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

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

Jan 1, 1953

By M. G. Corson

THE iron-silicon alloy series has always been one of the most puzzling among the binary alloys. Examining the well known mechanical properties of the iron-rich alloys only we meet the following situation: The ultimate strength and yield point of alloys worked and annealed under the usual conditions represent nearly a straight line function of the silicon content up to 4.5 per cent. silicon (Fig. 1). Starting at the ultimate strength of 35,000 lb. and at a yield point of 16,000 lb. for pure electrolytic iron, one reaches a maximum strength of 93,000 lb. and a maximum yield point of 74,000 lb. at 4.5 per cent. silicon. This corresponds to an increase in ultimate strength by 13,000 lb. per each per cent. of silicon added and nearly the same rate applies to the yield point. The data mentioned are taken from the investigation by T. D. Yensen,1 and while they do not exactly corroborate the results obtained by earlier investigators, they seem to be the most correct. Plastic properties of the alloys are controlled by a much more complicated relationship. Up to 2.5 per cent. Si, the elongation stays close to 50 per cent. (in 2 in.) and the area reduction amounts to 85 per cent;, a situation that forms the usual feature of all alloys representing strictly solid solutions. The plasticity of the latter is always nearly equal to that of their base metal. Beyond 2.5 per cent. silicon, the situation becomes much more complicated. Yensen observed an enormous drop in elongation and area reduction at about 2.65 per cent. silicon, where the first hardly reaches 10 per cent. and the second is still lower; he found, however, a considerable recovery in plasticity at about 2.8 per cent. Si and up to 4.5 per cent. Si it is represented by 20 per cent. for the elongation and 30 per cent. for area reduction.

Jan 1, 1928

By G. K. Manning, W. E. Few

WORK on the effect of vacuum heat treatment of 0.040 in. diam sintered and wrought molybdenum wires has been sponsored by the Office of Naval Research at Battelle for the past several years. An electrical resistance furnace' capable of maintaining a vacuum of less than 0.1 micron of mercury at temperatures as high as 4000 °F was used for heat treating the wires. Early in the work, it was found that the introduction of a few microns pressure of oxygen into the furnace resulted in a rapid increase in the oxygen content of the wire specimens and the appearance of a discrete oxide phase. Subsequent elimination of the oxygen atmosphere caused the disappearance of the oxide phase. This was used to determine the solid solubility of oxygen in molybdenum over the temperature range of 2000" to 3000°F.2 It was observed that, with the disappearance of the oxide phase, the wires regained some ductility. Single-phased wires possessed from 5 to as much as 40 pct elongation in 2 in. Later, attention became centered on determining the cause of this wide range in ductility. Wires containing less than 0.002 pct C, less than 0.0007 pct 0, less than 0.0005 pct N, and less than 0.00003 pct H exhibited the erratic ductility noted above. These percentages represent approximately the limit of accuracy of presently available methods of analysis and thus it became apparent that chemical analysis would be of little help in the study. A number of possible explanations for the wide range in ductility were suggested during the course of the work. It was first suspected that variations in the grain size of the recrystallized wire specimens might be responsible. Wire from several lots of material was available. One of these lots tended to develop very large grains when recrystallized, the others all developed an ASTM grain size of 3 to 4 when heated above 2700°F. No correlation between grain size and ductility could be found. It was thought that back diffusion of oil from the diffusion pump might cause contamination of the wire, principally with carbon, but when wires were treated without cooling the cold trap in the pumping system,

Jan 1, 1956

By Ernest P. Hall

At the SME Fall Meeting held in Phoenix, Ariz. last October, Ernest P. Hall, addressing an Air and Water Pollution session, noted that water pollution caused by acid drainage from bituminous coal measures had begun long before recorded history. "Until recently," he said, "man did not begin to understand the physical phenomena which took place to cause [it] and even today he does not know what can be done to prevent it." CAUSES "It is known from the reports of early explorers that drainage from bituminous coal measures was causing water pollution before coal mines were opened on this continent. They noted the nature of the polluted water in the runs and creeks and predicted the presence of substantial deposits of coal based on the appearance and character of the water. Even today, polluted water drains from virgin coal areas which have not been touched by mining machines," Mr. Hall said.

Jan 1, 1966

By S. S. Nosseir

INTRODUCTION General Quebec Cartier Mining Co. (QCM) , Canadian subsidiary of U . S. Steel Corporation, operates two iron ore concentrators at the North Shore of Quebec, Canada. In its own operation at Mount-Wright, over 45 million tons per year of crude ore are ground, fully autogenous in six 32' x 11-1/2 Dominion Engineering mills. At Fire Lake/Lac Jeannine operation, property of Sidbec Normines Incorporated (SNI), over 11 million tons per year of crude ore are now ground, fully autogenous, in twelve 18' x 5' Hardinge mills. The Lac Jeannine concentrator was originally constructed by Q.C.M. in 1960 and. was since operated, in beneficiating the Lac Jeannine ore deposit until fully depleted in 1977, at an annual capacity of 18 million tons of crude per year. In 1976, the new company, Sidbec Normines, was incorporated by Sidbec Corporation, British Steel Corporation and Quebec Cartier Mining Co., in proportional holding of approximately 51 to 41 to 8 percent respectively. Since the acquisition of the Fire Lake ore deposit and Jeannine concentrator by the new company, QCM has continued managing the mine and concentrator operaions for S idbec Normines Inc . Flow-Sheet Design Jeannine concentrator comprises twelve identical mill lines grinding the ROM from 8" top size to 14 mesh nominal size range. Driven by 600 H.P. motor at 13.4 RPM corresponding to 73% critical speed, each mill is operated in a closed circuit with two 5' x 12' vibrating screens dressed with 2.5 x 25 mm slot opening cloth. The ground product or screen undersize at an average grade of 33.4% Fe is beneficiated by gravity separation to produce 66.5% Fe concentrate grade at 42.7% weight recovery. At the rougher stage, each mill line con-tains 128 Humphrey 13- 1/2" pitch spirals which produce a final tailing, middling and concentrate products. The rougher concentrate - so produced - is classified by 64 Humphrey pocket sizers into an underflow, which is a final concentrate product and an overflow which is further upgraded by 64 cleaner spirals. The cleaner concentrate together with the pocket sizer 's underflow are dewatered on a 13'[6] horizontal filter. The rougher middling together with the cleaner tailing are recycled in a closed circuit with the spirals. The rougher tailing after dewatering by hydrocyclones is disposed of by a

Jan 1, 1982

HE purpose of this chapter is to present a general outline of the basic open-hearth process for the benefit of students, practicing open-hearth operators, and metallurgists who wish to review the subject. The discussion is limited to a description of the sequence and purpose of the operations, illustrated by data and examples. Subsequent chapters deal with more detailed and fundamental studies of the subject. The function of the basic open-hearth furnace is to convert various types of ferrous material into finished steel of given composition and quality. In comparison with other steelmaking methods, the basic open-hearth process is one of the most versa- tile, both from the standpoint of the raw materials that can be used and the types of steel that can be produced. The process can be considered as a sequence involving melting, refining, and deoxidation. With some types of liquid-metal charges, the melting stage is not present, but refining and deoxidation in varying degrees are fundamental features of the process. GENERAL DISCUSSION OF BASIC OPEN-HEARTH PROCESS The first consideration in open-hearth practice is the type of charge on which the operation is based. This consists of three components-fluxing, oxidizing, and metallic materials. Fluxes. In the basic process the fluxing material is primarily lime, added in the form of either limestone (CaC03) or burnt lime (CaO). This is supplemented by magnesia (MgO) and lime from the furnace bottom and banks. The function of these fluxes is to form a slag with the silica (SiO2) , manganese oxide (MnO), iron oxides (FeO and Fe2O3), and phosphorus oxide (P2O5) that are produced by the oxidation of varying amounts of the silicon, manganese, iron, and phosphorus in the charge during melting and refining. The slag, composed of the basic fluxes and the neutral and acid oxides, floats on top of the steel bath when the charge is melted. The composition of this slag depends on the amount of each slag-forming element present in the charge and on the extent of oxidation of these elements during the course

Jan 1, 1951

THE purpose of this chapter is to present a general outline of the basic open-hearth process for the benefit of students, practicing open-hearth operators, and metallurgists who wish to review the subject. The discussion is limited to a description of the sequence and purpose of the operations, illustrated by data and examples. Subsequent chapters deal with more detailed and fundamental studies of the subject. The function of the basic open-hearth furnace is to convert various types of ferrous material into finished steel of given com- position and quality. In comparison with other steelmaking methods, the basic open-hearth process is one of the most versa- tile, both from the standpoint of the raw materials that can be used and the types of steel that can be produced. The process can be considered as a sequence involving melting, refining, and deoxidation. With some types of liquid-metal charges, the melting stage is not present, but refining and deoxidation in varying degrees are fundamental features of the process. GENERAL DISCUSSION OF BASIC OPEN-HEARTH PROCESS The first consideration in open-hearth practice is the type of charge on which the operation is based. This consists of three components-fluxing, oxidizing, and metallic materials. Fluxes. In the basic process the fluxing material is primarily lime, added in the form of either limestone (CaC03) or burnt lime (CaO) . This is supplemented by magnesia (MgO) and lime from the furnace bottom and banks. The function of these fluxes is to form a slag with the silica (SiO2) , manganese oxide (MnO), iron oxides (FeO and Fe203), and phosphorus oxide (P205) that are produced by the oxidation of varying amounts of the silicon, manganese, iron, and phosphorus in the charge during melting and refining. The slag, composed of the basic fluxes and the neutral and acid oxides, floats on top of the steel bath when the charge is melted. The composition of this slag depends on the amount of each slag-forming element present in the charge and on the extent of oxidation of these elements during the course

Jan 1, 1964

By F. O. Shuck, F. E. Butler

A diaphragm diffusion cell suitable for use with liquid metals was designed and tested by measuring the diffusion coefficients for a Hg-10 pct In alloy at 25°C. The binary diffusion coefficient and the coefficients for In and Hg tracers were measured at this composition. The measured coefficients for both tracers were less than the binary diffusion coefficient. When these coefficients were combined with the activity correction term of Darken, the predicted binary coefficient was somewhat higher than the experimental value. In recent years a number of investigators have been studying diffusion of liquid metals in order to gain a better understanding of the liquid state and to examine possible applications to liquid metal processing. The bulk of this work has involved either self-diffusion or diffusion of low concentrations of solute metals in an essentially pure solvent metal. The most common experimental technique employed has been the capillary-reservoir method of Anderson and saddington1 since it is well-suited to measurements involving low concentrations of solutes. As an expansion of previous studies, an investigation of the variation of diffusion coefficient over large composition ranges has been undertaken in this laboratory. Although it is possible to modify the capillary-reservoir method for such measurements, the technique loses its principal advantage of requiring only small quantities of solutes. Therefore, it was felt desirable to investigate other possible experimental techniques applicable to measurements over large composition ranges. A technique which has been used widely in measurements of other liquid systems and seemed potentially applicable to studies of liquid metals was the diaphragm cell. This method has been found to combine relative simplicity of operation with accurate and reproducible results. In use with normal liquids, the tyiical diaphragm cell utilizes a porous glass disk. However, because of the high surface tension, it is not possible to use a diaphragm of such fine pore structure with liquid metals. Furthermore. projected use at high temperatures makes the use of glass undesirable. Consequently, the first problem was the search for an appropriate cell design. EXPERLMENTAL Diaphragm Cell. A number of possible cell designs were examined. Prototypes of several were constructed and tested. The final design is shown in an exploded view in Fig. 1. The cell consists of two identical chambers, one on either side of a 0.20-in.-thick partition. The chambers are 0.15 in. deep and have a volume of 3.45 cu cm. Each chamber is provided with two small threaded holes for filling and emptying. The filling holes may be sealed with stainless-steel screws. Drilled lengthwise through the center partition is a 0.250-in.-diam hole. Inserted into this hole is a rod having seven 0.059-in.-diam holes drilled radially through it. The total "hole" volume is 0.078 cu cm. When the rod is properly aligned, the holes in it constitute the "diaphragm" through which diffusion occurs. The center section was of Teflon and the rod and face plates were of Plexiglas. Four such cells were constructed and used in this study. Subsequent to this investigation, a similar cell constructed entirely of iron was fabricated and tested at higher temperatures. Several considerations led to this final design. It is desirable to minimize the volume of the cell chambers to decrease the time required for a measurement. However, the total volume of metal in the diaphragm must be small in comparison with that in the chambers. To facilitate filling and emptying it is desirable to have a diaphragm which may be closed.

Jan 1, 1970

Discussion of the paper of BENJAMIN F. TILLSON, presented at the NEW York meeting, February, 1915, and printed in Bulletin No. 9S, February, 1915, pp. 505 to 528. T. E. STURTEVANT, * New York, N. Y.-Mr. Tillson's paper on hammer drills is of much interest to me. Early in 1909 I was invited to make tests of our drills at the Franklin mine of the New Jersey Zinc Co. The first drill that we tested gave very poor results. This was a drill having a hammer piston 1¾ in. in diameter and 3 ¼ -in. stroke, the hammer piston weighing about 6 1b., the 1 ¾ in. diameter being exposed to pressure at either end. Although this drill has given excellent results as a sinking drill, its performance as a stoping drill was poor. This was one of the surprises of the limestone as spoken of by Mr. Tillson. This led me to further investigation, and a second drill was developed, with a much lighter piston and a somewhat longer stroke, that gave better results. In the design of this drill, no attention was paid to the cost of construction, our whole attention being given to the increase in drilling speed and reduction of the quantity of air used. The first drill of this type had a piston weighing about 2 ½ lb. and a stroke of 3 ¼ in. The piston was made with a hammer-bar extension, and the cylinder was made with two diameters of the bore, one in which the hammer-bar extension moved and the larger one in which the piston head moved. The air was taken in at either end of the larger bore, thus giving a greater area to the

Jan 5, 1915

By J. T. Norton, N. J. Grant, A. M. Gervais

An investigation of the creep deformation of coarse grained specimens of high purity aluminum in the temperature range 800' to 1150°F, permitted the formulation of a theory explaining the formation of kink bands. The X-ray Laue back-reflection technique was used in conjunction with metallographic studies to determine the crystallographic elements involved in kinking and to measure the rotations of the bands. THAT metals deform by the formation of kink bands was first shown by Orowan1 in 1942. He manually compressed cadmium single-crystal wires, the basal planes of which were parallel to the wire axis and to the direction of compression. He found that kink bands formed quite suddenly. Similar experiments were performed by Hess and Barrett2 on zinc with a hydraulic testing machine to permit slower more careful compression. They observed that kink bands formed progressively with increasing compression. Recently Washburn and Parker3 observed the formation of kink bands in zinc single-crystal specimens during tension creep experiments. Each of these authors observed the formation of kink bands but did not make a complete analyses of the crystallographic relationships. In addition to these studies on hexagonal metals, extensive investigations of kink bands formed during deformation of aluminum in tension at room temperature have been reported. Two types of deformation bands have been observed during the deformation of aluminum at room temperature. These are: 1—kink bands: these exhibit a sharp curvature of the lattice along certain surfaces, and 2—bands formed by secondary slip along certain regions. As has already been shown by Honeycombe,4 it is important to point out the difference characterizing the two types of deformation bands. In the first case. for moderate deformation, only one system of slip planes normally is active; in the second case, however, two slip systems are active in the deformation bands. The latter have a rumpled surface because of the action of the two slip systems. In the present work only the first type of band was studied and to avoid any confusion the term kink band will be used exclusively in the discussion which follows. Honeycombe' observed that very narrow kink bands (width, 0.01 mm) formed along the (110) planes during the deformation of high purity aluminum at room temperature. He observed narrower ones in commercially pure aluminum and found also that their width decreased with decreasing temperatures. Chen and Mathewson5 reported the formation of kink bands during tensile testing of single crystals of high purity aluminum at room temperature and pointed out that some rotation occurred about a [211] direction. The influence of the bending moment on the formation of kink bands was illustrated by the experiments of Rohm and Kochendorferl0 who used a Polanyi apparatus to obtain pure shear during tensile testing of high purity aluminum single crystals. Under such conditions only one slip system was active and no kink bands were observed; consequently, no noticeable asterism was detected after deformation. The influence of the bending moment will be discussed later. Calnan8 gave a detailed account of the work performed on kink bands obtained during deformation of aluminum at room temperature. Because no explanation of the process of kink band formation in creep was given in the previous investigations and because some of the above observations are vital to the following discussion the brief review of the literature has been given. It is proposed in the present work to provide an explanation of kink band formation during creep deformation at elevated temperatures. Results and Discussion Kink bands were observed to form during tensile creep testing of high purity (99.995 pct) aluminum specimens, having a very large grain size, in the temperature range 800" to 1150°F. These observations were made in grains which occupied the whole cross section of the specimen. The specimens were originally round (diameter, 0.187 in.; gage length, 1 in.) and had parallel flats milled to permit easier metallographic and X-ray observations. The final

Jan 1, 1954

By R. A. Graham, R. W. Rohde, J. R. Holland

In a shock wave compression study of a martensitic Fe-30 pct Ni alloy, Graham, Anderson, and Holland' found a region of unusual compressibility extending from a few kilobars up to about 20 kbars. This region was characterized by a continuously decreasing shock wave velocity with increasing stress. In this note, we report the results of a study initiated to determine the source of this unusual compressibility. In earlier shock-loading experiments on martensitic Fe-30 pct Ni, Loree et a1.' determined that a phase change occurred at about 80 kbars. Subsequently, Bowden and elly found that samples of a similar material shock-loaded at about 100 kbars experienced a martensite-to-austenite transition. Their crystal-lographic analysis showed the transition was a direct reversal of the established martensite system to the austenite phase. The shock loading in the present experiments was accomplished by precisely controlled plane impact between two discs of the sample material. This configuration created a state of uniaxial strain in the two the front of a projectile which was accelerated to various velocities. Planarity between the impacting discs was controlled to 5 x 10-4 rad, and impact velocities were measured to 0.5 pct. From a knowledge of the Hugoniot relationships of the material and the impact velocity, the shock-wave stress can be calculated. Samples were shocked at 18, 50, 70, and 100 kbars. The specimen discs shocked at 18 and 50 kbars were instrumented with quartz gages to observe the stress time profile. A more detailed description of the experiment has been given previously.4 The shock-loaded specimens were recovered intact by decelerating them in a catcher filled with soft wood. Discs of Fe-30 pct Ni nominally 12.7 mm thick and 64 mm in diam were cut from bar stock. Chemical analysis of the material provided the following composition in weight percents: 29.5 Ni, 0.50 Mn, 0.21 Si, and 0.10 C, with traces of Cr, Cu, Mo, Al, and Co. The discs were austenitized at 650° C for 2 hr at a pressure of less than l0-' torr, and furnace-cooled. Martensite was then produced by quenching the discs at -196" and holding 168 hr. The initial martensitic structure formed is shown in Fig. l(a). Typical microstructures of samples shock-loaded at 18 and 100 kbars are shown in Figs. l(b) and l(c). The banded structure with the austenite regions running parallel to the shock propagation direction was characteristic of samples shock-loaded at all stresses. No such banding was found in samples that were not shock-loaded. Comparison of Figs. l(b) and l(c) shows that, although under the optical microscope the two microstructures are quite similar, the martensite plates of the specimen shocked at 100 kbars etched in a distinctly different manner. This unique etching behavior of martensite in samples shock-loaded above the 80 kbar transition point has also been observed by Leslie el al.' These investigators determined from X-ray and electron microscope studies that fcc martensite, similar in appearance to normal bcc martensite, had been formed under shock loading. A quantitative determination of the amount of austenite present after shock loading was made by X-ray techniques. Both the methods of Lindren' and Miller' were utilized. The results are shown in Table I. The error limits are those experimentally observed from two independent analyses of each sample and represent the precision of the experiment. The absolute error, which should be similar for each sample, is believed to be about 10 pct. It is seen that as the shock stress increases the amount of austenite present also increases. On the basis of the X-ray and microscopic observations, we conclude that shock loading below the 80 kbar ersal will initiate a martensitic reversal: the amount of reversal that occurs increases with in-

Jan 1, 1969

By W. L. Saunders

WHEN work was begun in September, 1910, on the rock excavation for the foundation of the gigantic dam at Valhalla, N. Y., which is to convert Kensico lake into an important storage reservoir of the Catskill Aqueduct system, one of the first steps taken by the contractor, H. S. Kerbaugh, Inc., was the development of a quarry to supply the stone needed in the construction work.The importance of a bountiful supply of suitable rock in an accessible location is apparent when it is considered that nearly a million cubic yards of cyclopean masonry will be contained in the completed structure, not to mention dimension and facing stones, concrete blocks, and mass concrete. The dam structure will be over 1800 ft. long and about 170 ft. above the present river bed. However, for a distance of some 800 ft., it will be carried down to solid ledge rock, which will make the finished structure about 300 ft. in maximum height. It will be about 200 ft. thick at the base and directly beneath the coping it will be 28 ft. thick. This dam will raise the reservoir surface 110 ft. above old Kensico lake. The reservoir capacity will be 29,000,000,000 gal.-equal to New York's total needs for over two months. The contract price for this work is nearly $8,000,000 and is second only in amount to the cost, over $12,600,000, of the Ashokan Reservoir work. Fig. 1 is a view of the dam site.

Jan 2, 1914

By R. K. Datta

Eluropium -activated yttrium vanadate, excited by short- and long-wavelength ultraviolet radiations, shows enzission lines near 6100A, the principal ones correspondirzg to transitions of EU+3 ions from 5Do to the F2 energy level. The ~neclmlallistns of absorption and etnissiorz of this phosphor have been empirically studied. The absorption is caused by two separate processes in the matrix. The phosphor YVO4:Eu and tlie matrix YVO, haue essentially the same resectance spectra in the region 2500 to 4000if. There are two broat ah~o?~ption bands: natnely, around 2600 and 3600A regions. Whet? compared with the reflectance spectra of the constituent oxides, namely, Y2O3, V205, Eu2 03, the absorption bands of the tnatvix and the phosphor in the short- and long-wavelength ultraviolet regions can be interpreted as due to charge-transfer processes involving i) Y-O and ii) 17-0, respecti~~ely. The excitation spectrum' of the phosphor has two broad bands with peaks at about 2600 and 3600A regions. U can be postulated that enevgy absorbed under short- crud long-wavelength ultraziolet excitatzon, respectzcely, by Y-0 and V-O parts of the niatrix is transferred by radcatio~zless process to EU+3 ions. Thzs postulate can empirically be proved on the basis of the spectra of the systems (YVO4,-YPO4,):Eu. PO? ~ons do not have' any appreciable absorption in the short or long uv regions. When P0't3 ions are substitlited for v0i3 ions in YVO,:Eu phosphors, the absorption and excitation in the lo~zg uv region are gradually reduced. Ailoreover, the £«+3 emission under 3650A excitation is decreased zuitlz increase in PO^ content, lt~lzereas the emission under 253711 excitation remains esserztially constant with as IILUCIL as 60 mole pct of YPO, in YVO,:En. EUROPIUM-activated yttrium vanadate (YV04:Eu) is a well-known phosptor.'-3 When excited by cathode rays, 2537, or 3650A radiations, YV04:Eu emits typical narrow-band spectrum of EU'3 fluorescence in the region of 5900 to 7100A, a very strong maximum occurring at about 6190A. This emission is considered to be due to 5Do — 7F2 transition of excite: EU*3 in 4f state. Moreover, the emission under 3650A excitation increases with temperature markedly. Because of these properties, YV04:Eu phosphor finds wide application in industries, namely, in color television tube, laser, and high-pressure mercury-vapor lamps. It is the purpose of this paper 1) to present the empirical study of the mechanism of absorption and excitation of YV04:Eu phosphor by ultraviolet radiation, and 2) to offer an explanation for the process of emission. It should be mentioned that a theoretical discussion on the mechanism of absorption in terms of the crystal or ligand field theory is beyond the scope of this paper. Empirical studies presented here are based primarily on spectroscopic and crystal-chemical investigations. EXPERIMENTAL i) Preparation of Materials. The synthesis of vanadate phosphorinvolves preparation of (Yi-.tEuj^Oj, blending the mixed oxide with an oxidic compound of vanadium, such as V205 or NH4V03, and firing the mixture at about 1000°C for several hours when YVO4:Eu forms as a primary phase. (Y1-xEux)203 compositions are prepared by coprecipitation of oxalates, and igniting them at about 1000°C. The vanadium compound is added in excess of the stoichiometric proportion for fluxing purposes. The charge is cooled, ground, and the excess of vanadium is removed by a hot wash (-80°C) of alkali or ammonia. Y(VP)04:Eu samples are prepared by mixing (Yi-xEux)203 with stoichio-metric proportions of (NH4)2HP04 and the vanadium compound. The mixtures are prefired at 700" to 800°C for 1 or 2 hr, then ground and refired at 1150°C. The firings of the phosphors are done in silica crucibles, and the homogeneity of the final products checked by X-ray diffraction analysis. ii) Spectroscopic Measurements. Diffuse reflectance sqectra of the samples within the range 2500 to 7000A are obtained by using CaF2 as standard in Cary Recording Spectrophotometer, Model No. 14. The emission spectra from phosphor plaques, excited under different ultraviolet sources, are obtained by a direct-recording spectroradiometer4 adapted with a grating monochromator with nearly constant dispersion. Maximym sensitivity in the spectral region from 2500 to 7000A is obtained with a quartz-windowed, S-20 response p$otomultiplier. The total' band pass is kept about 30A. The spectra are calibrated against the light from a standard tungsten filament lamp reflected from a magnesium-oxide plaque. Brightness data given throughout this report $re measured from the height of the main peak (6190A) of the emission spectra. The excitation spectra are measured using sodium salicy-late as standard. RESULTS AND DISCUSSION The diffuse reflectance spectra of both pure and activated YV04, along with their constituent components, are shown in Fig. 1. YVO4 shows two broad absorption bands, namely, around 2500 and 3600A, respectively. Since there is little difference between the reflectance spectraoof YVO4 and YVO,:Eu in the uv region (2500 to 4000A), it can be postulated that excitation of the phosphor is mainly due to absorption by the matrix, i.e., YVO4. The question, now, is whether the matrix (Yv04) is excited as a whole, or different components are responsible for the two absorption bands. The characteristic absorption spectra of molecular ions involving transition metal ions, both in aqueous solutions and in crystals, are due to electronic transi-

Jan 1, 1968

By Arthur L. Hawthorne

10.1-1. Relative Position of Maintenance as Compared to the Overall Mining Costs. The basic issue regarding the importance of maintenance in the modern mining industry must be faced squarely by the top manage- ment of each company before any real progress can be made in organizing a maintenance program for optimum effectiveness. Just a few decades ago the maintenance at coal mines consisted primarily of a blacksmith for sharpening picks and shoeing mules; as a result, probably less than 5%of the total mining cost went to maintenance and some 80% was operating expenses (operating labor). With each succeeding advance in equipment design towards larger, more complex, and more productive units, the pendu- lum swings the other way. As an example, haulage trucks have progressed through various stages in the past 20 years from 15-ton units to a 240-ton truck now in the "shakedown" or experimental stage. The following com- parison between 15-ton, 50-ton, and 100-ton haulage trucks clearly illus- trates this changing cost pattern in terms of percent of overall costs for running each size unit. [Maintenance 24% 44 % 51 % Operating labor 59 % 33 % 16% Operating supplies (fuel oil) 4 %. 4% 3% Labor burden and vac. pay 6 % 4% 3% Depreciation Total] From the preceding figures it is interesting to note that, as a rule, operat- ing costs go down as the equipment gets larger and the maintenance costs increase with the larger units. This same trend in cost variation applies to nearly all mechanical equipment used in surface mining from the large

Jan 1, 1968

In accordance with the provision of the Constitution, notice is here given to all Members, Associates, and Junior Members, that the clues of the year 1918 will be payable on Jan. 1. 191.8, at the office of the Secretary. The dues for Members and Associates are $12 per year and the sum of 83 additional is asked of those Members and Associates who desire to have the three volumes bound in the Institute's standard half morocco binding. The dues of Junior Members are $5 per year.

Jan 12, 1917

In accordance with the provision of the Constitution, notice is here given to all Members, Associates, and Junior Associates, that the dues of the year 1919 will be payable on Jan. 1, 1919, at the office of the Secretary. The clues for Members and Associates are $12 per year and the sum of. $2 additional is asked of those Members and Associates who desire to 'have the two volumes bound in the Institute's standard binding. The clues of Junior Associates are $5 per year.

Jan 12, 1918

In accordance with the provision of the Constitution, notice is here given to all Members, Associates, and Junior Members, that the dues of the year 1918 will be payable on Jan. 1, 1918, at the office of the Secretary. The dues for Members and Associates are $12 per year and the sum of $3 additional is asked of those Members and Associates who desire to have the three volumes bound in the Institute's standard half-morocco binding. The dues of Junior Members are $5 per year.

Jan 1, 1918

John J. Porter, Cincinnati, Ohio (communication to the Secretary *):—The remarks of Mr. Firmstone concerning the presence of nickel in Oriskany ores, call to my mind some additional evidence on this point. In 1903, while engaged in the determination of zinc in a number of samples of ore from the Oriskany mine of the Alleghany Ore & Iron Co., I was surprised to discover the presence of nickel and cobalt. As far as I was then able to discover, their present;! had up to this time remained unnoticed. The amounts ranged from 0.05 up to 0.10 per cent. of the combined oxides, and while no attempt was made to separate the metals, the presence of both nickel and cobalt was conclusively proven. Since that time I have learned that traces of these metals are of quite general occurrence in Virginia iron-ores, and more especially in the ores of the Potsdam formation from the western slopes of the Blue Ridge. In certain manganese-ores from this formation, I have found as high as 0.50 per cent. of nickel and cobalt oxides. Any one interested in this subject will find further information in a volume l written by Andrew 8. McCreath, and printed in 1884 for distribution by the Norfolk & Western railway. A number of complete and accurate analyses of Virginia iron-and manganese-ores are given, and practically all show nickel and cobalt in appreciable quantity. Still another source of information on the occurrence of nickel in iron-ores in the United States, for which I am indebted to Charles Catlett, is found in the Tenth Census. Several analyses of Oriskany ores are given: all of which show the presence of nickel, with less cobalt, while the single representative from the Potsdam formation shows nickel, with no cobalt.

Jan 1, 1909

By Gregory Dybalski

The purpose of this paper is to illustrate the forecast capability of the econometric model of the cobalt industry1/ as utilized by the Federal Preparedness Agency. Forecasts from this model are illustrated from the premise that the leading producer continues production of cobalt. An alternate forecast is presented where the model structure is altered to reflect the condition where the leading producer leaves the market. All estimations and forecasts presented here are shown for illustrative purposes. The cobalt industry is highly concentrated; one company, owned by the Zaire government, accounts for approximately three-fifths of world production. The cobalt supply outside of Zaire is determined by the level of activity of copper or nickel markets, as cobalt is mined as a by-product of copper or nickel. The demand for cobalt reflects a diversified usage pattern; cobalt is used mainly in heat and corrosion-resistant materials, high- strength materials and permanent magnets. According to 1974 U.S. consumption data superalloys accounted for 22%, magnetic alloys 18%, cutting and wear-resistant materials 13%, and catalyst 7%. Foreign consumption is probably similar in terms of usage categories, but the relative order of the categories is in variance.2/ The Cobalt Model The cobalt model's object is to explain consumption, supply and price movements by utilizing statistically estimated equations. Central to the econometric model is the role of Zaire as the profit-maximizing "dominant firm". Zaire sets the price that is most profitable for itself. The price of cobalt depends on industrial demand, production of other firms, and net exogenous purchases, such as government

Jan 1, 1977

By Erwin S. Sperry

The oxidation of metals melted in contact with air takes place with dissimilar results. Tin, lead or zinc are examples of a class, the oxides of which float on the surface of the melted metal. First a film is produced, which covers the surface; then, if agitation from any cause exposes new metal to the action of the air, additional oxidation takes place, and the film is increased in volume. This change goes on until a considerable quantity of oxide (or " dross," as it is technically called) is formed; depending, of course, upon the duration of the exposure of the metal to the atmosphere. When such metals are poured, the dross may be skimmed off; and clean metal will be left underneath. The removal of such oxides is, therefore, merely a mechanical process. In the case of copper, however, the result is quite different. The sub-oxide of copper (Cu2O) is readily soluble in molten copper; and therefore, instead of the formation of a film of oxide, to be finally removed as dross, the surface of the metal remains bright and clear, because the oxide has been dissolved as soon as it was produced. It is customary in the process of copper-refining to leave a small quantity of oxide in the metal, in order to oxidize any traces of bismuth, arsenic or antimony which have not been entirely removed. As a result, these metals exist in the commercial product as oxides, and not as metals, which would form an

Jan 1, 1901