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KNOWING the endpoint, or the equilibrium state, in steelmaking reactions is only part of the story. The rate at which the reactions proceed can be equally important. But the power of thermodynamics, which enables us to estimate the endpoint, is that a knowledge of the mechanism is not required. The methods of kinetics, however, are step-by-step analysis in which a knowledge of the detailed reaction mechanism is essential. As is evident from Chapter 16, a great deal of thermo- dynamic data for steelmaking are available and the underlying theory rests on a completely sound basis. This is far from the case with kinetic data and even kinetic theory. Nevertheless, it is worthwhile to examine the present state of knowledge, to see how far it may be applied to electric furnace reactions. KINETIC THEORY Heterogeneous Reactions. Classical kinetic theory and experimentation have been mainly concerned with homogeneous reactions taking place between different chemical species in a gas or liquid phase. The species are mixed together and the progress of the reaction can then be observed. This is possible because most experiments have been done at relatively low temperatures where the characteristic time for the mixing process is much shorter than the time for the chemical reaction to be completed. For example, in the homogeneous gas reaction, H2 (g) + I2 (g) 2HI (g) hydrogen and iodine may be added to opposite ends of a tube containing a diaphragm. When this is withdrawn, gaseous diffusion (and convection) mixes the two types of molecule almost completely before any hydrogen iodide molecules begin to appear. Such an experiment is inconceivable at more elevated temperatures, since the rate of the chemical process is so sensitive to temperature that reaction would be completed almost instantaneously wherever hydrogen and iodine came into contact; the rate of the mixing process would then determine the rate at which hydrogen iodide was formed. We should not, therefore, expect to observe many homogeneous reac-

Jan 1, 1964

By David H. Carlson, John H. Johnson

The paper presents background information, a description of mine characteristics that affect air monitoring techniques, and a review of Portable measurement techniques and instruments for gas and particulate matter sampling. A general review of the laboratory and field research being conducted at Michigan Technological University in the area of diesel emissions is presented. The facilities involved with this research are also described. These are the experimental mine, the diesel dilution tunnel test cell, the mine air monitoring lab (MAML), portable instruments, and the production mines used.

Jan 1, 1982

By J. A. Barr

Tennessee phosphates are commercially divided into three varieties: Brown, Blue, and White.

Jan 1, 1915

By Frederick N. Rhines

BECAUSE of the nature of the environments in which metals are handled, it is natural that gases should be suspected of intruding into metallurgical operations, there to produce effects both beneficial and detrimental. The problem of tracing and controlling such effects is often made difficult by the complexity of the conditions surrounding 'their occurrence, even though the fundamental mechanisms involved may be simple and of familiar type. Many gas-metal reactions are known to be implemented by processes of diffusion. These form a homogeneous group of phenomena which become more readily understandable when viewed together, in that the knowledge gained from one serves to interpret the next. It is the purpose of the present paper to present, by means of examples drawn from practice, a brief survey, of the ways in which gas-metal diffusion serves and obstructs the purposes of the metal-fabricating industries. The selection of the cases described was made by consulting more than thirty-six practicing experts whose combined experience provided an extensive coverage of the field and who were in a position to supply examples of occurrences of present day interest. The response was generous and it is regrettable that space permits the description of only a limited number of typical examples with but brief mention of parallel cases. THE NATURE OF GAS-METAL DIFFUSION The term "gas-metal diffusion," although commonly used, is ambiguous in so far as it implies that a definite group of substances may be identified as gases and may be expected to behave in a manner distinct from other substances in association with metals. "Gases" such as oxygen and hydrogen when diffusing through a liquid or solid metal are properly components of the liquid or solid solution; they behave as alloying elements and are not to be distinguished in their diffusion characteristics from other elements, except that each has an individual rate of diffusion. On the other hand, a number of metals in certain temperature ranges are volatile to the extent that they may appear in the form of vapor in metallurgical operations. For the sake of greater definiteness, therefore, it will be convenient to- regard as "gas-metal diffusion" any process in which the result depends upon one or more of the diffusing elements appearing, at some stage, in the gaseous state, or as a compound gas. No element, gaseous or otherwise, can diffuse through a liquid or solid metal unless it is at least slightly soluble in that metal. The elements of low atomic number

Jan 1, 1944

By H. J. French

AT THE request of a committee of the Engineering Division,1 National Research Council, a study of the properties of boiler plate at various temperatures up to about 900° F. (482° C.) has been instigated. The following is a report of preliminary tests made on two grades of ½ -in. plate and includes a description of the apparatus used in the determination of the proportional limit. Detailed reference to the many published investigations in connection with the properties of steel at various temperatures will be omitted from this report. Suffice to state that results obtained for variation in tensile strength elongation, and reduction in area with temperature are in substantial agreement with the effects now generally considered to be correct. Comparison of proportional limit values with results obtained by other investigators will be found in the conclusions.

Jan 2, 1920

By H. E. Rorschach

Activity in Oklahoma oil fields made 1937 one of the best years since 1926. During the year, 3454 wells were completed, an increase of about 25 per cent over the year 1936. Purchasers reports filed with the Corporation Commission of the State of Oklahoma showed a total of 221,842,-788 bbl. of oil purchased from leases in 1937, an increase of about 10 per cent over 1936. The assembly of a complete table of all of the oil fields in Oklahoma has not yet been achieved. Many of the early records of operators and pipe-line companies are incomplete. Table 1 includes all of the new fields, and this year there has been added work done covering pools discovered in previous years, so that most of the important fields in the state of Oklahoma are included therein. The outstanding development of the year was the discovery of the producing horizon classified as the Wilcox in western Payne County by the Mid-Continent Petroleum Corporation on a unitized block in sec. 18, Tp. 18 N., R. 2 E. This block is operated hy the Mid-Continent and owned in conjunction with the Carter Oil Co., Transwestern Oil Co. and Sinclair-Prairie Oil Co. Another important development of the year was the extension of the deep zone in the old Fox-Milroy area of Carter and Stephens Counties. Some of the other discoveries made during the year 1937 are South Cromwell, discovered by Sinclair-Prairie Oil Co.; Cromwell extension of the Fitts pool in Pontotoc County; discovery of the Langston area in Logan County; discovery of the Sporn area in Lincoln County by Skelly Oil Co. and the discovery of the North Wellston area in Lincoln County by Standard Oil & Gas Co. Table 2 shows the new oil areas discovered in Oklahoma during the year 1937 and areas that were discovered in 1936 but developed in 1937. Fox-Milroy Area.—Three wells were completed to the deep producing zone during the year. One of the wells completed in the early part of the year uas the Carter Oil Company's No. 1 Harley in sec. 24, Tp. 2 S., R. 4 W., 3 1/2 miles northwest of the original discovery well, the Ruth

Jan 1, 1938

By E. P. Polushkin

This work has for its purpose the establishment of a new method for determining the structural composition of alloys. The area occupied by a constituent on a few representative photomicrographs of the alloy is measured, by a planimeter, especially designed for metallographic work, and the volume and proportional weight of the constituent calculated. Experiments have shown that the results are accurate enough to justify the application of the method to many problems in metallographic research instead of chemical analysis. The advantage of the method is the possibility of determining the amount of the constituents without separating them from the alloy; their composition may also be determined if the ultimate chemical analysis of the alloy is known. Suppose Fig. 1 represents a part of a photomicrograph on which the total area of the black figures is to be found. By a system of parallel lines drawn short equal distances apart all figures may be divided into trapezoids. As the area of a trapezoid is equal to its median multiplied by its altitude, the relation between the total areas of the black and the white figures comprised within each strip is equal to the relation between the sums of medians for these figures respectively. This is also true for the whole area of the photomicrograph. Therefore, to determine the total areas of the black and white figures we must first find the proportion between the sums of the medians and then divide the area of the whole photomicrograph in the same proportion.

Jan 1, 1925

By J. C. Motz

Introduction The variations in crushing plant design seen during the past 30 years provide a valuable source of information and experience from which one can select the optimum arrangement for a specific requirement. The purpose of this paper is to examine some specific equipment configurations as they relate to operating efficiency, plant availability and final product size in the form of mill feed. Due to the varied ore properties, physical space limitations, size of ore body and financial resources, there is no single crushing or grinding flowsheet that is best. Since energy costs have risen dramatically during the recent past, it became obvious that significant savings are possible by selecting equipment and a circuit which offers low power requirements balanced with low wear metal and installed equipment costs. Relatively clear and measurable are the metal and maintenance costs and the ever increasing cost of energy. Metal costs in the form of crusher liners have not quite doubled in the last 20 years, while power costs have increased by a factor of four or five, depending on the region considered. Estimates made only a few years ago on the increased cost of energy are obsolete in view of the recent unstable conditions. Since power is therefore becoming the largest cost area, it behooves us to investigate potential cost saving methods in the form of lowering the KWH/Ton of crude. Crushing To reduce run-of-mine to mill feed requires reduction in a series of stages. The physical size and power requirements of a crusher capable of reducing hard rock vary depending on the application. Extended experience in most crushing plants show that a minus 19MM (3/4 in.) rod mill feed can be and is being produced in three stages of crushing. In the majority of cases, the last crushing stage is closed circuited using anywhere from 19MM (3/4 in.) to 14MM (9/16 in.) slotted openings on the sizing deck. In some copper concentrators, the mill feed is all passing 13MM (1/2 in.) using three stages of crushing and 14MM (9/16 in.) square openings on the closed circuit screens. It was felt by some that crushing to this fine size is only possible if the ore is friable and is relatively soft in comparison to the harder ores. Our results show that some of the copper ores are as hard as taconite and are crush-

Jan 1, 1982

By Maurice Cook

NORMALLY the grain size of cold-rolled and annealed copper sheet is of the order of 0.02 to 0.06 mm., and 0.1 min., for example, would, for many purposes, he regarded as undesirably large. The occurrence of very large grain sizes in a few isolated cases of copper sheet led the authors to inquire into the causes giving rise to such unusual results. During the course of this work a very large number of experiments have been carried out to determine the effect of varying the conditions of the final and penultimate rolling and annealing operations, as well as of earlier rolling and annealing treatments. A correspondingly large number of observations have been made, but within the space of one paper it is possible only to outline relatively briefly what appear to be the more important of these experiments and observations. The presentation of the results does not follow chronologically the order in which the experiments were carried out and they have been rearranged for the sake of simplicity. In recent years a considerable amount of work has been done in connection with the recrystallization and grain growth in metals and alloys that take place on annealing, and a number of generalizations have been reached. It is known that the crystal size in wrought material in the annealed condition depends on a number of factors, including the time and temperature of the annealing operations and the nature and amount of cold-work to which the material has been subjected. Results, however, that are not covered by these generalizations can be obtained, which, in some instances, may even appear to he contradictory to them. According to these generalizations gradual changes in grain size are effected by progressive variation of the factors involved in annealing or cold-working. The work recorded in the present paper, however, relates to the development of grain sizes which are far beyond those normally encountered in ordinary annealing operations and far in excess of grain sizes which, according to ordinary standards, would be classified as coarse or large.

Jan 1, 1938

By N. Albon, J. F. Miller, R. W. Coutant

The deposition of nickel from nickel carbonyl onto amorphous substrates has been studied, with attention being paid to the specific effects of the physical and chemical nature of the substrate and to the effect of oxygen on the crystal morphology. With substrates having microscratches or etch lines, nu-cleation was observed to occur preferentially at these surface features. Flame polishing of the substrate surfaces was found to remove any regularity in preferred nucleation sites. Nucleation was observed to occur less readily on substrates having relatively low surface energies, e.g., Teflon and carbon, than on materials having relatively high surface energies such as fused silica. At low oxygen concentrations [Ni(CO)4/O2 > 54 x 1031, apparently pure and well-formed nickel crystals were observed to nucleate and grow irrespective of the presence of oxygen. At higher concentrations of oxygen, a secondary growth process, dependent upon oxygen concentration and resulting in a gradual change in crystal morphology, was observed. It is concluded that the influence of oxygen on the nucleation and growth of nickel is determined by the relative kinetics of the various possible reactions, and that under the experimental conditions employed the 0-Ni interaction occurs at some nucleation or prenuclea-tion stage. THE purpose of the research on crystal nucleation in chemical vapor deposition as described in this paper has been twofold: 1) to examine some effects arising from the use of amorphous substrates, and 2) to study the specific effects of oxygen on the nucleation and growth of nickel in a nickel carbonyl-carbon monoxide system. The nickel-nickel carbonyl system was chosen for study for several reasons: 1) nickel films are of potential interest in electronic technology, and 2) the deposition can be carried out at moderate temperatures, thus making possible detailed study of the processes occurring and the use of a variety of substrate materials (including some which melt at relatively low temperatures). Fairly well-characterized chemical kinetics and a broad background of information are available on the py-rolysis reactions and on the mechanisms of Ni-O interactions. NUCLEATION AND GROWTH THEORY The theoretical background for the analysis of nucleation and growth by vapor deposition for a one-component system (physical vapor deposition) and the problems encountered therein have been reviewed by Hirth and pound.' More recently Mande12 has indicated the difficulties of applying such theory to chemical systems. One of the major problems involved is the possible multiplicity of chemical reactions and deposition routes. For example, those reactions which are probably of significance in a discussion of the pyrolytic deposition of nickel from nickel carbonyl under the conditions of the present experimental work are illustrated in Fig. 1. As is true with most cases of chemical deposition, many of the quantitative data necessary for a complete analysis of the system are either not available or not directly measurable. However, with the present system, sufficient data are available for a discussion of nucleation and growth on a qualitative basis. Classically, the rate of nucleation of a monatomic species being deposited from a vapor phase is given by

Jan 1, 1965

The following is an incomplete list of members and guests who called at Institute headquarters `during the period Aug. 10, 1918 to Sept. 10, 1918. Amil A. Anderson, Hill City, S. D. A. A. Holland. H. G. S: Anderson, Hurley, N. Al. Paul S. King, Wilmington, Del. Louis A. Barton, Capt., Engineers, U. S. A. Herbert G. Officer, Washington, D. C. K. Baumgarten, lst Lieut., U. S. R. A. B. Parsons. Charles W. Boise, Belgian Congo. Robert R. Pollock, San Francisco, Cal. Henry C. Carlisle, The Pas, Manitoba. Frank A. Smith, Edgewood, Md. J. Ross Corbin, Boyertown, Pa. Edward C. Thompson, Kennett, Cal. S. Le Fevre, Forest Glen, N. V. Malcolm M. Thompson, Morsemere, N. J. Harold P. Ford, Cleveland, 0. Lester C. Uren, Berkeley, Cal. William L. Hogg, Waynesboro, Va. Harold W. Aldrich has been appointed assistant general superintendent of the Inspiration Consolidated Copper Co. at Inspiration, Ariz. Capt. Percy E. Barbour, formerly with the New York State Troopers, has been granted a leave of absence from the Department for the period of the war, by the Governor, and has been appointed Captain in the Engineer Corps, U. S. A. He served on the Mexican border in the New York State National Guard. A. C. Barke, formerly with the United States Smelting, Refining and Mining Exploration Co., has accepted a position with the United States Fuel Co. at' Salt Lake City, Utah.

Jan 10, 1918

ALTHOUGH the refining period of the heat is generally defined A as starting after the charge has been completely melted, it may more properly be considered as beginning with the first efforts to facilitate the shaping up of the slag and the making of corrective additions for the control of slag or metal composition. Such actions may be initiated during the latter half of the lime boil. The early part of the refining period may, then, in essence overlap the latter part of the melting period. The primary aims of the refining period are: (1) to reduce phosphorus and sulfur from the steel bath to levels safely below the maximum contents specified; (2) to eliminate carbon to a specified level as rapidly as possible and still allow time for proper conditioning of the slag and attainment of the necessary bath temperature; and (3) to have the heat ready for tapping or furnace deoxidation, with slag in the proper physical and chemical condition, and with carbon and oxygen contents and the temperature of the steel at the proper levels for the composition and grade of steel being produced. The particular conditions that fulfill these aims are distinctly different, depending upon whether the steel is to be finished according to fully killed semikilled, or rimming practice and also depending upon the carbon range specified. Regardless of the type of charging practice employed, the object of the refining period is to produce repeatedly the desired finishing and tapping conditions for the grade of steel being produced. The variations and proportions of raw materials used in the charge may cause some variations in the degree of control required during refining, but not in the method of control. The refining period can therefore be discussed from a viewpoint largely independent of charging and melting practice. SHAPING UP THE SLAG In the first helper's vocabulary, refining practice consists in

Jan 1, 1964

By S. J. Kidder, G. C. McCartney

THE Helen Mine, of the Algoma Steel Corporation, in the Michipicoten district, Ontario, Canada, has produced more than 6,240,290 tons of iron ore. Prior to and during World War I, 2,823,369 gross tons of brown ore were shipped, and from 1939 to the end of the 1944 season, 3,416,921 gross tons of siderite ore were produced from open-pit operations. Brief descriptions are given of the nature of the ore, the mining methods employed and the manner of treatment of the ore. Shipment of the finished product, known as Algoma sinter, is made to blast furnaces in both Canada and the United States. The iron-ore bodies-i.e., the oxide ores of the Old Helen and the siderite of the New Helen-are a part of a tabular shaped area of iron formation that extends over a length of more than 10,000 ft. and has a maximum width of 1000 ft. The ores are considered to be a product of introduction of iron-bearing material accompanied by replacement of the rocks already present. It is shown that introduction took place subsequent to the development of the major folded structures. It is believed the iron-bearing material emanated from an igneous source.

Jan 1, 1946

By V. J. Kniazeff, S. A. Naville

The problem of unsteady-state condensate-gas flow through porous media leads to a set of second-order non-linear partial differential equations. Such a set of equations is numerically solved in the case of radial two-phase flow around a well, taking into consideration both the thermodynamical properties of the fluid and the mechanical properties of the reservoir. The fluid properties, reflecting the PVT relationship of the gaseous and liquid phases, are expressed by using the partial specific masses of the two main separator products in these phases. The flow properties of the reservoir rock are expressed by the generalized Darcy's law for the liquid phase and by a quadratic relationship between the rate of flow and the pressure gradient for the gaseous phase. The numerical solution of the equations for pressure and saturation US radius and time is worked out through programs written for a computer. The evolution of bottom-hole pressures, well productivities or- deliverabilities and effluent compositions with the depletion of the reservoir is easily derived. The application to the Saharian gas-condensate field Hassi R'Mel led to a better understanding of the drainage mechanism. A zone of fairly high liquid saturation develops around the wells, reducing the effective permeability, and represents a loss of condensible products in addition to the PVT-like retrograde condensation. lnside this zone, near the well, the deviation from Darcy's law for the flow of the gaseous phase governs the well deliver-ability. A back-pressure test has been computed and correlates with the field results. INTRODUCTION Two-phase flow of volatile hydrocarbons, like condensate gas or light crude oil, may be treated as the flow of a binary mixture by an arbitrary division of the chemical components into two groups. This is translated into two equations of mass continuity, which constitute a set of relation- ships for the pressure and the saturations vs the space coordinates and the time. The equations contain the laws governing the composition and the motion of the phases. The problem so defined is solved with the assumption that the compositions of the phases at any pressure are respectively the same as those observed in a PVT measuring cell under differential liberation. In a first series of computations, it was assumed that the flow obeys the generalized Darcy's law. A satisfactory representation of the retrograde condensation around the well was thus obtained. In addition, the trend toward decreasing effective permeabilities was obtained, and the computed composition of the effluent checked the laboratory values. However, it has not been possible within this basic assumption to represent the non-linear relationship between the production rate and the bottom-hole pressure drawdown as observed for gas wells in the field. Following the advice of A. Houpeurt it was decided to consider the relative permeability to gas as a function of the velocity of the gas Phase.1 The necessary physical determinations were made by E. COstaséque using a method devised by A. Houpeurt and R. Iffly. As numerical processing of the equations progressed, several difficulties were encountered which were overcome through collaboration with the computer manufacturer. This mathematical model of two-phase flow in porous media had been primarily intended for and extensively applied to the case of the Hassi R'Mel gas-condensate field, operated by SN Repal for SEHR, a joint subsidiary of SN Repal and CFP (A). The programs have also found their applications to forecast the behavior of several fields in the Sahara area containing light and volatile hydrocarbons. BASIC EQUATIONS We will consider a zone in the porous reservoir where the flow properties and the in situ composition of the fluids can be assumed to be uniform. A part of the equations of transient flow can be written with the specific gravity of the fluids being taken equal to the sum of the contributions due to the

Jan 1, 1966

By Mrs. V. J. DeCarlo, G. P. Salvo, H. W. Schadler, L. M. Osika

The lattice parameter of the inlerrnetallic compound Nb3Sn has been measured as a function of temperature from 80° to 1290°K. The results are compared with published data on the thermal ex- ThE recent interest in the intermetallic compound, Nb3Sn, as an engineering material for the production of superconducting devices has necessitated that certain engineering data be obtained. Because of the difficulty encountered in producing bulk pansion of niobium and indicate that the compound when made by diffusion of tin into niobium at 1000°C, would be subjected to a tensile strain of about 0.1 pct when cooled to room temperature. material which is single phase, the coefficient of thermal expansion has not been measured by dilata-tional methods. Therefore the lattice parameters of fine-grained samples of Nb3Sn produced on the surface of a niobium sheet by heating in molten tin at 950°C have been obtained as a function of temperature. The results are compared with published data on niobium2 and Nb3Sn3 and with lattice-parameter measurements made on small single crystals of Nb3Sn.

Jan 1, 1964

By C. O. Worden, E. K. Landgraf, C. A. Zapffe

Following the discovery of Parke and Ham that deoxidation control of cast molybdenum can be predicated upon simple fractographic examination, a special study of that metal was undertaken to investigate those patterns ascribed to forge-ability and nonforgeability. An elaborately developed system of cleavage patterns immediately rewarded the study; and they are reported here as a necessarily preliminary contribution calling attention to information which is both new in type and in origin. In general, the present observations confirm those of Parke and Ham, and Wood-side; but they also disclose a wealth of detail and correlated phenomena which greatly expand the earlier information. For example, the oxide pattern of nonforgeability is found to be complex, perhaps involving as many as three distinctive patterns, And the nature of the carbide seems to be at least twofold. In addition, transgranular facets are here shown for the first time. Elaborately complex, but in a characteristic manner, these facets depict distortion in original crystal growth which provides truly extraordinary patterns. No carbide and oxide forms display themselves transgranularly, except in profile as exceedingly thin superficial films at the grain boundaries. Crys-tallographic features are also rare—a condition undoubtedly resulting from the great substructural distortion; but occasionally registrations are found of cleavage on {00I}, and faulted areas believed to be Neumann-type deformation on I I121. Introduction Parbe and Ham,' and again Woodside,2 have reported that the forgeability of molybdenum cast by their Vacuum-electric-arc Process can be predicted with great dependability by a simple fractographic observation. They state that nonforgeability is the result of a grain boundary oxide which can be readily identified on the fracture facet at high magnification; and they convert the nonforgeable condition to a forgeable one by increasing the carbon content of the melt until the oxide structures subsequently observed in the fracto-graph become replaced by a second strongly marked pattern characteristic of carbide and coincidentally indicative of forgeability. Considerable importance immediately attaches to such observations: (I) because of their direct commercial application to one of metallurgy's inviting and relatively unexplored metals; (2) because of a general scientific curiosity regarding the nature of these characteristic markings; and (3) perhaps more important, because of

Jan 1, 1949

By F. E. Bash

A GREAT many industrial operations require the application of heat to carry on or complete processes, in which cases the temperatures must often be controlled within very narrow limits. For the lower temperatures, this control is not, as a rule, difficult as a number of types of reliable pyrometers are available for the work; for example, the mercury and resistance thermometers and the thermocouple. For temperatures above a red heat, thermocouples, platinum resistance thermometers, and total radiation and optical pyrometers may be used, depending on conditions. It is often undesirable, and sometimes impossible, to take temperatures of material by immersing the pyrometer in it or by placing the temperature-measuring device in a position in which it will attain the temperature of the material. The pyrometer may contaminate the product; the temperature may be so high that the pyrometer will not hold its calibration, clue to ineffectual protection and consequent contamination; the object may be inaccessible, as a lamp filament, etc. In such cases, a total radiation or optical pyrometer must be used. The disappearing-filament, or Morse, type of optical pyrometer works on the following principle: An objective lens, Fig. 1, focuses the image of the object whose temperature is desired in the plane of the lamp filament at F, which is at the principal focus of the ocular lens shown in the eye-piece. By this arrangement the eye will not have to accommodate itself first to the lamp filament and then to the object at a distance, and the lamp filament will appear superposed on the object. To balance the instrument, the current is adjusted by means of a rheostat until the tip of the lamp filament just disappears against the object as a background. Figs. 2, 3, and 4 show the appearance of the filament when too cold, too bright, and just balanced.

Jan 8, 1919

By M. M. Wong, D. E. Couch, G. M. Martinez

The Bureau of Mines electrowon hafnium metal with an average oxygen content of' 150 ppm at 700°C from an electrolyte containing 27 wt pct LiCl, 62 wt pct RbCl, and 11 wt pct HfC14. The average anode and cathode current efficiencies were 90 pct at anode and initial cathode current densities of 86 amp per sq ft. Haf-nium metal with an average oxygen content of 440 ppm was electrowon at 800oC from an electrolyte containing 90 wt pct KC1 and 10 wt pct HfCl4. The average anode and cathode current efficiencies were similar to those obtained in the LiCL-RbCl-HfCl, electrolyte. The chlorine gas given off at the graphite anode was vented through either a silica or a graphite tube to prevent cell corrosion. THE current method for the commercial production of high-purity hafnium is the thermal decomposition of Hfl4.1 The iodide method is not adaptable to continuous process techniques. Nettle, Hiegel, and Baker2 studied the electrorefining of hafnium from hafnium sponge containing 800 ppm oxygen. They failed to obtain hafnium with 600 ppm oxygen in their initial deposits and obtained AEC specification for oxygen only after 75 pct of the soluble hafnium had been removed from the electrolyte. Calculations using their data indicated this was approximately 4 lb of hafnium. The electrolyte was then used to produce approximately 3 lb of hafnium with a low oxygen content. However, no data are shown concerning the amount of anode material initially used or what percent of it was dissolved, therefore, results are not suitable for evaluation of a continuous operation. In general, it was not possible to consistently obtain low oxygen content metal with the electrolytes described by Nettle, Hiegel, and Baker. Wong, Hiegel, and Martinez3 investigated the electrorefining process for hafnium and showed that even by strict control of electrolyte composition only relatively low oxygen reduction could be obtained. The oxygen contained in the hafnium anode material tended to transfer to the cathode deposit and only a limited purification was possible. Both the "iodide" and the "electrorefining" processes depend upon hafnium sponge as a starting material. The sponge is normally produced by magnesium reduction of HfC14 ' and does not meet AEC specifications for hafnium metal. Since only 30 pct of the anode feed could be utilized3 in the electrorefining cells, the Bureau of Mines developed an electrowinning process. HfC14 was used as the feed material for the electro-winning process described in this report. Many of the electrolytes used in the electrorefining studies3 ap- peared to be suitable carrier-electrolytes for HfC14. However, in the initial studies on electrowinning, it was desirable to use electrolytes that had low solidus temperatures and could be operated over a wide temperature range to investigate parameters of the process. Therefore, electrolytes containing LiC1, NaC1, KC1, RbC1, CsC1, and HfC14, in various combinations were explored. EQUIPMENT Chlorinator. Hafnium carbide was chlorinated to produce HfC14 in the batch-type chlorination shown in Fig. 1. Chlorination temperatures were measured with a thermocouple placed in the center of the HfC charge. A flow meter was used to monitor the helium and chlorine. The exhaust side of the silica chlorina-tor tube was equipped with a flask for collecting organic material released during the initial heating of the HfC. The temperature of an internal heater, which extended from the HfC14 condensing flask to the hot end of the chlorinator, was adjusted to prevent the HfC14 from condensing before entering the collection flask. Helium and excess chlorine were exhausted through the lid of the collection flask to an aqueous NaOH solution. Sublimer. Initial studies were conducted using a sublimer, Fig. 2, made by placing a 13/8-in. OD nickel thimble 11 in. long, inside a 11/2-in. ID nickel bell 12 in. long, and locking it in place. This unit was loaded with HfC14 and partially immersed in the molten electrolyte for sublimation directly into the electrolyte. In another sublimer shown in Fig. 3, the HfC14 was contained in a "resin reaction flask". Quartz wool, previously heated to 600aC, secured between two nickel wire screens, was placed just above the HfC14 powder. The lid contained a vacuum outlet, a gage, an argon inlet, and an air-cooled pipe for condensing the HfC14. This sublimer was evacuated and heated. The sublimation temperature was not critical and the sublimer operated satisfactorily at all temperatures between 250" and 350°C. Electrolytic Cell. The electrolyte chamber, Fig. 4, was made of mild steel 8-in. schedule 20 pipe, 30 in. long. The exterior was metallized with a Ni-Cr alloy. The electrolytes were contained in a 16 gage nickel or iron liner with a nickel heat shield on top. The cell was heated by a resistance furnace. A 21/2-in. ID by 25 in. long air lock was connected to one port of a two-port cell cover assembly through a slide valve. The cover assembly of the air lock was electrically insulated from the cell and was equipped with a rubber sleeve that provided for the passage of the cathode lead. This allowed the cathode deposits to be removed and a new nickel cathode to be introduced without allowing air to enter the cell. A tube-rod assembly was bolted to the other port on the cell cover assembly and was sealed by a packing seal. The tube-rod assembly consists of a graphite

Jan 1, 1970

By George A. Komadina

The Pima mine lies 20 miles southwest of Tucson, Ariz., and 45 miles north of the Mexican border. It is located on a hillside overlooking Tucson, which allows for gravity flow generally through the plant. In April 1965, an expansion was authorized by the mine's board of directors. This will triple the mine's output to 18,000 tpd. At this rate, it is estimated that there is sufficient ore to last 20 years.

Jan 6, 1965