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By C. E. Barnett, G. R. Durland

LUMINESCENT materials have been used in an increasing variety of ways in recent years. Such uses range from the screens on which the picture or image is presented in television and other cathode ray tubes to fluorescent lamps, fluorescent effects in decorative, theatrical, and display lighting, and the many applications of phosphorescence in paints, textiles, paper, and plastics. During the war the screens for a radar set or the "night-seeing" devices were not fundamentally different from those in other cathode ray tubes, but nevertheless they presented special problems for the phosphor manufacturer. It was essential that the "pips" on a radar screen continue to glow after the exciting beam had swept on, but this afterglow would be ruinous to a television screen. In the image tube used for seeing at night with infrared instead of visible light, electrons emitted by an infrared-sensitive receiving surface were amplified and converted to visible light after striking a fluorescent screen. The small size of the screen caused special problems in reducing the grain size of the phosphor to obtain adequate resolution. Other devices used phosphor surfaces which could be stimulated directly by infrared radiation to emit visible light. Energy was stored in the phosphors by prior excitation with short-wave-length radiation, and the stored energy released on subsequent exposure to infrared radiation. Maps, navigational charts, bombing manuals, and computers of various sorts were printed on fluorescent paper or lettered with fluorescent inks. Fluorescent markings excited by small ultraviolet lamps were used on airplane instrument dials. A large amount of research was done to determine the best color for the emitted light and other properties for the fluorescent materials, and on the best methods for their fabrication into the items listed above. Phosphorescent materials found wide use during blackout restrictions to mark safe passageways, to delineate traffic hazards, to identify packages, and to mark tools and other items of equipment.

Jan 1, 1948

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

The Helen Mine, of the Algoma Steel Corporation, in the Michipicoten district, Ontario, Canada, has produced more than 6,240,290 tons of iron ore. Prior to and during World War I, 2,823,369 gross tons of brown ore were shipped, and from 1939 to the end of the 1944 season, 3,416,921 gross tons of siderite ore were produced from open-pit operations. Brief descriptions are given of the nature of the ore, the mining methods employed and the manner of treatment of the ore. Shipment of the finished product, known as Algoma sinter, is made to blast furnaces in both Canada and the United States. The iron-ore bodies—i.e., the oxide ores of the Old Helen and the siderite of the New Helen—are a part of a tabular shaped area of iron formation that extends over a length of more than 100,000 ft. and has a maximum width of 1000 ft. The ores are considered to be a product of introduction of iron-bearing material accompanied by replacement of the rocks already present. It is shown that introduction took place subsequent to the development of the major folded structures. It is believed the iron-bearing material emanated from an igneous source. Introduction The Michipicoten mining district derives its name from the Indian word1 meaning "place of bold promontories" or "region of big places," and anyone who has visited this part of Canada will agree that the district is well named. In 1897, there was active prospecting for gold in the district and the Ontario Bureau of Mines2 opened a recording office at the Hudson's Bay post at Michipicoten River. In the summer of 1897, Ben Boyer, probably searching for gold, discovered an outcrop of brown iron ore at the east end of a small lake, less than 8 miles, in an air line, northeast of the nearest point on Michipicoten Harbour. In the following year, extensive surface exploration and diamond drilling disclosed a commercial body of nonbessemer brown ore, possibly 700 ft. long and 200 ft. wide, of about the following analysis:3 Fe (natural), 57.15 per cent; S, dried at 212°F.. 0.113; SiO2, dried at 212°F., 4.00; P, dried at 212°F., 0.125. The property (Figs. 1-3) was taken over by E. V. Clergue and ultimately was transferred to the Algoma Steel Corporation. The Algoma Central Railway shortly afterward built its line from Michipicoten Harbour to the mine, together with an ore dock at the Harbour. Thus, within three years of its discovery, the mine had adequate shipping facilities and a market for its ore. Production of Brown Ore and Pyrite The first shipment of brown ore was made in July 1930. By 1939, the mine was shipping at the rate of 170,000 long tons

Jan 1, 1949

By Oscar Harder

IT is now just a quarter of a century since Fred W. Taylor§(23) pub-lished his classical paper On the Art of Cutting Metals, describing -his researches in which he, in cooperation with Maunsel White, had developed what is essentially the modern method of heat-treating high-speed steels. Regarding this research, Dr. Sauveur, (22) in his address on Steel Wizards, Past and Present, at the annual banquet of the American Society for Steel Treating in Philadelphia in 1920 said, "The discovery of high-speed steel, or if you prefer, of the treatment imparting high-speed properties to certain steels by Taylor and Maunsel White I am inclined to consider as our one epoch-making contribution to the metallurgy of steel." It was at about that same time (1900) that Taylor exhibited high-speed steels, heat-treated by the improved process, at the World's Exposition in Paris and attracted much attention by showing that the steels would operate at such feeds and speeds that the tips of the tools were visibly red hot. This observation must have started metallurgists to wondering regarding the relative hardness of the various steels at red-heat temperatures. Considerable work has indeed been done in an effort to measure the hardness of high-speed steels and. related materials in the red-heat range, using various methods. . The results, however, have been only partly satisfactory, owing to experimental difficulties. The present investigation had as its immediate inception an address by J. V. Emmons, of the Cleveland Twist Drill Co., to the Columbus Chapter of the American Society for Steel Treating in 1931, in which he deplored the fact that comparatively little was known with regard to the hardness of high-speed steels at elevated temperatures, in spite

Jan 1, 1933

By G. F. Comstock

In the literature of metallography there is a large amount of material describing the various non-metallic inclusions found in iron and steel, and the appearance of sulfides, silicates, oxides, or alumina in steel under the microscope is fairly well known. The inclusions found in non-ferrous metals are, however, not so well known, at least judging from published writings, and the author has been interested in examining small castings of copper, brass, or bronze with certain inclusions purposely mixed with the metal, to see what was the characteristic appearance of each kind of inclusion, and if they could be readily distinguished from one another. The method employed in most cases consisted in overheating and oxidizing a small charge of copper, then cooling it somewhat, and adding a suitable amount of the element whose oxide it was desired to observe. This element was stirred in well and given time to react with the oxygen in the copper, then the melt was poured in a sand mold in the form of a cylinder about 21/2 in. (63 mm.) in each dimension, with a sprue about 11/2 in. (38 mm.) in diameter and 3 in. (76 mm.) high on top of the cylinder, the sprue forming the only riser. Samples for examination were cut sometimes from the center of the casting, and sometimes from the sprue or riser. A few of these samples were cast in chill molds. The appearance of sulfides was studied in an alloy containing 10 per cent, each of tin and lead, with which a flux of plaster of Paris was used. The appearance of foundry sand was studied in several alloys, one of them having sand stirred into the metal intentionally, and others having cut into the molds badly when poured, so that the castings were spoiled by included sand. As all this work was done on alloys having copper as the chief ingredient, the natural starting point was copper oxide, the appearance of which in a micro-section is well known. Cuprous oxide is soluble in molten copper, but separates out in freezing and forms a eutectic containing 3.5 per cent. Cu20, or 0.39 per cent. oxygen. If there is less

Jan 1, 1919

By Fred C., Bond

DETERMINATIONS of circulating load in a classifier operating in closed circuit with a grinding mill are usually made from screen analyses of the mill feed and classifier products. The percentage remaining on someone selected screen size must be used in the calculation, and, because of the wide variation in average particle size between the mill feed and classifier overflow, an accurate and representative result at the selected mesh is often difficult to obtain. To overcome this difficulty and reduce the time required in making the determination, I have devised a method which uses the liquid-solid relationship in the circuit rather than screen analyses. The quantities required for the calculation include only the usual dilution and feed tonnage measurements, which should be made regularly in the course of ordinary mill operation and, in addition, the amount of new water added to the classifier, or to the head of the mill with the new feed. If measurements are obtained on both of these quantities it is possible to check the calculated circulating load, and to calculate the percentage of moisture in the new feed to the mill; or, if the latter is known, to check the feed tonnage.

Jan 1, 1937

By K. E. Brown, A. R. Hagedorn

A 1,500-ft experimental well was used to study the pressure gradients occurring during continuous, vertical, two-phase flow through 1-in., 1 1/4-in. and 1 1/3-in. nominal size tubing. The test well was equipped with two gas-lijt valves and four Mathak electronic pressure transmitters as well as with instruments to measure the liquid production rate, air injection rate, temperatures and surface pressures. Tests were conducted for widely varying liquid flow, rates, gas-liquid ratios and liquid viscosities. From these data, an accucrate pressure-depth traverse was construcred for each test in each of the three tubing sizes. From the results of these tests, correlations have beer] developed which allow the accurate prediction of flowing pressure gradients for a wide variety of tubing sizes, flow conditions, and liquid properties. Also. the correlations and equations which are developed satisfy the necessary condition that they reduce to the relationships approprate to single-phase flow when the flow rate of either the gas or the liqutid phase becomes zero. All the correlations involve only dimensionless groups. which is a condition usually Sought for in similarity analysis but not always achieved. The correlations developed in this study have been used to calculate pressure gradients for pipes of larger diameter than those upon which the correlations are based. Comparisons of these calcuclaed gradients with experimetally determined gradients for the same flow conditions obtained from the literature indicate that extrapolation to these larger pipe sizes is possible with a degree of accuracy sufficient for engineering calculations. The extent of this extrapolation can only he determined with additional data from larger pipe diameters. INTRODUCTION The accurate prediction of the pressure drop expected to occur during the multiphase flow of fluids in the flow string of a well is a wideiy recognized problem in the petroleum industry. The problem has been brought even more into prominence with the advent of tubingless or slim-hole completions which use small-diameter tubing. Many of the correlations which give reasonably accurale results in the lager tubing sizes are greatly in error when applied to small-diameter conduits. Small-diameter conduits are defined as 1 1/2-in. nominal size tubing or smaller. The study of the pressure gradients which occur during multiphase flow of fluids in pipes is exceedingly complex because of the large number of variables involved. Further difficulties relate to the possibility of numerous flow regimes of widely varying geometry and mechanism and the instabilities of the fluid interfaces involved. Consequently, a solution to the problem by the approach normally used in classical fluid dynamics based on the formulation and solution of the Navier-Stokes equation has not been forthcoming. This is primarily the result of the nonlincarities involved and the difficulty of adequately describing the boundary conditions. As a result of the foregoing, most investigators have chosen semi-empirical or purely empirical approaches in an efford to obtain a practical solution to the problem. Much of the previous work in this area was done in short-tube models in the laboratory. A number of problems arise, however, when attempts are made to extrapolate these laboratory results to oilfield conditions where a much longer tube is encountered. In those few studies where data taken in long tubes were utilized, the data covered only a limited range of the variables, and as a result inaccuracies are introduced when the correlations are extended outside the range of the original data. Also, as a consequence of the limited amount of data available for these studies, the effects of several important variables were overlooked. The problem of predicting the pressure drop which occurs in multiphase flow differs from that of single-phase flow in that another source of pressure loss is introduced, namely, those pressure losses arising from slippage between the phases. This slippage is a result of the difference between the integrated average linear velocities of the two phases, which in turn is due to the physical properties of the fluids involved. In contrast to single-phase flow. the pressure losses in multiphase flow do not always increase with a decrease in the size of the conduit or an increase in production rate. This is attributed to the presence of the gas phase which tends to slip by the liquid phase without actually contributing to its lift. Many investigators have attempted to correlate both the slippage losses and the friction losses by means of a single energy-loss factor analogous to the one used in the single-phase flow problem. In an approach of this type, hourever, many of the important variables, such as

Jan 1, 1966

By C. Dirksen

This study investigates whether oxygen consumption during segregated forward combustion may be affected by natural convection. Linear theory indicates that thermal instability occurs in a horizontal porous medium when the modified Rayleigh number N 'Ra exceeds a critical value of about 40. Most experimental results, including those described here, indicate this value to be about an order of magnitude smaller. N ', is derived from "differential similarity" and the proper time scale factor is also obtained. The critical value of N'ra for a horizontal, water-saturated porous medium at atmospheric pressure subjected to a uertical temperature gradient was found to be about 3.0. The ambiguity in the value of N'R, arising when fluid properties cannot be assumed constant is indicated. Natural convection was observed for oblique systems below N 'Ra , while simultaneous horizontal flow did not affect N Racrit. The expected range of values for the various parameters pertaining to segregated forward combustion is indicated and the corresponding values of N 'Ra calculated. Only under very favorable conditions, such as high permeability, high pressure and low top temperature, can the critical value of N 'R, be exceeded. Thickness of the convection layer should not become too large, since the time required to obtain significant mixing is proportional to the square of the thickness. For an oblique combustion frant the conditions for significant mixing may be less strenuous. LNTRODUCTION Laboratory1,2 and field314 experiments have shown that a markedly upgraded oil can be produced by in situ forward combustion. Under certain conditions injected air may move through a high permeability, gas-saturated channel over the oil-saturated layer, while combustion takes place, exclusively, at the horizontal interface (Fig. 1). Such a channel may be a natural gas cap, or it may result from a forward combustion process in which injected air and combustion gases fingered through the top of the formation, causing a premature breakthrough at the production well. In this particular case of segregated forward combustion, the air stream moves parallel to the combustion front. Molecular diffusion and transverse mechanical dispersion will be insufficient to cause all the oxygen in the air stream to reach the combustion front. When the oxygen in the air stream is not completely consumed in the combustion process, it will reach the production well and create a serious fire hazard. In addition, the reduced efficiency may make the process economically unprofitable while also serious corrosion problems may be experienced in the production we11.3 This undesirable situation should, therefore, be prevented. However, in a situation as depicted in Fig. 1, an unstable temperature gradient exists in the gas phase. The combustion is taking place at the lower boundary at a nearly constant temperature that may be anywhere from 600 to 1,200F, depending on the conditions. The upper boundary of the gas phase is overlying, impermeable rock; its temperature might be around 100F, but may increase to 300F or higher due to conduction and convection as the combustion process continues. This represents a steep temperature gradient and it is conceivable that under those conditions free or natural convection will take place in the gas

Jan 1, 1967

By J. T. Crawford

Although nearly 10 pct of the total tonnage of coal produced annually within the United States is handled by bulk freighters on the Great Lakes, very little of the detail connected with it has been published other than occasional newspaper stories and publication of tonnage statistics. Of the total tonnage floated on the Lakes each year some 10,000,000 is stored and distributed from the port of Duluth-Superior, at the western end of Lake Superior commonly known as the Head of the Lakes. This port has the largest single area concentration of coal docks in the world. Since this area contains the largest ore docks, the largest movable material handling bridge, the largest and highest grain elevator and the largest coal bri-quetting plant in the world, it is entirely fitting and proper that here also should be located the largest coal dock and what we believe to be the world's largest clam shell. Of the sixteen coal docks operated by ten companies, five are owned and operated by the North Western-Hanna Fuel Co. which has two docks on the Superior, Wis., waterfront and three docks in Duluth, Minn. It is with these five docks that we are primarily concerned, General History In the summer of 1871 a small sailing vessel entered the harbor of Duluth-Superior with the first commercial coal cargo. All the coal brought up that first year did not amount to more than 3000 tons. During the year 1877 the first dock equipped for handling coal was built in Duluth. Coal receipts increased to 52,785 tons in 1879 the first year for which an official record was kept. Since then the volume of water-borne coal to the Head of the Lakes steadily increased to a maximum of 12,688,321 tons in the year 1923. This tonnage was nearly equalled in the year 1927 and the next highest tonnage recent year was in 1946 when 10,105,703 tons were unloaded. The average annual bring-up over a ten year period 1938 to 1947 was 8,605,231 tons. Approximately 30 pct of the coal unloaded at the Head of the Lakes is handled over the docks of the North Western-Hanna Fuel Co. Competition of other fuels coupled with expansion of coal fields in the mid-west have held coal receipts for Duluth-Superior at a relatively constant figure during the last eight years although the total tonnage of coal floated on the Great Lakes has more than doubled in the past 25 years. From the shovel and wheelbarrow method of unloading early cargoes to the horsepowered windlass derrick with a wooden tub was but a short step. The first movable coal handling, steam operated,

Jan 1, 1949

"Salt Lake City was founded July 24, 1847, by Mormons under the leadership of Brigham Young. It had a population of 118,110, according to the United States census of 1920, and of 151,968, according to a civic survey, January 1, 1925. The Salt Lake metropolitan district is estimated to have 180,079 inhabitants.The city's area is 51.8 square miles. Its altitude is 4,354 feet. It has 514 miles of streets, of which 91 miles are paved. The streets in the main portion of the city are 132 feet wide and the blocks are 660 feet long. It has 144 miles of street railway and 2,200 electric street lights. It has fifteen parks and playgrounds, forty public schools and six private schools. It has eighty-nine church edifices, of which forty-nine are devoted to denominations other than the Mormon Church.It is the capital of the state, the headquarters of the Mormon Church and the headquarters of most of the mining companies and many other business institutions of the state and adjacent territory.The State University, the State School of Mines and the Inter-Mountain Experiment Station of the U. S. Bureau of Mines are in the eastern part of the city. Fort Douglas is east of the University the country clubs are in the southeastern portion of the city. The State Fair Grounds are in the northwestern portion.The city is the center of a trade area about 700 miles in diameter and is in almost the exact center of a circle that embraces the principal western mining areas. It is the home of several widely-known mining supply companies and all the other leading concerns in that line are represented by agency or branch house."

Jan 1, 1925

By H. N. Thomson

GENERAL. THE Tooele plant of the International Smelting & Refining Co. is situated at the mouth of Pine canyon, Tooele county, Utah. It is connected with the main line of the San Pedro, Los Angeles & Salt Lake railroad by the Tooele Valley railway, and is about 7 miles from Tooele Junction. Fig. 1 is a general view of the plant. FIG. 1.-TOOELE PLANT OF THE INTERNATIONAL SMELTING & REFINING Co. The copper plant has been in operation since July, 1910, and the first blast furnace at the lead plant was blown in on Feb. 29, 1912. The location of the plant was selected on sloping ground with the idea of using gravity to the fullest extent and thus keeping labor at a minimum. Practically the entire plant is constructed of steel, reinforced concrete, and brick. Bingham ores, both lead and copper, are received over the Utah Consolidated Aerial Tramway. The tram buckets, each containing

Jan 7, 1913

By P. G. Shewman, T. L. Wilson

Using published surface-diffusion (D,) data and published sintering equations, it is shouln that surface difusion should dominate the neck-growth stage of intering for all materials in which D, has been measured (six metals and A1as). Also, grain boundary diffusion can be expected to contribute appreciably to shrinkage and possibly to neck growth below some critical temperature of the order of 70 pct 01- the absolute melting temperatuve. In view of the widespread conclusion in previous sintering work that volume diffusion dowzinates neck gvowth, experiments were conducted using spherical copper powders to test this conclusion. Scaling studies on neck growth at 950°and 1020°C clearly demonstrated that suyface diffusion dorninates. Kinetic studies on shrinkage gave more equivocal results that indicated an increasing role of' grain boundary transport at lower temperatures. Five diarszeters from 100 to 300 u were used in the scaling sludy and a temperature range of -650' 10 950 C was covered in the shrinkage studies. All experiments were conducted in dvy hydrogen. In 1949, Kuczynski published his now classic paper on the determination of the transport mechanism in sintering from the time laws of neck growth. In the interim, these laws have been applied to many systems and slightly modified by several authors. Essentially all these authors concluded that, for crystal- line materials, the dominant transport mechanism in neck growth is volume diffusion. This stems from the observation that the neck radius increases about as t"5 and that the activation energy approximates that for lattice diffusion. A related but independent series of studies stems from Mullins' rigorous analysis of the growth of the groove formed where a grain boundary meets a free surface." xperimental work stemming from this analysis has shown that for each crystalline material studied (Au, Ag, Cu, Ni, Fe, Pt, Al2O3) surface diffusion was clearly the dominant transport mechanism for groove widths up to the order 10 to 20 p. The ratio of the quantity of material being carried by lattice diffusion to that carried by surface diffusion increases linearly with the groove width, so surface diffusion is dominant for all widths under 10 to 20 u. The analysis of the relative contributions of surface and volume diffusion to grain boundary grooving, and to neck growth in sintering, shows that they are quite similar. Thus, using the available surface-diffusion data and the approximate equations of Kuczynski, or the more rigorous recent equations of Nichols and Mullins, 3 it can be shown that the small necks between particles must grow almost entirely by surface diffusion. The purpose of this study was to re-examine the basis for the conclusion that the neck-growth stage of sintering proceeds by volume diffusion. Using spherical copper powders, of several different diameters, precise experimental measurements were made of both neck growth and shrinkage. Application of Herring's scaling laws to the neck-growth data clearly indicated that neck growth occurred by surface transport, even though the neck radius increased as or Using the recent analysis of Mullins and Nichols as well as published data on surface diffusion, it is shown that the observed time law, as well as actual rate of neck growth, can be satisfactorily explained by a surface-diffusion mechanism.

Jan 1, 1967

By C. O. Rison

HIGH explosives, particularly nitroglycerin, have been used in torpedoes for the purpose of shooting oil and gas wells for more than 60 years. The early history of the oil industry in Pennsylvania is not clear as to who actually torpedoed the first well, although in 1865 the Roberts Torpedo Co. procured a patent covering the process. Gunpowder was first used, although nitroglycerin was substituted shortly afterwards. Wells are shot for the purpose of increasing the flow of oil and gas A shot-hole in the producing horizon, with its contributory fissures and fractures, increases the area of and stimulates drainage into the hole. The shot-hole also acts as a collecting basin from which the oil is pumped. As a rule, hard or close-grained sands or limes are shot, other more or less porous and soft formations usually do not require shooting. and might be injured by blasting. Shooting is also resorted to in mechanical trouble such as straightening crooked holes, sidetracking pipe or tools, and for severing frozen strings of casing or drill pipe. Explosives arc also used sometimes to extinguish oil or gas-well fires although that work, which involves unusual conditions and methods, does not properly come within the classification of oil-well shooting. Some Factors to Be Considered in Shooting Wells Although nitroglycerin has been used extensively for more than half a century in shooting oil and gas wells, there is still a great deal of uncertainty as to the proper method of shooting or the amount of explosive required to produce best results in a particular formation. The possibility of shooting unproductive or cavey formations above or below the productive horizons, shooting into lower water, destroying casing seats, and the splitting or collapsing of casing strings, are factors that require consideration. The engineering departments of a number of the larger oil companies are making a study of methods of shooting, and the amounts of liquid nitroglycerin or other explosives required in shooting various productive

Jan 1, 1929

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

The Helen Mine, of the Algoma Steel Corporation, in the Michipicoten district, Ontario, Canada, has produced more than 6,240,290 tons of iron ore. Prior to and during World War I, 2,823,369 gross tons of brown ore were shipped, and from 1939 to the end of the 1944 season, 3,416,921 gross tons of siderite ore were produced from open-pit operations. Brief descriptions are given of the nature of the ore, the mining methods employed and the manner of treatment of the ore. Shipment of the finished product, known as Algoma sinter, is made to blast furnaces in both Canada and the United States. The iron-ore bodies—i.e., the oxide ores of the Old Helen and the siderite of the New Helen—are a part of a tabular shaped area of iron formation that extends over a length of more than 100,000 ft. and has a maximum width of 1000 ft. The ores are considered to be a product of introduction of iron-bearing material accompanied by replacement of the rocks already present. It is shown that introduction took place subsequent to the development of the major folded structures. It is believed the iron-bearing material emanated from an igneous source. Introduction The Michipicoten mining district derives its name from the Indian word1 meaning "place of bold promontories" or "region of big places," and anyone who has visited this part of Canada will agree that the district is well named. In 1897, there was active prospecting for gold in the district and the Ontario Bureau of Mines2 opened a recording office at the Hudson's Bay post at Michipicoten River. In the summer of 1897, Ben Boyer, probably searching for gold, discovered an outcrop of brown iron ore at the east end of a small lake, less than 8 miles, in an air line, northeast of the nearest point on Michipicoten Harbour. In the following year, extensive surface exploration and diamond drilling disclosed a commercial body of nonbessemer brown ore, possibly 700 ft. long and 200 ft. wide, of about the following analysis:3 Fe (natural), 57.15 per cent; S, dried at 212°F.. 0.113; SiO2, dried at 212°F., 4.00; P, dried at 212°F., 0.125. The property (Figs. 1-3) was taken over by E. V. Clergue and ultimately was transferred to the Algoma Steel Corporation. The Algoma Central Railway shortly afterward built its line from Michipicoten Harbour to the mine, together with an ore dock at the Harbour. Thus, within three years of its discovery, the mine had adequate shipping facilities and a market for its ore. Production of Brown Ore and Pyrite The first shipment of brown ore was made in July 1930. By 1939, the mine was shipping at the rate of 170,000 long tons

Jan 1, 1949

By Yuri D. Tretyakov, Robert A. Rapp

The stoichiometry ranges ofNiOl+y and LiFe,O,-d were established by high-temperatwe electrochemical meas7rements in a stabilized-zirconia electrolyte cell. The results were consistent with doubly ionized cation vacancies in NiO,+y and interstitial lithium or iron ions in . The defect structure of the ternary ferrite was derived from the consideration of equilibration with respect to oxygen between the solid and the gas phase. The absolute magnitudes of defect concentrations were calculated. Pavtial molar enthalpies of oxygen in the compounds were calculated and interpreted in terms of the enthalpy of defect formation in these crystals. NICKEL oxide (NiO,,?) is a metal-deficient, p-type, extrinsic semiconductor whose properties are consistent with a structural model based on the presence of cation vacancies as the predominant ionic defect at sufficiently high temperatures and oxygen activities. A survey of previously reported conductivity studies and the presentation of some more recent conductivity measurements will be given in a later paper.' The absolute magnitude of the equilibrium vacancy concentration in NiO has been reported from combined conductivity and thermogravimetric data of ' However, disagreement exists concerning the state of ionization of the nickel vacancies in NiO. Some authors3-' have proposed that the predominant defects in NiO are singly ionized nickel vacancies and positive holes (h') formed by the reaction where, accorhng to the notation of Kroger and Vink,6'7 Oq represents an oxygen ion on its normal lattice site. Other authors"27E have proposed that doubly ionized nickel vacancies (V{i ) and positive holes are predominant and are formed by the reaction One purpose of the present investigation was to establish the nature of the predominant defect in NiO,+? as well as its equilibrium concentration and thermo-dynamic properties at elevated temperatures and known oxygen activities. To accomplish this purpose, the coulometric titration of oxygen into and out of NiO was accomplished using a galvanic cell involving the calcia-stabilized zirconia electrolyte. The ternary oxide, lithium ferrite (LiFe50,-6) is ferromagnetic and has the inverse spinel structure LiFe,O,-d Thus, in the ideal stoichiometric XY204 lattice, Fe3 ions occupy one-eighth of the tetrahedral (A) sites, and i' and Fe3' ions share at random one-half of the octahedral (B) sites within the fcc sublattice of oxygen ions.g The structure and thermodynamics of the spinel structures have been comprehensively decribed.'-' A recent compilation of literature for lithium ferrite is also available. 15 Oxygen-excess LiFe50sis not expected to exist because both i' and 17e3& ions are in their highest normal valency states (positive hole formation is not favorable). As will be discussed, equilibration of the ferrite crystal with oxygen of a surrounding gaseous phase will result in the introduction of equilibrium concentrations of ionic and electronic defects. In the Results and Discussion section a defect model for LiFe50,-d is proposed. This defect model is tested by high-temperature coulometric titration experiments. EXPERIMENT The oxygen activities in nonstoichiometric NiOl+, (and also LiFe,O,-d) were measured by means of coulometric titration with the high-temperature galvanic cell The critical characteristic of a suitable experimental cell is the complete isolation of the phase to be investigated in a minimum sized chamber which is free from extraneous sources and sinks for oxygen (leakage). Then oxygen is only admitted to the chamber or removed from it in known amounts by coulometric titration, which involves the passage of oxygen ions through the solid electrolyte with electrochemical oxidation and reduction reactions at the platinum contacts to the electrolyte. The experimental cell is shown in Fig. 1. The cap of the cell was the tip from a closed-end alumina tube, which was found to be leak-free from a helium leak-detector test. This alumina cap was about 1.2 cm OD and about 1.5 cm high. A Zircoa calcia-stabilized zirconia tablet (crucible lid) of 1.5 cm diam and 0.3 cm thickness served as the solid electrolyte. A Pyrex ring of about 0.1 cm thickness was placed between the electrolyte and the cap. The electrolyte tablet was painted with platinum paste on the entire outer face and on that part of the inner face which would be within the enclosure; these electrodes were further prepared by heating in air at 1000°C for 2 hr. Nickel oxide powder, listed as 99.999 pct pure, was purchased from Leico Industries, Inc. Pills of the NiO were cold-pressed and sintered at 1050°C for 3 hr in a platinum crucible. This poorly sintered NiO was crushed, and chunks were wrapped in 52-mesh Pt gauze (to catalyze the solid-gas exchange) for place-

Jan 1, 1970

By Edward Jeffrey

THE use of coke in metallurgy, to any important degree, dates from the middle of the 18th century. Its utilization came most opportunely for European civilization. The forests of Europe, except in the most remote and inaccessible regions, had been largely fed, in the form of charcoal, into the smelting furnaces. For a hundred years-the middle of the 17th to the middle of the 18th century-there was a stationary condition of population corresponding to the exhaustion of European forests. This situation, which was particularly evident in Great Britain, was due to the fact that the forests had been depleted and the practical utilization of coke had not begun. The coking industry is essential for our metallurgical industries, which in turn are basal to healthy economic progress. But coke is of great importance, not only on its own account, but for its byproducts, which enter fundamentally into all the arts of peace and war. The dyestuff industry and the manufacture of explosives are intimately connected with one another, as was shown by the recent war. The subject of coking coal, therefore, is well worthy the serious attention both of practical industry and the scientific investigator. The most valuable coking coals, from the metallurgical standpoint, are derived from the coals of highest ranks. Coals, for example, that have a carbon ratio of from 70 to 80 per cent. yield the most valuable coke for the blast furnace. The difficulty of investigating these coals, however, is great, for they are rather friable and delicate and possess a high carbon content, which makes them difficult to manipulate. They present, on account of their high carbon content, a considerable degree of opacity when examined, in thin sections, under the microscope. The tenderness of structure and blackness of such high-grade coking coals as those of Connellsville and the Pocahontas region make them extremely difficult to investigate.

Jan 1, 1925

By W. B. Plank

THE figures on enrollment in the engineering schools of the United States and Canada indicate that the total number of students in these schools for the current year, 1949-50, is about 10% less than it was a year ago. This year, 226 - 533 undergraduates and graduate students are studying engineering in the United States and Canada as compared with. 249,913 students last year. These figures are taken from advance data in the Journal of Engineering Education for February 1950.

Jan 1, 1950

By N. W. Sager, H. W. Mossman

The arrangement and general dimensions of the reverberatory furnaces and waste-heat boilers for the Nos. 2 and 3 smelting units at the McGill plant of the Nevada Consolidated Copper Corporation are shown in Fig. 1. Each of the two reverberatory furnaces has its own set of waste-heat boilers, and before February, 1932, each furnace, when it was in operation, delivered waste-heat gases to its own boilers only. In January, 1933, the idea was suggested of using some of the waste-heat boilers as economizers to operate in conjunction with the waste-heat boilers that were generating steam. The execution of this idea gave rise to the gas-flow scheme depicted in Fig. 1, the advantages of which were obvious, particularly so in view of the fact that for some months prior to the adoption of this scheme the smelting had been confined to No. 2 furnace, with No. 3 furnace and its boilers idle. The waste-heat gases from No. 2 furnace pass through the boilers serving this furnace as steam-generating units, thence through the original exit duct to a point where a bulkhead diverts the gases in a reverse direction through two of the boilers of No. 3 furnace. After the gases have traversed these two boilers, another bulkhead placed in the duct between No. 3 furnace and its boilers causes them to traverse still one more boiler, from which the gas path leads to the stack. In this scheme the last three boilers traversed by the gases, i.e., the boilers behind No. 3 furnace, function as economizers and preheat the feed water for the two steam-generating units directly serving No. 2 furnace. This discussion will give consideration to the results obtained in waste-heat recovery by the scheme shown in Fig. 1, and, further, will compare these results with those obtained before the boilers of No. 3 furnace were set up to act as economizers, but before going into the detail of heat generation, distribution and recovery, will present some additional details of the equipment. All boilers in this waste-heat plant are of the Stirling type. The two behind No. 2 furnace, acting as steam-generating units, of class 13, are 40 tubes wide and rated at 1112 boiler hp., while the three boilers behind No. 3 furnace, acting as economizers, are also of class 13, but 28 tubes

Jan 1, 1934

(Under. this heading will he published notes sent to the Secretary of the Institute by members or other persons introduced by members.) Member; age 31, technical graduate, 8 years' experience in copper and nickel mining, desires to make a change. No. 480. Member, age 34, married, 16 years' experience as railroad construction engineer and as superintendent of iron, chrome and manganese mines. Especially successful in rush construction work and development of new mining properties. No straight salary proposition will be considered. No. 481. Member desires change of position. Four years experience in flotation, cyaniding, and mill design and construction. Married, technical graduate. No. 482. Member, age 33, married, graduate Columbia School of Mines. Nine years' experience as engineer and mining and oil geologist; experience in Mexico, Peru and Siberia. Speaks Spanish and Russian. No. 483.

Jan 9, 1918

By James H. TaVoularis, William J. Wiehagen

This paper discusses the application of commercially available microcomputers for assisting trainers in the delivery and evaluation of new hire, refresher, and occupational training. A brief overview of mine training highlights major issues facing the mine training community. The use of computer-based training has a potential for reducing costs and improving the transfer of conventional training to the job.

Jan 1, 1983

By T. R. Wright

THE Corporation operates concentrators in four camps: Casapalca. Morococha, Cerro de Pa-co, and Mahr. The present concentrator at Cerro de Pasco is the newest having been completed in 1943. and that at Casapalca the oldest, having been built originally as a gravity concentrator, in 1889. Prior to 1925 the Corporation's milling operations were confined to the beneficiation of silver-bearing copper ores, and treatment of these ore: by flotation was started in 1918. Although fairly large deposits of complex, fine-grained lead-zinc ores existed, little progress had been made in the treatment of such ores--in Peru or elsewhere-until the early 'twentics. The Casapalca concentrator began the selettive concentration of complex leadzinc ores by all-flotation methods in 1925, or contemporaneously with the commercial development of selective lead-zinc flotation in the United State:.

Jan 1, 1945