with the assent of the Brazilian Government engineers from the United States went down to study the problem. One of the means advocated by a former Chief of Metals and Minerals Branch of the Board of Economic Warfare, Mr. Carl Schwegler, was the use of stripping machinery. On a pegmatite dike favorable for stripping, a small number of miners could produce as much mica per day as an underground mine employing many times the same number of men. TYPE OF DEPOSIT FAVORABLE The most favorable type of pegmatite for stripping is that which lies more or less parallel to the surface of the slope of a hill. Pegmatite dikes that cut directly into a hill are not suitable for stripping except where a long outcrop extends along the slope. Then just the outcrop could be stripped to some advantage. The ratio at no time should be greater than I:3; i.e., I cu. m. of pegmatite to 3 cu. m. of waste, unless the pegmatite was extremely rich throughout the dike. THE ECONOMICS OF STRIPPING When a mineral is badly needed to win a war, not too much heed can be paid to costs. The object is to produce rapidly and in quantity. Again, a deposit containing a superior grade of mica may be worked although the pegmatite is more costly to work than another deposit containing a considerably greater amount of poor-grade mica. For example: one deposit may have a little mica that will run II per cent good stain and better when trimmed and contain 2 kg. of crude mica per cubic meter of pegmatite, while another may run 0.2 per cent of good stain and better, and have a mica content of 10 kg. per cubic meter. A number of stripping projects were found in the vicinity of Raul Soares, Minas Gerais. These were sampled in the various old workings by cutting out a cubic meter of pegmatite and saving the usable mica. Because of the proximity to the surface of most stripping projects, about 34 per cent only of the mica is good for trimming. The other 66 per cent is too badly weathered to be of use. In Table I are given data collected on five properties near Raul Soares. In Table I, "value per cubic meter of pegmatite" means the value of the qualified mica obtainable. This does not include the half trimmed and splittings. By "value per cubic meter of matter" is meant the value of the qualified mica per cubic meter of material excavated; i.e. both waste and pegmatite. This is the figure that should he used to determine whether the operation will be profitable or not, as the cost of stripping is about $0.I4 per cubic meter. With new machinery not subject to breakdowns, the cost per cubic meter should be around $0.10 to $0.I5. To this should be

Jan 1, 1946

By J. R. Szedon, T. L. Chu, G. A. Gruber

Amorphous adherent filnzs of silicon dioxide have been deposited on silicon substrates by the oxidation of silane at temperatures ranging from 650 to 1050C. Various diluents (argon, nitrogen, hydrogen) were used to suppress the formation of SiO2 in the gas phase. Deposition rates of the oxide were determined over the temperature range in question as functions of' re-actant flow rates. Etch rate studies were used for a cursory comparison of structural properties of deposited and thermally grown oxides. From electrical evaluation of metal-insulator-silicon capacitors it was determined that the interface charge density of deposited films is similar go that of dry-oxygen-grown films in the 850° to 1050 C temperature range. Deposited films exhibit several ionic instability effects which differ in detail from those reported for thermal oxides. Stable passivating films of silicon nitride over deposited oxides appear to be practical for use in silicon planar device fabrication. Such films can be prepared under temperature conditions which have less effect on substrate impurity distributions than in the case of grown oxides. AMORPHOUS silicon dioxide (silica) is compatible with silicon in electrical properties and is the most widely used dielectric in silicon devices at present. Silica films can be prepared by the oxidation of silicon or deposited on silicon or other substrate surfaces by chemical reactions or vacuum techniques. The ability of thermally grown silicon dioxide films to passivate silicon surfaces forms one of the practical bases of the planar device technology. Properly produced and treated films of grown SiO 2 can have low densities of interface charge (-1 X 10" charges per sq cm) and can be stable as regards fast migrating ionic sgecies. 1 To maintain these properties, even with an otherwise hermetically sealed ambient, the Sia layers must be at least l000 A thick. Such thicknesses require oxidation in dry oxygen for periods of 7.8 hr at 900°C or 2 hr at 1000°C. Although oxidation in steam or wet oxygen can reduce these times to 17 and 5 min, the resulting oxides must be annealed to produce acceptable levels of interface charge., Oxidation or annealing involving moderate to high temperatures for extended periods of time can be undesirable. Under some conditions, there can be changes in the distribution of impurities within the underlying substrate. A chemical deposition technique using gaseous am-bients is particularly attractive and flexible for preparing oxide films. With a wide range of deposition rates available, films can be produced under condi- tions of time and temperature less detrimental to impurity distributions in the silicon than in the case of thermal oxidation. The pyrolysis of alkoxysilanes, the hydrolysis of silicon halides, and various modifications of these reactions are most commonly used for the deposition of silica films.3 Silica films obtained in this manner are likely to be contaminated by the by-products of the reaction, organic impurities, or hydrogen halides. The use of the oxidation of silane for the deposition process has been reported recently.4 The deposition of silica films on single-crystal silicon substrates by the oxidation of silane in a gas flow system has been studied in this work. The deposition variables studied were the crystallographic orientation of the substrate surface, the substrate temperature, and the nature of the diluent gas. The electrical charge behavior of Si-SiO2-A1 structures prepared under various conditions was investigated by capacitance-voltage (C-V) measurements of metal-insulator-semiconductor (MIS) capacitors. The experimental approaches and results are discussed in this paper. 1) DEPOSITION OF SILICA FILMS The overall reaction for the oxidation of silane is: The equilibrium constants of this reaction in the temperature range 500° to 1500°K, calculated from the JANAF thermochemical data,= are shown in Fig. 1. In addition to the large equilibrium constants, the oxidation of silane is also kinetically feasible at room temperature and above. However, the strong reactivity of silane toward oxygen tends to promote the nucleation of silica in the gas phase through homogeneous reactions, and the deposition of this silica on the substrate would yield nonadherent material. The formation of silica in the gas phase can be reduced by using low partial pressures of the reactants. Argon, hydrogen, and nitrogen were used as diluents in this work. 1.1) Experimental. The deposition of silica films by the oxidation of silane was carried out in a gas flow system using an apparatus shown schematically in Fig. 2. Appropriate flow meters and valves were used to control the flow of various reactants, i.e., argon, hydrogen, nitrogen, oxygen, and silane. Semiconductor-grade silane, argon of 99.999 pct minimum purity, oxygen of 99.95 pct minimum purity, and nitrogen of 99.997 pct minimum purity, all purchased from the Matheson Co., were used without further purification. In several instances, a silicon nitride film was deposited over the silica film. This was achieved by the nitridation of silane with ammonia using anhydrous ammonia of better than 99.99 pct purity supplied by the Matheson CO.' The reactant mixture of the desired composition was passed through a Millipore filter into a horizontal water-cooled fused silica tube of 55 mm

Jan 1, 1969

By E. P. Jennings

The abundance and value of the tellurium minerals of Colorado is well known, but, as yet, few analyses have been made of them, and I offer these as a small contribution to the chemistry of these valuable ores. 1. Native Tellurium.—The specimens from which the analyses of this mineral were made are from the " John Jay" Mine, Boulder County, Colorado, where it occurs in quite large masses, though mixed with more or less silica and iron pyrites. It is usually a finegrained, tin-white mineral, but sometimes occurs in distorted, hexagonal prisms in cavities in the quartz. Before the blowpipe it gives the reactions for tellurium, sulphur and iron; by cupellation, it yields a small amount of gold. An analysis of a coarsely crystallized specilnen gave the following results : Specific gravity, 5.10.5. Tellurium,.........68.40 Gold, :.........1.36 Iron pyrites,........24 92 Ferric oxide,.....4.37 Silica and silicates,........11.54 Silver, lead, and mercury,... traces. 100.59 Deducting the pyrites, iron oxide and silica, we have for the con]position of the mineral: Tellurium,..........97.78 Gold,.......... 2.27 100.00 Or, considering the gold to be in combination with tellurium to form sylvanite, we have : Nativc tellurium,........96.50 Sylvanite (An, Te3,),........4.50 100.00

Jan 1, 1879

By T. E. Watkins, M. D. Nelson

INTRODUCTION Deeper drilling for oil is becoming more and more the rule rather than the exception. With deeper drilling come additional problems, perhaps the greatest being those brought on by the higher temperatures encountered down the hole. particularly in the Gulf Coast region of Texas and Louisiana. Temperature gradients of the order of 1.8° to 2.0°F/100 ft are not unusual, and a gradient of 2.3"F.'100 ft is found in some areas of Texas. With a mean surface temperature of 74oF, the following temperatures could be expected for a geothermal gradient of 2.0°F; 100 ft: at 10,000 it. 271°F. 12,000 ft, 314°F: 14,000 ft, 354,oF; and 16.000 ft. 394°F. Severe gelation of lime-base drilling fluid in wells that have high bottom hole temperatures has become perhaps the most serious difficulty enconntered in drilling under such conditions. Lime-base drilling fluids have been very succesefully and widely used in the drilling of wells in the Gulf Coast region because of their inherent stability toward contaminants. their ability to suppress the swelling dispersion of bentonitic shales, and their ease of maintainance. The gradual recognition: during the past few years, that these muds were. in themselve. the cause of many difficulties experienced in drilling has led to wide-pread efforts by the drilling industry. to determine the reasons for the failure of these mud systems and to develop mud systems capable of performing satisfactorily under high-temperature conditios. MANIFESTATIONS OF HIGH-TEMPERATURE GELATION it is generally possible to recognize the symptons of high-temperature gelation early enough that advance predictions can be made of serious difficulties. in mud control, and the useful life of the drilling fluids can be extended by proper treatment. Following i.; a list of the manifestations of high-temperature gelation: (1) The drill string 'takes weight' while going in the hole after a trip. In early stages of high-temperature gelation it is possible to notice a slight reduction in drill string weight as the drill pipe is lowred near the bottom of the hole. (2) Excessive pump pressure is required to .tart the circulation of drilling fluid at or near the bottom of the hole when going hack to bottom after a trip. As the severity of the gelation increases it may be necessary to break circulation a number of times when going in the hole. (3) The drilling fluid from the bottom of the hole is thick and often granular or lumpy when pumped up after making a round trip. In a severely gelled drilling fluid system such a condition may be irreversible; that is, it cannot be stirred or chemically treated to produce a satisfactory drilling fluid. (4) Completion tool.. such as logging tools or perforating guns will not sink to the bottom of the hole. On some occasions completion tools will become stuck and require a fishing job to retrieve them if the wire line attached to them is broken. It is often difficult to determine whether the condition of the drilling fluid is responsible for sticking the tool or whether the wire line becomes key seated in a crooked hole and causes the allow difficulty. When there are 110 other symptoms of high-temperature gelation. then the difficulty may usually be attributed to the latter cause. (5) In extreme cases of high-temperature gelation it is necessary to "wash" and "ream" when going back to bottom after coming out of the hole. (6) In many -instance. it has been found to be extremely difficult and expensive to 1111 production packers 2nd tubing in moderately deep oil wells which had been drilled with a lime-base drilling fluid. In such instances-the original mud had apparently "set" to a consistency approaching that of a weak cement. CAUSES OF HIGH-TEMPERATURE GELATION Extensive test; have indicated that a lime-base mud does not develop a highly gelled condition at temperatures below 250°F. whereas above that temperature such condition often develops rapidly. (Fig. 1) concurrently. the following changes are evident ill the mud: (1) The alkalinity of the mud decreases to a very low value. with both caustic soda and lime being consumed. (2) The quartz content of the mud decreases sharply. (3) The bentonitic content of the mud decreases or di-appears, with concurrent decrease or loss of base exchange capacity of mud solids. (4) New compounds formed in the mud have been found to be cal-cium silicate, calcium aluminum silicate, and calcium sodium aluminum silicate. (5) The mud loses the ability to form a filter cake of low permeability. The above characteristics have been discussed, in part. by other authors

Jan 1, 1953

By N. F. Fiore, M. F. McGuire

THIS communication describes a series of experiments in which dislocation etch pitting was used to ascertain the depth of damage in crystals which were mechanically polished or which were cut with either a commercial metallographic cut-off wheel,* a com- All specimens were cut from single crystals of American Smelting and Refining Co. 99.999+ pct pure copper which were grown from the melt by the Bridge-man technique. The test specimens were disks, with faces being (111) planes and the disk axis a (111) direction. The disks were annealed in a vacuum of 10-5 Torr for 24 hr at 950°C prior to cutting or polishing and were given a light electropolishing in an ortho-phosphoric acid bath before etch pitting. Both Youngs1 and Livingston's2 reagents were used for etch pitting and the reagents gave identical quantitative results; however Livingston's reagent produced less staining and so all photomicrographs shown are of {111) surfaces etched with this solution. The surface of the annealed crystals showed well-defined subboundaries and a density of dislocations of about 1 X 106 per sq cm excluding those present in subboundaries, Fig. 1. The depth of cold work produced during mechanical polishing was determined after an annealed specimen was mounted in a paraffin holding block to protect it from extraneous damage. The exposed (111) surface was ground on metallographic papers and then polished on billiard cloth through 0.05-p alumina abrasive. It was necessary to remove about 0.3 mm (-0.01 in.) to obtain a structure representative of the annealed sur- face, indicating that the crystal was damaged to this depth during mechanical polishing. The cold work caused by standard cutting methods was measured in another series of tests in which cuts

Jan 1, 1967

By W. L. Hill, W. H. Armiger, S. D. Gooch

The physical properties, chemical behavior under thermal treatment, and fertilizer value of fluorine-containing pseudowavellite (hydrous calcium aluminum phosphate) that occurs as phosphate clay admixed with quartz sand in an extensive deposit near Bartow, Fla., were determined by experiments in laboratory, pilot-plant, and greenhouse. When the mineral was heated at 500°C, 80 pct of the phosphorus become citrate soluble. The heated product, however, deteriorates markedly under moist conditions such as obtain in the soil. EXTENSIVE beds of a soft aluminiferous phosphate lie in the Bartow-Pembroke region of Florida. Although the extent of the deposit is unknown, it is thought that the equivalent of at least five million tons of material containing 25 pct P,Os exists on one large mine property alone, and soft phosphates similar in nature are known to occur elsewhere in the state. This aluminum phosphate, unlike fluorapatite, is rendered fairly soluble in neutral ammonium citrate solution merely by heating it at a temperature below 600 °C, a property made the basis of a process patent by the junior author.' The possibility of producing an available form of phosphorus from what has hitherto been a worthless natural phosphate prompted the Bureau of Plant Industry, Soils, and Agricultural Engineering to make a brief study of the Pembroke phos- phate during the war years with a view towards determining the optimal temperature for heat treatment and the reactions involved in the process. The results of this study supplemented by data and information furnished by the junior author are presented in this paper. Description of Natural Phosphate: The phosphate with admixed quartz sand and siliceous matter occurs as a low-grade (8 to 9 pct P2O5) clay-like material that can be beneficiated cheaply by making a water separation of the very fine material from the sand, floating off the fine material, settling the suspension to a thick slurry, and finally de-watering the slurry by vacuum filtration followed by drying. The product dried at 100 °C contains about 16 pct water and 25 pct P2O5, about 1/12 of which is citrate soluble. Partial analyses of representative samples of the crude ore and corresponding concentrate are given in table I. The concentrate is light yellow in color and even after being dried at 100°C sticks very noticeably to laboratory grinding and screening equipment. Under the microscope the ground material is predominantly light brown crystalline aggregates with index of refraction near 1.61. The principal phosphate mineral constituent was identified as pseudo-wavellite with admixed phosphosiderite.2 Pseudo-

Jan 1, 1951

By W. L. Hill, W. H. Armiger, S. D. Gooch

The physical properties, chemical behavior under thermal treatment, and fertilizer value of fluorine-containing pseudowavellite (hydrous calcium aluminum phosphate) that occurs as phosphate clay admixed with quartz sand in an extensive deposit near Bartow, Fla., were determined by experiments in laboratory, pilot-plant, and greenhouse. When the mineral was heated at 500°C, 80 pct of the phosphorus become citrate soluble. The heated product, however, deteriorates markedly under moist conditions such as obtain in the soil. EXTENSIVE beds of a soft aluminiferous phosphate lie in the Bartow-Pembroke region of Florida. Although the extent of the deposit is unknown, it is thought that the equivalent of at least five million tons of material containing 25 pct P,Os exists on one large mine property alone, and soft phosphates similar in nature are known to occur elsewhere in the state. This aluminum phosphate, unlike fluorapatite, is rendered fairly soluble in neutral ammonium citrate solution merely by heating it at a temperature below 600 °C, a property made the basis of a process patent by the junior author.' The possibility of producing an available form of phosphorus from what has hitherto been a worthless natural phosphate prompted the Bureau of Plant Industry, Soils, and Agricultural Engineering to make a brief study of the Pembroke phos- phate during the war years with a view towards determining the optimal temperature for heat treatment and the reactions involved in the process. The results of this study supplemented by data and information furnished by the junior author are presented in this paper. Description of Natural Phosphate: The phosphate with admixed quartz sand and siliceous matter occurs as a low-grade (8 to 9 pct P2O5) clay-like material that can be beneficiated cheaply by making a water separation of the very fine material from the sand, floating off the fine material, settling the suspension to a thick slurry, and finally de-watering the slurry by vacuum filtration followed by drying. The product dried at 100 °C contains about 16 pct water and 25 pct P2O5, about 1/12 of which is citrate soluble. Partial analyses of representative samples of the crude ore and corresponding concentrate are given in table I. The concentrate is light yellow in color and even after being dried at 100°C sticks very noticeably to laboratory grinding and screening equipment. Under the microscope the ground material is predominantly light brown crystalline aggregates with index of refraction near 1.61. The principal phosphate mineral constituent was identified as pseudo-wavellite with admixed phosphosiderite.2 Pseudo-

Jan 1, 1951

By F. W. Clark

At the present time, when lixiviation versus amalgamation is being so thoroughly discussed by practical men, and published information is so meagre, the following tests, made by students in the mining laboratory of the Massachusetts Institute of Technology, may be of interest to others. The ore experimented upon was obtained from the Sombrerete mines near Zacatecas, Mexico. A careful analysis of the dried sample resulted as follows : Per cent. SiO2,............62.79 S.............13.86 Al2O3............4.39 Fe,............11.26 Zn,............1.57 CaO.............2.91 MgO,........... 0.06 Cu,.............0.12 Pb,.............0.40 Sb and As,..........trace CO2,............2.35 Ag,.............0.16 99.87

Jan 1, 1886

THE discussion of this topic at the Open-hearth Conference at Detroit on Nov. 3, 1927, was opened by statements of the general principles involved, made by manufacturers of molds. Because of their general interest they are printed below. WILLIAM HAIL RAMAGE,* Hubbard, Ohio.-I did not come prepared to read a paper, thinking. the most I would be called upon to do would be to make a few, remarks by way of discussion. A number of our friends have pre-viously asked questions. similar to this which really does not permit a direct "yes" or "no" answer. If I may he pardoned for so doing, I believe it advisable to discuss rather what we consider the principal factors which in-fluence mold life. I think possibly a little undue weight has been given to the subject of the analysis of the metal. For the last eight years we have spent a lot of time, effort, and money investigating this very problem from a chemical, physical and microscopic standpoint. We have had the benefit of complete records and history of over 100,000 molds in service at a variety of plants and over long periods of time. Obviously, I cannot be so specific that I should divulge information that is really a trade secret. In our opinion the principal factors influencing mold life are: (1) design of the mold; (2) process of manu-facture, including workmanship; (3) care in the steel plant or what might be termed "the use or abuse" in the steel plant; (4) the analysis of the iron and the physical con-dition of it. Under normal conditions these factors are of importance in the order named, although in specific cases they might be rearranged in any order you choose. For instance, the best mold made can be destroyed in one or two pours by subjecting it to certain conditions which are occasion-ally met in steel plant practice. Obviously, in that case, nothing else matters but that one item. On the other hand, I have seen molds made of such a terrible design that it was a foregone conclusion it would have to be broken after the second pour of the ingot to get it out. In that case, nothing but design mattered. As to the effect of process of manufacture, let me cite a case. Some years ago there were two batches of molds sent to a certain company. They were the same sized molds, used under the same conditions and in the same kind of service. There were, 20 molds in each batch. The second batch sent gave ten times the life of the first batch. It is true that the design was changed a little, but not very much, and it was not. a bad mold to begin with. It is possible that the iron may have been better in the second consignment but not very much. In my opinion, it is con-servative to say that of the 900 per cent improvement in life, 5 per cent was probably due to better iron, 25 per cent to better design and the remaining 870 per cent to process of manufacture and workmanship.

Jan 2, 1928

By C. K. Leith

IN telling the story of Canada's minerals many interesting and spectacular details will be passed over to permit pointing out some of the significant inter- national aspects. No country now has enough of all minerals for its own use. The problems of satisfaction of both national and world demands under these conditions have become international in scope, and history supplies no obvious solutions. The minerals of Canada are coming to play a prominent part in such problems. Production and Reserves In the last decade Canada has rapidly advanced in mineral production. In 1928 the total value of mineral products from Canadian sources reached 273 millions of dollars. Canada ranks first in production of nickel, first in asbestos, second in cobalt, third in gold and silver, fourth in lead and copper, and sixth in zinc.

Jan 1, 1929

By H. L. Hopkins, L. W. Kempf

Aluminum alloys, in common with most other metallic alloys exhibit slight density changes with variations in temper achieved by heat-treatment, which usually are the result of the variation with temperature of the solid solubility of the various alloy constituents in the solvent metal. Changes in density are, of course, most marked in conditions that exhibit the maximum variation in solid solubility of the constituents. In aluminum alloys these conditions usually prevail when alloys are quenched from just below the melting point and are subsequently reheated to some lower temperature. Since commercial heat-treatments may be of this type, the density changes, although small (of the order of 0.3 per cent which may be compared with the density change of about 1.5 per cent involved in the transformation, at ordinary temperatures, of gamma to alpha iron during the hardening of steel), may in some specific applications necessitate quantitative consideration. This phenomenon has been investigated extensively in the laboratories of the Aluminum Company of America over a period of years. A number of investigators '-5t have observed and measured the density changes accompanying the heat-treatment of aluminum alloys. In general, these changes have not been directly translated to dimensional changes and their significance has been overlooked to some extent by the practical user of aluminum alloys. It is the purpose of this paper to consider some practical aspects of these density and dimensional changes. These density changes were given some consideration in 1917 in connection with the use of aluminum-alloy pistons for aircraft engines. Investigations by Lea and Shakespear were reported in some confidential reports of the British Advisory Committee for Aeronautics, Light Alloys Subcommittee, during 1917 and 1918, which are not generally available in published form. In these reports the term "permanent growth" was applied to the dimensional changes occurring in the pistons at the tem-

Jan 1, 1936

By E. T. Turkdogan, L. S. Darken, R. J. Fruehan

Further consideration is given to the application of the quadratic formalism to evaluate the thermodynamics of binary metallic solutions from experimental data. The use of the thermodynamic relation, in(r1/r2) dN2= 0, in the evaluation of activity data is discussed. The empirical correlations derived previously for enthalpies and entropies of solutions in Part II are shown to be predicted theoretically for a special case. The applicability of the quadratic formalism to the activity coefficients for binary organic solutions is demonstrated. DARKEN&apos; introduced a quadratic formalism describing the composition dependence of the activity coefficient in the terminal regions of binary metallic solutions. In a subsequent paper (Part II) Turkdogan and Darkeen2 extended this formalism to the enthalpy and excess entropy of binary metallic solutions, and showed that the available data for the activity coefficients and heats of mixing of many solid and liquid binary metallic solutions confirm reasonable applicability of the quadratic formalism. Much variation was noted, however, in the extent of the terminal regions from one system to another, commonly from about 10 to 70 at. pct. For the present purpose, equations derived previously need be given only for one of the terminal regions, e.g. region (I), 0 < N2 < N&apos;2: where subscripts 1 and 2 indicate quantities for components 1 and 2 and superscript ° the values at infinite dilution; other terms are: N = atom fraction, y = activity coefficient, = partial molar enthalpy of solution, ?HM = molar heat of solution, ?Sx = excess partial molar entropy, ?Sx = excess molar entropy. The heat and entropy like terms (constants) el, and S12 are defined in the following expression for the temperature dependence of a12, thus a12 £12 — s12 rnl 2.303RT 2.303 R l J Using this formalism, the thermodynamics of binary systems in the terminal regions may be described over a temperature range of experisental interest in terms of eight quantities: Lº1—Lº2, ?Sx1,?Sxº2 , £12 ,£21,fiai, S12, and S21. In the previous paper, these quantities were evaluated for many solid and liquid binary solutions, and two significant correlations were observed between these thermodynamic quantities pertaining to the terminal regions, thus [10] and [11] Combining Eqs. [9], [l0], and [ll] and rearranging gives a12 -a21 = 1.382R log rº2- 0.08(?S2xº- ?S1xº) [12] Since the second term involving entropies is small and Eqs. 1101 and [ll] are empirical relations, the above equation may be simplified to a12 = 2.74 log rº2 [13] Using the values of a&apos;s and y°&apos;s compiled in Parts I and 11, a12 - a21 is plotted against log(rº2/rº1) in Fig. 1; the line drawn has a slope of 2.74. For Hg-K at 300°C, log(yº2 /yº1)= —5.10, not shown in Fig. 1, and from correlation [13], a12 - a21 = -13.97; this is to be compared with -10.76 derived from the activity data (Part II).

Jan 1, 1970

By C. E. Wood, T. L. Joseph

This paper is a brief report of experimental work undertaken determine whether barium oxide in any quantity increases the desulfur ing action of blast-furnace slags. Industrial furnace operation wi slag containing small quantities of barium oxide, referred to later, intc ested S. A. Sanford of the Commercial Chemical Co., Youngstown, Oh to conduct experiments to furnish comparative results on desulfurizati with normal slag and slag containing small quantities of barium oxic The U. S. Bureau of Mines agreed to assist on the problem because the possible saving in fuel if the desulfurizing action of blast-furna slag can be substantially increased, also because the experiments woi yield new information on sulfur elimination in general, a matter economic importance in furnace practice. A more complete and func mental study of desulfurization of iron by slag is in progress. Distribution of Sulfur iN the Blast Furnace More than 90 per cent. of the total sulfur entering the blast furnz is in the coke. Sponge iron formed by reduction of iron oxides absor part of the sulfur as ferrous sulfide. Kinney&apos;s examination of sample taken from various levels of a 3004,011 furnace, shows that the me continues to take up sulfur until it reaches a level near the tuyer Desulfurization must therefore take place as the metal falls through t slag and as the slag and metal exist as layers in the crucible. The relative amounts of sulfur removed while the metal falls throu the slag and while the slag and metal exist as layers in t crucible are not definitely known. Preliminary experiments by t

Jan 1, 1929

By I. S. Servi, N. W. Marr

TIN markedly increases the softening temperature of pure copper with only a moderate effect on conductivity. Smart and smith&apos; indicated a substantial increase in softening temperature upon addition of different levels of tin up to 0.05 pct in oxygen-free copper. However, after finding no effect of tin in copper containing about 0.025 pct O, they concluded that "the presence of oxygen completely nullifies these changes in properties by precipitation of SnO2.&apos;&apos; Since preliminary tests on Cu-Sn-0 alloys indicated that this conclusion is not valid outside the extremely limited tin range investigated by Smart and Smith, research was primarily directed toward the partition of tin between the copper-base matrix and the oxide phases. Experimental. Material was prepared by sealing an 80 to 100-g charge consisting of oxygen-free copper, tin, and copper oxide into a y-in.-ID quartz capsule which was evacuated and back-filled with tank-grade argon to 3 atm. The sealed vials were heated to 1125ºC, kept at temperature for 30 min, occasionally agitated, and then allowed to air-cool outside the furnace ("as-cast"). The castings were cold-swaged to 0.370 in., annealed 1 hr at 600°C ("as-annealed"), and cold-swaged 16.5 pct ("as-swaged"). Cross sectional wafers were annealed for 1 hr at various temperatures and Rockwell F hardness measured. The "softening temperature" was defined as the interpolated temperature at which the hardness was 50 Rockwell F. Electrical resistance was measured by an ac poten-tiometric method on 0.040-in.-diam wires after a 1 hr anneal at 600°C. Relative accuracy was of the order of 1 pct. Chemical analyses for tin were performed by two methods, identified as "Acid flux" and "HN03 dissolution". The first consisted of fusing the sample with potassium pyrosulfate and leaching the resulting melt with 10 pct sulfuric acid. The spectrophotometric procedure which followed is described in Ref. 2. Oxygen analyses were performed by the vacuum-fusion method with a bath temperature of 1650°C. Tin content of oxides and copper phases was measured with the X-ray microprobe, using a calibration curve based on a series of oxygen-free Cu-Sn alloys. Results. In Fig. 1, the nominal tin composition for alloys containing nominally 400 ppm O was plotted vs the analyzed or the computed tin content—the latter derived from one of the following: 1) "acid flux" chemical analysis; 2) "HN03 dissolution" chemical analysis; 3) X-ray microprobe analysis of the copper matrix; 4) equivalent tin content, based on the measured increase in electrical resistivity (an increase in resistivity of 1.6 microhm-cm is approximately equivalent to 1 wt pct of sn1,3). It is evident from Fig. 1 that the results of the acid flux analysis are consistent with the nominal composition while the HNO3 dissolution method generally yields lower values, consistent with those obtained from electrical resistivity measurements and somewhat higher than those obtained by microprobe analysis. Microprobe and resistivity values are affected only by the tin in solid solution; hence the HN03 method

Jan 1, 1970

By G. W. Housner

The series of earthquakes in the vicinity of Koyna Dam in south- western India, which included a very damaging magnitude 6.5 shock on Dec. 11, 1967 (Dec. 10 GMT), is of much interest. The events are exceptionally well documented, which is a tribute to Indian geologists, seismologists, and engineers. To help in disseminating the information in the United States, this chapter presents a brief summary of the pertinent data and lists references. Koynanagar (Koynatown), which began as the construction camp for the dam, is located about 140 miles southeast of Bombay and 70 miles south of Poona at 17.4ºN and 73.7ºE, about 40 miles inland from the Arabian Sea. Koyna River flows almost due south from its source a distance of about 38 miles and then makes an abrupt turn to the east and travels some 480 miles to empty into the Bay of Bengal. Koyna Dam is located about 3 miles north of this turn. The approximately north-south trending continental divide is a few miles west of Koyna and the terrain drops steeply about 1700 ft to where the hydroelectric generating station is located. The reservoir behind Koyna Dam forms a long, narrow lake (Shiva- jisagar Lake) with mean water level (MWL) at 2160-ft elevation. The 345-sq-mile watershed receives an annual rainfall of about 200 in., most of which falls between mid-June and mid-October. The peak storage is 99 x l09 cu ft. A controlled flow passes under the continental divide in a tunnel and then down to the electric generating station about 5 miles WNW of the dam. The inflow not used for power generation is released to Koyna River. The Koyna project is a major source of electric power for Bombay and produces 540 MW at peak load.

Jan 1, 1970

By JAMES H. McGRAW

P UBLZCLTY and engineers do not mix. In the very words of my subject, there is an apparent contradiction. In the past, publicity has been abhorrent to the engineer. It seems to be true that the engineer, because of his training or his background, has developed a state of mind which omits publicity. At any rate he has done a poor publicity job for himself. The average engineer is self-conscious; he ought to be class-conscious. If T should ask the men in this hall to get up one by one and tell who they are and what they have done, there would be an instinctive reaction in the mind of each man-a feeling that this was out of place. If I should ask each man to get up and tell something about his neighbor, I should find that each neighbor, once he got acquainted with the man next to him and understood what he was doing, would be as human and as generous-hearted in telling about his brother engineer as is any professional man.

Jan 1, 1920

By William M. Kester

INTRODUCTION The Coal Research Bureau of the School of Mines at West Virginia University is presently conducting laboratory-scale tests to determine the technical feasibility of beneficiating pulverized coal and coal fines with high-intensity electromagnetic fields. Interest in magnetic processes for cleaning fine coals was stimulated by results obtained by Yurovsky, et a1 in 1958.1 This work, while not new in concept,2,3 indicated that pulverized coal which had been thermally treated in a rotary drum in the presence of superheated steam and air underwent thermo- chemical reactions. Films of the ferromagnetic minerals magnetite (Fe2O3), hematite (Fe3O4), and pyrrhotite (FeS[3]) were reported to be formed on the surfaces of the pyrite grains associated with fine coal during the foregoing treatment at temperatures ranging from 120 to 360°C. After thermal treatment the coal was magnetically separated in an experimental magnetic device having a field strength of 10,000 oersteds.

Jan 5, 1965

By Charles E. Lundin

The character of the Er-D system was established by determining pressure-temperature-composition relationships. A Sieuerts&apos; apparatus was employed to make measurements in the temperature range, 473" to 1223"K, the composition range of erbium to ErD3, and the pressure range of 10~s to 760 Torr. The system is characterized by three homogeneous phase regions: the nzetal-rich, the dideuteride, and the trideuteride phases. These phases and their solubility boundaries were deduced from the family of isotherms of the system zchich relate the pressure-temperature-composition variables. The equilibrium plateau decomposition relationships in the two-phase regions were determined from can&apos;t Hoff plots to be: The differential heats of reaction in these two regions are AH = - 53.0 * 0.2 and -20.0 *0.1 kcal per mole of D2, respecticely. The differential entropies of reaction are AS = - 36.3 * 0.2 and - 31.0 * 0.2 cal per mole D2. deg, respectively. Relative partial molal and intepal thermodynamic quantities were calculated from the pure metal to the dideuteride phase. The study of the Er-D system was undertaken as a logical complement to an earlier study of the Er-H system.&apos; The primary interest was to compare the characteristics of the two systems and relate the difference to the isotopic effect. Studies of rare earth-deuterium systems by other investigators have been very limited in number and scope. Furthermore, there is even less information available wherein an investigator has systematically compared a binary rare earth-hydrogen system with the corresponding rare earth-deuterium system. The available information consists primarily of dissociation pressure measurements in the plateau pressure region of a few rare earths. Warf and Korst&apos; determined dissociation pressure relationships for the La- and Ce-D systems in the plateau region and several isotherms for each system in the dideuteride region. They compared these data with those of the corresponding hydrided systems. The study of these systems as a whole was very cursory and did not give sufficient data for a thorough comparison of the effect of the hydrogen vs the deuterium in the respective rare earths. The heat capacities and related thermodynamic functions of the intermediate phases, YH, and YD2, were determined by Flotow, Osborne, and Otto,~ and the investigation was again repeated for YH3 and YD3 by Flotow, Osborne, Otto, and Abraham.4 This investigation studied only these specific phases. Jones, Southall, and Goodhead5 surveyed the hydrides and deu-terides of a series of rare earths for thermal stability including erbium. They experimentally determined isotherms of selected hydrides and plateau dissociation pressures for deuterides. These data allowed comparison of the enthalpy and entropies of formation of the dihydrides and dideuterides. To date, no one rare earth has been selected to thoroughly establish the complete pressure-temperature-composition (PTC) relationships of binary solute additions of hydrogen and deuterium, respectively. The objective in this investigation was to provide the first comparison of a complete family of isotherms of a rare earth-deuterium system with those of a rare earth-hydrogen system. This would allow one to determine what differences exist, if any, in the various phase boundaries and the thermodynamic relationships in various regions of the systems. I) EXPERIMENTAL PROCEDURE A Sieverts&apos; apparatus was employed to conduct the experimental measurements. Briefly, it consisted of a source of pure deuterium, a precision gas-measuring buret, a heated reaction chamber, a mercury manometer, and two McLeod gages (a CVC, GMl00A and a CVC, GM110). Pure deuterium was obtained by passing deuterium through a heated Pd-Ag thimble. A 100-ml precision gas buret graduated to 0.1-ml divisions was used to measure and admit deuterium to the reaction chamber. The reaction unit consisted of a quartz tube surrounded by a nichrome-wound furnace. The furnace temperature was controlled by a recorder-controller to . An independent measurement of the sample temperature in the quartz tube was made by means of a chromel-alumel thermocouple situated outside, but adjacent to, the quartz tube near the specimen. Pressure in the manometer range was measured to k0.5 Torr and in the McLeod range (10~4 to 10 Torr) to *3 pct. The deuterium compositions in erbium were calculated in terms of deuterium-to-erbium atomic ratio. These compositions were estimated to be *0.01 D/Er ratio. The erbium metal was obtained from the Lunex Co. in the form of sponge. The metal was nuclear grade with a purity of 99.9+ pct. The oxygen content was reported to be 340 ppm and the nitrogen not detectable. Metallographically the structure was almost free of second phase (<i vol pct). A quantity of sponge was arc-melted for use as charge material. The solid material was compared with the sponge in the PTC relationships. They were found to be identical. Therefore, sponge material was used henceforth, so that equilibrium could be attained more rapidly. The specimen size was about 0.2 gr for each loading of the reaction chamber. The procedure employed to obtain the PTC data was to develop experimentally a family of isothermal curves of composition vs pressure. First, a specimen

Jan 1, 1969

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

The effect of alumina particles on the nucleation and growth of cracks through a silver- chloride matrzx has been investigated. It has been found possible to promote fibrous cracking in dispersion-strengthened silver, chloride under notch-impact conditions at temperatures at which silver chloride alone cleaves brittlely The modification) of fracture beIzavzor is thought to be due to the relaxation of hydrostatrc stress beneath a notch by the nucleation of cavities near alumina particles. In recent years, composite or dispersion-strengthened materials have been studied primarily to understand their high resistance to plastic flow particularly at elevated temperatures. Dislocation models have been developed with which it is possible to deduce with fair success the effects of interparticle distance, particle size, temperature, upon yielding and creep behavior.l-4 Much less attention has been paid to the fracture behavior of these materials (with the notable exception of common structural steels) and little is known experimentally about the manner in which inclusions affect the nucleation and growth of cracks through a matrix. Nevertheless a beginning has been made in connection with fibrous cracking in ductile matrices where inclusions appear to play an essential ro1e.5-7 During the severe localized plastic deformation which accompanies necking in a tensile test, cavities are believed to develop at inclusions; these cavities subsequently grow and coalesce by plastic flow until separation is complete. It is of interest to consider whether inclusions can affect fracture behavior under loading conditions which restrict the plasticity of the matrix itself (for example, cleavage under conditions of a high imposed strain rate at low temperatures). It is particularly interesting to study these effects in a solid which shows a spectrum of behavior ranging from fully ductile to semi-brittle behavior. Such a solid is silver chloride whose mechanical behavior depends sensitively upon temperature and strain rate.&apos;," The present paper is concerned with a study of the influence of inclusions (in the form of alumina particles) on the fracture behavior of silver chloride loaded uniaxially at low strain rates at room temper- ature and also under notch impact conditions over a wide range of temperature. In particular, it will be shown that the alumina particles can exert a startling effect on the ductile-brittle transition temperature of notched silver chloride and that the magnitude and nature of the effect depends upon both the quantity of alumina and the shape of the alumina particles. 1. EXPERIMENTAL PROCEDURE 1.1 Materials Used. Silver chloride powder of analytical reagent (AR) quality having an average particle size 6 was supplied by the Mallinckrodt Chemical Works (st. Louis, MO.). Acid washed 900 mesh alumina powder, designated A38-900, was supplied by the Norton Co. (Cambridge, Mass.). This powder was added to silver chloride in two forms: a) the as-received condition in which the individual particles were of random irregular shape; their statistical average size was 7; b) in a condition in which each particle was spherically shaped by a fusion technique. In this case, the statistical average particle size determined with the optical microscope was approximately the same (about 5p) but electron micrographic evidence indicated that many ultra fine particles were present in the spheroidized powder. 1.2 Preparation of Composite Materials. Silver chloride-alumina composites containing 2.5, 5, and 15 pct by volume of alumina were produced by the extrusion of mechanically mixed powders blended in a ball mill for 24 hr at room temperature. The mixtures were compacted at 50,000 psi at room temperature in the form of billets 3/4 in. in diameter and 1 in. long which were then extruded with a 16:l reduction ratio at 370°C through a radius-type steel die having a 5 deg lead-in angle. An extrusion temperature of 370°C was selected to ensure that all composites had sufficient plasticity to be extruded. Apart from this general requirement, the choice was arbitrary. 1.3 Microstructure of Composites. Attempts were made to check the distribution of alumina metallo-graphically by polishing transverse and longitudinal sections of the extruded rod. Specimens were wet-ground to 600 emery paper and lapped successively with 5 and 0.25-p grades of diamond paste. They were etched for 10 sec in 10 pct sodium thiosulfate solution and lightly polished in concentrated ammonium hydroxide. The most effective way to render the alumina particles and grain boundaries visible was to radiate the surface with intense white light to decorate the grain boundaries and the particle-matrix interfaces photolytically.

Jan 1, 1962

By Leroy Gardner

EVERY reader of this paper is well aware of the fact that the prolonged inhalation of large amounts of free silica dust results in fibrosis of the lungs, and that other inorganic dusts, except those of asbestos and the mineral poisons, are thought to be relatively harmless. But probably few have had opportunity to visualize the effects of silica, asbestos and other minerals upon living tissues. The ideal demonstration would be based upon sections of lungs from human beings that had inhaled com-parable concentrations of different dusts for a unit period of time. Such material is generally difficult to obtain and in some instances is of ques-tionable value because the subject has been exposed to more than one kind of dust. A demonstration could be prepared from the lungs of animals. However, so many months or even years are required to com-plete the exposure to each kind of dust that enough material has not been accumulated. For a general survey of the action of different types of dust, I am therefore compelled to use the tissues of animals that have been injected with suspensions of dust particles. The injection method offers certain advantages. The quantity, the particle size and the state of dispersion can be controlled with sufficient accuracy so that the tissue responses to different minerals can be accu-rately compared. The method insures contact between the tissues and the mineral particles; protective mechanisms, which may prevent the inhalation of certain types of foreign body, never come into play. If the pathway of injection be one that minimizes nonspecific injury, the tissue responses may simulate those produced by inhalation but they develop somewhat more rapidly. It should always be remembered that injection methods merely demonstrate the capacity of various kinds of minerals to provoke reaction in the tissues; whether the same substances are inhaled from atmospheric suspension and accumulate in the lungs in dangerous quantities can be demonstrated only by inhalation.

Jan 1, 1938