Search Documents

By D. H. Forbes, H. M. Manasevit, F. L. Morritz

Single-crystal thin films of molybdenum have been grown. by the pyrolytic decomposition of molybdenum hexafluoride in a hydrogen ambient on various insulating substrates at temperatures front 650° to 900° C. Single-crystal discs of various orientations of magnesium aluminate spinel, a aluminum oxide, magnesium oxide, and the natural facets of beryllium oxide were all observed to exert epitaxial control on the depositing film. Determinations of the crystallographic relationships existing between film and substrates have been made, using X-ray diffraction three-circle goniometry and Laue back-reflection techniques. Using these data, crystallographic overlays have been constructed which suggest a possible interfacial geometry on the basis of a match between metal deposit atoms and metal ion sites in the substrate. A continuing program has been in effect in the Auto-netics Laboratories over the past several years aimed at the development of electronic materials in new and useful forms using chemical vapor deposition techniques. During the course of these investigations, the epitaxy of silicon1"5 and tungstenep7 on single-crystal metal oxide insulators was studied extensively. The deposition of molybdenum is a logical extension of the tungsten work since the crystal structure is identical and the lattice dimensions differ by less than 1 pct. The pyrolytic decomposition of molybdenum hexafluoride in hydrogen was used to grow molybdenum films on the oxide substrates AlzOs, MgA1~04, MgO, and Be0 at from 650" to 900°C, depending on the substrate material. Under the experimental conditions to be described, monocrystalline films of controlled orientation were obtained. The materials investigated and their crystal structure are listed in Table I. EXPERIMENTAL The molybdenum depositions were effected by the hydrogen reduction of molybdenum hexafluoride (MoFe) in a flowing system of hydrogen at atmospheric pressure. The schematic of the apparatus is shown in Fig. 1. The hydrogen, purified by passage through a heated palladium thimble, was mixed with the vapor of the liquid MoFe maintained in a steel bottle at room temperature (25°C). The mixture was passed over the substrate, which was heated by rf induction of a sup-

Jan 1, 1969

By Alden Greninger

ALTHOUGH the crystallography of lattice transformations has been studied extensively during the past few years, these studies have been limited, with few exceptions1,2, to specimens in which the transformed lattice appears as a, segregate phase. A realization of the technical importance of the segregation mechanism, especially in the formation of martensitic structures and in age-hardening phenomena, has undoubtedly stimulated research in this direction. In the crystallographic studies of segregation, the general problem has been to relate the orientation of the parent crystal to that of the segregate crystals. The technique has been complicated by the fact that it has been necessary to deal with the presence of as many as 24 ideal segregate orientations within one parent lattice; furthermore, the segregate lattices are invariably scattered (seldom less than ±2°, often as much as 15° or 20°) about these ideal positions. It is probable that a more complete picture of phase transformations may result from a study in which complete lattice relationships between individual grains are evaluated, thereby providing an additional param-eter which, when it is necessary to work with multiple segregate-orienta-tions, cannot be evaluated. The present paper presents the results of such a study, ? wherein a peritectic reaction is made use of to produce the transformed lattices.

Jan 1, 1937

ALLERTON S. CUSHMAN, Middletown, Ohio (written discussion*).¬ This subject is one to which I have given much thought and study and which I have frequently discussed informally with Mr. Cain and others. I have long been convinced that the gaseous elements, either combined or entrained (occluded), in steel play a much more important role than is ordinarily admitted. This is probably due to the difficulties encountered in the accurate quantitative estimation of gases, some of which Mr. Cain has referred to, as well as to the fact that, considered from the weight-percentage basis, gas content is measurable only in hundredths or even thousandths of 1 per cent. Volumetrically, however, the results ob-tained by modern research are startling, to say the least. Baraduc-Muller,1 as cited by Mr. Cain, pumped out of 1000-lb. ingots of basic Bessemer steel 2100 l. of gas. or about 75 cu. ft., at normal temperature and pressure, per ton of steel. In other words, we are to understand that Bessemer steel normally carries about fifteen times its own volume of gas. According to Baraduc-Müller's table of results, which is given here-with, carbon monoxide, nitrogen, and hydrogen are important consti-tuents of Bessemer steel, the latter gas being undoubtedly formed by the

Jan 11, 1919

By Herbert Lang

Cord-wood, sawn into blocks of about a foot in length, is a regular constituent of our fuel-charge at Mineral, Idaho, our work being the matting of silver-ores by fusion in a blast-furnace. The furnace is a round water-jacket furnace, of 36 inches diameter at the tuyeres, and the charge of smelting-mixture weighs 950 Ibs., requiring 110 Ibs. of Connellsville coke to drive it. I replace half this coke with 135 lbs. of fir-wood, cut from dead and apparently perfectly dry trees. This mixtrire produces as high a sn~elting-temperature as all coke, whence I infer that the smel ting-effeot of a given weight of wood is to that of the same weight of coke as 11 to 27, or 1 to 25/11. A cord of wood sawed ready for use weighs 2840 lbs., costs $5.00, and is

Jan 1, 1892

By R. G. Hall

AN article on the subject of electrolytic zinc no longer needs to be preceded by an apology. The production of zinc by electrolysis is past the laboratory stage and has become an economic factor of considerable importance in the total production of zinc in the United States. The various methods of procedure to be, followed for the greatest economy of manufacture are fairly well known, consequently a detailed description of any method is no longer necessary or desirable. In this paper I shall endeavor to lay down some of the governing conditions in this industry, the relation of methods to ore deposits, freight rates, and sources of power supply. POWER POINTS Assuming for a moment that, for the present at least, the electrolytic production of zinc will be confined too those localities having developed water power, a glance at these powers so developed in the United States, with their relation to known zinc orebodies of economic size, will not be without interest. Northwest In the Northwest we have water powers, developed and undeveloped, in Washington and Montana. These must, of course, bear a close relation to the rapidly growing zinc production of the Coeur d'Alenes and of the Butte districts. In general, the power of the territory in question is relatively low-priced, at least as compared with the cost of developing power from coal, and the near neighborhood of large bodies of more or less complex zinc ores makes these water powers of more than usual interest. The same remarks may be applied equally to the developed water powers of the Canadian side of the line in the Northwest, where we have again commercially available complex ore deposits such as are being exploited today at and near Trail.

Jan 9, 1917

By Philip Wilson

Tun mines of the Calumet & Arizona Mining Co. are situated in the Warren Mining District, Cochise County, Arizona, between Bisbee and Warren and adjoin those of the Copper Queen Consolidated Mining Co. and the Shattuck Arizona Copper Co. Paleozoic limestones of considerable thickness have been intruded by granite porphyry. A great stock of the intrusive outcrops boldly near the city of Bisbee and is known as Sacramento Hill. From this central core the porphyry has tongued out into the limestone for many thousands of feet as dikes and sills of irregular shape and variable dimensions. Churn drilling has recently developed a large tonnage of secondarily enriched copper ore in the main porphyry mass of Sacramento Hill. While some ore has been found in porphyry in other parts of the district it is relatively unimportant compared with that which occurs in the Paleozoic limestone as irregular lenses replacing favorable beds near porphyry contacts or associated with well-marked fracture zones often many hundreds of feet away from the intrusive. In a zone extending from Sacramento Hill for a distance of from 1,500 to 3,000 ft. the limestone has been extensively metamorphosed and in this contact metamorphic zone the ore occurs through a known vertical thickness of upward of 900 ft. and individual orebodies often show extension in a vertical direction of over 200 ft. At a greater distance from the intrusive stock the ore occurs as lenses of greater horizontal than vertical dimensions with an average thickness of approximately 30 ft. An exception to this rule is found in the occasional steeply dipping mineralized fractures, almost true tabular veins, which are found long distances away from the zone of contact metamorphism.

Jan 7, 1916

By C. Law McCabe, R. G. Hudson

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

Jan 1, 1958

By Mark R. Lamb

The recent growth of a sentiment among cyanide-plant designers against the use of gravity-stamps for the crushing preliminary to cyanidation may be said to date from the almost simultaneous perfection of the ribbed tube-rnill liner and of the tall, air-agitation tank. The first step in the resulting change of practice mas the universal adoption of the tube-mill for fine-grinding and the use of coarse screening on the battery. This was the beginning of the surrender of supremacy by the gravity-stamp; since merely the single fact that it was a more economical machine for crushing fine had retained it in favor as conlpared with ball-mills, rolls, or steam-stamps. The surrender, however, is not yet complete.

Jan 1, 1911

By John W. Sweeney

Florida is blessed with some of the worlds greatest phosphate rock deposits, and doubly blessed in that those deposits are uraniferous. Until recently, the uranium con¬tained in phosphate rock had been ignored, but spot mar¬ket prices in the $40-per-pound range have spurred actions which will soon transform the state into a major uranium supplier. In 1978, two plants in Florida and one in Louisiana went it on- stream to recover uranium oxide from phosphoric acid, and construction began on three other extraction facilities. Together, these six plants will be cap¬able of recovering 1940 t/y (2140 stpy) of yellow cake from Florida phosphate in the early 1980s, equivalent to 15% of the projected US requirement. By the year 2000, Florida phosphates will have produced a projected 49 000 tons (54,000 st) of uranium oxide to fuel the nation's nuclear reactors.

Jan 9, 1979

By R. W. Jenkins

RACKLESS equipment is being used by the T Coplay Cement Manufacturing Co. to develop a folded limestone deposit economically and safely with inexperienced men. Cost and quality of development stone results in a saving when it is used instead of outside sources of limestone. This favorable cost has been attained by following a methods development and training program described in this paper. It is expected that further savings in favor of the mined stone will be made when stopes now being prepared are in production. The present equipment will be used for loading from stope draw points. The limestone is blended with quarried cement rock to serve as raw material for Portland cement, first produced in this country by Coplay Cement Manufacturing Co. from a process developed by its president, David 0. Saylor, in 1873. For many years the cement rock alone or with a small amount of added limestone was used for raw materials. Later as specifications were raised and the richer portions of quarries were depleted, limestone from outside sources was required in increasing amounts. In 1925 D. J. Uhle, the general manager, began to prospect company property for limestone. It was known that the argillaceous cement rock was underlain by crystalline high calcium limestone. After an extensive drilling program it was found that there were large reserves of limestone underlying a recumbent syncline exposed in the south wall of the company's No. 3 cement rock quarry. A quarry was started on the vertical limb of this fold in 1927, and by 1930 the full requirement of the plant was met. After 1945 production diminished because of the occurrence of dolomite beds in the south wall. The quarry floor was then 135 ft below the cement rock level and 285 ft below surface. In 1949 Gerald I?.

Jan 1, 1955

By Carl F. Floe, Hung Liang, Michael B. Bever

DATA on the solubility of hydrogen in iron-silicon alloys are of practical interest, as hydrogen causes gas unsoundness and embrittlement in iron and steel and is also a factor in the metallurgy of cast iron. Zapffe and Sims1 have recently demonstrated that in deoxidized iron and steel castings gassiness and bleeding are primarily functions of the hydrogen content of the liquid metal. These authors also suggested convincingly that ordinary melting and casting practice provides several sources of hydrogen for absorption by the metal. Norbury and Morgan,2 and Boyles3 have shown that dissolved hydrogen affects the graphitization of cast iron. Schneble and Chipman4 included in a study of the effects of superheating on the properties of cast iron an investigation of the part played by hydrogen. Schwartz, Guiler and Barnett6 investigated the significance of hydrogen in the metallurgy of malleable cast iron. A complete interpretation of investigations of this kind calls for equilibrium values of the solubility of hydrogen in the liquid and solid phases. From the theoretical standpoint, the solubility of gases, especially hydrogen, may reveal some aspects of the nature of liquid metallic solutions. This was implied in the early work of Sieverts6 on the effect of alloying additions on the solubility of hydrogen in copper. Recent work by Bever and Floe7 has shown that in liquid copper-tin alloys the solubility of hydrogen changes abruptly at the composition of the intermetallic compound Cu3Sn. It is of considerable interest to determine whether liquid alloys of iron also have compositions at which the solubility of hydrogen exhibits a discontinuous or otherwise unique behavior. Among the various alloys of iron the iron-silicon system is important because of the presence of silicon in various structural alloy steels, transformer sheets, cast irons and special acid-resisting castings. The various grades of ferrosilicon, finally, cover almost the entire remainder of the composition range. Published information on the solubility of hydrogen in iron-silicon alloys is meager. The first values for pure liquid - iron were reported in 1910-1911 by Sieverts and Krumbhaar8 and by Sieverts.9 They found that 100 grams of iron absorbs 28 C.C. of hydrogen at 1550°C. and one atmosphere pressure, and 31 C.C. at 1650°C. In 1938 Sieverts, Zapf and Moritz10 published a value of 26.3 c.c. at 1550°C. Data on the solubility of hydrogen in liquid iron-silicon alloys and in liquid silicon

Jan 1, 1946

By Edward Gridley

At the meeting of the Institute, held at Roanoke, Va., in June, 1883, I gave some facts in relation to charcoal pig iron of unusual strength, made from our carbonate ore taken from the mine at Amenia, N. Y. My object in again bringing the subject to the attention of the Institute, is to obtain, if possible, the solution of a prohlem in connection therewith. Our furnace is of the old type, stone stack 32 feet high by 9 feet 2 inches at top of bosh; bosh about 67O pitch; stone hearth; three tuyeres of 31/4-inch opening; fuel, a mixture of hard and soft coal; blast about & to # pound pressure, and heated to 400' to 600° Fahr. by iron pipe oven on top of stack. The analysis of the roasted carbonate ore, as before given to the Institute, is as follows:

Jan 1, 1884

By Robert W. Edwards

The Morris mine, operated by the Inland Steel Co., is located about 5 miles west of Ishpeming, Mich., near the west end of the Marquette Range. The ore, a soft hematite, is mined by sublevel caving and stoping. A considerable amount of surface water flows down through the cave into the ore or percolates down along footwall dikes in the iron formation. Because of this water, the broken ore cannot be stored in the raises and must be scraped from the sub directly into the tram cars. Efficient tramming, therefore, requires close coordination between the scraping and loading operations. In the past this has been hampered by the lack of a suitable means of communication between the mining contracts and the drawpoints on the tramming levels. Among the devices that have been tried unsuccessfully are flashing lights, air whistles, and electric buzzers.

Nov 1, 1955

By A. Werenfels

No PETROLEUM, in commercial quantities, is found in France except the small production of the Pechelbronn field (Fig. 1) in Alsace, which produced 75,000 tons in 1923; therefore the test of the petroleum prospects of the Limagne is most interesting. Under the superintendence of M. Termier, chief engineer of the French mines, a well near Crouelle (Fig. 2) was drilled in 1921 to a depth of 856.3 m. (2808 ft.); at different depths favorable showings were encountered. The well, however, was abandoned because of drilling difficulties. A second one is now being drilled near the same place.

Jan 1, 1925

By H. C. George

Since 1911, when J. L. Dunn first used compressed air for repressuring depleted oil sands in southeast Ohio, the rejuvenation of many depleted oil fields has been directly due to repressuring by means of air or gas. Developments in repressuring in recent years have resulted in its successful use in the early life of some deep, high-pressure oil fields, conserving the natural gas dissolved in and associated with the oil by returning it to the producing oil sand after it has been compressed above the existing rock pressure of the reservoir. One of the most successful operations of this type is that of the Humble Oil & Refining Co., on the DeWalt salt dome at Sugarland, Texas. I quote from a personal communication with reference to this field: "Structurally, the field is dome-shaped, having a closure of approximately 350 ft. Production comes from a sandy shale interbedded with a clean sand and lying over a cap rock which is about 3400 ft. deep on top of the structure." A feature of the operation of this field is the production of the required amount of oil with the minimum of gas production. Wells on top of the dome have high gas-oil ratios, while those down structure have lower ratios, depending upon the distance of the well from the peak. To date, it has been possible to produce the oil needed from the wells circling the dome above the water zone and below the gas zone, and in this manner the average gas-oil ratio has been kept low. The gas from all separators is turned into a gas system which serves the entire field. From this system, all drilling rigs and utilities requiring gas for a fuel draw their requirements, and the remainder of the gas (about two-thirds of the production) is delivered to a compressor plant which boosts the pressure until it can be returned to the sand at the top of the dome where the rock pressure is 1400 lb, per square inch. "The Sugarland wells produce through 2-in. tubing with a 3/8-in. choke in one wing of the well-head manifold. The pressure builds up as high as 1300 lb, per square inch on the casing while on the tubing it varies from 0 to 900 lb. per square inch, depending upon the amount of gas produced with the oil."

Jan 1, 1931

By R. I. Jaffee, F. C. Holden, H. R. Ogden

The effects of grain size and shape on alloys of titanium with nitrogen and aluminum have been determined. Increasing a grain size decreases strength and hardness and increases impact resistance. Quenching from the ß field produces subgrain markings delineating a plates in Ti-N alloys but not in Ti-AI alloys. This suggests a precipitation from the high nitrogen alloys. ALPHA titanium alloys are single-phase alloys with the hexagonal-close-packed structure of a titanium. If these alloys are worked and annealed within the a field, equiaxed structures result in which strength is derived from the solid solution of the alloying elements present. Strain hardening can be used to increase further the strength of a titanium alloys. This is the only other mode of strengthening the a type of alloy. Quenching from the ß field has been noted by many investigators to have little effect on the strength of iodide titanium and on commercial titanium. Ti-A1 alloys were found to be little different in hardness, whether annealed in the a field or quenched from the ß field.' These facts illustrate a characteristic of a titanium alloys: they are insensitive to heat treatments from the ß field. Underlying this heat-treatment insensitivity are the facts that the a-ß field is generally narrow in a titanium alloys, the transformation-temperature range increases with a-stabilizing content, and the a solubilities of the alloying elements are greater than the ß solubilities. When quenching is done from the ß field, there is no supersaturation of the alloying elements in the acicular transformation structure produced. Welds in a titanium alloys generally are ductile, because no transformation hardening occurs during cooling.1,2 Other desirable features of a alloys are: no thermal-stability problem, excellent toughness, and retention of strength at elevated temperatures better than a-ß or ß alloys of comparable room-temperature strength. The prime factors governing the properties of a titanium alloys are the amount and kind of solute present. This can change the a phase from a soft, tough material into a hard, brittle material with no apparent change in microstructure. Moreover, brit-tleness can exist over a wider alloy-content range, without change of phase, than in most other metals. The solutes for a titanium may be divided into interstitial and substitutional types. Oxygen and nitrogen dissolve interstitially in rather large amounts, extending well through the brittle range, and the transformation-temverature ranges are raised in the process.:' , carbon has a maximum interstitial solubility of about 0.5 pct at the peritectoid temperature, while at lower temperatures the solubility decreases to about 0.2 pct.3,5 Substitutional a solutes include aluminum and tin. Aluminum has a high a solubility of 25 pct Al, and increases the transformation-temperature range markedly.6,7 Tin has a high a solubility of about 20 pct, but has a relatively innocuous effect on the transformation-temperature range.' The choice between interstitial and substitutional solutes generally has been conceded to the substitutional solutes because of a belief that they do not have as adverse an effect on ductility and notch toughness. However, a recent investigation8 on the effect of hydrogen on titanium has shown that this element, which is not under compositional control, has a powerful detrimental effect on notch toughness. Hydrogen was shown to form a hydride which is practically insoluble (about 0.002 pct) in a titanium at room temperature, although the solubility at the eutectoid temperature of about 300°C is relatively high, about 0.16 pct. Limited data were presented on the effect of hydrogen on a alloys, where the same impairment of toughness as in unalloyed titanium is found. The work reported here describes the effects of interstitial and substitutional solutes on 1—the mechanical properties of high purity titanium free of titanium hydride and 2—the influence of structural variables on these properties. Nitrogen was selected as an example of an interstitial solute with high solubility and aluminum as a substitutional solute with high solubility. All compositions were well within the ductile range, since it was not intended to study the brittleness problem here, but to study only the factors influencing optimum mechanical properties. Procedures The alloys were prepared from iodide titanium as 1/2 Ib ingots double melted to insure homogeneity.

Jan 1, 1955

By H. H. Wade, N. F. Schulz

The large quantities of iron-bearing materials, including taconite, semi-taconite,* and other low-grade ferruginous materials occurring in Minnesota and elsewhere, constitute an important potential source of iron. Satisfactory grade and recovery of iron ore concentrate cannot ordinarily be obtained from these ferruginous materials by simple methods of beneficiation. Iron is distinctive in that the free metal and two of its oxides [magnetite (Fe2O3) and maghemite (gamma-Fe2O3) ] are strongly ferromagnetic. The successful magnetic separation of natural magnetite from taconite has already been established on a commercial scale. The iron in semi-taconite, however, occurs largely as goethite (Fe2O3-H4O) and hematite (Fe2O3) which do not respond to ordinary magnetic separation methods. Magnetic roasting converts these iron oxides to magnetite, which can, after liberation, be magnetically concentrated. MAGNETIC ROASTING Hematite undergoes a stepwise reduction when exposed at moderately elevated temperatures to a reducing atmosphere containing hydrogen or carbon monoxide: Fe2O3? Fe3O4 ? FeO ? Fe Since the desirable product in magnetic roasting is Fe3O4, the conversion is halted after the first stage by controlling the reduction potential of the gas mixture with water vapor or carbon dioxide. The reducing gas mixture must be such that the oxygen partial pressure at the solid-gas reaction interface will be maintained intermediately between the oxygen partial pressures in equilibrium with Fe2O3 and Fe3O4 at the prevailing temperature. Because of the rapid increase in decomposition pressure of Fe3O4 with increase in temperature, the practical upper limit of useful reaction temperature is about 1400°F, above which over-reduction usually occurs in atmospheres containing hydrogen or carbon monoxide. On the other hand, useful reaction rates usually occur only above 800°F. Goethite reacts similarly except that the combined water probably has to be driven off thermally before the reduction to magnetite occurs. Iron carbonate must also be decomposed thermally to an oxide before conversion to magnetite. Iron silicates are apparently not amenable to magnetic roasting. The rate of penetration of the reaction toward the interior of a given ore fragment is dependent on the chemical composition and physical structure of the solid. Most ore fragments tested here reduced satisfactorily to 1/4-in. depth in less than 14 min at 1200°F. Some very dense fragments, however, were reduced to less than 1/32-in. depth under the same conditions. Determination of the optimum temperature, gas composition, ore fragment size, or time of exposure

Jan 1, 1961

By W. O. Philbrook, K. Natesan

The oxidation kinetics of spherical pellets of zinc sulfide made from Santander concentrates were studied using a thermogravimetric technique. The experiments covered a temperature range-. of 740" to 102O°C, 0-N mixtures varying from 20 to LOO pct O2, and pellet diameters between 0.4 and 1.6 cm. Mathematical models were formulated to Predict the reaction rate on the assumption that a single transport or interface reaction step was rate -controlling. Analysis of the data indicated that the process of oxidation was predominantly controlled by transport through the zinc oxide reaction-Product layer. ROASTING processes, which are reactions between solids and gases, are very important because they are employed in the production of a number of basic metals. These processes are highly complicated, and one needs to consider the transport phenomena of heat and mass between the solids and gases in addition to the kinetics of various chemical reactions involved. Because of such complications there is a lack of knowledge concerning the rate-limiting factors, which may strongly depend on temperature, particle size, gas composition, and solid structure. The oxidation of zinc sulfide, which is of commercial importance in zinc production, falls into this class of reactions. The major goal of this work was to elucidate the roles played by different process variables, such as reaction temperature, gas composition, pellet size, and pellet porosity, on the kinetics of oxidation of single pellets of zinc sulfide. Roasting of zinc sulfide single particles has been a subject of both experimental and theoretical investigations.&apos;-&apos; The reaction is exothermic and may be considered to be irreversible. Such a reaction has been found to proceed in a topochemical manner. In other words, as the reaction proceeds, a progressively thicker outer shell of zinc oxide is formed, while the inner core of unreacted sulfide decreases. It has been found experimentally, both in the present work and in the previous investigations,1-9 that the particle retains its original dimensions and the process requires transport of gaseous oxygen across the porous product layer for continued reaction. The reaction may be represented by ZnS(s) + 3/2 O2(g) = ZnO(s) + SO2(g) [1] The solid product considered here is only zinc oxide, since the diffraction patterns of zinc sulfide pellets oxidized partially at &apos;798" and 960°C showed K. NATESAN, Junior Member AIME, formerly St. Joseph Lead Fellow, Department of Metallurgy and Materials Science, Carnegie-Mellon University, Pittsburgh, Pa., is now at Argonne National Laboratory, Argonne, Ill. W. 0. PHILBROOK, Member AIME, is Professor of Metallurgy and Materials Science, Carnegie-Mellon University. This paper is based on a them submitted by K. NATESAN in partial fulfillment of the requirements for the Ph.D. degree in Metallurgy and Materials Science at Carnegie-Mellon University. Manuscript submitted December 2, 1968. EMD lines corresponding to original zinc sulfide and the newly formed zinc oxide. OXIDATION MODEL The generalized model for gaseous oxidation of zinc sulfide is illustrated in Fig. 1. This depicts a partially oxidized sphere of zinc sulfide in a gas stream surrounded by a laminar film of gas. The spherical sample of zinc sulfide of unchanging external radius r0 is suspended in a flowing gas stream of total pressure PT and composition specified by the partial pressures of the individual components. Partial pressures of the gaseous species in the bulk gas phase, at the exterior surface of the pellet, at the ZnS/ZnO interface, and at equilibrium for Reaction [I] are identified by the superscripts b, o, i, and eq, respectively. The overall reaction involves the following ~te~s:&apos;~&apos;~&apos; Step 1. Transfer of reactant gas (oxygen) from the bulk gas stream across the gas boundary layer to the exterior surface of the pellet and the reverse transfer of the product gas (sulfur dioxide). Step 2. Diffusion and bulk flow of oxygen from the pellet surface through the product shell (ZnO) onto the ZnS/ZnO interface and the reverse transfer of sulfur dioxide. Step 3. Chemical reaction at the interface, which results in consumption of oxygen gas and generation of sulfur dioxide gas and heat; at the same time the _________ PARTICLE SURFACE / x^^^^n^X / MOVING INTERFACE core-----/ sJSNxy " /T^T^02 \ V\V$\ ^NWX/ "*/— GAS BOUNDARY x. \\ZnO SHELLV/ / \^ . / &apos; ^ BULK GAS --------N_______ _____,------p£ w \ P« / (f> \ / a \ <i) / <----------------- _(o) ^^--------------(b) °- pso, pso2 ro ri 0 ri ro RADIAL POSITION Fig. 1—Generalized model for oxidation of a sphere of zinc sulfide.

Jan 1, 1970

By H. L. Gilbert, W. W. Stephens

Production of anhydrous zirconium tetrachloride by direct chlor- ination of a zirconium oxide carbon mixture in a silica-brick-lined chlorinator is described. Theory and thermodynamics of reactions are discussed. A pilot-model chlorinator and full-scale production equipment are described and operating data are included. ANHYDROUS zirconium tetrachloride required as a starting material in the Kroll process for production of ductile zirconium has been produced in this country principally by chlorination of the carbide or "carbonitride" made by reduction of zircon sand concentrates with carbon in the arc furnace. This process and the equipment used have been fully described.&apos;.&apos; It is well known that zircon or badde-leyite ores may be chlorinated directly with chlorine in the presence of carbon, and this one-step approach would seem at first glance to be preferable to the two steps involved in the carbide-chloride operation. As previously discussed1 considerations leading to adoption of the longer process were: 1—Chlorination of the carbide proceeds rapidly at temperatures below 500°C, whereas temperatures above 900°C were considered necessary for chlorination of zircon-carbon mixtures. 2—The highly exothermic nature of the carbide-chlorine reaction makes it self-sustaining, while heat must be supplied continuously in direct chlorination of the ore. 3—Silicon was thought to be chlorinated along with zirconium in the direct chlorination of zircon, leading to high chlorine consumption. In production of carbide in the arc furnace, silicon is driven off as silicon monoxide and does not enter the chlorinator. 4—For efficient direct chlorination, the ore must be finely ground and intimately mixed with carbon, and the mixture briquetted. 5—Direct chlorination requires a much larger chlorinator for a given production capacity than chlorination of carbide. Recently it has become necessary to produce large quantities of zirconium metal from a chemically purified zirconium oxide. Since the cost of the latter is high, the relatively high losses encountered in production of carbide in the arc furnace could not be tolerated, and a graphite resistor furnace5 was developed for production of carbide, which was then chlorinated in equipment previously used for chlorinating arc-furnace carbide. This method of operation was quite satisfactory, and losses in the carbid-ing step were minimized. However, operating costs were relatively high, and the process did not lend itself particularly well to large-scale operation because of the multiplicity of small units required and the hand labor needed to load, unload, and maintain the furnaces. To chlorinate the carbide, a vertical-shaft chlorinator was used in which the charge was heated with a central split graphite-rod resistor.&apos; Operation of this chlorinator was somewhat less satisfactory with the resistor furnace carbide than it had been with the arc-furnace carbide due, principally, to the differences in physical properties of the carbide. The arc-furnace carbide is obtained as a fused metallic-appearing mass which can be crushed to -1/4 in. with production of a minimum of fines, whereas the resistor-furnace product is lightly sintered and produces a large proportion of fines in crushing and handling. These fines tend to pack in the chlorinator and promote channeling. which results in poor chlorine efficiency and low capacity. Data based on production of 22,000 lb of chloride from resistor-furnace carbide in this equipment are shown in Table I. Necessity for increasing production of chloride from about 2,000 to 15,000 lb per week led to further investigation of possible methods for direct chlorination of the oxide or oxide-carbon mixtures. Direct chlorination of the pure oxide presents much less difficulty than chlorination of zircon sand or oxide ores. The oxide is easily ground to —200 mesh, and no silica is present to cause excessive consumption of chlorine or contamination of the product. Theoretical Considerations The principal chemical reactions involved in chlorination of mixtures of zirconium oxide and carbon may be written as follows: ½ ZrO2 (c) + C(c) + Cl2(g) = ½ ZrCl,(g) + CO(g) [I] 1/2 ZrO, (c) + CO(g) + Cl2(g) = ½ ZrCl,(g) + CO2(g) 121 ½ ZrO2 (c) + ½ C(C) + Cl2(g) = 1/2 ZrCl4(g) + ½ CO2(g) [3]

Jan 1, 1953

By G. S. Brooks

(New York Meeting, February, 1913.) THE tendency of the oxides of such metals as aluminum, zinc, chromium, and calcium to form compounds at high temperatures with iron oxide is well established by past investigation. Data of this reaction, as developed in laboratory research, have been contributed by Burleigh, Hofman, and Wells, in America, and by many others abroad. A partial bibliography of the subject is appended. From these authorities we learn that the ferric oxide here has the function of an acid, giving in the case of ZnO a zinc ferrite, with a normal composition of ZnOFe2O3. This formation of zinc ferrite particularly affects the success of such processes as leaching or magnetic separation, and thus becomes practically important to the metallurgist. But the meager existing data do not entirely agree; and quantitative results from muffle-practice are conspicuously absent. Furthermore, it being of some general importance to the zinc smelter in both roasting and reduction, the following few notes of operations on a commercial scale are contributed

Jan 5, 1913