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By Martin Epner, Eric Gregory

DURING the past decade, considerable work has been carried out on various cermet systems in an effort to produce materials suitable for high-temperature applications in gas turbines. Most of the materials have not, as yet, met the requirements of the engine manufacturers, primarily because of their lack of room-temperature ductility and thermal shock resistance. In the field of tool materials, however, although ductility is still of prime importance, much has been accomplished by improving design parameters and the quality of carbide materials with a view to using cermet compositions successfully. The systems described in this paper were designed primarily for application in this field, although their development was a natural outcome of work on similar compositions designed for high-temperature service. In steel-bonded titanium carbide, the steel binder imparts heat treatability to the system while the carbide provides abrasion and wear resistance. Combining the carbide and the steel matrix in carefully controlled proportions results in a composite material which, when the steel is hardened, has man of the properties of cemented tungsten carbide. In the annealed condition, this material can be readily machined by the conventional chip-removal techniques. Titanium carbide has certain distinct advantages over many of the other carbides when combined with a steel matrix. It is among the hardest of the carbides and is one of the most stable. Liquid iron wets titanium carbide, and this wetting assists in the formation of a dense cermet. Once the composite structure has been formed, the titanium carbide acts as a relatively inert phase during the heat treatment of the matrix. PREPARATION OF ALLOYS The steel-bonded titanium-carbide materials described in this paper were prepared by the liquid-phase sintering technique. The titanium carbide used had an average particle size of 6 to 7 p, a total carbon content of 19.4 pct and 0.35 pct free carbon. This was blended with the elemental metal powders by ball milling them together in a hexane medium. After drying, paraffin wax was added to the blend to provide green strength in the pressed briquettes, and compacting was performed at 15 tsi. Liquid-phase sintering was carried out in vacuum at temperatures which depended on the chemical composition of the system involved, but which were usually around 2640° F. The resultant materials had a density approaching 100 pct of theoretical. The

Jan 1, 1961

By John C. Machisak

The thirty-fifth consecutive National Safety Competition sponsored and conducted annually by the Federal Bureau of Mines, Department of the Interior, closed with several noteworthy accomplishments to its credit. Some of them are: 1. A record low injury-frequency rate of 18.293 disabling work injuries per million man-hours equal to that established in 1957. 2. The third lowest injury-severity rate (4,335). 3. The second highest number of mines and quarries participating (672) 4. A record number of participants finishing the competitive year without a disabling work injury. 5. All recipients of Sentinels of Safety trophies free of disabling work injuries for the first time since 1952.

Jan 1, 1961

By H. C. Fuller

Depletion of iron ore in the Nation's large deposits has directed attention to other sources. One of these is the titaniferous iron ore of the Iron Mountain, Wyo., area. Tests were made to determine the feasibility of smelting this ore, which contains about 20 percent titanium dioxide (Ti02), in an electric-arc furnace to produce pig iron. Initial tests, which were made in a 30-pound-capacity induction furnace, demonstrated that the iron could be easily reduced to metal and that limestone was a suitable and effective flux. Larger scale tests then were made in a 50-pound-capacity electric-arc furnace to obtain the more detailed information necessary for the planned continuous operation of a still larger arc furnace. The principal facts determined by preliminary batch-smelting studies were that (1) 9 pounds of limestone flux was required for each 100 pounds of ore smelted, (2) expensive coke was not required because coal proved to be a satisfactory reductant (near stoichiometric carbon was optimum), and (3) overreduction, which produced a viscous slag, must be avoided.

Jan 1, 1961

By F. Petkovich, M. P. Sudbury

Development of a new method of treating flotation concentrates for the preparation of feed suitable for direct charging to blast furnaces or converters is described. The method takes advantage of the fact that pyrrhotite contained in the concentrates can be made to undergo exothermic reactions which, under properly controlled conditions, result information of oxidation products that serve to cement the concentrate particles together. Thus green concentrates either in the form of pellets or briquettes containing 5 to 8 pct moisture not only were hardened, but also completely dried autogenously by continuous countercu,vrent shaft treatment with air. The process was developed through pilot plant operations ranging from 35 1b per hr to 2.5 tph, culminating in products evaluation tests on a railway-car scale. Falconbridge Nickel Mines Ltd., Falconbridge, Ont., have practised sintering, on a travelling grate machine, for many years to prepare a pyr-rhotite-bearing Cu-Ni sulfide flotation concentrate for blast furnace smelting. In recent years the development of new mines, and the construction of concentration plants some 40 miles from the smelter has increased the quantity of concentrate shipped, and encouraged the search for a method of producing dry, hard pellets or briquettes suitable for direct charging to a blast furnace or converter, and capable of withstanding considerable handling. The cementing properties of pyrrhotite oxidation products were discovered during a search for a suitable agglomeration method for sulfide concentrates, and were exploited in a process subsequently developed for autogenously drying and hardening pellets and briquettes of pyrrhotite-bearing Cu-Ni sulfide flotation concentrate. EARLY TEST WORK The production of hard, dry pellets of concentrate filter cake was attempted in the drying plant of one of the new concentrators. While soft pellets were produced containing 5 pct moisture, attempts at further drying resulted in disintegration of the pellets and intolerable dusting. The plant therefore was controlled to produce a concentrate containing about 6 pct moisture. The partially dried concentrate, which was shipped to Falconbridge for sintering, tended to heat spontaneously in transit. An at- tempt to briquette the moist concentrate at Falconbridge, in a plant incorporating a muller, a 20-in. roll briquetting press, and a steam-heated travelling grate oven, was more successful, although the equipment corroded rapidly due to the acid nature of the concentrate after spontaneous heating had occurred. LABORATORY STUDIES OF SPONTANEOUS HEATING OF CONCENTRATE The spontaneous heating of partially dried concentrate was studied in the laboratory. Moist concen-

Jan 1, 1961

By Alan Lawley

AS part of a programme of experimental work on single crystals of rhenium and ruthenium, it was found necessary to have the crystallographic angles for these elements. The angles given in Table I were determined to the nearest minute of arc, by Univac Computer. The angle $ between (HKIL) and (hkil) is given by the formula: The angles given for rhenium should be particularly useful in view of the increasing interest in this element. For completeness, angular values are also given for cadmium zinc and magnesium; these form a more complete set of values than those given by Salkovitz.' The assistance of Professor J. Hobstetter and Mr. J. Crozier in the programming of this data is acknowledged. The work is sponsored by the Office of Naval Research under contract No. NONR 551 (19).

Jan 1, 1961

By W. L. Phillips

The recovery properties of compression-deformed lithium fluoride single crystals were investigated as a function of prior strain, annealing time, and annealing temperature. The recovery process was studied by observation of etch pits and birefringence stress patterns. The recovery process involved first a redistribution of the dislocations and then a decrease in their number. Only by annealing at high temperatures after small strains (<0.02 in. per in.) was it possible to obtain complete recovery of mechanical properties. LITHIUM fluoride affords unusual opportunities to extend the knowledge of deformation mechanisms of nonmetallic crystalline compounds. Single crystals of high purity are readily available. These crystals deform by slip on the (110) <110> system.&apos; Unlike those of several other ionic crystals, the stress-strain curves of annealed lithium fluoride are reproducible.2 Dislocations generated in the crystals during deformation can be revealed by etch pits.3 This fact makes possible more detailed studies of mechanisms than is usually the case with metals. Also, because lithium fluoride is transparent, it is possible to follow the recovery process with birefringence stress patterns. It has been shown that with metals an increase in temperature increases the amount of recovery for a given time, and the amount of recovery increases with increasing time at the same temperature.4-6 The yield stress has also been shown to be dependent on the rate of cooling after annealing.&apos; Annealing germanium, a covalent-bond material, at high temperatures after deformation redistributes the dislocations and reduces their number. The purpose of the present paper is to extend the knowledge of recovery properties to an ionic crystal, lithium fluoride. The effect of strain, time, and temperature of recovery on the stress-strain curve was investigated. The recovery process was followed by observations of etch pits and birefringence stress patterns. EXPERIMENTAL PROCEDURE Specimens measuring approximately 0.10 by 0,10 by 0.30 in. long were cleaved from a single bulk

Jan 1, 1961

By W. L. Dare

This report is one of a series published by the Federal Bureau of Mines to describe methods and costs of mining uranium on the Colorado Plateau. The Navajo Uranium Division of Kerr-McGee Oil Industries, Inc., mines uranium from several deposits of carnotite-type ores, which lie buried in the Lukachukai Mountains on the Navajo Indian Reservation, Apache County, Ariz. The country is rugged and isolated Constructing and maintaining roads has been a continuous task. The ore bodies occur within the Salt Wash member of the Jurassic Morrison formation and are similar to other such deposits on the plateau. The current mining activity in the Lukachukai Mountains is a result of uranium-ore discoveries in 1949, although the Navajos undoubtedly knew of the outcrops of yellow uranium minerals long before that time. The ruggedness of the country and the heavy soil cover over much of the surface hampered prospecting, but probably the main reason the ore was not found sooner is that no one took the trouble to look for it in the Lukachukai Mountains.

Jan 1, 1961

By W. L. Price

The intelligent selection of wire cloth and perforated plate for screening surfaces seems a rather confusing subject to the newcomer in aggregate processing. The proper application of various screening surfaces is a complicated one and one could consider himself an expert only after many years of working with all applications. However, part of the subject matter could be simplified considerably for, the average screen user. In this paper an attempt will be made to do this, by presenting some comparative specification data along with cost figures Unfortunately, it is impossible in the limited scope of this paper to give actual service comparison records between different cloths or cloth and plate. Anyone who has considered making actual service comparisons for competing screening media is well aware of the almost insurmountable problems Their solution would form the basis for a separate paper on that subject alone. Therefore, this paper will be limited to comparative data up to the point of installation.

Jan 1, 1961

By R. J. Gajan

As part of its research program on secondary metal refining, the Federal Bureau of Mines has developed a fast method for determining aluminum, iron, copper, cadmium, and lead in zinc-base alloys. The new method is intended for use by trained technicians in laboratories with inexpensive equipment. It can be used either in the analytical laboratories of the many small plants that are characteristic of the secondary metals industry or in laboratories engaged in basic research to improve refining processes. A complete analysis for the foregoing elements can be made in less than 3 hours from a single sample in solution. The method is especially helpful when a small amount of sample is available. Aluminum and iron are determined spectrophotometrically and the other elements polarographically. The new method is now being used for control analysis in metallurgical research, and the results compare favorably with previously used spectrographic methods. Luke and Braun4/ described a photometric method for the determination of aluminum in zinc diecasting alloys in which the aluminum was complexed with Aluminon reagent (ammonium salt of aurintricarboxylic acid), forming a red lake. An adaptation of this method was used for determining aluminum. Beers law is obeyed between 0.01 and 0.06 milligram of aluminum.

Jan 1, 1961

By H. Linder, W. H. Dennen

The graphitic carbon content of soils may be used to detect and delimit subsurface graphitic zones. Spectrographic measurement of carbon in C horizon soils from several areas in the northeastern United States shows good correlation with known graphitic bodies. Bodies of graphite and sulfides are readily located by electromagnetic prospecting methods, but these methods cannot generally discriminate between them. Usual practice, therefore, requires follow-up work on electrically anomalous areas by trenching, drilling, or soil sampling in order to determine the mineralogical nature of the conductor. The efficiency and cost of such follow-up is consequently an important factor in prospecting. The presence of buried sulfide deposits is often reflected in concentrations of metals in the superincumbent soil. Simple chemical tests for such metal concentrations have been developed and applied with considerable success. Bodies of graphite or mixtures of graphite and sulfides are, however, very common and a means whereby buried graphite could be detected by soil testing should provide valuable additional information in the search for ore sulfide and graphite deposits. Graphite is a notably stable substance and should persist in soil above graphite-rich horizons. Microscopic examination of soil samples high in carbon, however, failed to reveal any recognizable graphite fragments indicating a grain size in the clay range. Presumably such small particles would have some mobility in a soil by a translocation mechanism similar to that proposed for the movement of clay particles in a soil profile. Experimental data supports this idea since the boundary between background and anomalous soils carbon values is quite sharp, but the anomalous zone is slightly broader than the graphitic source rock. A simple spectrochemical technique for the determination of carbon in geological materials has been described by Dennen,1 and may be directly applied to soils. A modification of this technique which employs an arcing chamber through which nitrogen is passed is recommended to decrease contributions from atmospheric carbon dioxide. Tests indicate that soils over graphitic zones may be strongly enriched in carbon. The spectrochemical determination of carbon depends upon the formation of the cyanogen molecule (CN) from carbon in a sample and atmospheric nitrogen, under the high temperatures associated with a dc arc. Samples for analysis are dried, lumps broken, and screened. A small portion of the -100 mesh fraction is packed into a copper electrode and excited as the cathode of a dc arc. The band spectra of cyanogen are recorded photographically and the density of the bandhead CN 3883A is measured. The limit of detection of the method is about 0.01 pct C and its coefficient of variation is about 15 pct. Soils, of course, contain carbon in other forms than graphite, and the amount of interference from such sources was examined. The C horizon of several soils from Massachusetts, Maine, and Pennsylvania were found to have a carbon content of 0.3 to 0.5 pct by weight. This content is chiefly due to the presence of carbonates and vegetable matter in the sample and may be readily eliminated, or at least

Jan 1, 1961

By N. J. Grant, Hans Brunner

ThE materials used in this investigation were furnished by the Aluminum Co. of America and consisted of high-purity alurhinum (99.995 pct) and two aluminum-magnesium alloys containing approximately 2 and 5 pct Mg. The compositions of these alloys are listed in Table I. The materials were received as hot rolled 3/8-in. diam rods and were made from the same heats as the materials which were previously used in this laboratory.&apos;j3 The rods were cold swaged to 1/4-in. diam by 1 in. long, and then had two parallel flats machined over the gage length 0.085 in. apart. The test bars were annealed for 10 min at 700° F, and strained 1 pct in tension at room temperature. They were electropolished (80 pct acetic acid; 20 pct perchloric acid, 70 pct concentration) at a temperature of 60°F at approximately 20 v. A grid, transverse or square, spaced 0.2 mm apart, was impressed by rolling a fine threaded screw (128 threads per in.) across the flat surfaces. The depth of the grooves was less than 5 p. For final annealing and grain size control the specimens were enclosed in aluminum foil and sealed in Vycor tubes. Annealing conditions varied from 1 hr at 700° F to 5 days at 1050° F, depending on the alloy content, to give for most of the specimens a final grain size of about 1 mm. This treatment was followed by electropol-ishing as described above. For the test series presented in Figs. 4 and 5 round specimens were used instead of flat ones, and fine machining marks served as marker lines instead of the impressed grid lines. Electropolishing was omitted. The major advantage is that the spacing of the machining marks is only about 1 u as compared to the 200 u of the impressed grid lines, permitting higher precision in strain measurements. Unfortunately the strain annealing necessary for grain size control also resulted in some preferred orientation of the grains. The preferred orientation of three arbitrary specimens was measured by X-ray diffraction methods and the averaged results are shown in Fig. 1. The possible effects of the preferred orientation on the test results will be discussed later. The testing temperatures were 410°, 515", 725", and 940° F, with one exception in the case of the 5.1 pct Mg alloy. Since the solubility limit of this alloy is 520°F, a test temperature of 545°F was cho-se sen instead of 515°F. The selection of the test temperature was based on two considerations: 1) at 900°F and above, extensive grain boundary migration made it more difficult to measure grain boundary sliding; 2) at 400°F and below, there was so little grain boundary sliding that it was again difficult to make precise measurements. The stress was chosen to give a creep rate of approximately 2.7 pct per hr in connection with Figs. 2

Jan 1, 1961

By Robert H. Raring

Viewed abstractly, a mill may be defined as a mineral processing facility located somewhere between the mine and the tailings storage area, Just how mining operations and the demands of tailings storage affect mill design is, the subject of this paper. At the outset, it will be readily acknowledged that no two installations can, or ever will be the same. At one extreme is the bucket line dredge where the distance between the ?mine? and the tailings area is measured in terms of tens of feet. At the other extreme, the large open pit copper mines are frequently spread across twenty, miles or so of countryside with the ore moving to the mill, as exemplified by the operations at Bingham Canyon, Ray, or Ruth - the "upstream" counterparts of Garfield, Hayden and McGill. In each of these cases, mill location was largely determined by requirements for tailings storage and/or water supply.

Jan 1, 1961

By Samuel P. Polack

This report reviews investigations to determine the fire hazard in coal mining when using flammable petroleum hydraulic oils to actuate mining equipment and summarizes research by the Bureau of Mines and industry on fire-resistant hydraulic fluids. Tests were established to evaluate fire resistance and the necessary characteristics to assure adequate service when fire-resistant fluids are used to replace petroleum hydraulic oils. The research was conducted in the laboratory and field trials under actual operating conditions in underground mines. Bureau of Mines Schedule 30 became effective December 17, 1959; the first approval was granted on February 18, 1960, and the twelfth was granted on March 17, 1961. The approvals include nine ready-mixed (by the producer) fluids and seven concentrates to which water is added by the user according to instructions from the producer. Seven synthetic-type fire-resistant hydraulic fluids submitted by two producers are also approved. Over 100 coal mines are now using water-in-oil emulsion-type fire-resistant hydraulic fluids in varying degrees from a trial in one machine to all the hydraulic equipment in an entire mine.

Jan 1, 1961

By G. V. Jere, C. C. Patel

Chlorination of the various constituents of ilmenite by different chlorinating agents in presence of various reducing agents, have been considered on the basis of the standard free energy and standard enthalpy changes as a function of temperature. The standard free energy change considerations show that it is beneficial to chlorinate ilmenite by chlorine in the presence of carbon and also that iron constituent of ilmenite can be preferentially chlorinated by clzlorine, titanium tetrachloride or their mixture. These findilzgs have been corroborated from the published work. METALLURGICAL processes involving the use of titanium tetrachloride have gained in importance because of the use of the latter in the manufacture of titanium metal. Since ilmenite is more abundant in nature than any other titanium mineral, the future of the metallurgical processes depends on the utilization of ilmenite for the production of titanium tetrachloride. In these laboratories, investigations have been carried out on the chlorination of ilmenite under a variety of conditions.1&apos;2 During these studies, it was noticed that 1) preferential chlorination of iron was effected at low temperatures (400° to 600°C) and at low carbon content (6 to 7 pct), 2) carbonyl chloride retarded the chlorination of iron oxides and titania perceptibly, while 3) carbon-tetrachloride, compounds of sulphur and some other catalysts favored the chlorination. Moles3 has found that oxides of iron are chlorinated in preference to titania at high temperatures, while wilcox4 has claimed the preferential chlorination of titania between 1200" and 1500°C. It has been shown in this paper that preferential chlorination of titania claimed by Wilcox is not likely to occur. Daubenspeck and coworkers5,6 have claimed the preferential chlorination of iron by chlorine or by a mixture of titanium tetrachloride and chlorine between 700° and 1050°C in the absence of carbon. Even when plain titanium tetrachloride is employed as the chlorinating agent, pascaud7 noticed the preferential chlorination of iron and other oxides. The purpose of this paper is to explain from thermodynamical considerations, the various chlorination reactions studied so far. ILMENITE CONSTITUENTS AND THEIR CHLORINATION PRODUCTS Although the general composition of the ilmenite mineral is represented as FeTiO,, most of the ilmenites found in nature have variable quantities of TiO2 (44.6 to 64 pct), FeO (4.7 to 36 pct) and Fe2O3 (6.9 to 28 pct).8 The higher content of ferric iron in ilmenites was attributed by Millerg to the presence of arizonite (Fe2O3.3TiO2). But the X-ray studies by Overholt, Vaw, and odd" have shown that arizonite is a mixture of haematite, ilmenite, anatase, and rutile. Except for the anatase, similar views have been advanced by Lynd, Sigurdson, North, and Anderson8 from magnetic, X-ray, and optical and electron microscope studies. The ilmenite ores can, therefore, be assumed to consist of mineral aggregates of ilmenite, rutile and haematite. From the free energy of formation of ilmenite (FeTiO3), it has been shown by Kelley, Todd, and King11 that ilmenite is stable even up to its melting point (1367°C) and would not undergo decomposition into its constituent oxides. Schomate, Naylor, and Boericke12 have found that in the presence of a reducing agent the iron constituent of ilmenite is selectively reduced. The reaction of chlorine with ilmenite in presence of a reducing agent can, therefore, be synonymous with that of the reaction of chlorine with the constituents of ilmenite, viz., TiO2, FeO, and Fe2O3. Most of the reaction products of chlorination of ilmenite in the presence of reducing agents will be in equilibrium with their dissociation products, depending on the temperature. The titanium tetrachloride is, however, quite stable up to 1500°C due to its covalent nature. The equilibrium for the ferric chloride system has been investigated by Kangro and Bernstorff, 13, schafer14 and Kangro and petersen,15 and the results are summarized in Fig. 1, curves a, b, and c respectively. From these results, it is clear that the ferric chloride disociates as follows: 324° to 700°C FeaCl6(g) ?2FeCl2(c) + Cl2(g) [1] 324°to 900°C Fe2Cl6(g) =2 Fe Cl2 Reaction [I] (curve a) occurs in the forward direction to about 6 pct at 400°C but falls off very rapidly with increase in temperature and beyond 600°C, it is practically negligible, perhaps due to the formation of the stable monomer, FeC13(g). As the temperature is further increased, the amount of FeCl,(g) in-

Jan 1, 1961

By J. E. Gray

Before specifications are discussed it may be well to define the term "Mineral Aggregates." Professor K. B. Woods (1) defined "Mineral Aggregate--An aggregation of sand, gravel, crushed stone, slag, or other material of mineral composition used in combination with a binding medium to form bituminous and portland cement concrete, macadam, mastic, mortar, plaster, etc., or alone as in railroad ballast, filter beds, and various manufacturing processes, such as fluxing, etc. " This definition is too all inclusive for the purposes of this paper; therefore, this discussion will be confined to specifications for natural aggregates which means sand and gravel and crushed stone, and limited primarily to coarse aggregate which is aggregate larger than one-quarter inch in size. To the uninitiated, this may seem to be a very limited subject on an unimportant material. However, aggregates are essential in all types of construction. The tonnage and value of these two aggregates produced in the United States during 1959 as reported by the Bureau of Mines were as follows: Sand and Gravel 729,895,000 tons valued at $728,527,000 Crushed stone 581,721,000 tons valued at $824,411,000

Jan 1, 1961

By P. K. Guerrero, N. Arbiter

The correlation of power consumed by a tumbling mill with the dimensions, speed, and load has been attempted by three principal methods. One of these, the torque formula, has been reviewed critically elsewhere.&apos; This approach, while analytical, disregards the individual motion and speed of the tumbling bodies and assumes that the gross geometry of the entire load is sufficient to establish the power requirement. A more general approach, using dimensional analysis, has been applied in this laboratory by the present authors1&apos;1, and more recently by Rose.3 This disregards the internal conditions within the mill entirely and in effect is an empirical procedure for correlating data. Finally, the complete analysis of tumbling mill dynamics as first made by Davis&apos; attempts to develop the power requirement from individual ball and rod paths and velocities. Although Davis&apos; result is applicable only at a single speed for a given size and load it could be useful, since his optimum speed is at the upper limits of conventional tumbling mill practice. Where power values predicted by the Davis equation were compared with actual mill requirements, they were found too low for small mills and much too high for the largest mills. This suggested that the agreement with actual intermediate range requirements might be fortuitous, and the development of the equation was examined critically. The probable source of error was found to lie in an erroneous assumption made by Davis in converting the energy of ball or rod motion to power. With the same approach, but with different assumptions, a modified equation has been obtained which predicts results that are usually consistently high. This is to be expected, since it is assumed that there is no slip between load and shell and no interference among tumbling bodies. Both these effects should account for the difference. Development of Equation: When a cylindrical shell charged with a substantial weight of rods or balls is slowly rotated about a horizontal axis, the load surface first assumes an inclination that gradually increases to a maximum. Continued rotation results in failure within the load, characterized by a sliding of the top layers down the slope and a reduction in the angle of inclination. Further rotation again increases the angle, and the cycle repeats. If the speed is increased, there is continuous load failure and build-up and a continuous stream of rods or balls descends over the upcoming mass, which moves in circular arcs. At higher speeds the up-

Jan 1, 1961

By J. R. Nettle

The purpose of these studies by the Federal Bureau of Mines was to determine the feasibility of refining low-grade hafnium by an inert-gas-shielded molten-salt electrorefining technique to produce a hafnium metal meeting reactor specifications. The techniques were adapted from those used success-fully for titanium electrorefining. Three electrolytes containing hafnium chlorides were developed from which deposits having a Brinell hardness of 170 or below were recovered. A KC1 + NaC1 + HfC14 electrolyte produced deposits in the hardness range of 140 to 165 Brinell. Deposits with a hardness range of from 132 to 152 Brinell were pro-duced from an electrolyte composed of KC1 + LiC1 + HfC14. A third electrolyte composed of NaC1 + K3HfC17 produced deposits with a hardness as low as 139 Brinell. In a fourth electrolyte, composed of NaC1 + K2HfF6, a measure of refining was accomplished, but under the test conditions no metal meeting specifications was recovered; none was softer than 174 Brinell. A number of metallic impurities were reduced in quantity by the electro-refining process, notably iron, which normally was reduced from 250 p.p.m. to less than 50 p.p.m. Magnesium generally was reduced from 680 p.p.m. to less than 80 p.p.m. Manganese content was also reduced by the electrorefining process. Sponge containing 90 p.p.m. Mn yielded deposits containing a maximum of 50 p.p.m.; some deposits contained only 10 p.p.m.

Jan 1, 1961

By E. G. King

Many of the existing thermodynamic values for the titanium halides are estimates, including all the entropies and high-temperature heat contents of their crystalline and liquid phases. This report contains the results of low-temperature heat capacity measurents (which lead to entropy values at 298.15° K,) and high-temperature heat-content measurements of four halides - trichloride, tribromide, tetrabromide, and tetraiodide. The new data are combined with selected heat-of-formation values at 298.15° K. to obtain improved values of the heats and free energies of formation of these halides at high temperatures, thus supplementing the previous data of Kelley and Mah.5/ ACKNOWLEDGEMENTS This investigation was conducted under a cooperative arrangement between the Federal Bureau of Mines and the Department of the Navy, Office of Naval Research. The work was done by Bureau of Mines personnel using Bureau of Mines calorimetric equipment. The Office-of Naval Research supplied the supporting funds and arranged for procuring the samples of the titanium halides. The samples were prepared and analyzed by the Inorganic Chemistry Section, Division of Chemistry, National Bureau of Standards.

Jan 1, 1961

By J. F. Shea, O. F. Tangel

Battelle Memorial Institute participated in a program for the General Services Administration aimed at developing a nickel-cobalt separation process that could be integrated in the Nicaro nickel plant. At the time the programwas being carried out, the Nicaro process was a straight-through operation, in which the ore was reduced and leached, after which the pregnant solution was boiled to produce a so-called "bulk precipitate" which contained virtually all of the nickel and cobalt which had been dissolved in the leaching step. The weight ratio of nickel to cobalt in Nicaro ore is approximately 15 to 20:l. The weight ratio of nickel to cobalt in the finished product had to be 100:l or higher to meet specifications. Because the Nicaro process embodied no nickel-cobalt separation step, the only way that a bulk precipitate of the specified nicke1:cobalt ratio could be produced was to so adjust roasting and leaching conditions that nickel would be selectively leached and most of the cobalt would be rejected with the tailings. The required selectivity, however, was achieved at the expense of nickel recovery, which was 5 or more per cent less than might have been obtained with the existing equipment, utilities, man power, etc., had selectivity been no object. The over-all purpose of the program was to develop a separation step that could be fitted into or onto the Nicaro facilities and which would permit the manufacture of a product that would meet the desired specifications and still permit the recovery of a maximum amount of nickel. Battelle suggested that this might be accomplished by reprocessing off-specification bulk precipitate and specifically suggested the process based on ammonium sulphate leaching followed by hydrogen reduction of the leach solution according to techniques developed commercially by Sherritt Gordon Mines Limited. Such a process would not only satisfy the objectives of the research but would present two additional advantages. (1) It would produce a separate cobalt product which could be further processed into metal, alloys, oxides, or salts. (2) It would yield nickel in metallic form which might be more generally marketable and command a slightly higher price per unit of nickel than the Nicaro oxide product. DESCRIPTION OF THE PROCESS Figure 1 is a flowsheet of the process. The essential features are: (1) Extraction of about 97 per cent of the nickel and about 85 per cent of the cobalt from bulk precipitate by a principal leach with ainmonium sulphate solution (Step A). Extraction of virtually all of

Jan 1, 1961

By Dale W. Richardson

Ductile hafnium was not obtained consistently by the conventional Kroll process. The bimetal reduction modification produced a more ductile hafnium by lowering the impurities, especially oxygen, in the sponge metal. Hafnium oxide was chlorinated in the presence of carbon to form anhydrous hafnium tetrachloride, which was reduced by sodium and magnesium in an inert atmosphere to produce sponge hafnium metal. After vacuum distillation to remove the byproducts, the sponge was arc-melted into ingot and rolled into strip. Metallic impurities were decreased by evaporating the hafnium tetrachloride from a fused salt. An excessive amount (over 1,200 parts per million (p.p.m.)) of aluminum was contained in some of the hafnium oxide, much of which remained as aluminum chloride in the hafnium tetrachloride during chlorination. Evaporation of the hafnium tetrachloride from a fused NaCI-KCI mixture during the Mg-Na reduction greatly lowered its aluminum content, as most of the aluminum and some of the other metallic impurities were retained by the fused salt.

Jan 1, 1961