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By R. L. Ash, R. R. Rollins, C. J. Konya

An investigation was performed to determine conditions for optimizing the spacing of simultaneously initiated multiple explosive columns. This was done by using models of mortar, dolomite, and Plexiglas with 10-grain mild detonating fuse as the explosive charge. It was desired to simulate blastholes with multiple primers initiated by detonating fuse or when high-velocity explosives are used in low-velocity materials. It was found that optimum spacing between multiple charges was strongly influenced by charge length. At less than optimum charge length, the spacing at which complete shearing was possible between adjacent charges decreased exponentially with a subsequent loss of broken material volume. For charges fired simultaneously, larger burdens and spacings were possible as compared to those necessary for single-crater charges. For each material studied, there was a characteristic optimum charge length and a maximum attainable spacing at any given burden. Proper selection of the spacing distance between charges is fundamental to successful blasting. Its value directly affects the cost of drilling and explosives used per unit of broken material. In addition, the choice of a spacing that is Compatible with a given set of blasting conditions aids in the control of fragmentation sizing, ground vibrations, overbreak, and throw which in turn, influence other production costs. For example, normally loaded blastholes that are spaced too closely invariably promote overbreak and usually give coarse fragmentation. Unless care is taken, airblast and violent flyrock will occur and under certain conditions cutoffs and misfires may result. Too large a spacing, on the other hand, frequently leads to conditions that form bootlegs or toes. The choice of a particular spacicg to use, however, is largely a matter of individual experience and judgment, usually based on trial and error. Very little is known or can be found in the literature with regard to how the spacing between charges is related to field conditions and charge geometry. As a general rule, the firing time sequence of adjacent charges and properties of a material are thought to have the most significant influence on the spacing distance best suited for any given field condition. For example, delayed initiation of adjacent charges usually always requires a closer spacing than when charges are fired at the same time. This should be expected if one considers that the energy normally dissipated and lost in the surrounding ground from charges fired independently would be captured and utilized for breaking material between charges when they are initiated together. Spacing can be extended also when charges are aligned with structural planes of a material, such as jointing, along which shearing is relatively easy. It is customary to relate the spacing (S) between charges to their common burden (B) in the form of a spacing ratio, or SIB. The burden normally is considered as the optimum depth or distance from any single charge perpendicular to the nearest free or open face at which the desired fragmentation and maximum crater yield are obtained. For production blasting, value of the ratio is generally considered to vary from 1 to 2, depending on conditions.1-6 When adjacent charges are fired independent of one another, the value varies from 1 to about 1.4, the closer amount being employed to square corners or produce craters having the ideal 90" apex angle. The larger ratio is the geometric balance value for craters having an apex angle of 135". The basic ideal crater forms in the plane of the charge diameter for charges fired independently are shown in Fig. 1. In the event charges are fired simultaneously, geometric balance in the plane of their charge diameters suggests that a spacing ratio near 2 would be appropriate, as illustrated by Fig. 2. In practice, however, some compromise ratio value must be selected to conform with the specific ground conditions. An example would be where the jointing planes tend to produce 60° or 120° crater angles, the appropriate geometrically balanced charge arrangement being given by Fig. 3. In this condition, the spacing ratio is 1.15, not 1 or 1.4 as suggested for the 90° cratering of independently fired adjacent charges. In view of the foregoing, it would seem logical to assume that whenever charges all having the same burden are fired at the same time, spacing distances always can be greater than those permitted by charges fired independently. In practice this is not the case, however.

Jan 1, 1970

By E. J. Horwood

The varying physical character and large extent of the Broken Hill lode necesarily involve the employment of a variety of underground methods. The lode had its origin in an extensive fault plane traversing metamorphosed schists conformably, as a rule, with their beds of stratification. The underground waters carrying minerals in solution deposited their contents in the original cavities formed by the faulting action, and in the enlargements of these cavities due to dynamic forces brought to bear on the rocks, more especially on the hanging-wall side of the fault. This deposition was supplemented by metasomatic replacement of a portion of the original rock contents by the argentiferous sulphides of lead and zinc which form the staple products of the district. Although the orebody is practically continuous throughout the mines, its width varies greatly, ranging from a few feet to about 350 ft. The widest portions occur in conjunction with huge folds in the inclosing country rock, almost exclusively on the hanging-wall side. The ore in these folds pitches to the south in the southern half of the field, and to the north in the northern half; there are, however, undulations in these ore channels evidently due to compression of the rocks in the direction of the channels. In the earlier days, before the orebodies had been opened up, vertical cross-sections across these bulges in the hanging wall gave the lode the appearance of the "saddle formation," so well exemplified at Bendigo in Victoria; but subsequent development of the ore channels has long since proved that the formations in the two districts are entirely different. The depth reached by the zone of complete oxidation of the sulphides varies from about 259 to 550 ft, from the original outcrop, while partial oxidation extends in places below the 1,000-ft. level. The result of oxidizing influences has been the production of ore of every grade of cohesive-ness, from that of dry sand to that of hard compact rock. The methods of mining followed in this field, and even in individual mines, are varied in accordance with the character of the ore. The general practice of the field is to sink vertical shafts, generally on the foot-

Jan 1, 1916

By C. W. George, Bruce Chalmers

The authors enumerate the factors which appear, from their observations and practical experience of failure of aircraft components in Great Britain, to be responsible for causing a metal or alloy to fail by stress corrosion. The essential conditions for promoting failure by stress corrosion are: (I) tensile stress at the surface of the component, (either residual or applied), and (2) an attacking medium that may be a solution or a liquid metal. Particular attacking agents are effective only on certain metals. In all instances of stress-corrosion failure experienced, cracking of an intercrystalline form has occurred and examples of such failure in aluminum alloy, steel and copper alloys are described and illustrated. The relation between microstructure and stress corrosion is mentioned and methods of investigating the susceptibility to stress-corrosion failure of metallic materials are described. The precautions to be taken in selecting materials for particular aircraft components and the importance of adequate protection against chemical attack are considered. The authors have given a factual survey of stress corrosion and have made no attempt to advance any scientific explanation of the phenomenon.

Jan 1, 1945

By E. P. Sadowski, L. P. Trudeau, C. R. Cupp

The apparent high radiation resistance of two varieties of maraging steel is described and an indication is given of some phenomena that require further study. Two aspects were included in this work: a) effects of neutron irradiation on the room-ternperature tensile properties of 18 Ni (250) maraging steel; b) effects of neutron irradiation on the room-temperature tensile properties and on the impact resistance of 12 pct Ni-5pct Cr-3 pct Mo maraging steel. Subsize tensile and impact test specimens were used. The 18 pct Ni steel was irradiated to a neutron fluence of 3.3 x 10 n per sq cm (>1 mev). The 12-5-3 variety was irradiated to two neutron fluence levels: 1) 1.5 x 10 per sq CTTL (>I mev) 2) 3.1 x 10'9nper sq cm (>1 mev) In all respects both varieties showed unusually high resistance to change in strength and ductility after neutron irradiation. There was no noteuorthy over-aging in fully aged specimens. The aged 18 pct Ni variety showed a 4 pct drop in yield strength upon irradiation with little or no decrease in ductility. The aged 12-5-3 variety showed a 5 pct increase in yield strength on irradiation with a very slight decrease in ductility. The impact transition of the 12-5-3 variety only increased 35 to 45 Co upon irradiation, and the shear energy fracture value for the subsized specimens decreased only half as much as expected frorn experience with conventional steels. THE development of new reactor concepts and nuclear technology now depends to a large extent on the availability of new alloys capable of operating in stringent reactor environments. One of the most important new types of metallurgical material that has been developed in recent years is the maraging steels. This type of alloy is notable for its remarkable retention of toughness at high strength levels. In the course of a research program which incorporated ambient temperature radiation effects studies to determine the mechanisms of strengthening of 18 pct nickel maraging steel,' it became evident that the resistance of the alloy to neutron-induced changes in mechanical properties should be studied. This paper is to present evidence for the apparent high radiation resistance of maraging steel. The experimental program was in two parts: a) Effect of neutron irradiation on the room-temperature tensile properties of 18 Ni (250) maraging steel. b) Effect of neutron irradiation on the room-temperature tensile properties and on the impact resistance of 12 pct Ni-5 pct Cr-3 pct Mo maraging steel, a cobalt-free alloy. EXPERIMENTAL PROCEDURE 18 Ni (250) Maraging Steel. Tensile test specimens were machined to the dimensions shown in Fig. 1 from $-in.-diam hot-rolled bar of the composition shown in Table I. All specimens were austenitized for 1 hr at 1500°F (815°C) in argon and water-quenched. Half of the specimens were then mar aged for 3 hr at 900° F (482°C) in argon. The specimens were irradiated in a fast neutron transformer rod at approximately 120°F (50°C) to a neutron fluence of 3.3 x 10 10 n per sq cm (>1 mev). The irradiation was performed in the NRX reactor of Atomic Energy of Canada, Ltd., at Chalk River, Ontario, Canada. In all cases, the thermal neutron flux was three times as high as the reported (> 1 mev) fluxes. The room-temperature tensile tests were performed with an Instron tensile testing machine operating at a crosshead speed of 0.05 in. per min. The loading frame of the machine, mounted in a hot cell, was remotely controlled. The specimens were tested either

Jan 1, 1968

By Zay Jeffries

Tungsten has the highest melting point of all the known metals, namely 3350 C.; it is one of the hardest of the metals; it has the highest equiaxing or recrystallization temperature after strain hardening, of any pure metal known. It is particularly distinguished because, when composed of small equiaxed grains, it is extremely brittle and fragile at room temperature, and when possessing a fibrous structure it may be ductile and pliable at room temperature. The common ductile metals act in exactly the opposite manner in this respect. The present paper will include a brief note regarding the manufacture of wrought and ductile tungsten. The metallography of wrought and ductile tungsten in the various stages of manufacture will be considered more or less in detail. The general relationships between the properties of tungsten and other metals will also be considered. A discussion will be given explaining why fibrous tungsten is ductile at room temperature, even though past experience with other metals would indicate that it should be brittle. Finally, a brief note regarding some new fundamental metallographic propositions relating to all metals will be given. Manufacture of Wrought and Ductile Tungsten Up to about 10 years ago, it had not been possible to work tungsten mechanically. About the year 1908, Dr. William D. Coolidge, of the General Electrie Go., produced ductile tungsten from what was then supposed to be an inherently brittle metal and which, in fact, was inherently brittle in its normal state, that is, when composed of equiaxed grains. Since that time many products, chief among which are the filaments for electric incandescent lamps, have been made from wrought and ductile tungsten. Tungsten is produced chiefly from the minerals wolframite and scheelite.1-8 The ores may be reduced in many ways. For example, the ore may be fused with alkali carbonates and the fusion dissolved in water; sodium tungstate is formed, which is soluble in water. This

Jan 1, 1919

By Geo Ashley

THE following paper is intended to be suggestive only, and to open the way for discussion and further observation. Its preparation was requested only two days before the time limit set for the submission of the papers comprising this symposium. Thus no time existed for detailed studies so it is largely a memorandum of such facts as have come incidentally to the notice of the writer in the study of coal in the field. The field study of sulfur in coal has received very little special attention or description from coal students. The presence of sulfur concretions is noted in hundreds of descriptions, and certain benches of a coal bed may be described as "sulfury" or the presence and position of sulfur bands may be noted in coal sections in connection with sampling. It may be accepted that some sulfur is present in all coal. The amount varies greatly in different regions, in different beds, and in the same bed in different areas. The anthracite of Rhode Island comes the nearest of any coal known to the writer of being free from sulfur, several analyses of that coal showing less than 0.1 per cent. Subbituminous coals in Colorado in a few places have close to 0.2 per cent. of sulfur on the dry-coal basis and in other states subbituminous coals approach this lower limit. Bituminous coals seldom run under 0.4 per cent. of sulfur on the dry basis, though in a few places dry bituminous coals in Colorado and Washington have between 0.3 and 0.4 per cent. The better known bituminous coals have almost everywhere over 0.4 per cent. The best of the Pocahontas and New River coals run close to 0.4 per cent., but there is very little commercial coal in Pennsylvania, Ohio, Indiana, Illinois, Kentucky, or the other states that runs under 0.5 per cent. on the dry basis. From these minimum figures, the amount will range up to 5 or 6 per cent. or higher if visible sulfur is not excluded. It must be remembered that the usual -analysis of a coal bed is not intended to give the total proportion of sulfur in the bed but the amount in the coal after the removal of the more obvious and larger sulfur masses.

Jan 9, 1919

By J. L. Rodda, R. L. Wilcox, E. C. Truesdale

In recent years various problems in connection with research work on the preparation and properties of zinc-base alloys have required reliable information concerning the constitution of the zinc-rich portion of the iron-zinc equilibrium diagram. On numerous occasions rather positive indications were obtained that, for example, the solubility of iron in zinc was incorrectly represented on the current equilibrium diagrams. A careful study of all the available literature relating to the iron-zinc system led to the conclusion that much of the early work was unsatisfactory as measured by present standards of experimental accuracy, and as a result it was decided to redetermine the location of the liquidus curve and of adjacent portions of the diagram. Part I of this paper comprises a description of the experimental methods and a summary of the results by means of which the zinc-rich end of- the iron-zinc diagram has been revised in the following ways: 1. Measurements of the solubility of iron in liquid zinc by several different sampling methods, leading to a relocation of the liquidus curve. 2. Microscopic, conductivity, and X-ray studies of the solid solubility of iron in zinc, which, together with thermal analyses, have resulted in new values for the solid solubility and the eutectic temperature and composition. 3. Heating and cooling curves, obtained by a refined differential method, leading to new locations for the two peritectic horizontals. In Part I1 of the paper the attempt is made to review all of the published work having a bearing on the constitution of the iron-zinc system, and to correlate the present results, and some recently published data involving the use of X-ray technique, with the earlier work, much of which was done from 25 to 30 years ago.

Jan 1, 1936

By J. R. Vilelia

IN accordance with the custom of this society, we are gathered here, as we have every year since 1924, to honor the memory of the eminent American metallurgist and teacher, Professor Henry Marion Howe. Unlike many of the distinguished metallurgists who have preceded me as a Howe lecturer, I cannot bring to you reminiscences of his personality, for it was not my privilege to be associated with Professor Howe, or to be directly one of his students. Yet, Professor Howe and Professor Albert Sauveur, through the medium of their books, were my first teachers of metallography, as they have been of almost all American metallurgists of my generation. As a teacher, and for many years the acknowledged leader of American metallurgists, he exercised a profound influence in the growth of our science and was held in honor by the men of science of his time. I can speak no words of technical appreciation that will add luster to his fame, for by his prophetic vision, his teachings, and his researches he stands among the immortals in the memory of all metallurgists. In 1926, the third Howe Memorial Lecture was presented by Professor William Campbell' of Columbia University, who entitled it "Twenty-Five Years of Metallography." He took as a starting date for his chronology the turn of the century, which coincided with his arrival from England to work in association with Howe at the Columbia School of Mines. In that informative lecture Professor Campbell enumerated the important advances in metallography achieved during the first quarter of the century, and, it now appears, may have established the custom of reviewing such progress every twenty-five years. The scope of Professor Campbell's lecture was as broad as his metallurgical knowledge, for it embraced a wide portion of the field of metallography, both ferrous and nonferrous. Twenty-five years later, the Howe Memorial Lecture Committee saw fit to assign to me the honor of writing a lecture that would commemorate the work of Henry Marion Howe and would at the same time constitute the 25th anniversary of the lecture by Professor Campbell. The Committee suggested that this lecture might properly be called "Twenty-Five More Years of Metallography," a suggestion that I have adopted. I must confess, however, that I have not followed the precedent established by Campbell and have narrowed the scope of this lecture to an appraisal of those achievements which in my opinion have contributed most to the progress of microscopical metallography during the past twenty-five years. Progress in Metallography The metallographic methods most widely used today, with the exception of the electron microscope, were firmly established more than twenty-five years ago. In general, our specimens were prepared for microscopic examination in those days in much the same manner as they are today. It is true that new details of technique have been introduced from time to time, and that superior equipment is available today, but on the whole, these improvements have been in the nature of refinements, often a matter of personal preference, and none can be considered essential to the attainment of the ultimate goal of the art and science of metallography, which is to reveal the structure of metallic specimens with unequivocal clarity so that they may be interpreted correctly. Mechanical metallographic polishing, which was the only method available in 1926, is still universally practiced and still consists of abrading the metallic specimen with a series of abrasives of increasing fineness until a specular surface is attained. We have now the alternative method of electropolishing, but it is not widely used because, except in a few special cases, its results are inferior to those of competent mechanical polishing. Likewise, most of the etching reagents preferred today were in common use more than twenty-five years ago and were applied in the same manner as they are today. Valuable improvements have been made in the optical and mechanical performance of metallurgical microscopes, but there was no dearth in those days of excellent instruments equipped with achromatic and apochromatic objectives capable of yielding micrographs comparable in quality with the best that we can make today. In fact, it would be a difficult task for any metallographer today to make optical micrographs at magnifications in excess of 3000 diameters that would surpass those made by Lucas more than twenty-five years ago. One of these is shown in Fig. 1. Yet, it is unquestionable that on the whole, the micrographs appearing in the metallurgical literature today are vastly superior to those

Jan 1, 1952

THIS chapter and Chapter 19 deal with the heat quantities involved in open-hearth steelmaking, including the thermal efficiency of the furnace as a generator of high-temperature heat, the heat storage in the steel and slag produced and in the furnace walls, and the heats of the various chemical reactions involved in combustion, in the formation of slag, and the refining of steel. The fundamental laws to be considered are the first two laws of thermodynamics as applied to problems involving sensible and potential (or latent) heat only: 1. Heat input equals heat outflow plus storage. 2. Heat may be transferred only from a hotter body to a colder one. The first of these laws relates to the various heat quantities or the heat balance of the process. No one has as yet made an open-hearth heat balance that came out almost exactly balanced. The cause probably lies in the difficulties of accurate temperature and flow-rate measurements at the high temperatures involved and the inherent complexities in flow distribution and air leakage present in any real open-hearth furnace system. Some idea of the magnitude of the heat quantities involved can be obtained by a brief, crude outline of the heat balance of a 90-ton heat of steel. We will assume a 60 to 70 per cent hot- metal charge in a fairly fast working and only moderately efficient furnace, burning fuel oil, with a fuel consumption of around 4 million Btu per net ton of ingots produced. The time from start of charge to tap is 9 hr. During this period, the oil burned represents 360 million Btu and the sensible heat in the preheated air at the port ends is 117 million Btu, so that the total heat input at the ports is 477 million Btu. Heat stored in the steel and slag at the end of the heat, plus the various amounts absorbed by certain bath reactions, amounts to a total of 195 million Btu, but 120 million of this is supplied by the heat in the hot metal and by various heat-evolving reactions in the bath,

Jan 1, 1964

By Michael F. Dunn, Francis S. Kendorski

The fall of rock from strip coal mine highwalls continues to be the largest single source of fatal accidents, so methods to improve highwall stability through improved blasting practices were investigated in the field. This paper covers the results of a project to improve, using existing and proven technology, unstable highwall conditions through better blasting practices in Appalachian strip coal mines. Better borehole blasting agent distribution and optimization of burden, spacing, and delay periods allowing satisfactory breakage with minimal backbreak were the objectives. At a selected field site, geologic conditions were closely examined with regard to joint orientation and spacing, and resulting slope stability considerations. Utilizing surface blasting concepts of trying to achieve flexural failure of the rock mass both horizontally and longitudinally by appropriate relationships between burden, spacing, and hole length, as well as delay time sequence to achieve optimal confinement and breakage, successful results were achieved. A test series of eight blasts was completed and the resultant highwall monitored by repetitive photography. Actual blockfalls could be measured and the stability for each blast design thus quantified. The study of drilling and blasting economics along with equipment performance led to an economic model of blast parameters and the identification of blast design cost benefits. The work demonstrated that small strip mining companies are able to achieve a more stable highwall excavation utilizing presently available technology, equipment, and explosive products at improved operational cost and safety.

Jan 1, 1983

By Joshua I. Tracey, Mackenzie Gordon

THE bauxite deposits in central Arkansas were formed by weather¬ing, in early Eocene time, of fresh or kaolinized nepheline syenite above the water table in a subtropical climate of fairly continuous moisture. Four types are recognized: (1) residual bauxite deposits on kaolinized nepheline syenite, (2) residual deposits on kaolin and bauxite detritus, (3) alluvial deposits of sorted pebbles and pisolites of early Wilcox age, and (4) rubble deposits of later Wilcox age. All were invaded by kaolin and siderite during subsequent burial by Eocene sediments. PART I-FIELD RELATIONS OF THE DEPOSITS The Arkansas bauxite region for years has produced about 95 pct of the domestic supply of bauxite of the United States and it contains today reserves of more than 40 million tons-nine tenths of the known domestic reserves. During World War II, the Arkansas bauxite deposits were explored jointly by the U. S. Geological Survey and the U. S. Bureau of Mines. Some 6000 holes were drilled by rotary rigs under contract to the Federal Govern¬ment, which resulted in the discovery and delimiting of approximately 20 million tons of ore in place. Detailed study of the many sections cored through the bauxite, of data from a much greater number of drill holes made available by all the operating companies, and of the extensive mine faces exposed in the strip pits, has yielded valuable geologic information about the origin of the deposits. It is now possible to piece together a paleotopographic picture of the deposits and the now-buried land surface on which they formed. The bauxite region in the center of Arkansas (Fig 1) contains two producing districts: one in Pulaski County, just south of Little Rock, and the other in Saline County, about 15 miles to the southwest. The deposits in both districts are associated with hills of nepheline syenite, bosses of a large batho¬lith that was intruded into Paleozoic rocks and later buried beneath coastal plain sediments deposited during Cenozoic time. The folded Paleozoic rocks are exposed in the northwest half of the state and are covered in the southeast half by the nearly flat-lying coastal plain sediments. The older rocks were intruded by nepheline syenite, probably in Late Cretaceous time, and sub¬sequently were eroded so as to expose the top of the batholith. In Paleocene time, marine limestone and laminated black silty clay of the Midway group were deposited in an advancing sea, and covered all but the most elevated parts of the batholith. Erosion of the islands of nepheline

Jan 1, 1952

By D. F. Hewett

ALTHOUGH most persons will agree that an individual or a nation can profit from the experience of other individuals or nations, there is always room for debate over the degree of similarity of their past and present conditions and of their future problems. Noting the increasing interest that Americans are showing in our mineral problems, I have felt that we could profit from reviews of the experiences in mineral exploitation acquired by the industrial nations of Europe. Whether we can learn much from Europe's experience in exploiting such minerals as petroleum may be debatable, but certainly, with a record of metal production extending back nearly 3000 years, Europe should hold much of value for America. A trip to Europe in 1926 permitted me to visit 28 mining districts, of which about half are now or have been in times past outstanding sources of several metals. The districts range from England to Greece and from Spain to Poland. To summarize briefly my impressions of these mining districts, as well as such reactions to the thought and life of Europe as so short a visit permits, I shall only venture the opinion that Americans can review with great profit the ideas and actions of Europeans, with regard not only to the production of metals but to many expressions of life. I believe that America has made and is making new contributions to the art of living, as well as to the arts of mining and metallurgy, but in so far as Europe is and has been a laboratory of economic, social and political experiments, the results she has attained deserve the thoughtful attention of America. I have come to believe that many of the problems that harass Europe lie in our path not far ahead. I have therefore hoped that a review of metal production in Europe in the light of its geologic, economic and political background may serve to clear our vision with regard to our own metal production. One can not examine the literature of national metal production without being impressed that the countries of continental Europe, especially Germany and Austria, have shown greater interest and devoted more time to research into the record of metal production than Great

Jan 1, 1929

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 J. W. Leonard, J. C. Anderson, C. T. Holland

PREPARATION CONTROL IN UNDERGROUND MINING Selective Mining According to district Depending upon the particular geographic loca- tion or seam characteristics, modern raw coal preparation practices can be used to obtain improved product quality and uniformity. Nevertheless, certain coal markets may require only marginal quality while others may require very high quality, and these objectives may be sought by commencing the preparation of coal underground at the "working face." Under- ground preparation involves choosing those portions of the seam which can be cleaned to satisfy predetermined market requirements involving ( 1 ) maintenance of uniformity in chemical quality, (2) elimination of removable impurities, (3) control of sizes and size ratios, and (4) control of moisture. The methods employed to attain these objectives vary widely with the (1 ) seam under development, (2) mining equipment available, and (3) changing trends in the consuming markets. When a mining property is opened and development progresses from one section to another, the (1) petrography of the coal in the seam does not remain uniform, (2) character of roof and floor are subject to change, and (3) character and prevalence of mineral impurities are subject to considerable variation. The quality of coal shipped to market from any mine depends upon intelligent foresight, planning, execution, and supervision. Mining becomes a highly technical art. The quality of coal as determined by chemical and petrographic analysis is without question one of the most important considerations in the development and life of any coal-mining property. Variations in such proper- ties as volatile matter, ash, sulfur, Btu content, and petrography are of considerable interest, and to a limited extent so are such properties as phosphorous content, free swelling index, plasticity, hardness, pressure formation during coking, and ash composition. The maximum and minimum specifications of these characteristics as established by competitive market conditions place definite limits on the marketability of a coal.

Jan 1, 1979

By T. Egleston

The Boston and Colorado Smelting Works are situated in the town of Black Hawk, Gilpin County, Colorado, on the Clear Creek Narrow Gauge Railway, 55 miles from Denver, in the Rocky Mountains, at an altitude of 7800 feet. It was one of the first works erected for the metallurgical treatment of gold ores, and the only one established in Colorado on a large scale which has been uniformly successful. Both gold and silver ores are treated, and gold, silver, and copper produced. The lead is not separated from the ores nor paid for, if it exists, and is entirely lost in the residues. The works were planned and built by Professor Hill, formerly Professor of Chemistry in Brown University, Providence, R. I., and is still managed by him, assisted by Mr. Richard Pearce, formerly professor in the School of Mines at Truro, England. They are very advantageously situated with regard to the ore-producing regions, having Boulder County on the north, which produces, besides ordinary gold ores, a series of tellurium minerals, such as altaite, sylvanite, and hessite, which are very rich in gold and silver. They are associated with copper and iron pyrites, blende, galena, and the carbonate and oxides of iron. Gilpin County itself produces for the most part the pyrites of iron and copper rich in gold, with a small quantity of galena and blende, which is rich in silver. In

By R. D. Young, E. A. Harre

Nitrogen exists in two broad categories commonly designated as elemental nitrogen and fixed nitrogen. Elemental nitrogen is found in nature as a diatomic molecule and constitutes about 78%, by volume, of the earth's atmosphere. Fixed nitrogen is a common term used for nitrogen that is chemically bound to other elements. Although elemental nitrogen is very abundant, nonleguminous plants cannot utilize nitrogen unless it is in the chemically combined form. The content of this chapter is confined to fixed nitrogen since the uses and properties of elemental nitrogen and the fixed nitrogen compounds are different. Certain bacteria associated with legumes are able to fix atmospheric nitrogen, but not to the extent required by succeeding nonleguminous crops. The need to use fertilizers containing fixed nitrogen compounds to grow food crops has been recognized for hundreds of years, and from antiquity farmers have used organic wastes such as animal manures, vegetable wastes, sewage sludge, fish scraps, etc., containing these compounds for fertilizers. These organic materials have a low nitrogen content, however, and cannot support large-scale food production. Known commercial-size deposits of natural nitrates containing much higher nitrogen content exist only in Chile, and the possibility of the discovery of other significant deposits is remote. The Chilean deposits were the major source of nitrogenous fertilizers until the Haber-Bosch process for the production of synthetic ammonia was developed. In the Haber-Bosch process, nitrogen reacts with hydrogen at high temperatures and pressures and in the presence of a catalyst to form ammonia. Modern plants use air, water, and natural gas or other hydrogen sources to produce the ammonia that is now the key building block of the fixed nitrogen industry. Several major problems that developed in the 1970s continue with the nitrogen industry into the 1980s. These are (1) the continuing sharp escalation in the cost of feedstocks for ammonia production as well as all energy sources, and (2) the very steep increase in the investment cost of production facilities. More than 75% of the fixed nitrogen produced domestically is consumed as fertilizers. The types of materials used as fertilizers have changed significantly during the past years. There has been a trend from the use of low-analysis fertilizers to types which contain high percentages of plant nutrients. The average plant nutrient content (N + P2O5 + K2O) of fertilizers used in the United States has increased from 18% in 1930 to 32% in 1960 and today approaches an average of 44%. In the case of nitrogen fertilizers, the low analysis natural nitrates (16% N) gave way to ammonium sulfate (20% N) after about 1920. After World War II, ammonium nitrate (33.5% N) previously used in munitions, became established as the leading nitrogen fertilizer. Urea use as a fertilizer (46% N) began in the 1960s, and in the past 10 years has become the world's leading solid nitrogen fertilizer. Nitrogen Materials Anhydrous Ammonia-Anhydrous ammonia is a colorless gas at ambient temperatures and pressures and has a sharp pungent odor. Anhydrous ammonia is stored and transported as a liquid in high-pressure cylinders and tanks at ambient temperature, and in low-pressure tanks, barges, and ships at -28°F. Anhydrous ammonia is applied directly at 4 to 7-in. depths in the soil as a high-pressure liquid by special applicators, after which it expands to a gas that dissolves in the soil moisture or is absorbed on soil colloids. In other systems ammonia is metered into irrigation water and is thereby introduced into the soil.

Jan 1, 1983

By J. H. L. Vogt

TABLE OF COKTENTS. [ ]

Jan 1, 1902

By T. PH. D. Egleston

THE Boston and Colorado Smelting Works are situated in the town of Black Hawk, Gilpin County, Colorado, on the Clear Creek Narrow Gauge Railway, 55 miles from Denver, in the Rocky Mountains, at an altitude of 7800 feet. It was one of the first works erected for the metallurgical treatment of gold ores, and the only one established in Colorado on a large scale which has been uniformly successful. Both gold and silver ores are treated, and gold, silver, and copper produced. The lead is not separated from the ores nor paid for, if it exists, and is entirely lost in the residues. The works were planned and built by Professor Hill, formerly Professor of Chemistry in Brown University, Providence, R. I., and is still managed by him, assisted by Mr. Richard Pearce, formerly professor in the School of Mines at Truro, England. They are very advantageously situated with regard to the ore-producing regions, having Boulder County on the north, which produces, besides ordinary gold ores, a series of tellurium minerals, such as altaite, sylvanite, and hessite, which are very rich in gold and silver. They are associated with copper and iron pyrites, blende, galena, and the carbonate and oxides of iron. Gilpin County itself produces for the most part the pyrites of iron and copper rich in gold, with a small quantity of galena and blende, which is rich in silver. In * By consent of the council of the Institute, this paper was first published in London Engineering, from which the engravings are here reproduced.

Jan 1, 1876

By F. E. Smith, David R. Mitchell, B. M. Bird

DENSE-MEDIA processes utilize the familiar laboratory float-and- sink procedure on a commercial scale. Just as wood chips float on water and sand sinks, ,so coal floats and refuse sinks when placed in a medium intermediate in specific gravity between the coal and refuse. Liquids intermediate in specific gravity between coal and refuse used in commercial plants are of four types: (1) Organic liquids of high specific gravity-halogenated hydrocarbons; (2) dissolved, salts in water; (3) pseudo liquids obtained by suspending solids, such as sand, in water, and (4) fluidizing a mass of sand or other solids by air currents. Those most widely used for cleaning coal are solutions of calcium chloride in water and a suspended-sand pseudo liquid. Laboratory float-and-sink testing is an intermittent operation during which every opportunity is given for particles lighter than the medium to float and particles heavier to sink. Commercial processes are continuous, vertical and horizontal currents of the separating medium occur as either part of the process or unavoidably produced by the introduction of feed and withdrawal of products, so that the exact separation of the laboratory technique is not duplicated by commercial processes. However, separations close to the theoretical are obtained in commercial machines by careful technical control of the process. Most machines in commercial installations are crowded to get as much out of the equipment as possible, so that careful technical control is necessary to get the recoveries and grade of product desired. Sizes usually cleaned are plus 3/16-in. or plus 1/8-in. in the United States and plus 1/16-in. in Great Britain: Coal as small as 1 mm. has been cleaned in some experimental installations. The separation of coal from refuse in sizes finer than about in. is made difficult by viscosity' effects and hence at the present time cleaning is confined to the coarser sizes. Technical advances in the art of cleaning coal by dense-media

Jan 1, 1943

By H. Foster Bain

Jan 1, 1910