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By David T. Peterson

Calcium metal was found to deoxidize thorizcm at 1000° to 1200° C. The reaction kinetics were determilled and related to the diffusion coefficients of oxygen in thorium. The solubility of oxygen in thorium, the minimum oxygen concentration, and the diffusion coefficient were determined from 1000° to 1200°C. This firocess results in the lowest oxygen concentrations zohich have been reported for thorium metal. FOR many years it has been known that calcium metal will reduce thorium oxide to thorium metal. This reaction has been the basis for several methods of preparing thorium metal. From the equations giv-by Kubaschewski and vans, ' AF" for the reaction Cao, + Tho,(,) - CaO(,, + Th(,) was calculated and found to be -3.4 kcal at 1000°C, -2.5 kcal at llOO°C, and -2.0 kcal at 1200°c. Thorium is very slightly soluble in liquid calcium, and the solubility of calcium in solid thorium is very low. Consequently these metals would be in essentially their reference states. If thorium containing oxygen were equilibrated with liquid calcium between 1000° and 1200°C, the oxygen content of the thorium would have to be below the solubility limit in thorium. Oxygen is one of the impurities most difficult to remove from thorium and is the most abundant impurity in metal prepared by almost all known methods. Fortunately, oxygen does not have a large influence on the properties of thorium because the solubility in solid thorium is very low. EvenT in thorium containing 100 ppm of 0, particles of thorium oxide can be observed in the microstructure. In view of the incompatibility of thorium oxide and liquid calcium and the low solubility of thorium oxide in thorium, the deoxidation of thorium by this method was investigated. For thorium containing an amount of oxygen well in excess of the solubility limit, the reaction should proceed in the following sequence. The oxygen content of the thorium matrix near the surface would be depleted by the diffusion of oxygen to the surface. At the surface, the oxygen would react with calcium to form calcium oxide. To maintain equilibrium within the thorium, thorium oxide would dissolve to keep the matrix saturated. Consequently, the thorium-oxide particles would disappear first at the surface and then the particle-free rim would grow in thickness. If the rate-controlling step were the diffusion of oxygen through this layer of thorium which was growing in thickness in direct proportion to the amount of oxygen removed, the well known parabolic time law should be observed. If the oxygen concentration at the surface of the thorium and at the inner surface of the deoxidized rim were known, the diffusion coefficient of oxygen in thorium could be calculated from the parabolic rate constant. EXPERIMENTAL PROCEDURE The thorium metal used in this study was prepared by calcium reduction of ThF, by the method described by Wilhelm.' The analysis of this metal is given in Table I. The carbon was determined by combustion, the oxygen by the HC1-insoluble residue method, nitrogen by the Kjeldahl method, and the other elements by emission spectroscopy. A section of this ingot was hot rolled at 600°C to 1/4 and 1/8-in. thick plates. Specimens approximately 7/8 in. square were cut from these plates, and all surfaces of the specimens were cleaned and smoothed by filing with a clean file. Individual specimens were placed in 1-in. diam by 2-in.-long tantalum capsules. Approximately 1 g of clean, high-purity calcium was placed in the capsules and an end closure arc-welded in place. The tantalum capsules were sealed in Inconel crucibles to protect the reactive metals from oxidation. The entire loading procedure was done in a glove box filled with pure argon. The loaded crucibles were placed in a muffle furnace, controlled within 2OC of the desired temperature, for a measured length of time. After the specimen had cooled to room temperature, it was sectioned perpendicular to the large faces and through the mid-point of two of the sides. The sectioned specimen was mounted and polished through Linde A abrasive. The rim which was free of thorium-oxide particles could be clearly observed microscopically as mechanically polished. Twenty measurements of the thickness of the rim were made at equally spaced points far enough from the end of the

Jan 1, 1962

By Leo Brewer, Gerd M. Rosenblatt

Thermodynamic calculations predict the species vaporizing from metal-oxide mixtures when reliable free energy functions, enthalpies of formation, and dissociation energies are available for the possible gaseous and condensed oxide components. Calculations of the oxygen to metal ratio in the vapor phase compared with the oxygen to metal ratio in a liquid metal saturated with oxide impurity are presented The possibility of purifying metals contaminated with oxide by vacuum melting or by distillation is discussed. Kinetic considerations affecting rates are neglected. IN recent years extensive information has been obtained on the thermodynamic stability of gaseous oxides of metals due to a variety of new types of measurement. Perhaps the greatest amount of information has come from the application of mass spec-trometry to the study of high-temperature vapors.' In many instances oxides of quite unusual oxidation states are found to be important in the high-temperature vapors. At low temperatures the standard free energy change for a reaction as given by the equation ?F° = ?H° - T?S° is determined primarily by the AH" value. However, at higher temperatures where the value of T in the T?S° term is large, the entropy term becomes equal to or greater than the AH term. At low temperatures only reactions for which AH is negative or only slightly endothermic are of importance. This restricts the main equilibrium species largely to those with completed octets or those with the principle oxidation number of the element. At

Jan 1, 1962

By Harold M. Feder, Irving Johnson

Tkermodynamic functions for dilute solutions of uranium in liquid cadmium were obtained from galvanic cell measurements. Deviations from Henvy's law were observed at concentvations down to 2 x 10-3 atom fraction. Unusually large negative values of the pavtial molal relative enthalpy and excess entvopy of uranium, suggestive of the occu,vvenctwe of partial ovdering of cadmium around uranium in these solutions, were found. The negative relative partial molal enthalpy of uranium at the liquidus accounts for the observed retrogvade solubility of metallic uranium between 473" and about 630°C. The standard free enevgy of formation of UCd,, from a-uranium and liquid cadmium is given by F,° THE constitutional diagram of the U-Cd system,' Fig. 1, is unusual in several respects. The near equality of the Goldschmidt atomic radii2 (Cd, 1.52A U, 1.56A) might be expected to give rise to extensive mutual solubility of the elements except for the restrictions imposed by differences in valence and electronegativity.3 The latter factors must be strongly influential because mutual solubilities in the terminal solid phases are probably negligible, and the solubility of uranium in liquid cadmium in the readily accessible range is only about 1 at. pct. Interestingly, the solubility of uranium in liquid cadmium actually decveases slightly with increasing temperature from 473" to about 630°C. Such a retrograde solubility in a liquid phase is a rare phenomenon in metallic systems; no other authenticated examples were found among the nearly 700 binary phase diagrams compiled by Hansen and Anderko.2 These observations suggested the existence of some unusual interaction between uranium and cadmium. Greater insight into the nature of this interaction was sought by measurement of the thermodynamic properties of the system. EXPERIMENTAL PROCEDURE The emf of cells denoted by the scheme was measured. Each cell consisted of two uranium and two alloy electrodes immersed in a molten lithium chloride-potassium chloride eutectic mixture containing uranium trichloride. The physical arrangement is shown in Fig. 2. The potential between any pair of electrodes could be measured with a Leeds and Northrup Type K-3 potentiometer. The measurements were made at points marked in Fig. 1. It should be noted that points on the phase boundaries represent the concentrations of uranium in the saturated liquid phases of heterogeneous alloys. Uranium Electrodes. Uranium, which is not a particularly soft metal, is capable of retaining residual stresses, and its potential may depend upon its physical condition. Electrodes were prepared from 3-mm diam rods of hot-rolled high-purity4

Jan 1, 1962

By D. F. Stoneburner

The thermoelectric power and electrical conductivity of a series of liquid alloys of thallium were determined in order to study the relation of chemical bonding to semiconduction in liquids. The results indicate metallic behavior for the alloys of thallium with arsenic, antimony, and bismuth, while the sulfides, selenides, and tellurides indicate semiconduction. The results are compared with the Properties of the same alloys in the solid state. This work supports the observation that long-range order is not a necessary requirement for semiconduction. PREVIOUS work1,5 has shown that some sulfides and oxides behave as semiconductors in the liquid state. Although the band theory has been of great help in understanding the properties of solid semiconductors, its quantitative application to liquids is difficult. The very existence of liquid electronic semiconductors shows that ascribing the discrete structure of the energy spectrum to strict lattice periodicity, or long-range order, is not always satisfactory. Rather, the short-range order determines the structure of energy levels and the width of the forbidden gap and, consequently, the concentration of free holes and electrons. This is borne out by the analysis of data accumulated by Regel and coworkers.6 The similarity of electronic structure of liquid and solid phases of certain liquid metals was pointed out by Knight et a1.,7 who examined nuclear resonance in solid and liquid Li, Na, Rb, Cs, Mg, Al, Ga, Sn, and Bi. They found noticeable changes in the electronic structure upon melting only in the cases of bismuth and gallium. They concluded that "a liquid metal possesses a band structure which is very like that of the solid, provided the short-range structure is not altered during melting." In semiconductors in which the near-neighbor arrangement remains the same on fusion, the material would be expected to retain its semiconducting properties. The quantum theory of semiconductors, with its band structure of energy levels, is linked exclusively to long-range order. Furthermore, it has limited usefulness in predicting new semiconductors. Many sulfide8-12 have made comparisons of properties on the basis of crystal structure or the position in the periodic table, both methods involving the same factors as chemical bonding. Mooser and Pearson8"10 have pointed out that crystal structure depends on chemical bonding, and that this bonding is a property of the atoms themselves. As the periodic arrangement of the atoms offers an easy comparison of such factors as atomic weight and number of valence electrons it provides clues to expected similarities of bonding for various elements or groups of elements. This approach has led Mooser and Pearson to formulate their valence-bond theory of semiconduction, in which they define a semiconducting bond. These authors state that "semiconductivity is the result of the presence in a solid of predominantly covalent bonds. These lead, through the process of electron sharing, to completely filled s and p orbi-tals in the valence shells of all atoms of elemental semiconductors while in semiconducting compounds only one atom of any two bonded together need acquire closed s and p orbitals. The presence of empty 'metallic' orbitals in some atoms of a compound does not destroy the semiconductivity provided that these atoms are not bonded together; it may, however, give rise to pivoting resonance in

Jan 1, 1965

By E. M. Elkin, J. H. Schloen

All known methods of treating and recovering the various components of copper refinery slimes are discussed. The slimes treatment processes presently used by five copper refineries are described and flowsheets are given. A bibliography is appended. THE recent increase in anode copper production at the Noranda smelter placed an additional load on the Montreal East plant of Canadian Copper Refiners Limited. The consequent increase in the amount of anode slimes led to a careful consideration of the various methods of slimes treatment. A critical review of these methods is presented here in the belief that it would be of interest to copper refiners. No such review has yet been published, although a number of individual flowsheets have been described. To make the information of greater value, a questionnaire was sent to all copper refineries. While the overall response to the questionnaire was not entirely satisfactory, the foreign refiners gave much detail in their answers and expressed willingness to cooperate further if needed. Although the data below do not cover all refineries, it is thought that examples of all flowsheets currently in use are included. A comparison of these flowsheets should prove of interest. The paper is divided into two parts. One part deals with a discussion of all known methods of treating and recovering the various components of the slimes. The second describes the processes now in use at various copper refineries for the treatment of raw slimes up to the production of Doré bullion. A brief description of the two main electrolytic methods of parting Doré bullion is appended. Since the first commercial application of electrolytic refining of copper by J. B. Elkington in 1865, the treatment of anode mud or slimes has undergone many changes. The object of treating slimes has always been the recovery and separation of precious metals. With the passage of time, increasing attention has been paid to improvement in recovery and quality of byproducts, mainly selenium and tellurium. The original methods of treatment were crude, although relatively direct. For example," the slimes were fused on a dolomitic clay bed in a reverbera-tory furnace; the slag was removed and the resulting metal cupelled to silver and gold. In another process, the dried slimes were oxidized and scorified on the lead bath of a cupelling furnace. Later, these pyrometallurgical methods were modified by sulphuric acid leaching, followed by fusion with niter in a reverb eratory furnace. A preliminary oxidizing roast improved the leaching step. Straight hydro-metallurgy has not found practical application. No matter what method is employed, the result is Dorb metal—a silver-gold alloy, with or without the metals of the platinum group. Characteristics of the Slimes Anode slimes are made up of those components of the anodes which are not soluble in the electrolyte. They contain varying quantities of copper, silver, gold, sulphur, selenium, tellurium, lead, arsenic, antimony, nickel, iron, silica, etc. The color of raw slimes is grayish black and the particle size is —200 mesh. However, Baraboshkin and Gaev (Ref. 1, p. 37), describe light gray colored slimes from the electrolysis of secondary copper which are composed predominantly of sulphates and of basic salts. In anode furnace practice primary and secondary metals are not usually segregated and such slimes do not commonly occur. Copper in the slimes originates to a large extent in the cuprous oxide of the anodes and is therefore dependent on the oxygen content of the latter: Cu2O + H2SO4 + CuSO4 + H2O + Cu [I] Opinions have been expressed that some of the copper is formed by decomposition of cuprous to cupric sulphate Cu2SO4 ? CuSO4 + Cu PI The product of either reaction is very finely divided. Depending on the slimes composition, much of the copper is combined with sulphur, selenium, tellurium, etc. The balance of the copper is in the free metallic state.

Jan 1, 1951

By D. B. Smith, John Chipman

THIS investigation was undertaken as a prerequisite to the study of sulphur activities in the liquid system Fe-Cu-Ni, a continuation of the work of Sherman, Elvander, and Chipman,¹ using the same equipment and the same experimental technique. Temperature measurements are made with a disappearing filament optical pyrometer, sighting through a prism onto the surface of the melt which is heated by induction. To obtain true temperatures by this means, a calibration is necessary, since, in the absence of true black-body conditions, the observed temperature is always lower than the true temperature. This calibration is actually an emissivity correction, since the emissivity is a function of both temperature and melt composition. The original furnace was used with a deeper metal bath to provide sufficient depth of immersion for the thermocouple which was inserted through the sampling hole. The atmosphere was a 50-50 mixture or argon and hydrogen passing through the furnace at a rate of 1000 ml per min, and preheated by means of a molybdenum resistance coil. It was assumed that the rapid gas flow effectively eliminated any error which might have resulted from the presence of metallic vapor. The charge in each case consisted of about 300 g of metal, contained in a high purity, dense alumina crucible. At each melt composition, readings of the optical pyrometer and of a thermocouple immersed in the molten metal were taken simultaneously. Calibration curves of optical vs. true temperature were then made for each melt composition investigated. Thermocouples were made of 0.010 in. platinum and platinum-10 pct rhodium. They were checked against the melting point of chemically pure copper. Silica protection tubes with an outer diameter of approximately 1/8 in. were used. The depth of immersion of the tip in the molten metal was approximately 1 14 in. The life of these small thermocouples was relatively short, varying from approximately 1 min at 1550°C to 10 min or longer at 1300°C. Melts containing iron corroded the protection tubes more than those without iron present. Measurements taken while heating checked those taken while cooling, indicating the absence of a temperature gradient between the molten metal and the thermocouple. Results The temperature range of the. measurements on copper-free metals extended from the melting point to 1600°C. For copper the upper limit was 1380°C, and the data were extrapolated linearly for comparison with observations on the other metals and alloys at 1535°C. Examples of typical calibration curves for various melt compositions are shown in Fig. 1. These curves, besides providing a calibration system for the given experimental conditions, also give a basis for the calculation of true emissivities at the effective wavelength of the pyrometer, 0.65 micron. The starting point of the calculations is the value of the emissivity of iron at its melting point. Taking the melting point of electrolytic iron under hydrogen as 1535°C, and using the corresponding emissivity value of 0.43, as determined by Dastur and Gokcen,² the emissivities can be determined as functions of composition (and temperature, if desired). The relationship used is the Wien equation: ln(Ea)=C2/?(1/T1-1/Ta where E is the emissivity; a, the transmissivity of the optical system; C,, the fundamental constant, 14,380 micron-degrees; A, the wave length of light used (0.65 micron); Tt, the true temperature, OK; and T., the apparent temperature, OK. At the melting point of iron the observed temperature was 1358"; this gives 0.62 for the transmissivity, which compares with 0.65 in the similar system used by Dastur and Gokcen. The emissivities of all the compositions investigated were determined at 1535°C, after obtaining from each calibration curve the corresponding temperature. These results

Jan 1, 1953

By F. Habashi

"A short account will be presented on the extraction of rare earths from monazite sand, bastnasite ore, and phosphate rock of igneous origin. This includes mineral beneficiation, leaching methods, fractional crystallization [of historical interest], ion exchange, solvent extraction, precipitation from solution, and reduction to metals. INTRODUCTIONOriginally, the term rare earths was only used for the oxides, R2O3, which are similar to one other in their chemical and physical properties and are therefore difficult to separate. Within the rare earth group, the elements scandium, yttrium, and lanthanum differ in their atomic structure from the elements cerium to lutetium (the lanthanides, Ln). Scandium occupies a special position with respect to this classification and its other properties, and therefore does not belong to either of these groups. The rare earth elements always occur in nature in association with each other. The isolation of groups of rare earth elements or of individual elements requires costly separation and fractionation processes owing to the great similarity of the chemical and physical properties of their compounds, which explains why the history of their discovery has extended over such a long period.The word “rare”, when used to describe this group of elements, originates from the fact it was thought that these elements could only be isolated from very rare minerals. Considering their abundance in the Earth’s crust, the term rare is now inappropriate. These elements are lithophilic and are therefore concentrated in oxidic compounds such as carbonates, silicates, titano-tantalo-niobates, and phosphates.The abundance of the rare earth elements taken together is quite considerable. Cerium, the most common rare earth, is more abundant than cobalt. Yttrium is more abundant than lead, whereas Lu and Tm are as abundant as Sb, Hg, Bi, and Ag. For all practical purposes promethium does not occur in nature. It forms only in nuclear reactors."

Jan 1, 2012

By C. D. Anderson

A variety of processing technologies exist for recovery from both primary and secondary sources of rhenium. Currently, there are no known primary rhenium deposits; thus, the method in which primary rhenium is produced is dependent on the commodity of which it is a byproduct, e.g., copper, molybdenum, uranium, etc. In addition, focus on the recovery of rhenium from secondary sources, such as alloy scraps and catalysts, is continually growing. This paper presents a review of both primary and secondary processing technologies for the recovery of rhenium.

By D. R. Spink

An historical background is presented to provide a basis for the lack of normally expected developmental effort over the first 20-25 years of viable zirconium production operations. This is followed by a description of developing technology, which is the result of years of research and piloting effort directed to the development of a more economical method to produce high-grade metallic zirconium. It is predicted that many of the process improvements described will have a significant impact on future zirconium production methods and consequently on future prices and markets.

Jan 1, 1977

By R. E. Allen, A. C. Jephson

ELECTROLYTIC zinc plants of the American Smelting and Refining Co. are located adjacent to the present city limits of Corpus Christi, Texas. The original plant commenced operations during 1942, and is designed for the production of special high grade zinc from zinc sulfide concentrates.' Subsequent changes include the erection of an additional acid plant during 1950, and additions for increased generating and production capacity during 1951. New Electrolytic Plant—The new electrolytic plant is a separate unit erected for the treatment of densified fume produced at Asarco plants located in El Paso, Texas and Chihuahua, Mexico. Construction was completed and operation commenced during June, 1953. Decision for the erection of a separate plant for the treatment of densified fume is based on several factors. One of the principal reasons is the assurance of continued production rate of the original plant, which might have been jeopardized by combined treatment of calcine and fume. Of equal importance is the advantage of locating a plant on a site with adequate space for eventual expansion. General Description—The new plant for the treatment of densified fume consists of four main buildings for the following operations: storage and grinding of fume, leaching and purification, electrolyzing and casting, and rectifier units. Auxiliary buildings include a baghouse, reagent storage, and a lunch room. Leaching of ground fume with electrolyte from the cells is a batch type operation in tanks equipped with mechanical agitators and weightometers. Completed leaches are pressure filtered, the resultant residue being recovered for shipment to El Paso by conventional use of thickeners, drum type vacuum filters, and a direct-fired dryer. Filtrates from the filter section are purified in mechanically agitated tanks, filtered after completion through plate and frame presses, and then pumped to an evaporative type cooling tower. Solution discharged from the basin of the cooling tower is collected in storage tanks for use in the cells. The cool purified solutions are pumped as required from storage to the solution circuit for circulation of electrolyte through the cells. Except for the addition of purified feed solution and withdrawal of electrolyte for leaching, the circulating system for the cells is essentially a closed continuous circuit that includes the use of evaporative cooling towers for control of solution temperatures. Aluminum cathodes and Ag-Pb anodes are used for electrolysis, which is maintained at a current density of about 82 amp per sq ft. Cathode zinc produced is melted in a gas-fired reverberatory furnace and then cast into slabs on a straight line casting machine. Unloading and Storage—Fume produced by the Chihuahua plant is shipped in box cars, and fume by the El Paso plant in hopper bottom dump cars. Shipments as received are weighed on a 7 5-ton capacity railroad scale, sampled, and then moved over one of the two unloading hoppers with a car puller. The cars are then unloaded with mechanized equipment, a car scoop being used for unloading of box cars and a car shaker for the hopper bottom cars

Jan 1, 1958

By J. F. Mitchell, R. Bainbridge, E. A. Melvin

IN the fall of 1953, The Consolidated Mining and Smelting Co. of Canada Ltd. put into operation a completely new and modern plant for sintering the rather complex assortment of materials which comprise the feed to the Lead Smelter at Trail, British Columbia. This Lead Smelter is one section of an integrated metallurgical plant producing lead, zinc, silver, gold, cadmium and other metals. Since most of the incoming lead concentrate contains appreci- able zinc values, and most of the zinc concentrate similarly contains appreciable lead values, the cross-routing of residues or tails from the respective lead and zinc plants offers obvious advantages in recovery of metals, and has been practiced for many years. A disparity has existed, however, between the output of zinc plant residue and the capacity of the Lead Smelter to treat it, with the result that over the years a stock-pile of residue had been accumulating, and by the end of World War II had reached the formidable total of half a million tons. To treat this stock-pile, in addition to all current zinc plant residues and, of course, the regular quota of lead concentrates, became a prime objective of the Lead Smelter following World War 11. As zinc plant residue plays an important part in the operations to be discussed in this paper, some consideration of its

Jan 1, 1958

By B. C. Raynes

IN the early part of 1952, under the auspices of the U. S. Atomic Energy Commission, Horizons Inc. undertook an investigation dealing with the preparation of high purity thorium metal in order to develop an economically competitive production process for this metal based on a recovery of the metal by a fused salt electrolysis, since a survey of the literature of thorium chemistry indicated that electrolytic methods had not received much attention, despite the consideration that electrochemical production methods often offer attractive commercial potentialities. Thorium metal has been prepared by methods which fall into four general categories: 1) reduction of halides or double halides; 2) reduction of the oxide; 3) thermal decomposition of halides; and 4) electrolytic methods. Some of the important results obtained by various investigators since about 1900 in recorded attempts to prepare pure thorium metal are summarized in Table I. A bibliography of pertinent literature is included in this paper. Thorium is strongly electropositive and possesses a great affinity for oxygen and nitrogen. As a result the prospects for the production of high purity thorium from aqueous media or oxygen bearing compounds are remote. The most promising and profitable area of investigation for production of thorium metal lies in fused salt electrolysis. Thorium has been produced previously by this technique from halide salts in fused alkali chloride eutectic mixtures. Until recently, however, the lack of known large uses for thorium has inhibited the investigation of these methods. The basic problem in an investigation into fused salt production methods for thorium is to develop a suitable fused salt system for the economic preparation of thorium. The first portion of the work in these laboratories was a small scale investigation of the electrolysis of potassium thorium fluoride, KThF5, under a variety of conditions. High purity thorium was prepared in this manner, but the process did not appear to offer the simplest and most attractive continuous commercial operation. The work reported here relates to an all-chloride system employing thorium chloride as the cell feed. ThCL4 was produced as an anhydrous material stabilized in molten sodium chloride. This product, further diluted in NaCl, was subjected to electrolysis. The electrolytic process has been studied in cells capable of holding up to 50 lb total salt charge. Ductile, pure thorium metal has been reproducibly obtained in this operation. Considerable experimentation was carried out in the preparation of ThCL as a cell feed free from moisture, oxides, and other impurities. Thorium was cathodically deposited as a coarsely crystalline powder interspersed with residual bath salts. Aqueous procedures for separating and recovering the metal were developed. The thorium metal powder obtained has been evaluated with respect to its hardness, chemical purity, and certain other physical properties. Preparation of ThC1,—Thorium chloride, and the chlorides of some other metals (aluminum, beryllium, tantalum, zirconium, etc.) cannot be obtained from aqueous solution by direct heating and evaporation. Evaporation and heating of a solution of thorium chloride yields a hydrated salt or partially hydrated salt, and finally Tho,. Anhydrous thorium chloride is obtained by forming a hydrated ammonium chloride complex salt in acidified water solution, dehydrating this compound, and finally decomposing the double salt and subliming the ammonium chloride component. Various methods for the preparation of anhydrous thorium chloride, in accordance with this concept, were investigated as indicated in Table I1 from hydrated thorium chloride (ThCl, . 3H2O), and from thorium oxycarbonate (ThOCO,). In the method found most satisfactory for this work, thorium oxycarbonate was dissolved in an excess of concentrated HC1 to give a clear yellow solution. At least 2 mol NH,Cl were added to the solution per mol of contained thorium. Ammonium thorium chloride hydrate was crystallized from solution by cooling and saturation with HC1. The resultant complex, (NH,Cl),ThCl;xH,O, was dehydrated by evaporation at 130° to 150°C and thoroughly dried at about 250°C. The dried ammanium thorium chloride was then mixed with sodium chloride in proportions to form NaThCL or to produce a ThCL4-NaCl mixture with a given thorium content. The ammonium chloride was sublimed off at temperatures above 500°C in an inert atmosphere furnace to give an anhydrous chloride source electrolyte, essentially free of Tho, and of NKC1.

Jan 1, 1958

By L. M. Pidgeon, P. G. Thornhill

A LTHOUGH a considerable number of experi--ti mental investigations dealing with the roasting of sulfide minerals have been reported in the past,'"" the behavior of the single roasting particle does not appear to have received the attention it perhaps deserves. This is understandable in that the natural sulfide counterpart of the slab or sheet of metal normally used in high temperature oxidation studies is difficult to obtain and prepare, and is, in most cases, virtually impossible to maintain in one piece at roasting temperatures. The employment, on the other hand, of static aggregations of small particles in masses great enough to permit evaluation of the roasting reactions by means of thermobalances or gas analyses introduces other complications, such as localized overheating, sintering, and variable gas-solid contact. In this investigation a compromise between the above extremes was attempted. Closely sized (e.g., 30 to 40 mesh) particles of natural sulfide minerals were isothermally roasted, out of contact with one another, in an air-swept system. The progress of the roasting reactions was followed by examination in polished section of the treated particles and by X-ray and chemical analysis of their residual sulfide kernels. In this way some conclusions respecting the mechanism of roasting reactions were drawn. Roasting Furnace—The vertical tube furnace used for roasting the sulfide particles had a heated zone 10 1/2 in. long in which four retractable light gage stainless steel trays were suspended. Each tray, and an accompanying baffle, was mounted on a 2 in. lengtn of 3/8 in. stainless steel tubing. These assemblies were axially suspended on a 30 in. length of ¼ in. stainless tubing, by means of which they could be lifted from the hot zone to a water-cooled brass chamber at the top of the furnace. Since each tray unit could slide freely on the 30 in. tube, any desired number of the trays could be retained in the cooling chamber by the manipulation of a horizontal plunger during a momentary withdrawal of the four trays from the hot zone. Although three heating coils, each equipped with variable external resistance, were employed, it was found impossible to avoid a drop of 10o to 15oC between the temperature at the top tray and that of the lower three. Consequently, only the bottom three trays were used for roasting. Temperature readings inside the furnace were made by means of a thermocouple inserted down the tray support tube at tray levels, and a separate thermocouple, inserted adjacent to the middle heating coil, was connected to a Micromax temperature control unit. Experimental Method—The sulfide minerals were obtained in a form as free as possible from gangue and contaminating sulfides, and were crushed and screened to the required particle size range. The tray assembly was kept inside the furnace during the heating-up period and, when a steady temperature had been reached, the trays were withdrawn. Each tray was sprinkled with from 200 to 500 mg of the sulfide grains, and the assembly was lowered into the furnace without delay in order to minimize the time required to achieve the operating temperature. The furnace top was then clamped into position and the thermocouple inserted down the center tube to the required level. It was found that, when this procedure was used, the trays achieved their former temperature within 2 min, after which time the flow of dry air was begun at a rate of 1 liter per min, and timing of the run was started. At the required intervals of time the trays were successively withdrawn from the hot zone and stored in the cooling chamber by means of the retention plunger. On completion of the run the treated particles were removed from the trays to be set aside for examination. The roasted particles were mounted in Lucite on a Buehler press Operating at a temperature of 140°C

Jan 1, 1958

By V. F. Leferrer

A new process for the treatment of silver crusts from desilverization of lead has been developed by Societe de Penarroya. The zinc contained in the crusts is recuperated by vacuum distillation at low temperature. The use of special retort crucibles is avoided. AT Noyelles-Godault the Parkes process (zinc addition to a silver-bearing lead melt) is used to desilverize lead bullion from the blast furnace. The crust which rises to the surface of the bath is removed and pressed by a well-known process in a press of the Howard type. The pressed crust, called zinc crust or silver crust, contains 10 pct Ag, 30 pct Zn, and 60 pct Pb. It is melted under a salt bed in a small, narrow, and deep kettle heated only in its upper part. A liquid concentrated alloy is obtained which is called T.A.C. in France (triple alliage concentr6) analyzing approximately 25 pct Ag, 65 pct Zn, 8 to 10 pct Pb, and 1 to 1.5 pct Cu. This T.A.C. is a real metallic alloy, completely deoxidized, and can be stored indefinitely. The process used at Noyelles-Godault consists in distilling this alloy in a tight furnace, under low vacuum and at low temperature, so that only the zinc distills and is condensed into liquid form. The residual silver-bearing lead is almost entirely free from zinc and oxidized dross. The vacuum dezincing equipment, see Figs. 1 and 2, consists of: 1) A furnace, constituted of a casing of steel plate lined with refractory bricks, heated internally by means of graphite resistors. The temperature of the furnace is measured by a thermocouple device and controlled by an automatic temperature regulator which acts upon the flow of the current passing through the resistors. Two doors, numbered 1 and 2 in Fig. 2, are provided for, one for charging the T.A.C., the other for tapping the high silver-bearing lead. 2) A condenser, and an ordinary room lined with good heat conductor refractory material. This condenser is provided with a graphite resistor which serves to bring to temperature when starting the furnace. A thermocouple records the temperature of the zinc melt and controls the temperature in the furnace, that is, the flow of current through the resistors, by means of the above mentioned regulator, so that the distillation rate in the furnace does not exceed that of the condensation. The condenser is connected to the vacuum pump by a filter. The whole equipment should, of course, be fluid-tight. The operation is carried out under a vacuum of about 10 mm Hg.

Jan 1, 1958

By V. I. Kefeli

Public-private partnership efforts are working to create green landscapes from abandoned industrial sites. Fabricated soils, potentially an essential element of such landscapes, are designed to substitute for topsoil on the areas free from ground cover and plant community. The aluminosilicate matrix and humus form the soil micelle - the primary unit of any soil complex. Humus formation is a process based on carbon-nitrogen interaction. Sources of carbon can be materials rich in easily composted products like cellulose and polyphenols (plant leaves) or aged lignin polymers (saw dust from different woody plants). The pathways of carbon-nitrogen complexes are discussed. Properties of the fabricated soil components were examined by bio-tests and plant models.

Jan 1, 2002

By Kazuya Kitatani, Gen Sasaki, Naoto Ohta, Hideharu Fukunaga, Makoto Yoshida, Jin Pan, Kenya Nagahisa, Toshihiro Ishikawa

"A sintered SiC (Tyranno-SA) fiber-reinforced MAS glass matrix composite was fabricated by using a slurry infiltration method and hot-pressing. The microstructure and mechanical properties were investigated: To prepare the preform, the MAS glass slurry including a dispersing agent was infiltrated into a bundle of the fibers. The preform was then hot-pressed under the conditions of 1473 K, 30 MPa, 3.6 ksec. A unidirectionally-reinforced oxide matrix composite with 50% Vf. of the fiber and a density of 2.84 g/cm3 was obtained. As the mechanical properties at room temperature, the three-point flexural strength- and quasi-static adsorbed energy were 500 MPa arid 6,000 J/m2, respectively. Without graphite or an h-BN pre-coating on the surface of the fiber, pull-out and bridging of the fibers from the matrix was found, and this leads to a high value of the adsorbed energy. By TEM observation, nano-scale crystalline products were found between the fibers and the glass matrix. The push-out test reveals that this layer causes the appropriate debonding of the interface during the fracture process of the composite.Introduction It is known that the CFCCs (continuous-fiber-reinforced ceramic matrix composites) are characterized by their non-linear fracture behavior, which is' hardly found in monolithic ceramic materials. It is inevitable for the CFCCs to exhibit a large fracture toughness so 'that debonding of the fiber/matrix interface; pull-out and bridging of the fibers then' occurs during the fracture process. This series of fracture behavior is known as the so-called ""the mechanism of toughening of the CFCCs"". Thus, different from the MMCs in which strong interfacial bonding is necessary, the interfacial strength of the CFCCs has to be controlled. As techniques for controlling the interfacial strength, it is also known that both a CVD-graphite coating and an h-BN coating are effective to induce the mechanism of toughening[1,2]. In the case, of the Si-C-O or Si-Ti-C-O fibers/glass or crystalline oxide matrix composites, it is reported that the formation of the in-situ graphite layer, which is also effective to increase the fracture toughness of the CFCCs, is often found during the fabrication process such as hot-pressing. The lower the crystallinity of the Si-C-O fibers, the higher is the tendency to form the in-situ graphite layer as found by the chemical reaction between the fibers and the glass matrices[3-12]. On the-other hand crystallized stoichiometric 'SiC fibers are attractive for high temperature service because of the higher phase stability compared to the Si¬C-O or Si-Ti-C-O fibers. However, in the previous, studies, the mechanical properties and the interfacial chemical reaction of the crystallized SiC fibers / glass matrix Composites have still been unknown. In this study, a polycrystalline 'sintered SiC fiber-reinforced MAS glass composite was fabricated. The mechanical properties and microstructure were then investigated. The slurry infiltration technique followed by hot-pressing was used to prepare the composites. The formation of the in-situ graphite layer and the relationship between microstructure and mechanical properties at room temperature were examined by the TEM observation of the fiber/matrix interface."

Jan 1, 2000

By G. L. Craig

COPPER containing a small amount of arsenic has been used extensively abroad, and a number of reports, particularly those by English workers, have indicated that such copper is better suited for certain uses than high-conductivity copper. Inasmuch as a large percentage of the copper fabricated is used for nonelectrical purposes where high conductivity is not at all essential, it has been suggested that arsenical copper might be at least as suitable as high-conductivity copper for many purposes. An investigation spon-sored by the Calumet & Hecla Consolidated Copper Co. at Battelle Memorial Institute was therefore undertaken with the object of determin-ing the effect of small amounts of arsenic (up to 0.75 per cent) on the properties of copper. In this work the effect of arsenic on the basic properties of tough-pitch and of phosphorized copper have been critically studied and many data collected from laboratory experiments which have been supplemented by mill-scale tests. The results of these tests, with coppers of the type referred to, in the annealed condition and after various degrees of reduction, show that the basic properties of copper are not greatly affected by small amounts of arsenic, an increase in strength being observed with increasing arsenic with no corresponding decrease in ductility. It is well known that the evaluation of material for plastic deforma-tion, on the basis of laboratory tests, may not be directly comparable with its performance in commercial operations. In order, therefore, to substantiate the data obtained at the Institute, the cooperation of the Wolverine Tube Co. was obtained for a series of production tests on the fabrication characteristics of phosphorized arsenical copper in the manu-facture of seamless copper tubing. In these tests the behavior of the arsenical coppers was carefully observed in comparison with that of representative types of phosphorized arsenic-free copper, which were fabricated under the same conditions.

Jan 1, 1933

By Yong .. Jun Wu

Laminated ceramics have received widely scientific and commercial attention because their properties, such as mechanical properties and electrical properties, can be tailored by adjusting the structure, thickness and composition of the different layers. For example, ferroelectric Bi4Ti3O12 (BIT) which has a positive temperature coefficient of dielectric constant (,E) can be used to modify the negative tE of typical microwave dielectric ceramic BaNd2Ti4O12(BNT), However, BaNd2Ti4O12/Bi4TiO12/Bi4Ti3O12/BaNd2Ti4O12 (BNT/BIT/BNT) laminated ceramics could not be prepared by the general method because the optimal sintering temperature of BaNd2Ti4O12 ceramic (around 1350°C) was much higher than that of Bi4Ti3O12 ceramic (around 1100°C). In this research, a new method of spark plasma sintering (SPS) combined with post-sintering was successfully proposed to prepare BNT/BIT/BNT laminated ceramics. It was divided into three steps. In first step, the BaNd2Ti4O12 ceramics were prepared by conventional sintering method. In second step, the calcined and pre-pressed Bi4Ti3O12 powders were sandwiched between BaNd2Ti4O12 ceramic pellets and spark plasma sintered at 900°C for 10min to synthesize BNT/BIT/BNT composite ceramics. In the last step, a post-sintering was employed to reoxidize the partially reduced BNT/BIT/BNT composite ceramics. The results of scanning electron microscopy (SEM) and electron probe microanalysis (EPMA) showed that BNT layer and BIT layer were well bonded and no significant interfacial infiltration between them was observed. The sandwiched BNT/BIT/BNT ceramic with 10.7% BIT in volume has a dielectric constant of 92.85, a low dielectric loss of 01068 and a small temperature coefficient of dielectric constant of 35 ppm/°C at MHz.

Jan 1, 2003

Laminated ceramics have received widely scientific and commercial attention because their properties, such as mechanical properties and electrical properties, can be tailored by adjusting the structure, thickness and composition of the different layers. For example, ferroelectric Bi4T13O12 (BIT) which has a positive temperature coefficient of dielectric constant (TE) can be used to modify the negative of typical microwave dielectric ceramic BaNd2Ti4O12(BMT). However, BaNd2Ti4O12/Bi4Ti3O12/BaNd1Ti4O12 (BNT/BIT/BNT) laminated ceramics could not be prepared by the general method because the optimal sintering temperature of BaNd2Ti4O12 ceramic (around 1350°C was much higher than that of Bi4Ti3O12 ceramic (around /1100°C). in this research, a new method of spark plasma sintering (SPS) combined with post-sintering was successfully proposed to prepare BNT/BIT/BNT laminated divided proposed to prepare ceramics. It was divided into three steps. In first step, the BaNd2Ti4O12 ceramics were prepared by conventional sintering method. In second mop, the calcined and pre-pressed Bi4Ti3O12 powders were sandwiched between BaNd2Ti1O12 ceramic pellets and spark plasma sintered at 900'C for 10min to synthesize BNT/BIT/BNT composite ceramics. In the last step, a post-sintering was employed to reoxidize the partially reduced BNT/BIT/BNT composite ceramics. The results of scanning electron microscopy (SEM) and electron probe mircoanalysis (EPMA) showed that BNT layer and BIT layer were well bonded and no significant interfacial infiltration between them was observed. The sandwiched BNT/B1T/BNT ceramic with 10.7% BIT in volume has a dielectric constant of 92.8, a low dielectric loss of 0.0068 and a small temperature coefficient of dielectric constant v/35 ppm/C at 1 MHz.

Jan 1, 2003

By M. Meratian

The in-situ methods have been developed in production of aluminum matrix composites. A commonly adopted in-situ method involves reaction between a metal oxide and aluminum to produce alumina particles or whisker reinforcements. Aluminum-alumina particle composite was fabricated by in-situ method where alumina particles were produced from reduction of copper and silicon oxides by melting and casting aluminum. Aluminum matrix composites reinforced by Copper and Silicon alloying elements and alumina particles have been obtained. The size and shape of alumina particles were studied by scanning electron microscopy (SEM). The size of alumina obtained from mixture of SiO2 and CuO was bigger than the alumina particles obtained from CuO.

Jan 1, 2007