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By S. Brunauer

The hydration of portland cement is treated as a chemical reaction and the changes in matter, in energy and the rate of change of the process are discussed, Portland cement is a mixture of four major and at least as many important minor constituents. In the hydration process, the four major compounds (trical-cium silicate, dicalcium silicate, tricalcium alumi-nate and tetracalcium aluminoferrite), plus gypsum and water form five or six new compounds. In spite o the great complexity of the reaction, considerable progress has been made in its understanding, primarily with the help of such research tools as X-ray diffraction and electron microscopy. The rate of the reaction can be followed by direct and indirect methods of measurements. The effects o composition, particle size (or specific surface), temperature and water-cement ratio on the rates of hydration are discussed. The hydration of portland cement is a chemical reaction accompanied by such highly important physical phenomena as heat evolution, setting and hardening. It is a vast and complex subject, on which hundreds of papers have been published. At the time of the writing of this paper, in October 1962, a two-volume book, which alone contains dozens of papers pertaining to cement hydration appeared in print.' The present paper deals with a few aspects of this vast subject, and the selection was not easy. The work reported here deals with some of the most recent investigations in the field. In any chemical reaction, the physical chemist is primarily interested in three things: changes in matter, changes in energy and the rate of change of the process or the speed of the reaction. This is true also of the chemical reaction between portland cement and water, and all three aspects of the reaction will be discussed. These three aspects are of vital interest to the engineer as well. Portland cement is not a cementing material — the hydration products, the new materials which form in the reaction, have the cementing action. The energy changes manifest themselves in a considerable evolution of heat, which may be useful or harmful. It is useful, for example, in winter concreting, but in very large concrete structures like dams, a large evolution of heat, which cannot be easily dissipated, may produce distress in the structure. Primarily for such a purpose was the Type IV or low heat portland cement developed. The speed of the chemical reaction is important because it determines the time of setting and hardening. The initial reaction must be slow enough to permit placing of the concrete before setting occurs. On the other hand, after the placing of concrete it is often highly desirable to obtain as rapid chemical reaction as possible. For this purpose the Type 111 or high early strength portland cement was developed. CHANGES IN MATTER Portland Cement: In a basic investigation, before one begins to study a reaction, one either knows the quantities and compositions of the starting materials, the reactants, or one determines them. This is obvious; the chemist expresses the changes in matter that occur in a reaction by a chemical equation, which has the quantities and compositions of the reactants on the left side of the equation and the quantities and compositions of the reaction products on the right side. The first question is then what to put on the left side of the equation in the reaction between portland cement and water? It is not very easy to answer this question. Portland cement is not a single chemical compound but a mixture of many compounds. Four of these are considered the major compounds, and at least four of the minor compounds also play important roles in the hydration reaction. In order to avoid complicating matters, the present discussion will be restricted primarily to the four major compounds, which constitute usually more than 90% of a portland cement. The relative amounts of these compounds vary from cement to cement. Actually not only the amounts but the compositions of these constituents also vary to some extent, but the variation in composition of the individual components will be neglected for simplicity.

Jan 1, 1963

By R. E. Zimmerman, Michael Sokaski, E. R. Palowitch, M. R. Geer, H. F. Yancey, W. Deurbrouck, S. C. Sun

PART 1: DENSE MEDIUM SEPARATION by M. SOKASKI, M. R. GEER and H. F. YANCEY INTRODUCTION In the early days of coarse-coal treatment by the dense-medium process in Europe, loess was one of the materials used for medium solids. Newly developed cyclones were used to reclaim and thicken :he loess suspension. On occasion, when the cyclone thickener at the Maurits mine in the Netherlands plugged, the overflow was found to be filled with clean coal free of impurity. From this observation stemmed the concept of the cyclone as a cleaning device. Development took place during World War 11 in the laboratory of the Dutch State Mines under the direction of M. G. Driessen. A 15-ton-per-hour pilot plant was in operation in the laboratory by 1945, when, in September, Driessen made the first public disclosure of the process in a paper presented to the Institute of Fuel in London. In April 1945,2 operation of this pilot plant was observed by one of the authors, who was so impressed with the potential of the cyclone process that, on his return to the United States, a research program on the cyclone was started by the Bureau of Mines immediately. This work led to an AIME paper in 1946 in which the first details of cyclone operation on American coals was made available. Commercial adoption of the cyclone proceeded in Europe, initially in the Netherlands, Germany, and France. In the United States, where coal is less costly and most of the coals are so easy to clean they respond well to simpler cleaning systems, the first cyclone plant was not built until 1961.3 As of the spring of 1967, a total of 31 commercial cy- clone plants had been installed or were under construction in the United States; this does not include eight Dynawhirlpool plants. The capacity of the cyclone plants ranges from 50 to 1300 tons per hour and totals 6600. THEORY Before discussing the theory of a dense medium cyclone, a brief description may be helpful to some readers who are not familiar with its basic operation. In a typical dense-medium cyclone, illustrated in figure 10-1, the mixture of medium and raw coal enters tangentially near the top of the cylindrical section, thus forming a strong vertical flow. The refuse moves along the wall of the cyclone and is discharged through the under- flow orifice. The washed coal moves toward the longitudinal axis of the cyclone and passes through the vortex finder to the overflow chamber.

Jan 1, 1968

By E. W. Engle

Fox several years the Fansteel Products Co. has been engaged in the production and development of various of the rarer metals. It is at present engaged in the commercial production of tantalum, tungsten, and molybdenum in a very high state of purity. The information contained in this paper is partly a general compilation from various sources and partly information obtained as a result of recent years of work in the laboratory of this company. Tantalum, tungsten, and molybdenum form a group peculiar to themselves among the commercially available metals. Their very high melting points (tantalum 2770° C., tungsten 3350° C., and molybdenum 2550° C.) set them apart so far as the metallurgical processes for their production are concerned. Further, when properly prepared and treated they will stand a somewhat unusual degree of cold work, that is work below the temperature at which marked crystal growth takes place. Such cold-worked metal may show a high tensile strength; tantalum to 130,000 lb. per sq. in., tungsten to 490,000 lb., and molybdenum to 260,000 lb., in the form of fine wire. In physical appearance, these metals are not unlike some steels; they may be better described by saying that polished tantalum some¬what resembles lead; polished tungsten, iron; and polished molybdenum, nickel. The polished surfaces of all three remain untarnished in ordinary air. Air containing corrosion-producing impurities will, in general, show molybdenum the least resistant to corrosion and tantalum the most resistant. Molybdenum has, however, a high degree of resistance to corrosion by hydrochloric acid, a property that should render it of commercial interest. On the other hand, it is markedly attacked by some of the weaker organic acids.

Jan 3, 1925

By W. E. D. Jr. Stokes

THE application of aviation to mining and petroleum operations, on the basis of economy and attainment, has become a demonstrated fact. According to Dominion Government records, 30. Canadian companies engaged in air transportation with northland mining camps, carried 13,000 tons of freight in 1935, and in 1936 carried 16,000 tons. In addition, many mining companies used planes to transport prospectors with canoes, outboard motors, gasoline drums and supplies to remote locations, and one company maintained a plane to take radium-bearing ore from its mine on Great Bear Lake nearly 1000 miles south to the rail-way at Waterways, Alberta. Heavy pieces of mining machinery weighing 2 tons are being carried by Ford trimotor planes over the Andes, at an altitude of not less than 15,000 feet. At Bulolo, New Guinea, 17,500 tons of disassembled gold-dredging equipment has been flown over inaccessible terrain, while supplies and building materials for a, community of 1000 whites have been transported by airplane. A 3 1/2-ton shaft was carried on one notable trip, while at another time an automobile, 2 tons of rice and a large safe went over the mountains in one plane. Fig. 1 shows an electric generator that was carried by plane to Bulolo.

Jan 1, 1937

By R. D. Carnahan, J. E. White

A study of dispersion strengthening in TD-Nickel (nickel plus 2 vol pct Tho2) was conducted employing microstrain techniques at ambient room temperature. It was found that optimum strength was due primarily to the incorporation of stored energy developed by a variety of thermal-mechanical treatments. The relatively low strength of the recrys-tallized condition implies that the dispersed particles themselves offer only token resistance to deformation. The development of resistance to large-scale recovery or recrystallization at temperatures near the melting point requires a more extensive sequence of strain-anneal cycles than does the development of optimum strength. A micro-Bauschinger effect was observed which appears to be related to the lattice resistance to the movement of free dislocations. The effect was nearly identical to that in pure nickel indicating that the presence of the dispersed phase and considerably increased dislocation density (stored energy) only alters the number or effectiveness of barriers. THE early stages of deformation of engineering materials can be conveniently studied by utilizing strain-gage techniques which permit resolution of strains less than 5 X 10-7 in. per in. for testing in four-point bending (Carnahan and white1). The present investigation, part of a continuing study on the very early stages of deformation, was designed to reveal the true role of a dispersed phase in promoting high strength in a commercially available dispersion-strengthened alloy. Although this technique has been used for some time to study microdeformation in pure metals and alloys, it has just recently received attention as a means of investigating dispersion strengthening. Studying the very early stages of deformation in alloys which depend upon a finely dispersed inert phase for strength may prove to be a very important method for a better understanding of these materials. It is essential to obtain considerable clarification of actual dislocation movement and the kinds of deformation barriers which exist before optimum properties can be designed into this type of material with any degree of confidence. Considerable research on a variety of dispersion-strengthened materials has resulted in two different schools of thought regarding the strengthening mechanism. One faction2-4 favors the idea that the particles themselves resist the motion of dislocations. The criterion for yielding is the fracture of the dispersed second-phase particles due to an array of piled-up dislocations. Other invesfigators5-a have shown that particles are effective primarily by allowing a greater buildup of stored energy or dislocation density through thermal-mechanical treatments in the composite than the pure matrix material. The particles themselves, then, are not exclusive obstacles, but the complex network of particles, dislocation tangles, subboundaries, and grain boundaries are strength determining. The development of such a complex dislocation network in SAP has been studied recently in some detail by Goodrich and Ansell. The ability of dispersion-strengthened alloys to resist softening or recrystallization is also of considerable importance; however, the criteria for maximum stability may not necessarily be those for maximum strength. In this study, in addition to the evaluation of the microstrain properties of TD-Nickel, it is felt that considerable clarification of the true dependence of strength and stability on the dispersed phase is shown. I) MATERIAL AND PROCEDURE TD-Nickel is a dispersion-strengthened alloy developed by the E. I. DuPont de Nemours Co., which contains 2 vol pct thoria (Tho2) in a pure-nickel matrix. The average ThO2 particle size is approximately 0.1 p and the interparticle spacing is less than 1 u. The material was supplied by DuPont in two conditions: hot-extruded bar stock, and stress-relieved cold-rolled sheet 0.025 in. in thickness. The bar was extruded at 2200°F from a cold-pressed and sintered billet. The sheet stock was prepared from the extruded material by a process involving ten or more 50-pct cold reductions by rolling with intermediate anneals at 1800° to 2000°F. Test specimens used in this study were prepared in the form of rectangular parallelepipeds measuring 0.375 by 1.375 in. in thicknesses ranging from 0.025 to 0.040 in. Samples prepared from sheet and extruded stock were mechanically polished before heat treatment and were handled with extreme

Jan 1, 1964

By C. E. Mills

STUDIES of ground movement and subsidence resulting from mining operations cover a broad field. It is also a very important consideration and one that eventually affects nearly every mining operation of any extent. The damage to surface buildings, removal of mine surface plants and replacements of main hoisting shafts must reach an astounding expenditure were these cost figures available over a period of years. Were the subject one of mathematical formula and dependent only on the angle of draw of the walls or country rocks, the problem would be relatively simple. Consideration must be given to depth and extent of workings; structural conditions of the orebodies and enclosing country rock; physical properties of these same rocks, including schistosity, bedding, jointing, slips, dikes, faults, and other structural weaknesses. The method of mining, extent of openings, supporting pillars, and amount of moisture or water underground are other pertinent factors. With such a large number of variable factors, it is apparent that the subject of subsidence is one that must be based largely on experience and results at other mines where conditions are somewhat comparable. In presenting this paper, it is the intent to describe the progressive results of past ground movements at the United Verde, to bring out physical conditions largely responsible for this movement, but to refrain from theorizing on the ultimate extent of subsidence resulting from future mining operations.

Jan 1, 1934

By J. J. Crowe, G. K. Burgess

PAGE, Theories of Allotropy of Iron........... 667 Previous Determinations of A2 and A3 in Iron........ 668 Critical Ranges as Determined by Expansion........ 669 Critical Ranges by Thermoelectric Observations........ Critical Ranges in Terms of Crystalline Structure....... 670 Critical Ranges as Detected by Mechanical Methods...... 670 Critical Ranges as Given by Electrical Resistance....... 670 Critical Ranges as Determined Magnetically........ 671 Critical Ranges as Determined Calorimetrically....... 673 Critical Ranges from Heating and Cooling Curves....... 673 Summary of Previous Determinations of A3 and A2 in Pure Iron.... 675 The Present Investigation............ 678 The Experimental Method........... 678 Arrangement of the Apparatus.......... 679 The Measurements of Temperaturc.......... 679 The Measurement of Time........... 679 The Thermocouples............ 681 Temperature Scale and Calibration of Thermocouples...... 681 Mounting of Thermocouples........... 682 The Differential Measurements.......... 682 The Furnace and Accessories........... 682 The Vacuum Pump............ 683 The Energy Supply............683 The Rheostat.............. 683 The Materials Investigated............ 685 Sources of Iron............. 685 Preparation and Description of Samples......... 685 Chemical Analyses............. 687 The Experimental Data............. 688 The Preliminary Observations.......... 688 The Definite Series............691 Description of the Plotted Curves........... 694 The Effect of Plotting at Different Intervals........ 694 The Curves of the Definite Series.......... 695 . The Curves of the Preliminary Series......... The Existence of Other Critical Ranges......... 696 The Microscopical Examination........... 697 Summary and Conclusions............ 698 Bibliography............... 701 Plates................ 704

Jan 1, 1914

By W. N. Poundstone, G. R. Spindler

A comprehensive report on extensive experimentation in degasification of the Pittsburgh Coal seam is presented. Detailed accounts of the procedures and results are given for permeability tests, vertical bore hole tests, measurement of gas flow from sealed drainage areas, horizontal rib hole tests, and water infusion tests. The removal of methane gas from coal seams in advance of mining is not a new idea with mining men—much attention has been given to the possibility for many years. In other parts of the world, a principal concern has been in the recovery and utilization of the gas and a number of successful projects have been developed in Europe and elsewhere. In this country, the principal motivation has been related to the safety aspect with some possible side benefits concerning costs and efficiency in mining as secondary objectives. To date, experimental work in this country has been largely or entirely exploratory to determine bed characteristics with respect to the liberation of combustible gases to investigate or establish the possibility of degasification in advance of mining and as an aid in projecting mine ventilation systems to provide for safe, effective and economical handling of combustible gases liberated during mining. With these objectives in mind, the School of Mines and Engineering Experiment Station at West Virginia University, in cooperation with the Christopher Coal Co. of Osage, W. Va., initiated some experimental work in May 1952 and the project has been more or less continuous since that time. The work has been centered entirely in mines of the cooperating company in Monongalia County, W. Va., and Greene County, Pa. LOCATION AND GENERAL CONDITIONS OF THE AREA The principal mining in the area involved is in the Pittsburgh coal seam which lies at the bottom of the Monongahela series of the Pennsylvanian. The Pittsburgh coal in the area is generally uniform in its structure and physical characteristics. The bed thickness averages about 7 to 8 ft and the coal has a characteristic blocky structure as the result of pronounced face cleats and definite, but somewhat less pronounced, butt cleavage. It is a medium volatile coal, averaging about 37 pct, and is marketed principally as a steam fuel and for metallurgical purposes. The Pittsburgh coal outcrops along the Monongahela River and dips gradually, but not uniformly, slightly north of west (about N75°W). The westward extensions of the bed, from the areas contiguous to the Monongahela River which have been heavily mined, constitute the principal reserves and are all well below drainage with the depth of cover increasing with the distance from the river. In general, with deeper cover, it may be expected that methane liberation will be more of a problem in future mining as compared to areas mined previously; therein lies the interest in possible de-gasification in advance of mining. Fig. 1 shows the Pittsburgh coal area in the vicinity of Morgantown in Monongalia County, W. Va., and Greene County, Pa., in which the experimental work discussed is located. Fig. 2 shows the contours on the Pittsburgh coal in the test area. It will be noted that the first two bore holes for the experiments were at the edge of a bench or terrace with considerable change in the gradient in the immediate vicinity of the test holes and that the same general condition applies to later test areas. Mining is intensively mechanized in the area and in the mines involved in the experimental work with corresponding rapid advance of working faces a typical characteristic. In the areas now mined the total methane liberation ranges from moderate to relatively heavy, but the actual face liberation is extremely variable and may range from practically

Jan 1, 1961

[ ] DISCUSSION F A LORIA*-The method of testing gun steel for resistance to surface cracking described in this paper was restricted to the examination of small, rod-shaped specimens The writer would like to point out the importance of other factors in producing defects in forged and bored gun tubes which would not be apparent in this investigation because of the nature of )he test Actual section size would accentuate the possibility of internal wall (bore) defects arising from unequal expansion between the internal and external wall surfaces on firing, resulting in internal tearing Checks and tears on the inside walls arise from internal tensions and nonuniformity on cooling, but the internal tearing can be reduced by using alloys of low expansion and of good thermal conductivity so as to reduce the difference between the outer and inner wall surfaces Also, the possibility of the location of inclusion segregates within a machined gun tube becomes more likely than in a small test specimen The effect of these nonmetallics on gun life and performance is evident when one realizes that the inclusions are soft yet brittle They reduce the amount of plastic deformation which can take place before cohesive failure occurs Once localized fracture has occurred at the position of a chain of these inclusions, a sharp notch (crack) is formed which produces stress conditions more favorable to cohesive failure than to plastic deformation These cracks aid erosion by providing channelways for the explosive gases, eventually leading to the tearing out or spalling of blocks of metal Oxidation of the surface may be partly responsible for the change in the surface of gun steel during firing observed by the author The appearance of burn on the surface is an indication that high temperatures were reached on firing, resulting in a slight oxidation of the surface Since the color of the oxidized film depends on both temperature and time, a higher temperature is required for a given color to form when it is caused by explosive heat, which acts for only an extremely short time at a given spot, than when it is caused by ordinary tempering The cross section of the gun steel specimen, Fig 16, illustrates that the repeated firing temperatures were high enough to cause

Jan 1, 1948

By N. Schapiro, R. J. Gray, G. D. Coe

A petrographic and chemical investigation was conducted to determine the occurrence and distribution of the organic and inorganic forms of sulfur in various size and specific gravity fractions of a high volatile, A-rank, Pittsburgh seam coal. The investigation was conducted to aid in the resolution of the problem of how metallurgical coke of lower sulfur content can be produced from high sulfur coals. The Pittsburgh raw coal contains about 2.4% S in two dominant forms: pyritic and organic. Pyritic sulfur constitutes about 57% of the total sulfur in the raw coal and occurs in macroscopic and microscopic-size particles. A plant cleaning process mechanically separates between 50 and 60% of the pyritic sulfur, mainly the macroscopic particles. The organic sulfur constitutes 41% of the total sulfur in the raw coal and 55% of the sulfur in the washed coal. Thus, organic sulfur is not reduced by physical methods of separation. Organic sulfur occurs in all the coal entities, but in general, increases as the exinoid content of the coal increases. In this study, it was found that carbonizing certain selected low gravity coal fractions containing an average of 0.45% pyritic sulfur and 1.01% organic sulfur produced cokes containing an average of 0.22% pyritic sulfur and 0.91% organic sulfur. However, the organic sulfur in the coke is probably derived in part from the heating of pyrite in the presence of carbon. Thus, the total sulfur in the coal carbonized is the most important factor affecting the sulfur content of the coke produced. Concentration of microscopic pyritic and organic sulfur in the middling-type coal indicates the necessity for rejecting as much of this material as is economically feasible. Most of the sulfur introduced into the blast furnace originates from the coke. Although the sulfur content of the hot metal can be controlled by the addition of flux, the flux used restricts the productivity of the furnace by displacing ore and requires first to be smelted; therefore, low sulfur coke is highly desirable. Since the sulfur content of coke is dependent upon the sulfur content of the coals from which the coke is produced, low sulfur coals are required to produce low sulfur coke. In the western Pennsylvania area, large quantities of good coking coal are available from the Pittsburgh seam, but this coal unfortunately contains relatively large quantities of sulfur. To provide information that might be useful in reducing the sulfur content of this coal in the cleaning process, an investigation was conducted to determine the physical and chemical forms in which this sulfur occurs and with what petrographic components it might be associated. The Pittsburgh seam coal, like most other coals, contains two dominant forms of sulfur: one occurs as the minerals pyrite and/or marcasite and is referred to as pyritic sulfur; the other is combined with the coal substance and is called organic sulfur. Pyritic sulfur is amenable to physical methods of separation, whereas organic sulfur is not. Pyritic sulfur particles must be freed from the surrounding coal if they are to be removed in the washing process. Generally, this requires crushing; the required degree of crushing being a function of the size and distribution of the pyrite. The present investigation was conducted to 1) determine the size, distribution and association of sulfur-bearing minerals in the coal and 2) to determine whether the organic sulfur has a preferential association with specific coal entities. If a preferential association exists, this knowledge may be useful in devising a method for organic sulfur reduction. In addition, a study was made to determine the extent to which pyritic and organic forms of sulfur in the coal contribute to the sulfur in the coke produced from this coal. A representative 3%-ton sample of raw coal was crushed to —3 in. and screened into square-mesh sizes: 3 to 1 in., 1 to % in., % to % in., % in. to 10 mesh, 10 to 35 mesh, and 35 to 200 mesh. Separate samples of the -200-mesh fraction and the all-size composite were also collected. Each size fraction (except the -200 mesh) was fractionated on heavy liquids of the following specific gravities: 1.280, 1.300, 1.325, 1.350, 1.375, 1.400, 1.425, 1.450,

Jan 1, 1963

By N. A. Gokcen

THE data of Chaudron,1 Tonosaki,2 and Collins³ on the thermodynamic properties of MOO, disagree widely. These authors, by using essentially similar methods, studied the following reaction: 1/2MoO2(s) + H2(g) == i/2Mo(s) + Ph,o H2O(g),K = —----- [1] Ph2 Tonosaki used a vacuum system consisting of a furnace containing MOO, and a water saturator whose temperature was kept at 25 °C with a thermostat. After repeated evacuation, hydrogen was admitted slowly into the system. The experiments were based upon the fact that at a constant furnace temperature and constant partial pressure of water, the total pressure of gas mixture over MOO? + Mo is constant. Any attempt to vary the pressure by external forces would vary only the amounts of MoO2, and Mo, after which the pressure should return to the equilibrium value in accordance with the equilibrium constant of reaction 1. The actual value of K was determined from the total equilibrium pressure (sum of Ph2o + Ph2) at each temperature. The total pressure of gas was varied within the range of 80.2 to 125.4 mm Hg, within a temperature range of 645" to 823 °C. The results were summarized as log K = 0.9413 — 1444.6/T for reaction 1. The ratio of H2O/H2 was considered to be uniform in spite of the presence of a thermal gradient across the static gas phase. It was shown by Rosenqvist and Cox,' however, that in somewhat similar circumstances the error resulting from thermal diffusion may be large. Collins³ improved Tonosaki's method by attempting to avoid thermal diffusion errors. His equilibrium data were obtained at 700°, 800°, and 900° C, and the result for reaction 1 was expressed as log K = 1.258 — 1822/T. The purpose of this investigation was to study reaction 1, avoiding the thermal diffusion errors, and to obtain equilibrium data in a considerably wide temperature range for the reliable extrapolation of the resulting thermodynamic functions. Experimental Procedure The diagram of the apparatus is shown in Fig. 1. Tank hydrogen was passed through a tube containing platinized asbestos at 425 °C in order to convert a trace of oxygen into water vapor. The flow rate was carefully controlled with a capillary-type flow-meter B and a bubbling column D. The gas was then presaturated sufficiently at P and led into a condenser system immersed in a thermostat, controlled to within ±0.002C. The temperature of the thermostat was measured with a thermometer calibrated against a certified standard. The temperature of P was adjusted to avoid the condensation of unduly large amounts of water as judged from the rate of flow out of the capillary tube M. Argon was purified by passing it through magnesium chips kept at 630°C. After passing through the flowmeter B', it was mixed with moist hydrogen emerging from the thermostat. The resulting gas mixture was then led into the hot zone of the furnace through the heated glass tubing and the silica tube S, thus insuring the same ratio of PII2o/Ph2 from the condenser to the reaction chamber, thus avoiding thermal diffusion. The entire gas system was of all-glass construction, except at the magnesium train. The furnace comprised a glazed alumina tube over which a 15-in. platinum coil was wound. The lower end of the alumina tube was tightly closed with a brass bottom and a silicone rubber gasket, and the upper end with two glass disks, each with a hole of 1/16 in. in diameter, through which the gas mixture escaped into the atmosphere. A back-up coil of kanthal wire facilitated the temperature control of the furnace. A coil of annealed molybdenum strip of 99.99 pct purity, 0.005 in. thick and 0.050 in. wide, and weighing 17 g was hung in the furnace with a 0.010-in. platinum wire attached to one end of a sensitive analytical balance. The temperature of the furnace was measured with a Pt-Pt-10 pct Rh thermocouple checked against a standard. The experimental procedure consisted of heating the gas purification trains, adjusting the gas flow rates, attaining a constant thermostatic temperature, flushing the entire system for 2 hr while heating the furnace to well above the expected equilibrium temperature and then cooling it at a rate of 0.3°C per min during which time the change in the weight of molybdenum was observed on the balance. For a given thermostatic temperature, i.e., a constant Prr,o/Px,, molybdenum oxidized upon cooling slightly below the equilibrium temperature. The procedure was then repeated by heating the furnace and thus reaching a temperature slightly above the equilibrium value. The average of the two temperatures, differing by 2" to 3"C, was considered to be the true equilibrium temperature. In order to determine the stoichiometric composition of the oxide phase present in this investigation,

Jan 1, 1954

By Augustus Locke

In 1900, when. the public first heard of "secondary enrichment," the Butte chalcocite seemed clearly supergene. Mining, through successive regions of leached capping, bonanza sulfide, and sulfide less rich, had paused at lean bottom levels which, though chalcocite-bearing, suggested the waning of copper. The deepest chalcocite, at 1500 ft., was yet too shallow to disturb the supergene hypothesis. But, with deeper mining, lean levels yielded to fat ones. Here and there they showed, within the same vein, an inverted distribution, chalcopyrite above and chalcocite below. To the miners' astonishment, they carried chal-cocite, unaffected by cross faults, on an independent course to the depth of 2500 ft. The pattern of ore distribution, hitherto revealed only in fragments, was now appearing in perspective, and, in the depth of the chalcocite, was beginning to make Butte differ from all districts where the chalcocite is indubitably supergene. The idea of hypogene origin at length came into favor; by 1913, when Sales' advocated this origin, the argument had become a powerful one. This argument rested on field evidence; but, already, there was beginning to emerge microscopic evidence not included in this argument. Especially pertinent was the proof that (1) the deep chalcocite lies in-mixed with bornite, often microscopic; (2) the deep chalcocite often replaces bornite; and (3) replacement of bornite by chalcocite is accomplished more easily than that of pyrite, enargite, or chalcopyrite. The microscopic evidence has been accumulating for ten years and it demands

Jan 1, 1924

By R. G. Hudson, L. Yang

In electrochemical separation of metals, it is necessary to control the potential applied between the electrodes so that only the desired electrode reactions can occur. A knowledge of the minimum potential needed for a given electrode reaction to take place continuously is therefore pertinent to the success of the process. In molten chloride systems at high temperatures, activation polarization is believed to be small,1,2 so the minimum potential needed for the electrolytic decomposition of a molten metal chloride MC1n (n = valence of the metal ion) is therefore essentially the equilibrium electrode potential E of the metal-chlorine galvanic cell in the solution. If the decomposition products are pure M and chlorine at a pressure of p atm, E*Eo-rt/nf in [i] Since EO (the standard electrode potential of MCln) is a constant at a given temperature and R (the gas constant), and F (the Faraday's constant) are all constants, the variation of E with the electrolytic bath conditions is largely determined by the effect of the latter on the activity of the metal chloride amcln (standard state = pure MC1,). Measurement of E and study of how amCin varies with temperature and concentration, the nature of the solvent, and that of the coexisting solutes are therefore pertinent in the selection of optimum operating conditions for the electrochemical separation of metals. Because of its low melting point, high decomposition potentials of its components, and the low solubility of heavier metals in it, the LiC1-KC1 eutectic melt is a useful solvent and has been used in the electrodeposition of Mo,3Ce,4 and u5 metals. Senderoff and Brenner3 measured the potentials of Zn/Zn++, Fe/Fe++, Cu/Cu+, Mo/Mo+++, and Ag/Ag+ against an Ag/AgCl (pure) reference electrode at 600°C and a concentration of 4.1 mole pct of each chloride and came to the conclusion that complex ion formation occurred in some of the melts. Laitinen and LiUe gave an electromotive force series at 450°C for a number of {Metal/Metal ions (unit activity)) electrodes in LiC1-KC1 eutectic melt, the {pt/pt++ (unit activity)) electrode being chosen as the reference. Walker and Danly7 studied the ther-modynamic properties of NiC12 in LiC1-KC1 eutectic melt over a wide range of temperatures and concentrations by measuring the electrode potential between a nickel electrode and a chlorine electrode in the melt. Since potential measurements made by using the chlorine reference electrode are of more direct significance both in the study of electrochemical separation and in the evaluation of the thermodynamic properties of the melt, it is therefore decided to measure the electrode potentials of cells of the type {M/MCin (mole fraction = N) in LiC1-KC1 eutectic melt/Cl2 over a range of N values and temperature for a number of metal chlorides. The results should indicate the order by which the various metals plate out on the cathode and how this order is affected by temperature and the concentration of the metal chloride in the solu-

Jan 1, 1960

By R. B. Snow

THIS paper describes a technique of polishing and etching specimens of open-hearth furnace slags or hearth aggregates for identification of the crystalline constituents-lime (CaO), tricalcium silicate (3CaO•SiO2), dicalcium silicate (2CaO-SiO2), monticellite (CaO•MgO-SiO2), or forsterite (2MgO•SiO2), with especial emphasis on the mineral merwinite (3CaO-MgO.2SiO2). With proper standardization, this identification does not require the use of the petrographic microscope. The composition of basic open-hearth slags and furnace bottoms falls, almost without exception, within systems containing CaO, MgO, "FeO," MnO and SiO2, in which the number of basic molecules so greatly exceeds the orthosilicate ratio (two molecules of base to one of silica) that free basic oxides, and combinations between them such as aluminates or ferrites, are present in cooled specimens. Orthosilicates of (CaO + MgO) are the most common in such specimens, since in nearly all cases, except premelt slags, the molecular ratio of (CaO + MgO) to SiO2 is more than 2 to r. When sufficient lime is available it combines with the silica to form dicalcium silicate (2CaO•SiO2), which contains little, if any, MgO, FeO or MnO in solid solution whereas the latter oxides combine to form the oxide solid solution known as periclase. If the lime present is insufficient to form dicalcium silicate (2CaO•SiO2) it combines with MgO to form either merwinite (3CaO•MgO.2SiO2) or monticellite (CaO-MgO•SiO2); these minerals take little if any FeO or MnO into solid solution and the remaining MgO, FeO and MnO combine as periclase. This generalization seems to be valid for basic slags and furnace bottoms, since minerals such as CaO-MnO•SiO2 and CaO-FeO-SiO2 are found only in slags in which the lime-silica ratio is less than 2 and are not observed in specimens from furnace bottoms. The identification of crystalline constituents in such materials, especially of fine crystals in the groundmass, is difficult under the petrographic microscope. They are often masked by their neighbors because of their small size in relation to the thickness of the thin section and because of the presence of opaque or colored constituents. The indices of retraction and the optical sign of the mineral are sometimes difficult to determine because of the small size or because of twinning or of inclusions within the crystal. Moreover, the positive identification of merwinite (3CaO•MgO.2SiO2) from its optical properties is usually difficult in the presence of dicalcium silicate (2CaO•SiO2). CaO, MgO, 3CaO•SiO2 and 2CaO•SiO2 in open-hearth slags have been identified for a number of years in the U.S. Steel Corporation Laboratory by the usual

Jan 1, 1947

By Milton H. Fies

Although pig iron from iron ore and red cedar charcoal preceded the mining of coal by many years, for tradition says that Alabama iron was used to shoe the horses of Andrew Jackson's soldiers, coal was not produced until 1830. In that year, coal was mined in Tuscaloosa County, in the vicinity of what is now the University of Alabama, and shipped on flat boats (obviously during the wet season, for there were many shoals) down the Warrior River to Mobile. About that time, the first railroad, the Decatur & Tecumseh, was being constructed in northern Alabama to overcome the obstructions to freight traffic caused by the now well-known Muscle Shoals in the Tennessee River. This railroad was patterned after a railroad at Mauch Chunk, Pa., which was used for hauling anthracite from the Panther Creek valley. The Alabama railroad, which required about four years to complete, was 46 miles long and was used solely for the transportation of cotton. Although it was a failure, it demonstrated the practicability of the undertaking, and the succeeding railroads, which were begun in 1834, 1848, 1852, and 1853, added immeasurably to the development of the coal resources of the state. Between the years 1830 and 1860, practically all the coal mined in the state was dug from the outcrop near the river or from the river beds, and shipped by boat to Mobile. Transporting coal down the Warrior River was an undertaking of great risk, required much skill, and frequently had heavy losses. It is recorded that this coal was sold to the gas company in Mobile in 1844; it was most likely mined from the Black Creek Seam. In 1914, on the completion of Lock 17, the Warrior River became a navigable stream from 9 miles above Cordova, Ala., to Mobile and offers a great opportunity for the future development of the coal resources of the state. Coke for foundry use was first made in Alabama in 1855. It was 21 years later, however, in 1876, that pig iron was made from Alabama ore with Alabama coal.

Jan 1, 1925

By Walter H. Bruckner, George B. Clark

SINCE the end of World War II interest has been increasing in the use of shaped charges in the mining industry and in other industries using explosives for blasting purposes. Shaped charges employ the principle known as the "Munroe effect," which was discovered by Charles E. Munroe more than 50 years ago (in 1888). Details of their design have been explained e1sewhere.l,2,3 Fig I shows the essential features of design of two types of shaped charges (with conical and hemispherical cavities) and a schematic sketch of their action upon detonation. The following discussion deals with the behavior of the metal in the cavity liners when they are subjected to intense pressures exerted when the explosive charge is detonated. Among the conclusions reached in research on shaped explosive charges, the following have been established concerning cavity liners: 1,2 I. The optimum wall thickness of a conical cavity liner is dependent upon the apex angle of the cone as well as on the base diameter of the charge. Acute apex angles require thinner walls for optimum performance and more obtuse angles require thicker walls for the same base diameter. 2. Cones were more effective in forming a penetrating jet when the walls were tapered; i.e., the thickness of the wall of the cone increased from the apex down. 3. The physical and mechanical proper- ties of metals have a marked effect upon their performance as cavity-liner material. Boiling point, ductility, malleability, tensile strength, and hardness are among the properties that influence the effectiveness of a metal used as a cavity liner. Lead, for example, makes a wide, flat crater in steel plates. Aluminum makes a deeper crater than lead, and an aluminum alloy having a high tensile strength makes a deeper hole, but slightly smaller in diameter. Cast iron makes a deep, narrow hole. These findings, together with the following analysis under Metallographic Survey of Slug, offer solutions to many of the problems involved in solving the mechanism of the formation of Munroe jets. It has been fairly well established that cavity liners collapse in a manner similar to that indicated in Fig 2. Conical liners are known to collapse upon themselves while hemispherical liners are believed to turn inside out in the process of jet formation. The first has been definitely proved by recovery of collapsed portions of cones, while liners from partly detonated charges show that hemispheres may turn inside out. Fig 3 shows a sketch of a recovered slug from a 6-in. shaped charge using a 45° cone made of cast iron. (This size of charge drilled holes up to 3 ft in depth in solid granodiorite.)

Jan 1, 1947

By C. H. Li, R. J. Stokes, T. L. Johnson

The effect of alumina particles on the nucleation and growth of cracks through a silver- chloride matrzx has been investigated. It has been found possible to promote fibrous cracking in dispersion-strengthened silver, chloride under notch-impact conditions at temperatures at which silver chloride alone cleaves brittlely The modification) of fracture beIzavzor is thought to be due to the relaxation of hydrostatrc stress beneath a notch by the nucleation of cavities near alumina particles. In recent years, composite or dispersion-strengthened materials have been studied primarily to understand their high resistance to plastic flow particularly at elevated temperatures. Dislocation models have been developed with which it is possible to deduce with fair success the effects of interparticle distance, particle size, temperature, upon yielding and creep behavior.l-4 Much less attention has been paid to the fracture behavior of these materials (with the notable exception of common structural steels) and little is known experimentally about the manner in which inclusions affect the nucleation and growth of cracks through a matrix. Nevertheless a beginning has been made in connection with fibrous cracking in ductile matrices where inclusions appear to play an essential ro1e.5-7 During the severe localized plastic deformation which accompanies necking in a tensile test, cavities are believed to develop at inclusions; these cavities subsequently grow and coalesce by plastic flow until separation is complete. It is of interest to consider whether inclusions can affect fracture behavior under loading conditions which restrict the plasticity of the matrix itself (for example, cleavage under conditions of a high imposed strain rate at low temperatures). It is particularly interesting to study these effects in a solid which shows a spectrum of behavior ranging from fully ductile to semi-brittle behavior. Such a solid is silver chloride whose mechanical behavior depends sensitively upon temperature and strain rate.'," The present paper is concerned with a study of the influence of inclusions (in the form of alumina particles) on the fracture behavior of silver chloride loaded uniaxially at low strain rates at room temper- ature and also under notch impact conditions over a wide range of temperature. In particular, it will be shown that the alumina particles can exert a startling effect on the ductile-brittle transition temperature of notched silver chloride and that the magnitude and nature of the effect depends upon both the quantity of alumina and the shape of the alumina particles. 1. EXPERIMENTAL PROCEDURE 1.1 Materials Used. Silver chloride powder of analytical reagent (AR) quality having an average particle size 6 was supplied by the Mallinckrodt Chemical Works (st. Louis, MO.). Acid washed 900 mesh alumina powder, designated A38-900, was supplied by the Norton Co. (Cambridge, Mass.). This powder was added to silver chloride in two forms: a) the as-received condition in which the individual particles were of random irregular shape; their statistical average size was 7; b) in a condition in which each particle was spherically shaped by a fusion technique. In this case, the statistical average particle size determined with the optical microscope was approximately the same (about 5p) but electron micrographic evidence indicated that many ultra fine particles were present in the spheroidized powder. 1.2 Preparation of Composite Materials. Silver chloride-alumina composites containing 2.5, 5, and 15 pct by volume of alumina were produced by the extrusion of mechanically mixed powders blended in a ball mill for 24 hr at room temperature. The mixtures were compacted at 50,000 psi at room temperature in the form of billets 3/4 in. in diameter and 1 in. long which were then extruded with a 16:l reduction ratio at 370°C through a radius-type steel die having a 5 deg lead-in angle. An extrusion temperature of 370°C was selected to ensure that all composites had sufficient plasticity to be extruded. Apart from this general requirement, the choice was arbitrary. 1.3 Microstructure of Composites. Attempts were made to check the distribution of alumina metallo-graphically by polishing transverse and longitudinal sections of the extruded rod. Specimens were wet-ground to 600 emery paper and lapped successively with 5 and 0.25-p grades of diamond paste. They were etched for 10 sec in 10 pct sodium thiosulfate solution and lightly polished in concentrated ammonium hydroxide. The most effective way to render the alumina particles and grain boundaries visible was to radiate the surface with intense white light to decorate the grain boundaries and the particle-matrix interfaces photolytically.

Jan 1, 1962

By Charles T. Malcomson

In the United States, improvements in methods of combustion have made possible the use of the smaller sizes of anthracite. This coal is now being reclaimed from the culm banks accumulated by the miners in the more prodigal years. To-day the freshly mined "slush" is segrega,ted and stored against the time when, through briquetting or some other means, it may be utilized as a commercial fuel. For many years Europe has achieved enviable results in the conservation of her small coal by briquetting. This profitable industry, first placed on a commercial basis in France in 1842, has grown to such magnitude that the production during 1913 exceeded 36,000,000 short tons. Briquets produced in Great Britain are used principally for steam purposes and the greater part of the output is either exported or taken by the Admiralty. On the Continent the briquets are sold in all branches of the coal trade. The French railways consume from 16 to 40 per cent. of their fuel in briquet form, and in Germany the lignite briquets (of which 20,000,000 tons were produced in 1913) are as familiar and interesting to the American traveler as the huge porcelain stoves in which they are burned. It is not strange, therefore, that aggressive and far-sighted promoters heralded this means of converting our ubiquitous coal waste into revenue. To the superficial student the briquetting process seemed so simple as to make success easy. It is for this reason principally that the path of the industry in America has been strewn with failures. The rash enthusiast had either not worked out the mechanical problems involved or had failed to grasp the local conditions under which the briquets must be made and sold. It may be confidently stated, however, that in spite of the many vicissitudes through which it has passed, coal briquetting is now an accomplished economic success in this country, and as a profitable adjunct to the coal industry it has come to stay. Several valuable contributions relating to coal briquetting are found in the Transactions. Charles Dorrance, Jr., has sketched briefly the history of the anthracite briquetting plants from the time of Loiseau's pioneer plant down to that of the Lehigh Coal & Navigation Co. at Lans-ford. Since then this phase of the industry has remained practically at

Jan 1, 1915

By A. E. Wheeler, H. Y. Eagle

The copper industry in the Province of Katanga, in the Belgian Congo, which is now controlled and operated by the Union Minére du Haut Katanga, had its inception many years ago in the vision of a Scotsman, Robert Williams, now Sir Robert Williams, Baronet. He it was who personally negotiated the mineral concession with King Leopold of Belgium, sent in the prospecting parties who located most of the present mines of the company, later arranged for the Belgian participation from which the present company was formed, and has been its active mentor ever since. The idea back of his efforts was the establishment of an industry on the Congo-Zambezi divide, of sufficient importance to draw up to it the head of the Cape to Cairo Railroad, the dream of Sir Cecil Rhodes, and the consummation of which he had left as a legacy to Mr. Williams, his successor. The reports of the prospecting expeditions showed that copper in profitable quantity was there, but many difficulties lay in the way of the establishment of the infant industry. The isolated location of the mines, various tribal wars, the Boer War, and many other factors contributed to making progress very slow. However, in spite of these difficulties the railroad was finally built and a blast-furnace plant erected at Lubumbashi, near Elisabethville, the capital of the Province. Operations of this plant were started in 1911, treating high-grade oxidized ores and producing pig copper by a reducing smelting. Production has been continuous since that time and the company has grown so that at present it ranks as the largest individual copper producer in the industry. It is a fitting monument to the foresight, optimism and driving force of its founder, and the progressive policies of his Belgian colleagues. In January, 1914, the Union Miniere du Haut Katanga engaged as its consulting engineer, Archer E. Wheeler, metallurgical engineer, at that time general superintendent of the Great Falls plant of the Anaconda Copper Mining Co. Mr. Wheeler was commissioned by the Board of Directors to proceed into Katanga, and make all necessary investigations to enable him to report on a comprehensive development program, and to recommend a scheme of treatment particularly for their low grade

Jan 1, 1934

By Cyril Wells, Robert F. Mehl

The purpose of this investigation was to prepare high-purity iron-carbon alloys, to determine as precisely as possible the A3(GOS), the Acm(SE), and the A1(PSK) transformation temperatures in the meta-stable iron-iron carbide system (up to 1.4 per cent C), and to study the influence of carefully controlled and constant rates of heating and cooling (1/8 to 2o C. per minute) upon the transformation temperature and upon the resulting microstructure. Apart from the general metallurgical importance attending the completion of such a task, it will be noted that highly precise transformation temperatures are of interest and importance in the thermodynamic study of this system1. Several determinations of the iron-iron carbide diagram have been made2. These suffer generally from the low purity of the alloys used, and from the application of methods of investigation of low sensitivity. Attempts to compare and weight the many data available in an effort to construct as accurate a diagram as possible have, in the main, been unsuccessful. In general, the wide differences in the results of different workers, the lack of complete analytical data, the omission of important details relating to the heat-treatment of the alloys, and the meager description of the methods of investigation applied, render such a process of averaging nearly meaningless. It may be seen from the summaries by Epstein2 and Körber and Oelsenl that variations as great as 30' C. exist in the reported data on the A3 temperatures in iron-carbon alloys. Fortunately, the Aa temperature in pure iron is now known to be 910" C. ± 1° C.3 The best recent work on iron-carbon alloys is that of Esser4 on hypoeutectoid steels and that of Sato5 on both hypoeutectoid and hyper-eutectoid steels. Esser made a dilatometric and magnetic study of iron and iron-carbon alloys containing 0.06 to 0.86 per cent C, for which a high purity is claimed. Presumably the electrolytic iron was reasonably pure, but the alloys contained considerable impurities, on the average totaling 0.35 per

Jan 1, 1937