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By G. G. Gunther, C. L. Boeke

THE zinc deleading processes at the Parral and Santa Barbara mills are described separately to provide a basis for comparison. Although the two procedures are fundamentally alike, there are some differences in application to meet specific conditions. The Asarco mill at Parral in the State of Chihuahua is a flotation plant treating 1450 metric tons per day of complex sulphide copper-lead-zinc ores. In general, the procedure used for selective separation of the minerals into a copper, a lead, and a zinc concentrate follows the usual practice. First, a bulk copper-lead concentrate is floated and then separated into a final copper and a final lead concentrate by the sulphurous acid process. A small tonnage of high grade gravity lead concentrate is tabled from the bulk copper-lead cleaner tailing before it is reground so as to avoid undesirable over-grinding and sliming of this portion of the lead mineral. Next, a zinc concentrate is floated from the lead rougher tailing and, as described later, is separated into a final lead product and a final zinc concentrate. Finally, the zinc rougher tailing receives a strong scavenger float to remove all recoverable middling values for regrinding and return to the flotation circuits. The slime is separated from the scavenger flotation product, and only the sand portion goes to the regrind section. The minerals in the separated slime are extremely resistant to all methods of selective separation and pose one of the major problems awaiting solution. Nevertheless, the slime shows a profit when mixed with either the lead or the zinc concentrate, except when metal prices are very low, so it is accepted as a final product for lack of a more profitable method of handling it. In contrast, the minerals in the reground sands of the

Jan 1, 1953

By L. A. Bromley, R. L. McKisson

A high temperature calorimeter designed for use up to 1500°K is described and the theory of its operation presented. This calorimeter was used to measure the heats of formation of Na-Sn alloys ranging in composition from tin to Na2Sn. The values tend to support those reported by Kubaschewski and Seith. ONE method of obtaining the heat of formation of an alloy is to measure the heat of mixing of the elements at high temperature. The principal advantage of this method is that the desired quantity is measured directly, while in conventional room temperature methods the differences of the heats of solution of the elements and the alloy in a suitable solvent are measured. A method of improving the accuracy of the high temperature measurements, when the precision of the measurement is lower than that of the heat capacity values for the elements, is to add one component at room temperature to the other at the high temperature, so that part of the heat of reaction is dissipated in heating the cold component to the high temperature. Thus, only a fraction of the heat of reaction is measured, and a result of higher precision is obtained. The limitations of the high temperature technique are that volatile systems cannot be studied, and that many alloys melt at temperatures higher than those at which the calorimetric apparatus operates readily. Nevertheless, a calorimeter operating at 1500°K would be useful in investigating many of the lower melting alloy systems and the low melting mixed oxide systems. A unit designed for these applications was built and is described here. The Na-Sn system was chosen for investigation because the temperature involved, 880°K, would adequately test the operation of the calorimeter. Further, the data reported in the literature for the various alloys of sodium and tin differ markedly, and it was hoped that this investigation would help to fix the values of the heats of formation in this system. Design of Apparatus A detailed discussion of the considerations involved in the calorimeter design is given by Mc-Kisson and Bromley,' and a brief summary follows. Fig. 1 shows a sectional view of the calorimeter. The inner graphite chamber is maintained at constant temperature by means of the circulating molten tin bath in which it is submerged. The tin is contained in a graphite vat. This unit comprises a thermostat whose heat capacity is about 7000 cal per "C. The main heating element consists of a machined graphite spiral with a room temperature resistance of about 1/2 ohm. These parts are separated from the powdered carbon external insulation by the cage, a cylindrical graphite chamber. The electrical insulators and separators, the auxiliary heater spool, and the loading tube liner are made of sintered alumina. The tin vat stirrers, the sample stir-rer, the melt thermocouple well, and the power leads are made of molybdenum. The auxiliary heater is wound with molybdenum wire and serves to compensate for the heat loss up the loading tube. All of the individual components in the high temperature region of the calorimeter will withstand at least 2000°K, and the various contacting materials should easily withstand 1500°K. The external container for the insulating carbon powder is a copper shell upon which copper tubes are soldered to serve as cooling coils.

Jan 1, 1953

By J. E. Hawley, Y. Rimsaite, T. V. Lord

"IntroductionIN THE COURSE of. a spectrographic investigation of the platinum metal .content of various minerals in sulphide ores, the use of • fire-assay beads dissolved in gold-amalgam ( 1) was found suitable for the quantitative determination of palladium and platinum. Later work on platinum and bismuth-rich beads showed however, that these could not always be readily mixed uniformly in the amalgam. Accordingly another technique was sought which would allow the simultaneous determination of gold, silver, palladium, platinum, rhodium, and bismuth, the last .a common contaminant in fire-assay beads. The method evolved, which consists of dissolving fire-assay •beads in .lead, resembles in several respects the method of Scobie (2) in which silver was used. It has equally good sensitivity arid reproducibility, and allows the determination of silver as well as the other metals mentioned. The 'mutua1 standard' method of calculation (3a) is used to determine actual quantities present. This method has been applied to sulphide and arsenide minerals and •ores• of nickeliferous and non-nickelferous deposits• of both pre-and post Cambrian age, and, following a suggestion by Dr. G. S. Hume and the late Dr. H. V. Ellsworth, Geological Survey of Canada, has also been used for a peculiarly rich platiniferous uranium oxide ore from the Nicholson property, Lake Athakaska, Sask. More recently, the method has been .tested for the determination also of iridium and ruthenium and results indicate it may be applied, as• well to osmium."

Jan 1, 1953

By Edward Roberts

This is a progress report of an investigation by personnel of the Bureau of Mines from June to September 1951 to introduce preservative chemicals into growing timber. It also describes in detail the impregnation process, known as the collar method, developed by the United States Department of Agriculture2/ Twenty-eight trees were treated by this method, and a complete record was kept of each individual tree and of each timber cut from it. These timbers have been placed in a coal mine, and their tendency to decay is compared to that of adjacent untreated sets. Although several years will be required before final conclusions can be drawn, this report explains the appearance and encouraging results of the treated timber to date. Also included are some comparative costs of untreated timber, treated timber by the commercial pressure method, and treated timber by the collar method. INTRODUCTION In the hope of increasing the useful life of cut timber, experiments to impregnate growing trees with wood-preservative chemicals by utilizing the natural flow of sap have been carried on for centuries. None of the various methods used in these experiments has ever gained any widespread use because they have been commercially impractical.

Jan 1, 1953

By Will Mitchell, Ford F. Miskell, C. L. Sollenberger

Heat treatment of ore prior to comminution reduces power requirements for grinding, reduces grinding media wear, and improves recovery of iron values from a typical Minnesota magnetic taconite. Test data demonstrating this, as well as an analysis of the economics of commercial application of the technique, are presented. THE taconites in general are hard, tough ores, difficult to grind. Liberation of iron mineral constituents usually is accomplished by grinding the ore through at least 100 mesh, and often it has been found necessary to grind substantially through 325 mesh to achieve satisfactory recovery and grade in the concentration process. Because of the fineness of grind required and the enormous tonnages of material contemplated for treatment in the future, costs resulting from grinding media wear and power consumption, together with capital investment required for comminution, approach astronomical figures. Economy in any one of these elements per ton of material ground could very well reflect a considerable saving to the ferrous industry in yearly costs. With this in mind, the Research Laboratories of Allis-Chalmers Manufacturing Co. have launched a program to discover means of effecting this economy. The initial phase of the work as described here deals with a heat treatment of crushed raw ore, followed by thermal shock in cooling, for the preparation of rod mill feed. Several investigators1-" ave noted an improvement in the grindabilities of ores treated in this manner. One investigator2 subjected low grade iron ores to heat treatment in an electric furnace. Basing his conclusions on screen analyses of crushed products, he observed that treated ore was more easily crushed than the untreated. He reported that observation of the treated and untreated ore through a microscope revealed cracks following the grain boundaries in treated ore, whereas no cracks were present in untreated ore. However, few if any have quantified the improvement in terms of total hp hours saved, reduction of wear of grinding media, or reduction of capital costs of grinding equipment involved. By means of Bond rod mill and ball mill grindabilitiesh nd by comparative wear tests, the conditions maintained during this investigation have been definitely evaluated. Heat treatment experiments have been made on a batch scale in a muffle furnace, followed by continuous scale experiments in a rotary kiln under various conditions of temperature, atmosphere, retention time, and quenching to determine the combination that would give the greatest improvement in the grindability of a taconite without affecting adversely the magnetic susceptibility of the magnetite. From these data, relative costs have been calculated for grinding both untreated and heat- treated ore on a basis of plant capacity of 120 tons per hour. Heat requirements for a rotary kiln, as well as the kiln capacity required for the treatment, have been estimated. For these tests 50 tons of ore were obtained from the Aurora mine of the Erie Mining Co., Hibbing, Minn. The ore was reported7 to have been selected from the magnetic portion of the lower chert horizons. An average chemical analysis of' this portion is shown in Table I and an approximate mineralogi-cal analysis is shown in Table 11. No attempt was made to differentiate between the various silicates because the compositions vary widely on the different horizons and depend on the degree of oxidation. Minnesotite, however, is the predominant silicate. The siderite grains were dispersed throughout the ore but were essentially associated with the rock-forming minerals. In a series of preliminary tests in which batches of —6 mesh ore were heat-treated in a muffle fur-

Jan 1, 1953

By E. A. Calnan, B. E. Williams

IN the development of a new treatment for the prediction of deformation textures,'-' it was noted that for no metals are there experimentally determined tension textures with which the predictions may be compared. There is a considerable knowledge of drawing textures and previous workers have been content to consider these as equivalent to tension textures for the purposes of comparison. It is shown, however, in the new treatment that the tension and drawing textures are not necessarily identical, the radial compression exerted by the dies in the drawing operation producing some modification of the tension texture. In particular for the face-centered cubic metals it is predicted that for drawing the final texture should be [1ll] with a spread towards [211] (a more detailed derivation of this texture has been made by Calnan3). This has been amply confirmed by experiment, see Hibbard.6 For the pure tension case, however, the treatment predicts intermediate [1ll] and [loo] textures leading to a [211] end-point, while all previous treatments have predicted the final texture as [1ll] with in some cases an additional [loo] component. Thus evidence that the pure tension end-point is the [211], or at least that [1ll] and [l00] are not the final textures, should provide a valuable test of the new treatment. Accordingly some experiments were made on aluminum. Three aluminum specimens were examined in detail, one of cold-rolled high purity rod (99.99 pct), specimen A, and two of commercial extruded rod of purity 99.4 pct, specimens B and C. The initial annealing treatments were: A, 1½ hr at 400°C; B, 2 hr at 400°C; C, 1½ hr at 650°C. The principal difficulty is that of obtaining sufficient elongation before fracture occurs. This was overcome to some extent by giving a softening heat treatment, 1 hr at 300°C, after each 15 pct of extension. Vickers hardness measurements gave values before and after the softening treatment of about 30 and 28, respectively, in comparison with the initial value of about 19 corresponding to fully annealed material. From recent observations in this laboratory it is concluded that this small recovery corresponds to a polygonization process rather than recrystallization proper and consequently the preferred orientation is unaffected. At the higher extensions, however, some slight necking of the specimens took place and it was necessary to turn them down to a uniform cross-section before

Jan 1, 1953

By T. I. Moore, L. A. Painter

THE electrolytic zinc plant of the American Zinc Co. of Illinois was described by Davidson' in 1944. Since then, improvements as well as expansion of the plant facilities have been made. In order to increase the production of high grade zinc which was needed for war purposes, an expansion program designed to double the slab zinc capacity was started in 1942 and completed in March 1943. This expansion was propagated by a contract between the American Zinc Co. of Ill. and the Defense Plant Corp. The contract included the facilities of the Fairmont City, Ill., property of the American Zinc Co., where a suspension-type roaster with contact acid plant, cadmium distillation furnace, Waelz oxide and densifying plant, and horizontal retort furnaces were installed. The expanded Monsanto, Ill., plant and the additional facilities of' the Fairmont plant were designed to integrate the metallurgical treatment of zinc concentrates for the production of special high grade zinc at Monsanto with the production of acid, cadmium, high grade zinc from furnace skimmings and the Waelz treatment of leach residue at Fairmont. In general, the original flowsheet was not changed, except for the addition of the filtering, drying and reclaiming of leach residue, and the treatment of purification cake for the recovery of copper, cadmium sponge, and zinc. Fig. 1 is a flow diagram of present operations. The original plant facilities, desi-gned for 50 tons daily production of slab zinc, had some units which were more than adequate. Therefore, in expanding the facilities to 100 tons per day, it was not necessary to double all operating components. Table I gives the comparison of the changes made in the unit operating components for the original facilities, 1941, the 1943 expansion, and the 1951 facilities. During the past 11 years a number of improvenients have been made resulting in: 1—an increase in slab production, 2—higher recoveries on the calcine treated, 3—better quality of slab zinc produced, 4—higher current efficiencies, and 5—less man hours Table I. Changes in Operating Facilities Operating Unit 1941 1943 1951 Calcine unloading (pneumatic), 10 tons per hr 12 calcine unloading track hpr. and elev., 60 tons per hr 1 Calcine storage, tons 1,000 2,000 2,000 Leach tanks, 35 vol. tons. No. 3 5 6 slurry mixing 6x6 ft stainless tank, No. 1 Ball mill. 4.5 rt x 16 in. conical. No. 1 CLassifier duplex, No. 1 1 Thickeners. 50 it diam. No. 2 9 2 Filter thickeners, sq ft '-- Moore filters, sq ft 5.760 11,520 Drum filters, 10 ft diam x 16 ft, No. 3 3 Rotary arlers, No. 1 2 1st stage Cu-As purificatlon tank. 90 vol. tons, No. 3 Solution heaters, No. 3 Filter press, 30x30 bronze, No. 4 Zinc dust purification tanks, 45 vol tons. No. 3 5 4 Filter press, 36x36 bronze, No. 3 5 3 Cadmium recovery plant: Process tank. No. 5 2 Cake roaster, 20 ft diam x 4 hearth. No. 1 Filter press, 24x24, No. 4 1 Sponge wash box, 4x6 ft, No. 1 Evaporative cooling unit (vacuum), No. 1 Purified storage tank, vol. tons 400 400 400 Cell acid storage, vol. tons 400 400 400 Electrolytic cells, No. 180 372 372 Cell room ventilation, cu ft per min 35,000 125,000 125,000 Cell cooling water. gal per min 1,500 2,300 2,300 Deep well 16 in. x 95 ft, 1500 gal per min, No. 2 3 3 Melting and casting furnace, 130 ton. No. I Furnace fume scrubber unit, No. 1 Dross drums, No. 2 Dross roaster, 8 ft diam x 8 hearth, No. 1 Electrolysis power conversion, kw 6,250 23,750 23,750 Power transformers, 13,800/440, kva 1,000 1,500 2,000 Steam boilers fire tube, 15 psi, lb per hr 12,000 18,000 18,000 Steam boilers water tube. 125 psi, Ib per hr 30,000 Air compressor, 2 stage. 300 cu ft per min. 100 psi, No. 1 2 Air compressor, 1 stage, 300 cu ft per min, 20 psi, No. 1 Vacuum pumps, 18x7, 720 cu ft per day, No. - - . Vacuum pumps, 24x11, 1.633 cu ft per day, No. 3 3 Building area, sq ft 60,854 113,568 115,000 per ton of metal produced. In the summer of 1944, the "reverse" leaching process was placed in operation and since it has been described,' no further description will be given. Other facilities and changes which have contributed to the process improvements were the scrubbing of fume from the melting and

Jan 1, 1953

This paper is written as a supplement to that of Edwards, Baker and Knight on "The Geology of the Wonthaggi Coalfield" 1, the West Area pit being in an early developmental stage at the time of their paper. The thin seams to the west of Dudley Basin 2 had beenknown for many years but it was not until 1935 that it became necessary to work them. The West Area Pit came into production as Dudley Area Pit approached exhaustion in 1937. From available information it was estimated that early work would be in a 36in. bottom seam. The present top seam was not included in the reserves, but it was to be extracted where it proved thick enough for economical working.THE SEAMSEdwards, Baker and :Knight (1944) had insufficient information to correlate positively the West Area seams with those in the Dudley Basin. Their opinion was, however, that they were a westerly extension of the Bottom Seam. Since then the driving of the present north-east heading towards No. 4 Bench McBride Tunnel has established that the West Area seams are those worked as Bottom Seam in the Dudley Basin. West Area Top Seam is a seam that occurred above the Bottom Seam in the Dudley Basin. Only sporadic attempts have been made to work it in Central Area, because 30in. was considered an economic minimum height until recent times. This seam should not be confused with Top Seam, Dudley Basin, which lies some 300ft. above the bottom seam measures and except in isolated areas over deeper workings has been eroded away in West Area.

Jan 1, 1953

AIME 1953 DIRECTORY SUPPLEMENT COMMITTEES NOMINATING E. H. Rose, Chairman R. E. Byler J. F. Myers Grover Molt S. W. Engelmann S. J. Swainson EDUCATION A. C. Dorenfeld, Chairman G. P. Lutjen A. E. McHugh H. Rush Spedden T. G. Chapman T. M. Morris T. Barker S. R. B. Cooke W. O. McClintock

Jan 1, 1953

By W. A. Wissler, B. E. Field

COBALT is a silvery white metal with a slight bluish cast. It strongly resembles nickel in its appearance and properties, notably its resistance to corrosion, although its alloys with other metals differ decidedly in their properties from those of nickel. The name "cobalt" was derived from the German Kobold, meaning goblin, and this came to be applied to the cobalt minerals which, although they resembled ores, did not readily yield metal when smelted by the primitive processes available in the Middle Ages. Cobalt minerals were used as pigments by potters and glass- workers before the Christian era. Cobalt blue glass was found in the tombs of the Egyptians and in the ruins of Troy, and many colors used by the ancient Greeks and Romans contained cobalt. The ancients were entirely unaware that the colors they used were caused by cobalt and the metal itself was not isolated until about the middle of the eighteenth century, by Brandt, although the preparation of cobalt compounds had been carried on in a small way ever since the opening of the silver-cobalt deposits at Schneeberg, Germany, in 1470. By the middle of the nineteenth century, several firms in England were engaged in the refining of cobalt products and the consumption of cobalt oxide in the British ceramic industry in the year 1866 had reached 67,000 lb. COBALT METAL AS A NEW RAW MATERIAL IN ALLOY TECHNOLOGY Nickel and cobalt are usually found together and, although the relative amounts of the two have varied greatly in different ores, those

Jan 1, 1953

By Fred C. Bond

MOST investigators are aware of the present unsatisfactory investigatorsstate of information concerning the fundamentals of crushing and grinding. Considerable scattered empirical data exist, which andare useful for predicting machine performance and give acceptable accuracy when the installations and materials compared are quite similar. However, there is no widely accepted unifying principle or theory that can explain satisfactorily the actual energy input necessary canexplain commercial installations, or can greatly extend the range of empirical comparisons. Two mutually contradictory theories have long existed in the literature, the Rittinger and Kick. They were derived from different viewpoints and logically lead to different results. The Rittinger theory is the older and more widely accepted.'TheRittinger In its first form, as stated by P. R. Ritted.'tinger, it postulates that the useful work done in crushing and grinding is directly proportional to the new surface area produced and hence inversely proportional to the product diameter. In its second form it has been amplified and enlarged to include the concept of surface energy; in this form it was precisely stated by A. M. Gaudin' as follows: "The efficiency of a comminution operation is the ratio of the surface energy produced to the kinetic energy expended." According to the theory in its second form, measurements of the surface areas of the feed and product and determinations of the surface energy per unit of new surface area produced give the useful work accomplished. Computations using the best values of surface energy obtainable indicate that perhaps 99 pct of the work input in crushing and grinding is wasted. However, no method of comminution has yet been devised which results in a reasonably high mechanical efficiency under this definition. Laboratory tests have been reported- hat support the theory in its first form by indicating that the new surface produced in different grinds is proportional to the work input. However, most of these tests employ an unnatural feed consisting either of screened particles of one sieve size or a scalped feed which has had the fines removed. In these cases the proportion of work done on the finer product particles is greatly increased and distorted beyond that to be expected with a normal feed containing the natural fines. Tests on pure crystallized quartz are likely to be misleading, since it does not follow the regular breakage pattern of most materials but is regularrelativelybreakage harder to grind patternat the finer sizes, as will be shown later. This theory appears to be indefensible mathematically, since work is the product of force multiplied by distance, and the distance factor (particle deformation before breakage) is ignored. The Kick theory4 is based primarily upon the stress-strain diagram of cubes under compression, or the deformation factor. It states that the work required is proportional to the reduction in volume of the particles concerned. Where F represents the diameter of the feed particles and P is the diameter of the product particles, the reduction ratio Rr is F/P, and according to Kick the work input required for reduction to different sizes is proportional to log Rr /log 2." The Kick theory is mathematically more tenable than the Rittinger when cubes under compression are considered, but it obviously fails to assign a sufficient proportion of the total work in reduction to the production of fine particles. According to the Rittinger theory as demonstrated by the theoretical breakage of cubes the new surface produced, and consequently the useful work input, is proportional to Rr-l.V f a given reduction takes place in two or more stages, the overall reduction ratio is the product of the Rr values for each stage, and the sum of the work accomplished in all stages is proportional to the sum of each Rr-1 value multiplied by the relative surface area before each reduction stage. It appears that neither the Rittinger theory, which is concerned only with surface, nor the Kick theory, which is concerned only with volume, can be completely correct. Crushing and grinding are concerned both with surface and volume; the absorption of evenly applied stresses is proportional to the volume concerned, but breakage starts with a crack tip, usually on the surface, and the concentration of stresses on the surface motivates the formation of the crack tips. The evaluation of grinding results in terms of surface tons per kw-hr, based upon screen analysis, involves an assumption of the surface area of the subsieve product, which may cause important errors. The evaluation in terms of kw-hr per net ton of —200 mesh produced often leads to erroneous results when grinds of appreciably different fineness are compared, since the amount of —200 mesh material produced varies with the size distribution characteristics of the feed. This paper is concerned primarily with the development, proof, and application of a new Third Theory, which should eliminate the objections to the two old theories and serve as a practical unifying principle for comminution in all size ranges. Both of the old theories have been remarkably barren of practical results when applied to actual crushing and grinding installations. The need for a new satisfactory theory is more acute than those not directly concerned with crushing and grinding calculations can realize. In developing a new theory it is first necessary to re-examine critically the assumptions underlying

Jan 1, 1953

By Francis C. Frary

OF the five metals that now show the highest figures for annual tonnage production in the world, three (iron, copper, and lead) have been known and used by man for many thousands of years. The fourth (zinc) did not come into general use until the Middle Ages. Only the fifth (aluminum) is of, ultramodern origin, as far as mankind is concerned. Discovered in 1825, and first publicly exhibited at the Paris Exposition in 1855, aluminum was still so difficult to obtain that it was more expensive than silver, until the development of the dynamo provided cheap electricity and the development of the present electrolytic process for its production made it possible to make large quantities cheaply. Even today, the world production of aluminum is only about one per cent of the world production of iron, although about half that of copper by weight. The increase in production from a few tons to more than a million tons per year began with ,the development of the Hall-Héroult electrolytic process, which was first commercially operated by Mr. Hall's company, The Pittsburgh Reduction Co., in 1888. During the relatively short period of time that has elapsed since that date, it has been necessary to develop all the metallurgical and fabricating information required for the production of useful articles of the metal and its alloys, together with experience in both their production and their use, so as to be able to fit them satisfactorily into their proper places in our complex modern civilization. The fundamental properties upon which the usefulness of aluminum depends are its lightness, workability, resistance to corrosion,

Jan 1, 1953

By C. E. Birchenall, W. Batz, H. W. Mean

AT temperatures between 1095' and 1347ºC, 13 runs have been made on the diffusion of silicon in iron. In two of the runs the couple compositions were entirely within the loop of the Fe-Si system; the base alloys contained 0.0 and 1.0 wt pct Si. The other runs in which the couples consisted of a 2.3 wt pct Si alloy welded to a 3.7 pct Si alloy were a phase throughout. The alloys were made by melting electrolytic iron and commercially pure silicon. Trace impurities were not determined. The butt welded couples were diffused in an inert atmosphere of argon or hydrogen. After cooling, cuts of two mils or greater thickness were machined parallel to the weld interface. The chips were analyzed for silicon. When the concentration and distance data were examined on the conventional probability plot,' no marked variation of the diffusion coefficient with concentration was indicated over the narrow composition ranges employed. Therefore, a single diffusion coefficient is recorded for each run in Table I. The temperatures and atmospheres of the diffusion anneal are listed along with the compositions of the base alloys. For a iron the silicon diffusion coefficient is given by the equation: D = 0.44 e-48,000/RT where R is the gas Constant and T, the absolute temperature. However, since the scatter in the data is fairly large, the activation energy may be in error by as much as 6000 cal per g-atom. The two ? iron points do not permit estimation of the activation energy with any reasonable certainty. They do indicate that the coefficients reported by Smithells2 and Jost,3 based on the work of Fry,4 are much too high. Although very dilute solutions in iron of manganese,5 nickel,8 cobalt,7 and molybdenum8 give dif- fusion coefficients quite close to those obtained for self-diffusion in iron, the silicon values are considerably higher, though of the same order of magnitude. This seems to be consistent with the fact that the silicon atom is the only one of those listed here which is appreciably smaller than iron. The authors are grateful to the Office of Naval Research for their support of this work under Contract N6ori-47, Task order IV, Project NR 031-184, to J. K. Stanley and the Westinghouse Research Laboratories for the silicon alloys used, to several steel companies for the silicon analyses, and to C. Wells, of the Metals Research Laboratory, Carnegie Institute of Technology, for numerous suggestions during the course of the work. References 'C. Wells: Atom Movements (1951) Chapter 2. A.S.M. 2C. J. Smithells: Metals Reference Book (1949) p. 405. Interscience. Pub. Co. 3W. Jost: Diffusion (1952) p. 223. Academic Press. 4 A. Fry: Stahl und Eisen (1923) 43, p. 1039. T. Wells and R. F. Mehl: Trans. AIME (1941) 145, p. 315. "C. Wells and R. F. Mehl: Trans. AIME (1941) 145, p. 329. 7M. F. Hawkes and R. F. Mehl: Trans. AIME (1947) 172, p. 467; Metals Technology (August 1947). .J. L. Ham: Trans. A.S.M. (1945) 35, p. 331.

Jan 1, 1953

By D. R. McCord

Data of a known statistical quality has been successfully used in a system of conventional fluid mechanics equations essentially free of empirical "conformance factors to prediet early detailed field 03 in a reservoir where gravity drainage is important and oil and rock properties vary con. siderably. The system is useful where comparative recovery predictions for one or more cases of natural depletion and gas cap pressure maintenance are needed and the reservoir is not too heterogeneous. INTRODUCTION Many authors, have examined various facet* of the gravity drainage-gas cap pressure maintenance problem over the last several years. Two of them. Burtchaell and Elkins, have published practical studies. In the case described in the present paper the best development and operating plan for one of the important reservoirs of the Bolivar Coastal Field in Western Venezuela was urgently needed. It was requested that sound comparative economics be presented along with an engineering evaluation of no additional drilling, maximum drilling. several cases of gas pressure maintenance, of water flooding and combination cases. A rapid analysis of the effect on recovery of the range of crude and rock properties indicated that none of the published methods using average properties would yield adequate comparative predictions. This paper covers the predictive system developed to deal with natural depletion and gas cap pressure maintenance. The large amount of data available for this field permitted statistically reliable correlations to be made of most rock and oil properties, and the evident smooth areal variations of these properties encouraged the construction of a lineal mathematical model of material balance and fluid flow equations, which could be manipulated by a modified iterative procedure. The manipulation is much more adaptable to computing machines than manually operated calculators and subsequent studies have been prepared for the IBM Card Program Calculator. A matrix as opposed to linear model has been tentatively worked out by other members of our group to deal with more heterogeneous reservoirs. It is more adaptable to computers such as IBM-701 or the Remington-Rand Univac. In 1950, when the system reported below was developed, no rapid computing machines were available to the author. Their existence and promise encouraged an initial approach by hand. Some details of oil and rock Property correlation are included because there are a surprisingly large number of medium-sized reservoirs in the world that show systematic property variations which are significant for a rigorous analycon. All large reservoirs (over half a billion barrels recovery) with which the author is familiar contain at minimum a significant temperature variation. Using the rock and oil property correlations, past pressure and production, the gas-oil ratio history of the reservoir was computed and found to be in close agreement with field measurements. The future performance under cases of natural depletion, gas injection of 100 MMcf/day, and of 130 MMcf/day, was then computed; a 70 MMcf/day case was also carried far enough to provide data for comparative economics. The 130 MMcf/day case proved to be the most attractive. A 50,000 horsepower gas turbine driven centrifugal compressor plant to take this quantity of adjacent field gas from 30 to 1,950 psia and inject it into the reservoir is under construction. The total cost of the project will exceed 20 million dollars.

Jan 1, 1953

By P. T. Carter, A. B. Murad, H. B. Bell

The distribution of manganese and oxygen between molten iron and FeO-MnO-SiO2 slags not saturated with SiO2 has been determined and used to calculate activities of MnO and SiO2 in MnO-SiO2 slags. These were found to be intermediate between the corresponding activities in FeO-SiO2 and CaO-SiO2 slags. THE equilibrium constant for the reaction between molten iron containing manganese and slags containing FeO and MnO, namely: FeO(slag) + Mn = MnO (slag) + Fe(1iquid) is most conveniently represented by: (MnO) Kmn== (FeOHMn] [Fe] is omitted, since for dilute solutions of manganese in iron, afe is approximately constant. When activities are used for (MnO), (FeO) and [Mn], Kmn is a true equilibrium constant and will apply to all types of slags, but when weight percentages are used, the values obtained for Kmn for different slags vary considerably. The equilibrium between iron containing manganese and relatively pure FeO-MnO slags has been investigated by several workers;1-4 the most recent investigation reported is that of Chipman, Gero, and Winkler.4 Their results, corresponding to slags containing up to 4 pct SiO2, were represented by the equation: 6440 log KMn = +2.95 In this case both slag and metal may be assumed to be ideal solutions, therefore the values of Kmn so derived represent the true constant for the manganese reaction. As the molecular weights of MnO and FeO are almost equal, weight concentration of these oxides may also be used in the above expression. Acidic oxides such as SiO2 and P2O5 affect the activities of FeO and MnO differently, so that when total concentrations by weight of FeO and MnO are used in the above expression for Kmn the values obtained are no longer constant. These will be denoted by K'mn. Körber and Oelsen5 investigated the manganese reaction using silica-saturated iron-manganese-silicate slags and found: 7940 logK'mn =3.172 This corresponds to Kmn values much higher than those obtained for pure oxide slags. The results of Körber and Oelsen, and Chipman, Gero, and Winkler are summarized in Table I. In the present investigation it was decided to study the manganese reaction using iron-manganese-silicate slags not saturated with silica, and which fell mainly between the orthosilicate join 2FeO . SiO2 - 2MnO.SiO2 and the FeO-MnO side of the ternary system FeO-MnO-SiO2. It has been shown" that the phases present in solidified slags of this part of the diagram are (FeO, MnO) and (2Fe0.Si02, 2Mn0-SiO,) solid solutions. Such an investigation would be of interest in deoxidation and also gives information on activities in liquid slags. This equilibrium has not as yet been investigated successfully. Hilty and Crafts7 attempted to examine this reaction in a rotating crucible furnace, but were unable to obtain suitable slag samples. In the present investigation one series of experiments was carried out in a rotating crucible furnace, because the success of Taylor and Chipman8 with such a furnace in their study of oxygen distribution between molten iron and (CaO, MgO) — FeO-Si0, slags suggested that it would minimize contamination of the slag by the crucible material. A second series was carried out using a wire-wound resistance furnace. Rotating Crucible Furnace Experiments In all cases the metallic charge consisted of 800 to 1000 g Armco iron containing 0.02 pct C, 0.03 pct Mn, and traces of Si. Manganese and silicon additions consisted of electrolytic manganese (99.9 pct)

Jan 1, 1953

By E. I. Salkovitz, F. W. von Batchelder

AS Slawson1 and others have already shown, from a geometrical view twinning in the diamond structure may be considered as a reflection across a (111) plane or as a reflection across a (112) plane. An analysis by Ellis and Treuting2 showed that the twinning plane must be the (111) plane, but that a twin might have lateral boundaries along (112) planes. Earlier Slawson1 and Ellis3 had shown that only (111) twinning was present in diamond and germanium respectively. Since an ingot of silicon, 1 in. in diam and 1 1/2 in. long, prepared from Dupont silicon to which 0.2 pct Be had been added was available, it was examined for twinning. The ingot had been cooled slowly from the bottom. A section 1/16 in. thick was ground off from the bottom and then the ingot was sliced vertically through the center. Spectrographic analysis indicated only faint traces of iron and silver, in addition to the beryllium. The sample was first etched with a hot solution of 10 pct NaOH in water.and photographed. Back-reflection Laue patterns were made of the vertical and horizontal sections in the regions designated in Fig. 1. Orientations were obtained for each twin using the Greninger technique. Several regions of the same orientation were found; thus regions A and K were identical, similarly N and P, and C, G, J, and L. Knowing the angles between the traces of the twinning plane on the surface and the specimen axis, the indices of the twinning plane were deduced. In all cases the twinning plane was found to be (111); lateral boundaries, however, were found which were (112) such as the one indicated in Fig. 1. Therefore, as in the case of diamond1 and germanium' only (111) twinning occurs in silicon. We wish to thank Mr. Hino for the use of the ingot as well as for its metallographic preparation. References 1C. B. Slawson: American Mineralogist (1950) 35, p. 193. 2 W. C. Ellis and R. C. Treuting: Trans. AIME (1951) 191, p. 53; Journal of Metals (January 1951). 3W. C. Ellis: Trans. AIME (1950) 188, p. 886; Journal of Metals (June 1950).

Jan 1, 1953

By D. J. DeLazaro, W. Rostoker, R. E. Riley, M. Hansen

At very low concentrations, carbon dissolves interstitially in molybdenum resulting in a linear expansion of lattice parameter with increase of carbon in solid solution. Geometrical consideration of the relative size of carbon atom to size of interstice approximately predicts the observed volume expansion. THE element carbon, occurring in molybdenum, either as an unavoidable impurity, or purposely added, markedly affects the mechanical properties of molybdenum. Several investigators1-" have noted the occurrence of molybdenum carbide at the grain boundaries of cast molybdenum, and Fischer and Rengstorff' have shown that this intergranular constituent can induce intergranular brittleness. The appreciable change, with temperature, of the solid solubility of carbon in molybdenum, found by Few and Manning," suggests other important effects upon mechanical properties. Finally the relative atom diameters of carbon and molybdenum (the ratio of atom diameters is 0.59) are indicative, by analogy with iron (ratio of carbon atom diameter to iron atom diameter is 0.65), of a possible interstitial solid solution. If carbon dissolves intersti-tially in molybdenum, anelastic effects and age-hardening effects, similar to those observed in other body-centered cubic metals, could be expected. However, from the work of Sykes, Van Horn, and Tucker," it might be inferred that carbon forms only a substitutional solid solution with molybdenum. These considerations made it desirable to study the effect of carbon on the lattice parameter of molybdenum in greater detail than heretofore. All heat treating was done in a high temperature furnace7 built specifically for heat treatment of molybdenum. The temperatures and times of heat treatment were determined from the a solubility limit for the Mo-C system." These heat treatments were carried out in argon which was purified with respect to N, and H.!0." Purification of the argon was accomplished by passing the argon over hot (750°C) titanium and then through a magnesium perchlorate drying tower. As many as six samples were run concurrently and quenched at different times without interrupting the furnace cycle. Both the purity of the furnace atmosphere and ability to quench samples from any temperature up to 4000 °F were of prime importance in the successful heat treatment of samples for the lattice parameter investigation. Carbon Analysis The Leco Combustion apparatus was used for carbon analysis. This apparatus is capable of an accuracy of & 0.003 pct for a 1 g sample in the range below 0.10 pct. However, it is felt the degree of accuracy is somewhat better than this limit in view of the consistency evident by cross checking a number of determinations. The Battelle Analytical Laboratory consistently reported check results to within k 0.001 pct C. X-ray Measurements The molybdenum wire specimens (20 mils) were carefully filed down to about 12 mils and then etched with nitric acid to 8 mils. Carbon analyses were made on specimens before reduction in size; however, since there was no evidence of surface carburization, it is probable that the carbon was uniformly distributed throughout the sample. The resultant specimens were strain free and small enough to minimize the error in the lattice parameter determinations due to X-ray absorption. Diffraction patterns were obtained with a Debye-Scherrer powder camera 114.59 mm in diam utilizing the Straumanis type asymmetrical film mounting. Nickel-filtered copper. Ka radiation and zirconium-filtered molybdenum Ka radiation were used. Line positions on the film were measured with a traveling microscope equipped with a vernier scale permitting measurement to 0.001 cm. The average of five readings was used to determine the position of each line. The lattice parameter for each specimen was determined from the data by the extrapolation method of Bradley and Jay, Y.e., the intercept at 90" of the straight line obtained by plotting the apparent lat-

Jan 1, 1953

By C. J. McHargue

THE angles between the crystallographic planes in cubic crystals have been given by Bozorth,¹ in magnesium, zinc, and cadmium by Salkovitz,² and in tin by Nicholas. The determination of the orientation of single crystals and the study of plastic deformation require the knowledge of these angles and are often facilitated by use of a standard projection. Tables of these angles and standard projections have not been published for titanium or zirconium which have c/a ratios considerably less than those hexagonal metals for which this data is available. Accordingly, Table I has been prepared giving these angles. Fig. 1 presents a standard (0001) projection of titanium. The angle between (h1k1i1l1) and (h2k2i2l2) was calculated by means of the formula: h1h2 + K1K2 + 1/2 (h1k2 + h2k1 + cos 4 = [(hi2 + K + h1k1 + 3/4 l12 (h2² + C" a² 3/4 — l1 l2 C² k2²+ h2k2 + 3/4 —l2²) ] 1/2 c² The c/a ratio for titanium is taken from the data

Jan 1, 1953

By Adam L. Wesner, A. C. Richardson

This paper describes the development of a continuous float-and-sink process to produce coal low enough in ash content to be suitable for production of electrodes. The cleaned coal had a combined iron and silicon content of 0.239 pct. The efficiency of recovery was 84 pct. DURING World War I1 the demand for electrode carbon was greater than could be met by the supply of petroleum coke available for this use. It was believed that coke made from an extremely low-ash coal might be a suitable substitute for petroleum coke. Requirements for electrode carbon to be used for the production of aluminum are that the silicon plus iron content shall be not more than 0.14 pct of the coke. However, during the period when petroleum coke was in short supply, it appeared that relaxations of the specifications might be allowed to permit 0.4 pct iron plus silicon in the coke. For this work, the specifications were that the coal should contain less than 1 pct of ash, and the combined iron and silicon content of the coal should not exceed 0.28 pct. Heavy-liquid separations made on a number of coals showed that if certain size fractions of some coals Were separated at low specific gravities the resulting float products would meet the required specifications. The objective of this work was to develop a continuous, commercially feasible process for producing low-ash coal. After consideration of various processes, the method chosen was a float-and-sink separation using a solution of calcium chloride as the separating medium. Eagle Seam coal was used for the experiments. The —10 +35 mesh fraction was found to be the most promising feed for producing the low-ash content coal. A batch of 30 tons of — --in. coal was screened at 10 and 35 mesh; the yield of —10 +35 mesh was 20 pct of the feed. This fraction comprised the feed for the separation tests. In spite of the fact that this portion was screened a second time at 35 mesh, the coal still contained 16 pct that was finer than 35 mesh. Three-fourths of the undersize was in the —35 +48 mesh range. A representative portion of the —10 +35 mesh fraction was subjected to batch float-and-sink separations to determine the best gravity to be used in the continuous tests to obtain a high recovery of low-ash content coal. The heavy liquid used was a mixture of carbon tetrachloride and benzene which assured complete wetting of all of the particles. As usual in batch separations, adequate time was allowed for each separation so that even the near gravity particles had ample time to separate. The separations were made at increments of 0.01 sp gr from 1.25 to 1.28 and also at 1.32 and 1.59. Each specific-gravity increment was assayed for ash content. From these data it was concluded that 1.27 sp gr was best for the continuous separation of the coal. The products from the batch separation were composited into float 1.27 and sink 1.27 sp-gr fractions; these were assayed for ash, iron, and silicon. Table I shows the results of the batch separations. The composite float 1.27 fraction contained 66.04 pct of the total weight, and had an analysis of 0.79 pct ash, 0.073 pct iron, and 0.112 pct silicon, or 0.185 pct iron and silicon combined. These data are indicative of the results possible if a perfect separation is made at 1.27 sp gr under static conditions. Inasmuch as the method under investigation is a dynamic system these results could not be obtained. It remained to be determined, however, just how close to the theoretical results the actual continuous separation would be.

Jan 1, 1953

Jan 1, 1953