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By C. H. Frick

BEFORE presenting the main topic, as indicated by the title, this paper will give some of the high-spot history of the anthracite industry. INTRODUCTION The earliest recorded use of anthracite was in the year 1762, when a company of Connecticut pioneers discovered anthracite near the present city of Wilkes-Barre, Pennsylvania. In the early days of the industry, the coal was used only in large pieces, the smaller pieces being discarded to waste piles. As the output of the industry increased during the nineteenth century, uses were developed for somewhat smaller sizes down to and including pea coal. Early in the twentieth century, sizes smaller than pea, such as No. I and No. 2 buckwheat, were developed and used. Accu¬mulations of piles from current mining operations were still increasing; that is, the smaller sizes were still being discarded. It was not until after World War I that preparation of the so-called steam sizes began commercially. This was largely No. 3 buckwheat, which is screened through a 3f 6-in. round-hole screen and over a 332-in. or a M 6-in. round-hole screen. USE OF SMALLER SIZES The earliest recorded experience in burning the small sizes of anthracite for steam production, other than in a previous small experiment, was in the year 1913, when a size known as "boiler fuel" was introduced-a mixture of rice and barley (No. 2 and No. 3 buckwheat). At that time, there was still no method known for burning the still smaller sizes. TABLE I.-Screen Sizes Used for Small Sizes of Anthracite [ ] At the present time, various sizes down to and including No. 5 buckwheat are being prepared (Table I) from current mining and bank-reclaiming operations. The sizes of No. 4 and No. 5 buckwheat and smaller are generally being used for steam production in large boilers. The Pennsylvania Power and Light Co., following World War I, used 680,000 tons of anthracite per year, burned largely on stokers for production of steam, whereas for the year 1943 it used 1,940,000 tons of stoker sizes and 400,000 tons of smaller sizes for grinding and burning in pulverized form. This company has taken a very large part in the research and development of ways and means of burning these smaller sizes of anthracite, including the grinding of the very small sizes. This paper is particularly concerned with the latter feature.

Jan 1, 1946

By Richard H. Jahns

Gem materials, comprising those minerals and closely allied natural substances used for personal adornment, for the fashioning of ornamental objects, or for other decorative purposes, have been valued in human commerce for thousands of years. Amber, jet, natural glasses, and at least 15 mineral species were sought and used by primitive man, and most of the materials in common use today were known well before the time of Christ. Their variety is remarkably great, and the traceable relationships among their respective sources, modes of occurrence, properties, and histories of production, preparation, and valuation are extremely complex. Their uses have been affected by numerous shifts in fashion, and from time to time by superstition, by decrees of church and state, by personal interpretations of religious significance, and by various presumptions concerning medicinal value and influence on human behavior (Ball, 1935, 1950; Kunz, 1913; Pogue, 1915; Whitlock, 1946). Thanks to their durability, portability, and relative scarcity, some gem stones have been employed as media of exchange, and the investment value of the more precious stones has long been recognized and exploited, especially in Asiatic and European countries. Demands for gem materials have stimulated trade among various peoples for centuries, and they also were responsible for much early geographic exploration. During more recent times they have prompted numerous geological studies and a considerable amount of research on the growth and properties of crystals. Apart from decorative uses, some naturally occurring gem materials also are employed directly in numerous fields of industry. Substances that are manufactured for gem or industrial uses are termed synthetic gem materials; most of these correspond in composition and crystal structure to certain minerals found in nature. Imitation materials are those whose use is based upon their resemblance to substances of different composition and greater intrinsic value. Gem stone is a designation commonly restricted to those materials suitable for personal adornment, and the complementary term ornamental stone is applied to the remaining materials not used industrially. This distinction is arbitrary and somewhat inconsistent, owing to numerous geographic differences and historical shifts in end uses. Further, there is a complete gradation between the category of ornamental stones and that of dimension stone. Substances that lose their identity in use are excluded from the gem category; thus a transparent crystal of beryl would not be classified as a gem stone if it were processed as a source of beryllium metal. The adjectives precious and semiprecious have been employed as a means for distinguishing different gem materials on the basis of recognized value. Diamond, emerald, ruby, and sapphire consistently have been regarded as precious stones, and in cut form they commonly are referred to as the noble gems. Opal, pearl, turquoise, and chrysoberyl also have been classed as precious at various times. In recent years, however, it has been increasingly recognized that no satisfactory distinction can be based upon assessed value or any group of specific properties, and now all gem stones normally are referred to as precious. Indeed, the tendency is to extend this term to include many of the so-called ornamental stones, and the designation semiprecious has been essentially discontinued. Unlike most mineral commodities of economic value, gem materials are little altered in processing for end uses. Some stones are used in essentially their natural form, and most are reshaped and polished without significant changes in their fundamental properties. Thus the preparation of gem and ornamental stones is intended chiefly to emphasize or enhance

Jan 1, 1983

By S. H. McFarlane, K. H. Zaininger, G. W. Cullen, C. C. Wang, G. E. Gottlieb

Heteroepitaxy of silicon on stoichiometric spinel has been studied. Both boron-doped (p-type) and arsenic-doped (n-type) single-crystal silicon films have been grown by the pyrolysis of silane on sioichiometric spinel (MgAl2O4) substrates prepared by a flux technique. The spinel crystals are free from strain and subgrains, and exhibit no thermal instability at temperatures employed for silicon deposition. The growth parameters of epitaxial silicon have been studied. Effects of substrate orientation, surface preparation, and growth conditions on the silicon Properties have been determined. The silicon-spinel composite was characterized by X-ray diffraction, electron diffraction, electron microscopy, and optical techniques. Information on epitaxial orientation relationship, defect structures and film-substrate interface has been obtained. A parallel orientation relationship was found between silicon and spinel. The silicon films exhibit no subgrain structures. However, growth pyramids, microtwins, stacking faults, and dislocations are the prevalent defects. The deformation of epitaxial silicon was measured by an X-ray technique. It was found that the epitaxial silicon is strained under compres-sive stress due to the thermal expansion difference between the film and substrate. The stress was estimated using the classical plate theory and beam equation. Electrical properties of the epitaxial silicon have been measured, including resistivity, carrier concentration, and Hall mobility. MIS and vertical through diffused junction structures have been fabricated wing silicon-spinel composite. Information on MIS characteristics, minority carrier life time, and junction properties has been obtained. THE achievement of single-crystal growth of large area silicon semiconductor films on oxide insulating substrates is of technical importance to many solid state electronic devices. The semiconductor-insulator composite structure is also of scientific interest because the heteroepitaxy is determined by the spatial relationship between the atomic arrangement in the substrate and that of the atoms in the appropriate crystallographic plane of silicon. The degree of crystalline perfection of the silicon deposits depends also on the physical condition of substrate surface. Epitaxial growth of silicon on commercial flame fusion Al-rich spinel (MgO:3.3A12O3) has been reported by several investigators.'-4 The lattice of spinel of this composition is distorted. The material cracks and exsolves the excess alumina in the lattice at temperatures (-1200°C) used in fabricating silicon devices. Stoichiometric MgA12O4 spinel exhibits neither lattice distortion nor thermal instability. Results are given on the epitaxial growth and characterization of silicon on stoichiometric spinel. EXPERIMENTAL Fabrication of Silicon-Spinel Composite Structures. The MgA12O4 spinel substrate wafers were prepared from bulk single crystals grown at about 1200°C by a flux technique5 using a PbF2 flux. The crystals are free from strain and subgrains, and exhibit a typical dislocation density of less than 50 lines per sq cm. The crystals are thermally stable without cracking and exsolution of alumina to at least 1500°C. The spinel crystals were oriented for cutting by the Laue X-ray back-reflection method.6 Substrate wafers (about 25 mil thick) of (Ill), (loo), and (110) orientations have been obtained bu cutting the X-ray oriented crystals using a standard type diamond wheel. An accuracy of better than 1/2 deg is maintained throughout the operation. The spinel substrate wafers were mechanically lapped and polished to produce the flat and smooth surface which is required for silicon epitaxy. Lapping was carried out with about 30-µ boron carbide abrasives to obtain a flat coplanar surface. The lapped surface was further polished using successively finer grades of alumina, ending with the 0.3-µ grade. After polishing the wafers generally have a flatness of ±0.4 µ per cm, as revealed by interferometry. Fig. 1 shows (111) oriented MgA12O4 spinel wafers of various shapes.

Jan 1, 1970

By Walter O. Roberts

A TOTAL eclipse of the sun is a brief, exciting spectacle witnessed by most men but once or twice during a lifetime. But to an astronomer an eclipse of the sun is an event of utmost scientific importance. For then, certain phenomena of the sun normally obscured by the brilliant glare of sunlight become spectacularly visible. For over seventy years prior to 1930 astronomers vainly attempted to discover a means of observing all of these eclipse features of the sun without a natural eclipse. But in 1930, through the genius of the French scientist, Bernard Lyot, astronomers met final success. Dr. Lyot invented a new kind of telescope known as a coronagraph, which made possible photography of all of the eclipse features of the sun. In 1940 Harvard University completed final testing of its Lyot-type coronagraph. the only one in the Western Hemisphere, and shipped it to Climax, where Donald H. Menzel, of Harvard College Observatory, supervised its establishment on the southeastern edge of the mining community of the Climax Molybdenum Co., with whose help and advice the modern residence and telescope dome of the observatory were constructed. Ever since that summer the station has been operated by me, first as a graduate student, and now as a staff member of Harvard College Observatory.

Jan 1, 1946

By F. H. Wilson

Copper base alloys containing various amounts of aluminum and silicon are of considerable commercial interest. In particular the alloy containing 7 pct aluminum and 2 pet silicon shows an attractive combination of high strength with excellent, machinability. Since there is no evidence ill the literature that this ternary system has been studied since the recognition by Smith1 and Anderson2 in 1939 of the kappa phase of the binary copper-silicon system, the determination of the equilibrium phase relationships in the copper corner of the ternary diagram has been undertaken to provide a fundamental basis for understanding the behavior of these alloys. Phase boundaries have been determined by the micrographic examination of quenched samples while points on the liquidus surface have been obtained by thermal analysis. The results, of sufficient precision to serve their major purpose of providing a guide for the control of the manufacture of alloys in the region covered, are presented in a series of both isothermal and vertical sections of the diagram. Alloys StVdied For a rough survey of the copper corner of this ternary system the compositions listed in Table I (Series A) were employed. The results of examinations of these alloys indicated that the compositions listed in Table 2 (Series B) would further clarify regions of greater complexity. All alloys were prepared as 1200 g heats, the copper being melted under charcoal, and then first silicon and then aluminum were added. An excess of 0.05 pet silicon was allowed to cover deoxidation losses. Two small bars 5/8 by 1 1/4 by 5 1/4 in. were cast using Durville type casting equipment. Ailalyses were made on all alloys using material which was hot-rolled at 800 or 850°C and annealed 17 hr at 650°C. All analyses were found to be within 0.05 pet of the nominal composition. Since the precision of analysis is not much better than this, the points of both isothermal sections and vertical sections at fixed aluminum and silicon contents have been plotted at the compositions indicated by the nominal composition.

Jan 1, 1949

By R. L. Schmidt, J. D. Verhoeven

The diffusion coefficients and electrotralzsport mobilities of aluminum, gallium, and arsenic have been determined in molten germanium with the capillary reservoir technique. The diffusion coefficients are slightly higher than those determined by the solidification technique of Brirton et a1.1 It was found that aluminium and gallium migrate to the cathode in molten germanium) whereas arsenic migrates to the anode under an electric field. A possible technique for producing p-n junctions by means of electric field freezing is discussed in view of the experimental data. In the past decade or so the literature has abounded with articles concerning the solid-state properties of the semiconducting elements germanium and silicon. It is surprising by comparison how little has been published concerning the liquid-state properties of these materials. In the production of doped germanium or silicon the diffusion coefficient of the dopant in liquid germanium or silicon is an important quantity. Yet, to the best of our knowledge, no one has ever made a direct measurement of the diffusion coefficient of solutes in either molten germanium or silicon. A number of authors'-4 have determined some diffusion coefficients by the indirect technique developed by Burton et al.1 This technique appears to give numbers of the correct order of magnitude but it does depend upon a number of assumptions in the analysis and also requires prior knowledge of the viscosity of the melt. In the present work a more direct measure of the diffusion coefficients of arsenic, gallium: and aluminum in molten germanium has been made. It has been shown independently by two groups of authors5, 6 that, when an electric current is passed through the interface of a solidifying metal containing an impurity, the resulting electrotransport in the liquid boundary layer at the interface offers a mechanism for control over the redistribution of the impurity accompanying the solidification. These authors show that the degree of control is proportional to the mobility, U of the impurity atoms in the liquid boundary layer, where the mobility is defined as the drift velocity relative to the solvent per unit electric field. In principle the results apply to the solidification of a doped semiconductor and offer an interesting technique for control of the doping of a semiconductor. In the present work the mobilities of aluminum, gallium, and arsenic were determined in molten germanium in order to evaluate the potential usefulness of electro-transport as a technique for solute control when applied to the solidification of doped germanium. EXPERIMENTAL PROCEDURE Both the diffusion coefficients and the mobilities were measured using high-purity alumina capillaries and a resistivity technique for analysis. A schematic diagram of the electrotransport apparatus is shown in Fig. 1 and the details of the cell design are shown in Fig. 2. For the mobility experiments electrical contact with the bottom of the capillary was made with graphite, as shown in Fig. 2. In order to prevent electrical contact with the melt the graphite was coated with a thin layer of alumina using a plasma spray torch. The cell assembly, a graphite electrode, and another assembly containing two blank capillaries were fastened to the lavite disk shown in Fig. 1. To make a run the system was evacuated and the doped germanium was outgassed at the operating temperature of 1030°C. The cell and blank capillaries were then submerged beneath the melt and a slightly positive pressure of helium was introduced to fill them. After passing current through the cell for a given time the cell and blank capillaries were raised from the melt and the furnace was shut off. The temperature of the cells dropped below the freezing point of germanium within 1 to 2 min after the furnace was shut off.

Jan 1, 1968

[ ]

Jan 1, 1938

By Merton C. Flemings, Harold D. Brody

Analyses that include diffusion of solute in the solid phase are formulated to describe solute redistribution in dendritic solidification of metallic alloys. The analyses are based on conditions that include negligible undercooling before nucleation of solid phases, negligible increase of solute in advance of the tips of growing dendrites, complete diffusion within the liquid over distances the order of dendrite spacings, and a plate-like dendrite morphology. The classical nonequilibrium freezing equation, Cs = kCo(I - fS)k-l accurately describes solute redistribution between dendrite arms for the solidification processes considered, provided diffusion in the solid is negligible. To account for the effect of diffusion in the solid, an analytic expression is given which is similar inform to the classical expression. 172 addition, a numerical-analysis procedure is etnployed to examine in more detail the effect of diffusion both during and after solidification. The analyses are intended for application to solidification of castings and ingots to describe a) final solute distribution after solidification and cooling to room temperature (microsegregation) and b) local fraction solid as a function of ternperatcre within the solidifying casting or ingol. SOLUTE redistribution in cellular and dendritic solidification has been discussed quantitatively in recent papers'-3 and in a series of earlier work.4-6 However, none of the analyses developed have permitted close correlation of theory with final solute distribution (microsegregation) observed in castings and ingots. In this paper, discussion is given of approximations which may reasonably be made in mathematical treatment of microsegregation, and analyses are presented based on these approximations. Numerical results are given for Al-Cu alloys. In a second paper the analyses will be compared with exeriment.7 CLASSICAL ANALYSIS The classical quantitative treatment of solute redistribution within a closed "volume element" has been derived repeatedly, for example by Gulliver,4 Scheil,' and Pfann.' This "classical nonequilibrium solidification equation" is written for constant partition ratio: where Cs = interface composition of the solid when the weight-fraction solid within the "volume element" is fs (weight fraction, wt pct); k = equilibrium partition ratio; Co = initial alloy composition within the volume element (weight fraction, wt pct). Assumptions of Eq. [11 are: 1) There is negligible undercooling before nuclea-tion, or from curvature or kinetic effects. 2) There is no mass flow in or out of the volume

Jan 1, 1967

By R. C. Hall

In the present work, experiments determined the effect of the order-disorder reaction near the Fe,Al composition on the magnetic anisotropy and magnetostriction of single crystals: A material which is more difficult to magnetize in one direction than in another is anisotropic, that is, the ease with which ferromagnetic materials may be magnetized in different crystallographic directions determines the anisotropy. Two investigators have estimated the anisotropy of the aluminum iron alloys from poly-crystalline data;1,2 however, these estimates should not be considered to be reliable. Siege1 made two accurate measurements of the first anisotropy constant* from single crystals of 4.0 wt pct aluminum sotropy throughout the ferromagnetic aluminum iron system have been described. These results were obtained from single crystals which were slowly cooled and, hence, ordered near the Fe3Al composition.4 Magnetostriction is the change in length per unit length resulting from applying a magnetic field to a ferromagnetic material. For the purpose of this report, the saturation magnetostriction was measured. This is the maximum change in length per unit length resulting from an applied magnetic field large enough to saturate the material in a given direction. This magnetostriction has been determined for single crystals of the ferromagnetic aluminum-iron system.' The crystals near Fe3Al were also ordered. PREPARATION AND TREATMENT OF SINGLE CRYSTALS Single crystal bars were grown from the melt.' The raw materials for these crystals were iron and aluminum of 99.9 and 99.99 pct purity, respectively. From the bars, crystals in the shape of circular

Jan 1, 1959

By Noel H. Stearn

When the Age of Machinery was suddenly thrust upon civilization about the beginning of the 19th century, an unprecedented demand for mineral resources sprang up. This demand brought about the rapid development of the known ore deposits and the discovery of such other deposits as could be encountered by energetic and canny prospectors. Thus in the countries now reasonably accessible nearly all orebodies have been located except those which are totally concealed even from the eyes and "senses " of experienced and expert prospectors. The high rate of exhaustion of known ore deposits and the necessity of looking farther and farther ahead for raw materials as a matter of insurance on the stupendous capital outlays involved in mining, development, and conversion operations, have resulted in exceptional activity in three different fields of effort. The first is purely geographic. Prospectors are now penetrating the few hitherto inaccessible regions in the hope of stumbling upon exposed ore deposits or locating visible indications of their presence. The second is chemical. Industrial chemists and metallurgists are seeking to facilitate the exploitation of lower grade ores or to find methods of recovering valuable metals from common substances. In the third field of effort lie the activities of the economic geologist and the mining engineer, who endeavor to locate concealed ore deposits which would remain hidden from the prospector no matter how expert or conscientious he might be. Obviously the task which such a man must face is both exacting and indefinite, and the tools which he has heretofore been permitted to bring to it are, for the most part, abstract—a knowledge of certain fundamental principles and processes involved in the origin, occurrence, structure, and distribution of deposits of natural resources and of the rocks which form the environments of those deposits; and a process of reasoning by analogy supplemented by the use of the diamond drill, or such artificial exposure as the test pit, trench, shaft, or tunnel.

Jan 1, 1929

By R. H. Oliver

The purposes, types, preparation, and testing of flocculants are discussed. A flocculation compendium is included, indicating choice of flocculant for a given set of conditions. An economic evaluation of the process is presented. Solid-liquid separation is a major expense in most mineral processing flowsheets today. Proper use of flocculation can often lower the overall cost of a solid-liquid separation by reducing the size of sedimentation or filtration equipment. PURPOSE OF FLOCCULATION When is use of a flocculant justified in terms of overall process economy? 1) when it results in process improvement, such as producing a clear liquor for electrolysis, precipitation, ion exchange, or solvent extraction; 2) when it results in satisfying requirements of pollution abatement ordinances; 3) when it results in increased recovery of values that would otherwise be lost; or 4) when it results in considerable savings in capital expenditure due to use of smaller equipment. When can the use of a flocculant adversely effect overall process economy? 1) when it results in increased filter cake moisture, 2) when it results in decreased filtration rates, 3) when it results in considerable bulking of sedimentation underflow, 4) when it contaminates either the supernatant or sludge, or 5) when the cost of using the flocculant is greater than the savings due to its use. First step in consideration of flocculants for a given application is establishment of desired goals in terms of increased clarity of effluent, increased recovery of solids, or decreased size of equipment. The most economical solution to a solid-liquid separation problem is that combination of equipment and flocculant costs which meets the established goals at the lowest total annual expenditure. This economic decision can be made only after technical data has been obtained as outlined in next four sections. TYPES OF FLOCCULATION Flocculation is a process wherein individual particles are united into more or less tightly bound agglomerates or flocs, thereby increasing effective particle size of solids suspended in a liquid. Degree of flocculation of a suspension of finely divided solids in a liquid is controlled by a combination of probability of collision between particles and probability of adhesion after the collision has occurred.' Probability of collision can be increased commercially through use of a paddle-type flocculator, combination flocculator, and clarifier or flocculating-type feedwell. Probability of adhesion usually can be increased by addition of a reagent known as a flocculant. Reagents act as flocculants through one or a combination of three possible mechanisms. The first is electrolytic neutralization of inter molecular repulsive force due to Zeta potential. This neutralization enables Van der Waal's cohesive force to hold the particles together after they collide.' The second is the precipitation, within a definite pH range, of voluminous metallic hydroxide flocs which entrap fine particles. This process is known as coagulation.14 Third is the bridging of two or more particles by either natural or synthetic long-chain, high-molecular-weight organic polymers. This bridging is accomplished by adsorption of two particles at different sites on the same molecule or by bonding of two molecules, each adsorbed to a different particle. Considerable effort has been expended in explaining the action of these polyelec-trolytes and detailed accounts are available in the literature. CHOICE OF FLOCCULANTS It is impossible, at the present time, to specify the optimum type or amount of flocculant for a given application from a knowledge of the material to be treated. The standard procedure is to choose reagents or combination of reagents most likely to be effective on the slurry; then test them.' The accompanying Flocculation Compendium (Table I) contains details of all currently available reagents sold as flocculants and it should be used when selecting the group of reagents for tests. This selection can be based on information listed in columns 4 and 5. Column 4 presents industries in which each floc-

Jan 1, 1961

By R. Gibala

Internal-friction measurements on hydrogen-charged iron over the temperature range 4° to 300°K are reported. Two relaxation peaks, the hydrogen Snoek peak at 48 °K and the hydrogen cold-work peak in the range 145" to 2200K, are observed at 80 kc per sec. The effects of hydrogen-charging, aging, and deformation on the internal-friction results are determined and are used to show evidence of partitioning of hydrogen between solid solution and dislocations. The hydrogen-dislocation binding energy is estimated from the behaviors of the relaxation tiwzes and relaxation strengths of the Snoek peak and the cold-work peak. Its value is approxi,mately 6400 cal per mole. MANY investigators have demonstrated the usefulness of internal-friction measurements in determining the manner in which interstitial impurities interact with dislocations in bcc metals. Part of this success has resulted from the existence in bcc interstitial alloys of two anelastic relaxation peaks—the Snoek peak' and the cold-work or Koster peak2 (designated hereafter by SP and CWP, respectively). The SP has its origin in the redistribution of interstitials in solid solution among sites made energetically nonequivalent by an applied stress. The rate at which the redistribution occurs, measured by the relaxation time for the process, is related in a simple way to the diffusion rate of the interstitial in the free solution. The relaxation strength is proportional to the concentration of interstitial in solid solution. The CWP appears to have its origin in the relaxation of an interstitial-dislocation complex for which the relaxation time at a given temperature is much longer than that for the SP. The relaxation strength depends strongly on the concentration of interstitial and the amount of deformation at relatively low concentrations and deformations.2-8 From the dependence of the relaxation strength on interstitial concentration, the SP and CWP may serve as measures of the concentrations of interstitials in free solution and bound at dislocations, respectively. Thus their behaviors have been used to investigate interstitial-dislocation interactions in Fe-C, Fe-N, and several refractory metal systems.'-' However, the Fe-H system has not been studied extensively,? even though disputes in recent years over the mechanism of hydrogen embrittlement in steels involve argument over the extent to which lattice hydrogen and hydrogen-dislocation interactions play an important role.?-'' Previous work on Fe-H indicates the internal-friction behavior to be qualitatively consistent with that for other systems. Apparently, both a SP and a CWP are observed in the temperature ranges 30" to 50°K and 100°to 140°K, respectively (at 1 cps). However, there is neither sufficient nor accurate enough information to identify convincingly these peaks with their supposed counterparts in other systems. Nor have there been any attempts to make quantitative use of these peaks to study hydrogen diffusion, aging, or interaction processes. In this paper, an attempt is made to obtain more complete information on internal friction of hydrogen in iron than presently available. Internal-friction measurements in the range 4° to 300°K on hydrogen-charged iron show that the two peaks discussed above are in fact the hydrogen SP and CWP. Several effects of hydrogen charging, aging, and deformation on these peaks are observed and are used to determine the partitioning of hydrogen between solid solution and dislocation sites in iron. EXPERIMENTAL Materials. The starting material for this investigation was a high-purity iron supplied by National Research Corp. as a 1-in.-diam rod. The following analysis was given (inwt pct): C, 0.004; N, 0.0003; 0, 0.007; P, 0.002; S, 0.005; Si, 0.006; Mn, 0.001; Cu, 0.002; Ni, 0.005; Cr, 0.001; Mo, 0.001. After an initial vacuum anneal (-5 XTorr) at 700°C, the rod was cold-

Jan 1, 1968

By Leonard B. Gulbransen, John R. Lewis, W. Martin Fassell, J. Hugh Hamilton

T. E. Leontis (The Dow Chemical Co., Midland, Mich.)—This paper is of particular interest to me because of my own work with F. N. Rhines on the oxidation of magnesium and magnesium alloys a few years ago. The authors are to be complimented on their development of an accurate and reproducible technique for measuring ignition temperatures and on their comprehensive study of the many variables that affect the ignition temperature of magnesium. It is indeed gratifying to see that they have obtained a good correlation between ignition temperatures and the oxidation rates reported by us. The correlation is valid not only with composition within one alloy system but also between alloy systems; that is, alloying elements which effect the greatest increase in oxidation rate also produce the greatest decrease in ignition temperature. There are a few points upon which I would like to comment. In attempting to correlate ignition-temperature data, one must be sure that the same definition of this quantity is used by all investigators. It does not appear to me that such is the case in the authors' comparison of their data with the theoretically calculated values of Eyring and Zwolinski. The equation derived by these investigators defines the ignition temperature, To, as the temperature at the gadoxide interface, whereas the present authors use the metal temperature as the criterion for ignition. The contradiction in the effect of oxide-scale thickness on ignition temperature between the predictions of the Eyring-Zwolinski equation and the observations reported in this paper indicate that some variable has not been taken into consideration. Could that be the geometry and size of the specimen? There is a marked difference in the type of specimen used in this investigation and that used in our work which formed the basis of Eyring and Zwol-inski's theoretical treatment. Another factor which plays an important role in ignition is the vapor pressure or the rate of vaporization. Combustion can safely be assumed to take place in the vapor phase by the reaction between vaporized magnesium and oxygen. Thus, a more accurate theoretical analysis may be made on the basis of the rate of vaporization which may be the controlling rate of the process. The effect of a large number of alloying elements on the ignition temperature has been reported in this paper, but beryllium was not included. Practical experience dictates that beryllium markedly decreases the burning tendency of magnesium. I was wondering if the authors plan to study the effect of beryllium in their future work. The authors predict that concentrations of sulphur dioxide in the furnace atmosphere greater than 5.8 pct would be expected to increase the ignition temperature to values still higher than those they measured. I would like to mention that large concentrations of sulphur dioxide markedly increase the rate of combustion of magnesium once ignition has started. Although it has been shown in the paper that the ignition temperature of magnesium in oxygen increases with increasing sulphur dioxide content up to about 1 to 2 pct, in practice relatively low-melting commercial cast alloys (AZ63A and AZ92A) are being continuously heat treated at temperatures just below the melting point in air containing 0.5 to 0.75 pct SO*. In regard to the change in color of the oxide scale observed on magnesium and magnesium alloys just prior to ignition, I would like to mention that in our work alloying elements were found to color the usually white magnesium oxide even though ignition did not occur. For example, the oxide formed on Mg-A1 alloys was gray, increasing in intensity with aluminum content in the alloy. Finally, I might suggest that the authors indicate their source of the value of 0.8 g per cc for the density of MgO as it is formed on magnesium upon oxidation at elevated temperatures. W. M. Fassell, Jr. (authors' reply)—The comments by Dr. Leontis are very excellent ones and I will attempt to answer them in order. First, the problem of ignition of magnesium is a rather difficult one since many factors are involved. Concerning the comparison of the To in the Eyring-Zwolinski equation, eq 4, with the experimentally determined values, it will be noted that the calculated and experimental values of the ignition temperature in Table I are not self-consistent. In the case of the 1.78 pct A1-Mg alloy the calculated value is 49°C below the experimental value; for the 3.81 pct A1-Mg alloy, 122°C below the experimental value; for Mg with 5x10-' cm film, 19°C above the experimental value; for Mg with 2x10-I cm film, 28 °C below the experimental value. Thus, if it were merely a matter of difference of location of temperature measurement the calculated ignition temperature would always be below the experimental value, the difference being due to the thermal gradient through the oxide film. The possibility of a thermal gradient in the magnesium metal must be considered. From Carslaw and Jaeger,'Y t can be shown that the maximum temperature gradient that could exist between the oxide-metal interface and the center of the sample is of the order of O.Ol°C. The geometry and size of the specimen could certainly have some effect on the ignition temperature. The equation for ignition that has been proposed in reference 14 is of the following type containing terms to account for this and other factors: M dT AHv(T) =Cp--------------\-J(.T—TB) + ZAHl-M A dx where AH is the heat of reaction, v(T) is the velocity of the reaction at temperature, Cp is the heat capacity of sample, M is the mass of sample, A is the area of sample, t is time, J is the total coefficient of heat transfer outward from the reaction zone, TR is the temperature of the bath or furnace, and AH,, is the heat associated with any phase change involved. Prior to the instant of ignition, the vapor pressure of magnesium is of no special significance. After ignition, neither eq 4 nor the above equation is applicable. The actual combination of magnesium cannot safely be assumed to take place in the vapor phase. While experimental data is lacking to support a hypothesis that ignition does or does not occur in the vapor phase, some observation on the pressure ignition experiments may be of interest. At high oxygen pressures, once ignition has occurred, the reaction of magnesium with oxygen approaches near explosive violence, the entire sample being consumed in probably less than 1 sec. At atmospheric pressure it usually requires 15 to 20 sec. Thus it appears that the oxygen concentration becomes the rate determining factor. Further, if burning magnesium is observed through darkened glass (Lincoln Super-visibility Shade No. 12) the magnesium sample is very much hotter than the "smoke" and the outline of the sample is retained perfectly. No "flame" is visible above the metal. No work was done on Mg-Be alloys. We do, however, intend to study this problem in the near future.

Jan 1, 1952

By V. R. Garfias R. V. Whetsel

Production of crude petroleum in Mexico during 1935 totaled approximately 40,082,000 bbl., an increase of 1,925,000 bbl. over the previous year. Successful development continued in the Poza Rica field during the year, increasing production in that area from 3,708,000 bbl. in 1934 to 9,542,000 in 1935. The output of the South fields (Golden Lane) area decreased by 3,000,000 bbl. during the year, and the heavy-oil district of the Northern fields by 1,500,000 bbl. Production in the Tehuantepec fields showed a slight gain. Production of natural gasoline increased from 430,000 to 600,000 bbl. in 1935. Crude run to stills in local refineries is estimated at 30,000,000 bbl., some 4,000,000 bbl. more than in the previous year. Exports of crude and refined products were approximately 22,000,000 bbl., or 2,000,000 bbl. less than in 1934. Exclusive of ships bunkers, domestic consumption increased about 900,000 bbl. during the year, reaching an estimated total of 14,500,000 barrels. Only 74 wells were completed, as compared to 148 in 1934 and 91 in 1933. In proven areas 58 completions resulted in 33 producers and 25 failures. In northeastern Mexico, near the United States border, six wildcat wells were completed, all of which gave little or no encouraging results, except Rancheria No. 3, near Camargo, which is a fair-sized gas well. Four wildcats were drilled just northeast of the Northern fields (heavy-oil district), all of which were failures. A deep test was completed a short distance southeast of the Golden Lane (South fields) in Palo Blanco, which encountered small production not sufficient to exploit. On the Isthmus of Tehuantepec a wildcat well was completed for an estimated initial production of 2000 bbl. daily, a short distance south of the old Jalapa field, which was perhaps the most important new development of the year. Four other wildcats drilled in the Isthmus district resulted in failures. Fields Northern Fields (Heavy-oil District).—In the Northern fields, 18 producing wells and 20 failures were completed, as compared to 34 producers and 71 failures in 1934. The initial production of the new

Jan 1, 1936

By V. R. Garfias R. V. Whetsel

Production of crude petroleum in Mexico during 1935 totaled approximately 40,082,000 bbl., an increase of 1,925,000 bbl. over the previous year. Successful development continued in the Poza Rica field during the year, increasing production in that area from 3,708,000 bbl. in 1934 to 9,542,000 in 1935. The output of the South fields (Golden Lane) area decreased by 3,000,000 bbl. during the year, and the heavy-oil district of the Northern fields by 1,500,000 bbl. Production in the Tehuantepec fields showed a slight gain. Production of natural gasoline increased from 430,000 to 600,000 bbl. in 1935. Crude run to stills in local refineries is estimated at 30,000,000 bbl., some 4,000,000 bbl. more than in the previous year. Exports of crude and refined products were approximately 22,000,000 bbl., or 2,000,000 bbl. less than in 1934. Exclusive of ships bunkers, domestic consumption increased about 900,000 bbl. during the year, reaching an estimated total of 14,500,000 barrels. Only 74 wells were completed, as compared to 148 in 1934 and 91 in 1933. In proven areas 58 completions resulted in 33 producers and 25 failures. In northeastern Mexico, near the United States border, six wildcat wells were completed, all of which gave little or no encouraging results, except Rancheria No. 3, near Camargo, which is a fair-sized gas well. Four wildcats were drilled just northeast of the Northern fields (heavy-oil district), all of which were failures. A deep test was completed a short distance southeast of the Golden Lane (South fields) in Palo Blanco, which encountered small production not sufficient to exploit. On the Isthmus of Tehuantepec a wildcat well was completed for an estimated initial production of 2000 bbl. daily, a short distance south of the old Jalapa field, which was perhaps the most important new development of the year. Four other wildcats drilled in the Isthmus district resulted in failures. Fields Northern Fields (Heavy-oil District).—In the Northern fields, 18 producing wells and 20 failures were completed, as compared to 34 producers and 71 failures in 1934. The initial production of the new

Jan 1, 1936

By PHILIP N. MOORE

IT is a pleasure to realize even at that day the dignity of the engineer's calling was upheld. May I also add my firm belief that today there be many engineers who will qualify to the specifications of our interesting author. Since that time, the development of the world has been chiefly due to the engineer, and so far as human brain can foresee, the material tasks of the future will continue to follow the directions of his judgment. Popular opinion says this is the age of the engineer; literature, which in the long run, voices public sentiment, shows it in the number of engineers who figure as characters of fiction. The engineer has been doing the big things necessary to increase the comfort and efficiency of mankind, but while a certain amount of fame and repute falls to him, too often he figures as the hired man of the entrepreneur, using that term not in the offensive sense of a mere promoter, but to mean the great visioned master of enterprise who has seen ahead of other men, recognized the coming needs of the world, and through ability to inspire others and to hire capital for his use has also been able to hire engineers as needed. Justly enough, therefore, to such men comes the fame as well as the prize of the game.

Jan 1, 1926

By Charles H. Jacoby

In 1774 a Swedish chemist, C. W. Schule, first recognized manganese as an element. That same year Schule's associate, J. G. Gahn, isolated the element manganese for the first time. In 1856 the Bessemer process of steelmaking gave birth to the economic importance of manganese. Later, in 1882, Robert Hadfield discovered high manganese steels. Although the primary use of manganese is in the ferroalloy industry, two additional important uses for manganese are making chemicals and dry cell batteries. Manganese is also vital to plant and animal life. Various chemical compounds of manganese are used in fertilizers, feeds, glass manufacture, paints, varnishes, and for numerous medicinal and chemical purposes. For the study of industrial minerals and rocks, only the chemical and battery grade material is of- concern, but for the sake of comparison, metallurgical aspects are included in this presentation. Although currently the world's largest consumer of manganese, the United States is producing only minor amounts of ore at the present time. This is due primarily to the fact that although huge deposits of manganese occur within our borders, all are of such low grade as to be economically unfeasible to mine. For many years various government agencies and segments of private industry have devoted sizable sums of money and time in an attempt to upgrade ores from the various deposits, and also in an attempt to recover manganese from blast furnace slags. In view of current world prices, and the quantity of high grade material available, there is little likelihood that any of these approaches will be found to be economically feasible in the near future. Geology and Mineralogy Mineralogy There are over one hundred minerals that contain manganese. These minerals vary from those with compositions that are predominantly manganese to those having only minor percentages. [Chemical Mineral Composition % Mn Hausmannite Mn304 72 Polianite MnO2, 63.1 Pyrolusite MnO24 60-63 Cryptomelane KR8O16R (R=Mn) Variable PsilomelaneBa Mn Mn8O16 (OH).45-60 CoronaditePb R8O16R (R=Mn) Variable Hollandite Ba R8O16R (R=Mn) Variable Manganite Mn2O3•H20 62 Braunite 3 Mn2O3•MnSiO3 62 Tephroite 2 MnO•SiO2 54.3 Rhodochrosite MnCO3 47 Rhodonite MnSiO3 42 Spessartite 3 MnO•AI2O3•3SIO2 33.3 WadHydrous Mn OxidesVariable Franklinite(Fe Mn Zn)O(Fe Mn)sO3 Variable Asbolan Cobaltiferous wad Variable AlabanditeMnS63.14] Geology From a geological standpoint most manganese deposits are complex. In general, it can be said that all primary deposits of manganese are carbonates or silicates. The most productive and profitable have been those of sedimentary origin and residual concentrations. Examples of these residual types of deposits are associated with the metamorphosed lodes of Madhya, Pradesh, India, and the lateritic deposits of Orissa and Bihar, India; nodules in the residual clays of the Philippine Islands, US southern Appalachians and Arkansas, Ghana, and Brazil. Sedimentary manganese deposits are best exemplified by the Nikopol district of Russia and the Tchiatouri area of Georgia, USSR. Hydrothermal replacements are characterized by the rhodochrosite deposits of Butte and Phillipsburg, MT. In general, the hydrothermal type deposit has not resulted in any large tonnages being produced, but may have given

Jan 1, 1983

By Thiann R. Yu, William J. Quesnel

At Kidd Creek, the annual production of 4.5 million tonnes of ore has been achieved primarily with sublevel blasthole stoping. This mining method has allowed underground operations to meet the designed production capacity while maintaining an outstanding safety record. To achieve this goal, rock mechanics principles have been integrated into each facet of mining in the planning stage, in the production stage, and in various stages of ground support. This paper evaluates the two adopted mining sequences based on ground stress patterns, blasting control, ground reinforcement, backfill support, and numerical modelling for stope stability at the mines.

Jan 1, 1984

By R. W. Vander Laan

Conneaut has a long and illustrious history as a major Great Lakes port for coal and iron ore. The first dock was built in 1892 for unloading iron ore from the Mesabi Range for shipment to the Pittsburgh steel mills via the Shenango & Lake Erie Railroad, later to become the Bessemer & Lake Erie Railroad. The Pittsburgh & Conneaut Dock Company was incorporated in 1893. The world's first Hulett automatic ore unloader was constructed at Conneaut in 1899. Steam operated, it was the model for the giant electric Huletts used today, named after its inventor, George Hulett, who was a Conneaut resident.

Jan 3, 1974

By Allan B. Tanner

The effects of radon in drillholes on gamma-ray logs have been described by L. S. Hilpert and C. M. Bunker1 Since these effects may cause drastic error in the evaluation of uranium deposits, it is useful to know the conditions under which significant amounts of radon tend to accumulate in drill- holes. In the studies described here, atmospheric conditions were found to dominate in the control of the behavior of radon in drillholes in the vicinity of a uranium orebody. The site of the investigation was in McKinley County, New Mexico, about 12 miles north of Grants. Drillholes of 4 ¼ -in. diam, on 25-ft and 100- ft centers, penetrate ore in dry rock at a depth of about 100 ft. A geologic log of the drillhole of primary interest is shown in Fig. 1. Gamma-ray logs revealed three zones of ore-grade mineralization in the Todilto limestone. A 6-ft zone, the lowest of the three, assayed 0.20 pct U3O8 by chemical analysis. The limestone ores in this area contain disseminated uraninite and some yellow and orange secondary minerals.

Jan 7, 1959