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By J. E. Elliott, K. O. Miller

Solubility studies were carried out to establish the phase distributions for various Fe-Ni-Pb-C alloys at temperatures where the metallic components exist as liquid solutions. Temperature us composition diagrams for the Ni-Pb, Fe-Pb, Fe-Ni-Pb, and Ni-Pb-C systems are derived by employing various approximations in conjunction with the data. Results are summarized for 1550°C in a quaternary phase diagram of the Fe-Ni-Pb-C system. BECAUSE surprisingly little information has been published on the phase diagrams of the Ni-Pb, Fe-Pb, Fe-Pb-Ni, and Fe-Ni-Pb-C systems, a study of these systems was undertaken to ascertain the important phase relationships in the temperature range of 1300" to 1550°C. Measurements were also made on the carbon-saturated systems in the hope that they would assist in the interpretation of the systems without carbon. This paper reports the results obtained from the simple equilibration of the various liquid and solid phases. EXPERIMENTAL PROCEDURE The experimental technique involved holding appropriati quantities of the metals in an alumina crucible, or in a graphite crucible when saturation of the melt with carbon was desired, for sufficient time at the desired temperature to ensure equilibrium. Then a sample of each liquid phase presen was drawn into a small-bore silica tube. This sample was withdrawn quickly from the furnace, cooled, and sent to the chemical laboratory for analysis. The cell assembly used is shown in Fig. 1. Durin the work on the Fe-Pb-Ni system, it was placed in a furnace wound with 20 pct Rh-80 pct Pt wire. This furnace eventually failed and subsequent studies were carried out between 1350" and 1475°C in a tube furnace heated by silicon-carbide resistance elements. A protective atmosphere of argon with approximately 10 pct hydrogen was supplied to the cell assembly at a gage pressure of 1 in. of water. Hydrogen was passed over palladized alumina and then anhydrous calcium chloride for purification. Argon was purified of oxygen and water vapor by passing it over copper gauze at 550°C and then through a calcium chloride drying column. The gases were mixed and redried before they entered the equilibration cell. Temperature was measured by calibrated Pt/Pt-10 pct Rh thermocouples and a Rubicon Type B potentiometer. The thermocouples were standardized against the melting points of pure nickel

Jan 1, 1961

By J. A. Morgan, R. E. Lund, D. E. Warnes

The design, operation, and performance of an integrated pilot plant for recovering zinc and copper from a complex sulfide ore are described. Metallurqical processing comprised selective sulfate roasting in a fluid bed, leaching in a weak sulfuric acid solution, recovering copper by cementation with scrap iron, air oxidation to remove soluble iron, more-or-less conventional Purification for removal of impurities deleterious to zinc electrolysis, recovering zinc by electrolyzing solutions, and recycling spent electrolyte to the sulfating roaster. The effects of several feed preparation and roasting variables on the sulfation response of zinc, copper, and iron are set forth, together with the electrolyzing characteristics of the zinc solutions. SEVERAL years ago, St. Joseph Lead Co. undertook a research program to develop procedures for winning values from a complex ore. The deposit was a massive sulfide ore body containing upwards of 65 pct pyrite. Gangue, composed principally of quartz, calcite, dolomite, and alumina, comprised only 10 to 20 pct of the mineralized zones. Zinc, lead, and copper values were variable, but averaged about 6.7 pct Zn, 2.6 pct Pb, and 0.4 pct Cu. Early in the exploratory test work, it was established that the intimate physical association of the minerals in the ore made beneficiation by conventional flotation procedures difficult. Accordingly, in addition to a comprehensive program to investigate physical methods of ore beneficiation, a research program was established to develop a direct metallurgical method for processing the ore. After surveying a number of potential methods for recovery of both metal and sulfur values, effort was concentrated on the development of a sulfate roasting process. It is the pilot-plant development of the sulfate roasting-solution purification—electrolyzing procedures which forms the subject of the present paper. PREPILOT PLANT INVESTIGATIONS From a thermodynamic viewpoint, it is feasible to sulfate selectively a host of metals, including Zn, Cu, Pb, Cd, Ni, and Co, in an iron sulfide ore without sulfating iron. Of course, a number of conditions such as roasting temperature and gas composition must be controlled. In addition, as first disclosed by Hybinette,' an alkali metal salt is frequently beneficial in promoting the sulfation reactions. The application of fluid bed roasting to the sulfate roasting of nonferrous metals was pioneered by Stephens of Battelle Memorial Institute.' Subsequently, Falconbridge Nickel Mines, Ltd. developed an unique process for selectively sulfating and recovering nickel, copper, and cobalt from their nickeliferous pyrrhotite, which recently has been described in an excellent paper by Thornhill.3 One of the unique features of the Falconbridge process is that the feed is introduced into the fluidized roasting furnace in a manner such that the feed slurry is broken up into droplets and the droplets lose their moisture before contacting the surface of the fluidized bed. The dried droplets do not tend to cake or fuse, but rather remain as discrete agglomerates of concentrate particles and roast without significant degradation. St. Joseph, aware that Battelle Memorial Institute had participated in the development of the Falconbridge process, obtained permission from Falcon-

Jan 1, 1962

By F. A. Schaufelberger

Early work on chemical precipitation of metals from metal salt solutions is reviewed. The chemistry and thermodynamics of precipitating copper, nickel, cobalt, and cadmium metals by reaction with hydrogen are discussed. Mechanisms of metal precipitation, nu-cleation, growth, and agglomeration are reviewed, as well as some solubility phenomena of cleation,gases and solids at elevated temperatures. Experimental data presented deal mainly with the reaction of copper sulfate solution with Hz. METAL can be recovered from a leach solution either indirectly by precipitation as a compound that is later reduced or directly by electrolysis, cementation, or chemical reduction, for example, with hydrogen. The widely used electrowinning processes suffer from the inefficiency of converting fuel to low voltage dc and from low current efficiency when complete recovery is attempted. With the batch hydrogen reduction methods outlined here, a unit of fuel converted to hydrogen in modern gas reform plants will make two to three times as much metal as can be obtained with electrolysis. With continuous hydrogen reduction, four to six times as much metal is obtained. Precipitation by reducing a metal salt solution with H, has been known for almost 100 years.' Commercial use of the process, however, awaited the research and development program initiated by Chemical Construction Corp. Within the last few years this program has brought about construction of commercial plants, listed on p. 701. Ideal hydrogen reduction will precipitate a pure metal from a solution obtained by commercial leaching methods at a rapid rate without excessive temperatures and pressures. The metal precipitate will be of desired size and density, less than a percent left in the vessel being deposited on the wetted parts. The present discussion will outline Chemical Construction Corp.'s early development program and will discuss the chemistry and mechanics of reducing copper, nickel, cobalt, and cadmium from solution by H2. Work on selective reduction of nickel from cobalt has been described earlier.2 The article is not concerned with precipitation of copper by disproportionation of cuprous solutions where yield is limited" to 50 pet.* It does not discuss use of gaseous reducing agents other than hydrogen, such as SCV which may lead to contamination with sulfur, or CO," which is considerably more expensive than hydrogen and produces a gaseous reaction product, CO2.† The article does not include use of other nongaseous reducing agents: which are far more expensive than CO. Also, notes on the history, engineering design, and performance of commercial plants have been given elsewhere." It will be shown that a pure metal can be precipitated by reduction with hydrogen from solutions obtained by commercial leaching methods when the solution cohposition is controlled and proper acidity, proper metal ion concentration through controlled complex formation and hydrolysis, and adequate agitation for suspension of metal and for transfer of reducing gas are maintained. Reasonable temperatures and pressures are used which are less excessive than those used by previous workers, although they are maintained at above equilibrium values because of process kinetics.' It has also been found necessary to induce nuclea-tion and to control growth and agglomeration in order to get a powder product of suitable physical properties. Review of the Literature Muller, Schlecht, and Schubardt of I. G. Farbenm claimed a successive reduction of silver, copper, nickel, cobalt, and zinc from ammoniacal solution by applying progressively higher temperatures and hydrogen pressures. Metals produced by this technique were not pure, since no attempt was made to adjust the solution composition between the different reductions. It is doubtful that the zinc product contained any metallic zinc. The major contribution to the literature" was made by the Ipatiews,12 who prepared platinum, iridium, copper, nickel, cobalt, lead, tin, arsenic. antimony, and bismuth at often extreme conditions, up to the critical temperature of water (373"C), at 1500 to 7500 psi, for as long as several days. Even cadmium and zinc were claimed to have been observed in trace quantities precipitated together with basic salts. In the early experiments solutions were not stirred. Extensive formation of oxides and basic salts occurred. probably long before sufficient hydrogen could be supplied in the unstirred liquid to decrease the metal concentration in solution by reduction. The importance of hydrogen pressure was

Jan 1, 1957

By L. A. Hanson

Jan 1, 1964

By G. W. Toop

Jan 1, 1965

By G. W. P. Rengstorff, H. B. Goodwin

A method is described for purifying iron in batches of 150 Ib or more. Oxygen, carbon, nitrogen, and sulphur are removed from flakes of electrolytic iron by treatment in wet and then dry hydrogen. A special consumable-electrode arc furnace is used to remove hydrogen and to melt the flakes into ingots. A LTHOUGH iron and steel have been made and used for hundreds of years, there are still wide gaps in the knowledge of these metals. One reason for this is that the true properties of the base metal, iron, are not well known, simply because really pure iron has never been readily available for research purposes. Commercial iron, and even the "pure" irons which are readily available, are really complex alloys of iron with oxygen, nitrogen, hydrogen, carbon, sulphur, silicon, and other elements. With such materials, it has not been possible to prepare steels and other iron-base alloys in which all elements are present in exactly controlled amounts. It is an almost impossible task to determine the separate effects of each element or the intereffects of several elements unless alloys can be prepared containing only the desired elements. The ability to make controlled alloys of low impurity content is of far more than academic interest. It will assist in the study of such practical problems as the brittle failure of ship hulls or high pressure gas pipelines, determination of the factors which affect the deep-drawing properties of steels, the improvement of magnetic and electrical properties, the phenomenon of aging, and many others. In 1949, the American Iron and Steel Institute asked Battelle Memorial Institute to prepare high purity iron on a larger scale than had been attempted up to that time. The work was directed toward the preparation of iron as low as possible in carbon, oxygen, nitrogen, hydrogen, and sulphur because these are the contaminating elements of major interest in many research investigations on iron-base alloys. The initial goal was to prepare iron with not more than a few thousandths of one percent of each of these impurities. The purpose was to set up a "bank" of high purity iron on which researchers could draw when a supply was needed and which could be replenished from time to time as the stock became depleted. Of several possible purification methods, heating in hydrogen was selected as the most promising for the removal of both carbon and oxygen from solid iron. Metallic impurities are not removed by hydrogen. Electrolytic iron was chosen as a starting material because it is the most readily available form of iron low in metallic impurities. Decarburization and desulphurization were obtained by annealing in wet hydrogen at relatively low temperatures. The optimum temperature, as found by previous investigators,' is about 1400°F. This treatment also removes nitrogen. Deoxidation is favored by dry hydrogen and higher temperature. There is evidence from previous work that an anneal at 2200°F in dry hydrogen will deoxidize the iron, reduce the nitrogen content, and reduce the sulphur content. These facts suggested the use of a two-stage process: treatment in wet hydrogen followed by treatment in dry hydrogen. To carry out the purification process in a reasonable time, it was necessary that the iron be in thin pieces. Flakes of electrolytic iron were used. Because most research requires that the iron be in massive form, it was nccessary to melt the purified iron to consolidate it into large pieces. For this work, it was decided to prepare ingots weighing at least 15 lb by using a cold hearth arc-melting process in which the iron was melted in an inert atmosphere of argon or helium. This method of melting was selected because the water-cooled copper crucible is not wet by the iron and does not contaminate it as a refractory crucible would. Because the crucible is also the ingot mold, contamination from mold materials was also eliminated. Contamination from electrodes was avoided by making them from purified electrolytic iron. The melting procedure finally developed was an adaptation of the Kellogg electric ingot process.' Two batches of purified iron weighing about 100 Ib each in ingot form were prepared with analyses as shown in Table I. The remainder of this paper describes the procedures in more detail. In general, the process con-

Jan 1, 1956

By A. H. Roberson, L. H. Banning

DURING the past few years, a considerable tonnage of ilmenite has been produced as a byproduct of a monazite dredging operation and stockpiled near Boise, Idaho. This ilmenite has not been marketed because of the long distance from ilmenite-consuming areas and its comparatively low TiO2 content. Production of monazite from the alluvial sand deposits of Idaho is a mar- ginal venture when it is the only marketable product, and it will be necessary to establish a byproduct market before the operation becomes economically stable. Early in 1954, the Bureau of Mines Northwest Electrodevelopment Laboratory at Albany, Ore., conducted a series of tests which demonstrated that arc furnace smelting could be utilized to produce commercial quality pig iron and a high titanium content slag from these ilmenites. Additional studies showed that the slag chlorinated readily to produce a satisfactory yield of TiCl4. The investigation was carried out by two research teams. The Ferrous Metals Branch, with adequate

Jan 1, 1956

By R. Didchenko

THERE are many methods described in the older literature which claim to produce anhydrous rare-earth chlorides in general. and cerium chloiide in

Jan 1, 1960

By R. V. Horrigan

High purity ZrC14 (25 to 200 ppm of metallic impurities) can be readily prepared in simple apparatus by thermal decomposition of alkali chlorozirconate fused salts at 500° to 600°C and at atmospheric pressure. Suggested phase diagrams for the systems NaCI-ZrC14 and KCI-ZrCI, are presented. ALKALI chlorozirconate compositions — anhydrous fused mixtures of ZrCl4, NaC1, and KC1— are manufactured commercially and are used by the magnesium industry to introduce zirconium into magnesium alloys. Zirconium refines the grain size and improves the physical properties of many important magnesium alloys. In the course of working with chlorozirconate compositions of high ZrCl4 content, it was noticed that these salts decomposed progressively itwaswith increasing temperature to yield considerable amounts of a ZrCl4 sublimate of high purity together with a solid chlorozirconate residue. Further research led to: 1—improvements in the

Jan 1, 1956

By Charles L. Mantell, P. P. Napolitano

High-purity tellurium oJ semiconductor grade may be prepared by a combination of electrowinning from tellurium oxide, electrorefining and controlled atmosphere melting, as detailed in the paper. SEMICONDUCTOR devices such as transistors and rectifiers depend upon extremely pure forms of silicon, germanium, and selenium. Although tellurium is chemically related to these elements, it has not been studied as a semiconductor because commercial forms are too impure. Highly purified tellurium would be an interesting starting point for a study of its solid-state characteristics. Tellurium shows a greater electrical conductivity in the direction of the helices or chains forming the crystals than at right angles to the chains, and thus is a semiconductor. Unlike selenium, the conductivity is only slightly increased by exposure to light. Impurities such as Ag, Cu, Au, Fe, Sn, As, Sb, Bi, Br, and I provide accepters and make extrinsic tellurium of the P type. So far, however, no elements have been found which, when introduced, would act as donors. Small amounts of tellurium dioxide enormously increase the thermoelectric power. Many extremely pure metals have been made by electrolytic refining or electrowinning procedures. Tellurium forms compounds in a number of valences, as indicated in Table I. The physical properties given in Table II do not show any unusual conditions which would interfere with the formation of elec- trodes, or the deposition of the metal on a cathode. Tellurium dioxide could be obtained in relatively high purities of 98 pct TeO2 or better at reasonable prices. Tellurium dioxide is soluble in caustic to form tellurites, which are conductive, ionizable, and from which tellurium metal may be deposited at a cathode. Preliminary solubility tests to saturation of tellurium dioxide in approximately 10 pct sodium hydroxide gave the results of Table III. The temperature range is a practical one for electroplating. Electrochemical test facilities were set up and these met the operating conditions of Table IV. For a determination of purity of deposits, there was available a Jarrell Ash Co. quantitative emission

Jan 1, 1964

By G. A. Moore

A brief review is given of methods designed to produce metallic iron of high purity, and typical results are listed. A recent method, utilized at the National Bureau of Standards, consists of the extraction of ferric chloride by ether, reduction of this ferric chloride to ferrous chloride, further purification of this chloride, and the subsequent electrolytic deposition of metallic iron. iron produced by this procedure apparently is softer than, and otherwise different in properties from, any iron previously prepared and contains appreciably smaller amounts of impurities. THE history of attempts to produce "pure" iron reaches to antiquity and it may be presumed that each ancient armorer who succeeded in making a better steel concluded, correctly, that he had done a better job of removing the "base metals," and incorrectly, that he now at last had a "pure" metal. Early metallurgical papers mentioned use of "pure iron" in making alloys—this "pure" iron in most cases being inferior to some commercial stocks of the present time. Improvement has been continuous, and usually at a sufficient rate to convince each succeeding group of workers that they, at last, were using the really pure metal (until the analysts also improved their techniques to again discover the impurities). These adventures were reviewed in some detail by Cleaves and Thompson.' Although the ores of a metal may be abundant, difficulties in extracting it may make the pure metal very rare. When impurities are restricted to a total of a few parts per million, nearly all pure metals become rarities. Lead, copper, gold, mercury, silver, zinc, aluminum, bismuth, and the six platinum metals are claimed to be available with total impurities ranging from 2 to 50 ppm. The present small and scattered world supply of so-called "pure" iron holds an unimpressive place in another group of 16 metals having approximately 100 ppm of foreign material. Of about 20 less rare metals, only the platinum metals are more costly to prepare. While the production of such rare varieties of iron may appear insignificant in the presence of thousand-ton operations with 95 to 99 pct metal, it must be emphasized that all researches on commercially interesting irons and steels are in fact studies of the modifications of the properties of iron by additional materials. Until the properties of high purity iron are directly measured, all ferrous research must operate without known base values. Traces of impurities may affect the properties of a metal in many ways. Infinitesimal traces of solutes, by disturbing the electronic configuration, greatly change the electrical properties of transistors and semiconductors2-3 and slightly larger traces might alter these quantities in iron. Soluble impurities which disturb the perfection of lattice arrangement not only may alter the magnetic constants and electric properties, but by their close association with dislocation phenomena probably control the very existence of the "yield point"; determine the value of yield stress; and perhaps control the selection of slip and cleavage planes. It has been speculated that impurities might even cause the allotropic transformation in iron, but in any case their rearrangement must contribute to the unreliability of heat capacity and other thermodynamic measurements. Impurities which do not remain in solution may cause even greater effects on the properties. Microscopically visible amounts of phases other than ferrite can be found in all high purity irons which have come to my attention. It can be calculated that from 50 to as little as 2 ppm of an insoluble material might be sufficient to completely film all grain boundaries in irons having grain sizes from ASTM Nos. 10 to 1. Should this occur, such films, even though invisible, may be very important in fracture problems, especially at extremes of temperature:' Studies of grain growth and diffusion normally imply consideration of a single-phase system, hence, in the presence of insoluble impurities they can be expected to give ambiguous data." High purity iron is also in demand for use as chemical and spectro-chemical standards; for work in classifying the lines of the iron spectrum; for biological work in nutrition; and for work in nuclear physics. where the presence of some sensitive

Jan 1, 1954

By L. A. Bromley, A. W. Petersen

The van Arkel-deBoer method for producing ductile titanium by thermal decomposition of Til, vapor and deposition on an electrically heated filament is modified by film boiling Til liquid on a heated filament, resulting in similar titanium deposition on the filament and liberation of gaseous iodine. The deposition rate is higher and the energy requirement smaller than in the van Arkel process. Many problems must be solved before the process is commercially feasible. TITANIUM of 99.9 pct purity, called ductile titanium, has been produced by a modification of the van Arkel-deBoer&apos; method. In the van Arkel-deBoer method, an electrically heated wire is suspended from two electrodes, which are placed in a container holding TiI, vapor at a low&apos; vapor pressure (usually <5 mm Hg). The vapor diffuses to the hot wire, usually maintained at 1100" to 1600°C,&apos; and decomposes according to the reaction liberating gaseous atomic iodine and depositing solid crystalline titanium on the wire. Estimations based on the data of Runnalls and Pidgeon,&apos; indicate that the rate-control ling step is the diffusion of atomic iodine away from the wire. There appears to be nearly thermodynamic equilibrium at the wire with TiI, and iodine as the main gaseous species. TiI, is almost certainly an important gaseous species in the cooler regions.&apos; The liberated iodine diffuses to a heated source of crude titanium and reacts to form more TiI, vapor, which again diffuses to the hot wire and completes the cyclic process. The foregoing process may be modified by suspending the hot wire in liquid TiI,, instead of the vapor, and obtaining film boiling. This type of boiling is characterized by the formation of a continuous film of vapor over the wire surface. Since only vapor contacts the wire sul.face, the temperature of this surface may be raised as high as desirable, within the limit of mechanical strength requirements for the wire. By properly adjusting the input voltage. the temperature of the wire may be maintained above U0C"C; and by evacuating the vessel holding the liquid TiI, and maintaining a suitable condenser temperature, the vapor pressure of TiI, may be held low. Thus, the conditions of operation of the van Arkel-deBoer method may be approximated with film boiling; and hence, it is postulated that ductile titanium may be produced by this method. Preparation of Til, There are many methods available for the preparation of TiI,; that used in this research was prepared by the direct reaction of titanium sponge in controlled amounts with liquid iodine. Although no difficulty was encountered with this reaction, it has since been pointed out that this method is sometimes dangerous and should be used with caution. The resulting TiI, was purified by distillation. First Film Boiling Experiments Apparatus: The apparatus shown in Fig. 1 was used for film boiling TiI, on short wire filaments. The current to the filament was supplied through a bank of three 5 kva transformers connected in parallel. The current was controlled by adjusting the voltage over a 0 to 67.5 v range with a 7 kva variable transformer on the low voltage side of the bank of transformers. The current and voltage were measured by Weston meters. The sealed-in-glass tungsten electrodes were hard-soldered to the filament for the film boiling of TiI,. The bottom part of the reactor, containing TiI,, was wrapped with ni-chrome heating wires to maintain the TiI, in the liquid state. An ice or liquid nitrogen trap, for solidifying I, vapor and any TiI, not condensed, was attached to the low pressure side of the air-cooled condenser. A Megavac vacuum pump was used. Procedure: A 0.010 in. diam tungsten filament was hard-soldered to the tungsten electrodes. TiI, was melted (mp 156°C) and poured into the reactor chamber; the top of the reactor chamber, containing the electrodes, was replaced. Freezing of the TiI, was prevented by controlling the current to the ni-chrome wires wrapped around the reactor with a 1 kva variable transformer. The mechanical vacuum pump was started and the system evacuated to about 2 mm Hg TiI, vapor pressure. The current to the filament was turned on and the impressed voltage slowly increased with the variable transformer. A sudden drop in current at nearly constant im-

Jan 1, 1957

By C. H. Gorski

A method for preparing titanium tetrachloride is described which consists of reducing rutile with coke and chlorinating the reduced product at 200° to 500°C. The crude distillate is purified by treatment with copper powder and distillation. Recoveries, exceeding 90 pct of the titanium in the rutile, were obtained. IN recent years considerable interest in metallic titanium has been aroused because of its outstanding physical and chemical properties. The present commercial processes for preparing titanium are modifications of the Kroll1 process and consist essentially of the reduction of titanium tetrachloride with magnesium in an inert atmosphere to produce metallic titanium with magnesium chloride as a byproduct. At present,&apos; commercial titanium tetrachloride costs $0.32 a pound, which makes the price of the included titanium $1.28 a pound. As the titanium tetrachloride must be purified further before processing into metal, its ultimate cost obviously will be higher. Consequently, one of the prime requisites for the production of lower cost titanium metal is a source of low-cost titanium tetrachloride. Recently, Knickerbocker, Gorski, Kenworthy, and Starliper3 escribed a method for preparing titanium tetrachloride from low-grade Arkansas rutile by smelting the rutile with pyrite and coke to form a titanium matte and then chlorinating the titanium matte to prepare a crude titanium tetrachloride. This process had several inherent advantages. Low-grade rutile concentrates were utilized, the chlorination temperature was relatively low (approximately 200°C), and the reaction was strongly exothermic. However, this process had several disadvantages, chief of them being the rather low recoveries of titanium tetrachloride (65 to 81 pct) and the difficulty in purifying the crude titanium tetrachloride obtained. Because of the high-titanium and low-iron con- tents of rutile as compared to ilmenite, rutile should be of greater potential value as a source of titanium tetrachloride than ilmenite. Rutile, however, is not chlorinated directly in commercial practice, because reaction temperatures above 700 °C are required, at which point chlorine attacks most of the common materials of construction. The process now in use consists of converting the titanium in rutile to the cyanonitride by high-temperature reduction in an electric furnace, and then chlorinating this compound. The disadvantages of this process are the difficulty of producing the cyanonitride, the use of high-grade rutile concentrates in the charge, and the presence of several percent of silicon tetrachloride in the finished product. It would be of considerable interest to develop a new process for the preparation of titanium tetrachloride from rutile by chlorination at 200" to 500°C. Process Development Several investigators&apos;-&apos; have studied the reduction of titanium dioxide with carbon in an effort to prepare titanium monoxide. Invariably, the titanium monoxide formed in this manner was not pure, as it contained titanium carbide and one or more of the lower oxides of titanium. As these lower oxides of titanium are more reactive chemically than rutile, and as it is known that titanium carbide may be chlorinated readily, a study was made of the chlorination of carbon-reduced rutile. A sample of rutile concentrates from Hot Spring County, Ark., containing 76.19 pct TiO,, 5.65 pct Fe2O3, 4.18 pct SiO2, and 2.88 pct Al2O3, was used for this investigation. The experimental procedure consisted of making an intimate mixture of —100-mesh rutile and petroleum coke, adding water and molasses as a binder to foi-m a paste, charging into a graphite crucible that was covered, except for a vent to allow the

Jan 1, 1952

By R. E. Tate, F. W. Schonfeld

In 1899, Lebeau1 reported the preparation of the compound Lis As through reduction of lithium arse-nate with carbon. Brauer and zint12 have described the preparation of Li3 As by combining the elements in liquefied ammonia and by melting the elements in a zirconia crucible coated with lithium fluoride. In 1953, at the Los Alamos Scientific Laboratory, LisAs and a previously unreported compound, LiAs, were prepared by the reaction of the elements. PREPARATION OF THE COMPOUNDS Attempts to form lithium-arsenic compounds by

Jan 1, 1960

By R. Bakish, M. A. Badiali, N. W. Kirshenbaum

One pound of ultra pul-e molybdenum has been produced containing both metallic and nonmetallic impuvities close to or less than the limits of detection. various purification methods were investigated; althouglz the use of move than one purification step was consideved, it was found that a single, caefully-controlled sublimation of MoCl5 yielded a highly puvified product without prior treatment or recourse to repeated sublimation. Hydrogen reduction of MoC1, to metal was attempted at atmospheric pressure; however, reduced pressure was necessary to obtain substantial yields. The tubular deposits of metal were consolidated into bulk fovm by electron beam melting undev high vacuum yielding a very low gas content. Boblems involved in monitoring the puvity of these materials and analytical results obtained are also presented. THE pronounced effect of even trace amounts of impurities upon fundamental properties of materials is well known to metallurgists and solid-state physicists. Consequently, groups interested in basic studies of metals have in recent years immensely stimulated the preparation and production of numerous ultra-pure metals. Increased demand by scientists for these high purity materials has necessitated development of facilities to prepare them in significant quantities; the procedures reported here were devised to produce significant quantities of ultra-pure molybdenum. Previous work performed in the field of vapor phase purification and hydrogen reduction of several other refractory metal chlorides had demonstrated valuable techniques applicable to molybdenum.&apos; Various purification and reduction steps were individually investigated. Those procedures which showed the most favorable results with respect both to attainment of high purity and to ease of operation were then incorporated in the process utilized to produce the metal.&apos; STARTING MATERIALS It is well known that because of differences in volatility, chlorides may be separated by fractional distillation. It was presumed that distillation of molybdenum pentachloride offered a simple and straightforward method of purification due to its relatively low boiling point. Alternatively, sublimation of the solid chloride also appeared feasible since MoC15 has both a reasonably narrow temperature range in which it exists as a liquid (a property typical of refractory metal chlorides) and a low enthalpy of sublimation. Pertinent thermochemical data of MoC15 are given in Table I. It should be noted that this compound must be handled with care as it is extremely hygroscopic. Anhydrous MoC15 was obtained from the A Metal Climax Co. METHODS OF PURIFYING MOLYBDENUM PENTACHLORIDE Distillation. It was expected that distillation methods, while affording an efficient purification, would prove simple to control and would have a higher production rate than sublimation processes. Also considered was the possibility of effecting a high degree of purification by using both these volatilization methods in conjunction—possibly a distillation followed by sublimation of the solidified condensate. Distillation of MoC15 was investigated using a single stage distillation column packed with chemically resistant glass beads. Heating coils were wound around the column and collection tube (condenser). As-received MoCl5 was charged into a flask connected with the column using a side loading arm under an argon flow. After the column and condenser were brought to about 270" and 210°C, respectively, the apparatus was lowered until the flask was fully immersed in a constant temperature fused salt bath maintained at about 285 °C. Distillation was continued for about 10 or 15 min until 50 to 70 g of distillate had been collected. Analyses of these distillations indicated that several elements, e.g., Cu, Fe, Ni, Cr, and Mg, were lowered in quantity although not all were removed to the same extent. The occurrence of Na, B, Si, and A1 in the distillates appeared to be due to contamination, possibly from corrosion of the pyrex glass. An improved distillation system of larger capacity and longer distilling column was built. Improvements were effected in lowering the amounts of such impurities as B, Mn, Ni, Na, Mg, Cr, Cu, and Fe. These studies were pursued concomitantly with efforts to purify by sublimation; it was subsequently found that although improvements in purity were obtained by distillation, sublimation processes were simpler to control and effected a high degree of purity.

Jan 1, 1963

By R. Ellerman

The hydrometallurgical processing of an impure zinc oxide fume is described. Flowsheet includes roasting for fluorine elimination and countercurrent leaching to produce a neutral sulphate solution. This solution is combined with zinc sulphide leach solution for subsequent purification and electrolysis. Novel to the neutral leach step is the use of automatic pH control. THE electrolytic zinc plant of the Hudson Bay Mining and Smelting Co. Ltd. was erected in 1929-1930 to process zinc sulphide concentrates produced from ore mined at Flin Flon, Manitoba. Since 1930, production of high purity slab zinc has been continuous. In May 1951, construction of a fuming plant was completed and operations were started to recover zinc from copper smelter reverberatory slag. A second zinc-bearing material in the form of an impure zinc oxide fume was then made available for treatment. Coincident with the construction of the fuming plant, additions were made to the electrolytic zinc plant to recover the zinc in the fume as slab metal. The original plant capacity of 70 tons of slab zinc per day was steadily increased up to May 1951, at which time the daily production averaged 130 tons. With the advent of the fuming plant and the processing of zinc oxide fume, production was stepped up to the present capacity of 190 tons per day. Of this, approximately 48 pct is contributed by the processing of zinc oxide fume. This additional source of raw material has allowed a 20 pct cutback in mining and milling operations, thereby adding considerably to the life of the Flin Flon mine. Zinc sulphide concentrates are treated by the usual hydrometallurgical method. Details of this operation and plant were described by Carr and Reikie in 1935&apos; and Kent in 1951.8 The impure fume is treated in two operations. First, it is roasted to eliminate fluorine. Next, it is subjected to a countercurrent leach with spent electrolyte to extract the zinc as a neutral zinc sulphate solution. During this leaching step, soluble impur-

Jan 1, 1956

By L. W. Rowe, W. R. Opie

A brief history of TiCI, production and purification is given. Chlorinator feed materials for the production of TiCI4 are classified. The thermodynamics and kinetics of Ticl4 production by chlorination of TiO2 are discussed. Problems encountered in the chlorination and purification steps are outlined in detail. MOST of the current processes for the production of titanium metal require the use of TiC14 as a source of titanium values. This material can only be produced by a dry chlorination process, since it is immediately hydrolyzed in the presence of water. When pure, the tetrachloride is a colorless liquid boiling at 136°C. It fumes readily in moist air, reacting immediately with the moisture to form TiO, and HC1. History The tetrachloride was prepared as early as 1826 by DumasL who chlorinated a red hot mixture of carbon and TiO,. Since then, numerous other mixtures have been used including rutile, ilmenite, beneficiated ilmenites, titanium pigment, slags, and the various titanium metalloids such as TiN, TiCN, TiOC, and TiS2. S2Cl2, phosgene, and CC14 have been substituted for chlorine and CO has been used in place of carbon.

Jan 1, 1956

By Julian Glasser, Arthur Fleischer

THIS country was faced with the possible necessity of utilizing nonbauxitic ores for producing aluminum during World War 11. Construction of four experimental plants to treat such ores by four different processes was authorized1-4 including one at Salt Lake City, for the conversion of Marysvale alunite to metal-grade alumina and potassium sulphate by the Kalunite process.&apos; An aluminum reduction plant in Tacoma, Wash., with a capacity of 50 tons of aluminum per day, was constructed to handle the Kalunite alumina produced at the Salt Lake City plant. The alumina and aluminum plants were Defense Plant Corp. projects operated by Kalunite, Inc. and Olin Industries, Inc., respectively. Kalunite alumina differs from Bayer alumina in several respects, particularly in that the former contains potash instead of soda. The presence of potassium in the alumina feed to the cryolite bath was stated by aluminum technologists to be undesirable under the usual operating conditions of aluminum furnaces. In 1940, about 20 tons of Kalunite alumina produced in the Kalunite pilot plant, were reduced electrolytically in a 10,000 amp furnace at Battelle Memorial Institute and at the aluminum reduction plant at Neuhausen, Switzerland. These relatively small scale tests indicated that satisfactory commercial aluminum could be produced in a practical manner. The Tacoma plant reduced about 2,500,000 lb of Kalunite alumina to produce more than 1,200,000 lb of aluminum, in accordance with the accepted gractice for reducing Bayer alumina. It was desired to determine whether commercial aluminum could be produced on a large scale and to establish the technological differences in commercial reduction practice between Kalunite and Bayer alumina. In the course of collecting data, the effects of the abnormal chemical composition and physical properties of Kalunite alumina were observed wherever possible. Tacoma Reduction Plant The reduction plant had two pot lines, each with 120 cells in series, operated at approximately 32,000 amp. Each cell was provided with a single rectangular Soederberg continuous anode, with side-pin electrical contacts. Each cell was hooded and ventilated through a stack connected to 14 other cells, with 25,000 cfm blower. When the plant started operation in 1942, all of the cathode linings were of block construction. Rebuilt cells were of rammed paste construction.

Jan 1, 1952

By W. W. Stephens, W. J. Kroll, H. P. Holmes

THE only two methods for producing commercial quantities of malleable zirconium, up to now, have been using magnesium reduction of the anhydrous chloride under a neutral gas, and using purification of raw zirconium by the iodide dissociation method on a hot filament. The purity of the metal obtained by the latter process is about the same as that resulting from the chloride reduction, with the exception of the oxygen content, which may be about 0.05 pct lower in the iodide metal. Even traces of oxygen have a strong hardening effect on zirconium. Since, in the iodide process, the impurities, Si, Al, Fe, Ni, and Mg in the raw zirconium used, are carried over, it would appear uneconomical to use this method of refining solely to eliminate the traces of oxygen, unless very soft metal is desired. One important step to improve the iodide method, namely, dissociating pure iodide made from carbide and recycling the iodine, which would change this refining process into a method for extracting zirconium from the ore, has not yet been made. The Bureau of Mines, by using the chloride reduction, wanted to produce quantities of a reasonably pure and malleable metal at low cost for large-scale industrial use. This aim has been achieved, and a pilot plant permitting production of 600 lb of malleable zirconium per week will be described (fig. 1). Briefly, the Bureau of Mines process consists of reducing purified gaseous anhydrous zirconium chloride with fused magnesium under a noble-gas atmosphere. The reaction product, magnesium chloride, and any excess magnesium metal present are removed from the sponge zirconium in the next step by fusion and evaporation in a good vacuum at about 925°C. In this process, care is taken to keep air out of contact with the hot metal, which otherwise would contaminate the product with oxygen and nitrogen. Both these impurities embrittle zirconium even when present in an amount as low as 0.1 pct. A number of previous reports1-3 describe the method and the various improvements that finally led to a workable process. The major steps made were the production of large quantities of carbide, which is the raw material for producing the chloride, its chlorination with reasonable efficiencies, and the elimination of iron trichloride contained in the raw chloride, as well as that of the zirconium oxide which is always present in this product. The physical nature of the anhydrous chloride, which sublimes at 331°C at atmospheric pressure and melts at 420°C under a pressure of 25 atm, made it necessary to provide a special safety device on the purification and reduction vessels in the form of a lead-alloy seal, permitting escape of excess gases if pressure tended to build up. The main difficulties encountered in the reduction and in the following step, salt separation in a vacuum at elevated temperature, were caused by the material from which the reaction pot was constructed—iron. This metal reacts with zirconium at about 940°C with formation of a eutectic. The last step, salt separation by evaporation of the magnesium and magnesium chloride in a vacuum, is quite unconventional and has not been used before on such a scale. It is only due to the improved construction of high-vacuum pumps, especially oil-diffusion pumps, that such a method could be used. The various steps of the Bureau of Mines process, as described in the general outline above, may be summarized as follows: (1) production of the carbide, (2) chlorination of the carbide, (3) purification of the raw chloride, (4) reduction of the pure chloride with fused magnesium, (5) separation of excess magnesium and magnesium chloride in vacuum at elevated temperature, and (6) melting of the sponge obtained. Production of Carbide The arc furnace, described in a previous report,&apos; was improved both to reduce the graphite consumption caused by the burning of the bottom plates and to concentrate the heat in order to obtain better power efficiency. This was achieved by providing the bottom with graphite plates entirely embedded in refractory bricks, the contact with the current being made with three water-cooled copper plugs. Figs. 2 and 3 show the arrangement. The crucible, made

Jan 1, 1951

By T. E. Evans, C. T. Baroch

ZrB2 was produced in batches of 4 to 6 Ib by interaction of ZrO2, B4C, B203, and carbon at around 2000°C in a simple graphite resistance furnace. Techniques of production are discussed and the final design of a suitable furnace is described in detail. Several other borides were made by the same technique and the process appears to have possibilities for commercial production. N seeking out new hard and refractory com- pounds, many researchers have turned to the investigation of the borides and excellent papers have been published on the properties of these compounds. Few papers, however, have appeared on the techniques and problems concerned with the production of these high temperature substances. This report describes progress made in developing a method for preparing zirconium diboride, ZrB2, on a pilot plant scale. The literature of the borides and other refractory hard metals recently has been reviewed, annotated, and classified so completely&apos; that it is needless to attempt such an outline here. It is enough to say that three borides of zirconium have been reported: ZrB, ZrB2, and ZrB12.2 ZrB2 is the most stable of these and is especially stable in the presence of carbon up to and including its melting point of around 3000°C. Like most borides, it can be prepared in several ways. It can be prepared by synthesis of the elements, but these are expensive and difficult to produce in a high state of purity. Obviously, production directly from the oxides would have decided economic advantages. In electrolytic production such as that of calcium boride,:&apos; the product is recovered as a sludge mixed with electrolyte; and separation of product from adhering electrolyte and regeneration of the electrolyte is an involved and difficult process. The work on borides was started on a small scale in 1948. Late in 1949, Naval Ordnance expressed a specific interest in ZrB2 and the project then centered on this compound. After the usual experimental work necessary in a new field, ZrB2 of good quality was produced by heating mixtures of B4C, ZrO2, B2O3, and carbon to a temperature of about 2000 °C in a resistance-type electric furnace. Over 100 lb was made for experimental use tests, and the method of production probably could be expanded into a commercial operation. A similar process has been described by Kieffer and coworkers.&apos; The main chemical problems were the development of proper charges to insure complete reduction of the elements, determination of the proper temperature range at which these reductions took place, and adoption of techniques necessary to pre- vent inclusion of such impurities as carbon and nitrides. The mechanical problems consisted of developing a simple practical furnace that would attain the high temperatures required and permit use of a controlled atmosphere when necessary and determining of suitable refractories. Both problems were solved by designing a crucible resistance furnace. Crucible Resistance Electric Furnace Attempts were first made to produce ZrB2 in an electric arc furnace, but such a furnace would not provide the degree of carbon control required for producing clean graphite-free borides, so it was decided to try working in a crucible. Obviously, the furnace would have to be constructed of graphite, as the temperatures required are too high for other refractories or heating elements. Crucibles were made by hollowing out segments of graphite electrodes, which were fitted with a cover and clamped between two electrodes so that the current passing through the thin wall of the crucible would generate heat, using the principle of the Helberger crucible furnace."? Preliminary tests with this type of furnace were encouraging and led to the furnace design shown in Fig. 1. The essential components were a thin-walled graphite crucible resting on a graphite block, which formed the lower electrode assembly, and a top electrode assembly swung from a pipe column making contact with the top of the crucible. The space around the crucible was filled with graphite prepared from waste electrodes crushed to about ¼ in. This packing had excellent insulating properties, both electrically and thermally, and could be removed easily and quickly from around the crucible by means of an industrial vacuum cleaner. The largest resistor crucibles were machined from 8 in. electrode stock and were 26 in. long, with a side wall Yi in. thick and a 1 in. bottom. Temperatures were determined optically by sighting down a 1 in. hole drilled longitudinally through the top electrode and the crucible cover. Sealing this hole at the top was a water-cooled brass sight-glass assembly, shown in Fig. 2. An opening was provided for a light flow of helium to keep the sight opening clear of smoke, and a glass prism above the sight glass changed the line of sight to the horizontal for easier reading. More recently, the prism and optical pyrometer were replaced by a photoelectric recording pyrometer. At first the charges were placed directly in the resistor crucible but this meant that everything had to be withdrawn from the furnace every time the charge was emptied. Later, smaller crucibles were made up that could be placed inside the resistor

Jan 1, 1956