Search Documents

By B. R. Eichbaum, J. E. Murphy, J. A. Eisele

The US Bureau of Mines demonstrated ferric chloride leaching of galena concentrate on a continuous bench scale basis. Leaching was performed at 95°C (200°F) and with a contact time of 15 minutes. The ferric chloride leaching solution was continuously fed to a leaching tank at a constant rate for periods up to 45 hours. In each test, a constant redox potential was maintained in the slurry exiting the leaching tank by controlling the concentrate feed rate. In the 45 hour test, lead extraction exceeded 99.5%, and the lead chloride produced was 99.97% pure.

Jan 1, 1986

By H. M. Garrett

The basic cement making process is outlined relative to the fuel but chemically sensitive suspension preheater (SP) kiln which made its debut in the early 50s. The SP history is trailed through the process disasters of the late 50s; identification of chemical sensitivities in the 60s; and resurgence of the SP together with development of its stepchild process, the precalciner (PC) kiln, in the 70s. The current energy problem and related conversions to coal re-emphasize the process chemical sensitivity. Attention is focused on the basic problem of coal sulfur and ash variations and several solutions are presented.

Jan 1, 1981

By D. A. Sangrey, D. Marcus, S. A. Miller

A methodology was developed wherein the increase in compressive strength, mineralogical changes, and pore water composition were studied simultaneously as a function of moisturized spent shale curing time. From these results the relationship between the nature of cementation process and the composition of pore water was established. Heavy metals were entrapped in the cementing constituents and the pore water became mainly a solution of alkaline sulfates. The specific data are applicable only to the material studied. But the methodology and general conclusions are useful for evaluating the environmental factors in spent shale disposal and expected leachates composition.

Jan 1, 1986

By W. Ivanick, Frank W. Glaser

ORDERING reactions of Fe-Si compositions in the a region have been mentioned in a number of review articles.7-8 However, little is known in regard to the critical temperature, T at which this transformation takes place. Greiner and Stoughton,' in a study of the constitution of iron-rich Fe-Si alloys below 800°C, placed the onset of order at a composition of about 4 to 5 wt pct (7.5 to 9.5 atomic pct) Si. They observed that at this composition the ductility and strength begin to decrease sharply and brittleness develops. During X-ray studies they observed only the appearance of superlattice lines for compositions containing 12.5 atomic pct Si. More recent X-ray diffraction studies- etected the appearance of superstructure lines (corresponding to the calculated positions of [Ill] and [ZOO] reflections) for alloys containing 9.5 atomic pct. This fact confirms Greiner and Stoughton's original hypothesis in regard to the onset of order at compositions containing about 7.5 to 9.5 atomic pct Si. The physical properties.of Fe-Si alloys containing more than 10 atomic pct Si have been studied only to a limited extent. Their extreme brittleness and difficulties of sample preparation render them of little industrial use in comparison with alloys in the 0 to 10 atomic pct Si range. The properties of Fe-Si alloys reported to date are mostly properties measured at room temperature on ordered compositions It appears that because of experimental difficulties fully disordered alloys could not be produced in the critical composition ranges and their properties could therefore not be reported. In Figs. la, lb, and lc, a summary of physical properties of Fe-Si alloys, measured during recent investigations of the influence of silicon additions to iron, is presented. No mention of determination of the critical temperature, T for disorder could be found in the literature. The following is an account of work done in an attempt to: 1) produce the disordered state of various Fe-Si alloys and establish the critical temperature, T for disordering, and 2) compare the electrical and thermal conductivity characteristics of the ordered and disordered phases as functions of composition. Materials, Preparation of Test Samples, and Testing Methods Fe-Si alloys with high silicon contents (about 10 atomic pct) are usually prepared using powder metallurgy techniques. This method insures accurate compositions and high purity through the use of protective atmospheres during solid state diffusion alloying of the mixed powders."" Iron and silicon powders were mixed in the desired proportions, cold or hot pressed, and then homogenized at 1150°C for periods ranging from 6 to 12 hr under a protective getter and in a hydrogen atmosphere. Fully homogenized samples were quenched in water from various and successively higher temperatures to establish the critical temperature for disorder. Temperatures were determined using Pt—Pt-Rh thermocouples in contact with the test samples. Test bars were approximately 0.6x1.25x7.5 cm. Electrical measurements were made at room temperature by determining the potential drop over a 1.5 cm span for a current of 10 amp. Densities of the samples were determined by immersion. High temperature electrical resistivities were measured using previously described techniques.'" Specific heat conductivity up to 200°C was measured by heating one end of the test bar and water-cooling the other; heat conductivity was then obtained by subtracting the rate at which heat entered the water from the

Jan 1, 1957

By R. H. Walpole, J. M. Kane

IN all probability the mining and metallurgical industry as a whole can demonstrate a larger ecorlomic return from installation of dust-control equipment than any other major industrial group. This fact has partially accounted for the marked increase of dust-control installations made during the past decade. While the primary objectives for installation of dust-collecting systems are improved working and operating conditions for men and equipment, the fact that an economic return can be anticipated on salvageable materials is an added advantage which shows in partial or complete equipment write-off. The conditions apply to most phases of the mining, milling, and smelting industry, both non-metallic and metallic. As with any mechanical devices, selection of suitable dust collector equipment involves evaluation of available products with characteristics most nearly meeting conditions of the application at hand. When there is valuable product to be collected, and/or when there are possibilities of air pollution or public nuisance, collector selection is often guided by the maxim of "highest available collection efficiency at reasonable cost and reasonable maintenance." A brief review of dust collector designs will permit outlining of major characteristics of each group. Final selection will involve detailed data against a background of the problem under consideration. The dry centrifugal collectors, see Fig. 1, represent a group of low cost units with minimum maintenance. They are subject to abrasion under heavy abrasive dust loads and to plugging with moist materials. Efficiency drops off rapidly on particle sizes below the 10 to 20 micron group. Because of the large amounts of —10 micron particles in most mining dust problems, they will normally be used as primary collectors and will be followed by high efficiency units. This combination is cspecially popular where the bulk of material is desired in a dry state with wet collection indicated for the final cleanup portion. In remote plant locations, dry centrifugal~ can be used alone if product in dust form has no value or if dust loading is light enough to eliminate a nuisance in the plant area. Where high efficiency dust colleotion equipment must be selected, choice will normally involve fabric arresters, wet collectors, or high voltage Electro-Static precip-itators. Fabric arresters, see Fig. 2, rely on the passing of dust-laden air at low velocity through filter fabric. Velocity ranges from 1 to 3 fpm for the usual installation and may be as high as 10 to 20 fpm in arrangements where automatic frequent vibration or continuous cleaning of the filter media is employed. Fabric is normally suspended in either stocking type or in an enlvelope shape. Collection efficiency is excellent even on sub-micron particle sizes. Equipment is bulky, must be vibrated to remove the collected dust load, and is restricted in applications from temperature and moisture standpoints. Condensation of moisture on the fabric filter mcdia causes plugging of the passages with great reduction in air flow. Temperatures for the usual medias of cotton or wool are 180" and 200°F maximum, although the introduction of synthetic materials such as nylon, orlon, and glass cloth have increased the possibilities of this type of collector for higher temperature applications. The wet-type collector may employ a number of different principles so that entering dust particles in the gas stream are wetted and removed. Principles usually include impingement on collector surface or water droplets, often in combination with centrifugal forces. Variety of wet collector designs is indicated by typical collectors illustrated in Figs. 3 and 4. Collection efficiency is a function of the particular design, although the better collectors will have high collection efficiency on particles in the 1-micron range. Wet collectors have the advantage of handling hot or moist gases, take up small space, and eliminate secondary dust problems during the disposal of the material. At times collection of the material wet is a disadvantage. Wet collectors may also be subject to corrosion and freezing factors. The high voltage Electro-Static precipitator, see Fig. 5, is probably the most expensive type of high efficiency collector. It finds its applications generally in problems in which collectors previously discussed cannot be employed. Its collection efficiency is based on its design features and can be excellent on the finest of fume particles. Material is normally collected dry. Gas temperatures are of no great concern as long as condensation does not occur within the dry type of precipitator and the temperatures do not exceed the limits for materials used in its construction. As with the fabric arrester, provisions

Jan 1, 1954

By Gerald Edmunds

Castings of pure metals and many alloys usually have a coarse-grained structure characterized by long columnar grains throughout the main body of the casting. Frequently, the surface exhibits finer, sometimes nearly equiaxed grains, and such grains may also compose other parts of the casting. This paper deals .primarily with determinations of the grain-orientation textures of the columnar and surface grains of polycrystalline zinc castings. It includes some results upon a cadmium casting and a magnesium casting. A hypothesis is developed to account for the observations on columnar grains and to use as a basis for predicting orientations in other cast metals. A general description of the position of the columnar grains in castings is that their long axes are approximately parallel to the direction of the thermal gradient during crystallization. Thus, in cylindrical castings the columnar grain axes tend to be radial, and in large flat castings where most of the cooling is through one or both of the large mold surfaces they tend to be perpendicular to the mold surfaces. At the edges and corners the direction of heat flow and therefore the position of the grains is more cornplex. Actually observation shows that even in castings made in flat molds the cooling seems to be somewhat irregular, since columnar grains tend to emanate from certain areas of the cooling surface, indicating that thermal contact was better there than in neighboring areas. The nucleus from which a columnar grain grows may be so oriented that its direction of maximum growth rate does not coincide with the direction of the thermal gradient. In this case the long axis of the grain probably assumes an intermediate position. Notwithstanding these minor irregularities, the situation does exist that the long axes of the columnar grains are generally disposed approximately perpendicular to the mold surface. Schmid and Wassermanl and Nix and Schmid2 have determined the orientation texture of columnar grains in castings of several cubic, tetragonal, hexagonal close-packed and rhombohedra1 metals. For zinc and cadmium, they report the basal plane to be parallel to the columnar grain axes, with no preference for any particular direction in this plane to coincide with the grain axes. This texture, termed a ring fiber texture,3 is uncommon in metals; zinc and cadmium are the only ones reported to exhibit it. Generally, it is stated, a simpler texture exists in which a principal, though not necessarily the most closely packed, crystallographic direction is parallel to the direction of heat flow. In cast magnesium (also hexagonal close packed) they report a digonal axis I, [100] direction, parallel to the direction of heat flow. The writer is not aware of any other orientation-texture determinations on cast polycrystalline hexagonal metals. In view of the observations reported in the present paper it is of interest also to note that Nix and Schmid stated that a

Jan 1, 1941

By Gerald Edmunds

Castings of pure metals and many alloys usually have a coarse-grained structure characterized by long columnar grains throughout the main body of the casting. Frequently, the surface exhibits finer, sometimes nearly equiaxed grains, and such grains may also compose other parts of the casting. This paper deals .primarily with determinations of the grain-orientation textures of the columnar and surface grains of polycrystalline zinc castings. It includes some results upon a cadmium casting and a magnesium casting. A hypothesis is developed to account for the observations on columnar grains and to use as a basis for predicting orientations in other cast metals. A general description of the position of the columnar grains in castings is that their long axes are approximately parallel to the direction of the thermal gradient during crystallization. Thus, in cylindrical castings the columnar grain axes tend to be radial, and in large flat castings where most of the cooling is through one or both of the large mold surfaces they tend to be perpendicular to the mold surfaces. At the edges and corners the direction of heat flow and therefore the position of the grains is more cornplex. Actually observation shows that even in castings made in flat molds the cooling seems to be somewhat irregular, since columnar grains tend to emanate from certain areas of the cooling surface, indicating that thermal contact was better there than in neighboring areas. The nucleus from which a columnar grain grows may be so oriented that its direction of maximum growth rate does not coincide with the direction of the thermal gradient. In this case the long axis of the grain probably assumes an intermediate position. Notwithstanding these minor irregularities, the situation does exist that the long axes of the columnar grains are generally disposed approximately perpendicular to the mold surface. Schmid and Wassermanl and Nix and Schmid2 have determined the orientation texture of columnar grains in castings of several cubic, tetragonal, hexagonal close-packed and rhombohedra1 metals. For zinc and cadmium, they report the basal plane to be parallel to the columnar grain axes, with no preference for any particular direction in this plane to coincide with the grain axes. This texture, termed a ring fiber texture,3 is uncommon in metals; zinc and cadmium are the only ones reported to exhibit it. Generally, it is stated, a simpler texture exists in which a principal, though not necessarily the most closely packed, crystallographic direction is parallel to the direction of heat flow. In cast magnesium (also hexagonal close packed) they report a digonal axis I, [100] direction, parallel to the direction of heat flow. The writer is not aware of any other orientation-texture determinations on cast polycrystalline hexagonal metals. In view of the observations reported in the present paper it is of interest also to note that Nix and Schmid stated that a

Jan 1, 1941

By T. A. Read, M. S. Wechsler, D. S. Lieberman

A theoretical analysis of the austenite-martensite transformation is presented which predicts the habit plane, orientation relationships, and macroscopic distortions from a knowledge only of the crystal structures of the initial and final phases. THIS paper presents a new theory of the formation of martensite. This theory makes possible the calculation of the austenite planes on which the martensite plates form, the orientation relationship between the austenite and martensite crystal axes, and the macroscopic distortions which are observed. The only input data needed are the crystal structures and lattice parameters of the austenite and martensite. Considerable effort has been devoted over the past thirty years to the development of an understanding of the crystallographic features of martensite reactions. Much of this work has been done on steels and iron-nickel alloys, for which a great deal of data has been accumulated concerning the shape and orientation of the martensite plates, the relative orientations of the austenite and martensite crystal axes, and the observable distortions which result from transformation. These observations are reviewed in refs. 1, 2, and 3. The first major step toward an understanding of these phenomena was made in 1924 by Bain,' who showed that the a body-centered cubic structure can be produced from the 7 face-centered cubic structure by a contraction of about 17 pct in the direction of one of the austenite cube axes and an expansion of 12 pct in all directions perpendicular to it. Since that time, most of the efforts at further interpretation have been made by investigators who have worked from the phenomenological data, incorporating some of the information from the lattice properties, and have sought an analysis into likely deformations which would produce the observed results."- "11 but the three most recent papers on the subject have already been reviewed in some detail." Machlin and Cohenl0 measured the components of the distortion matrix and verified that the habit plane is a plane of zero distortion and rotation for the (259) case. They showed that the measured distortion matrix, when applied to the parent lattice, does not yield the product lattice and hence some inhomogeneous distortion must occur. Frank,u working from the lattice properties and taking some clues from the observations, considered the correspondence of close-packed rows and planes in the austenite and martensite. He predicted substantially the observed lattice relationship and habit plane for certain steels which have a (225) habit. Geisler12 suggested that there is a natural tendency for the habit plane to be a (111) and postulated certain slip processes to account for the fact that the experimentally observed habit plane is irrational and deviates from the assumed one. The present work differs from previous treatments of martensite formation in that it permits calculation of all the major manifestations of the process. Habit plane indices, orientation relationships, and observable distortions are all calculated from a knowledge of the crystal structures of the initial and final phases alone. The calculations contain no adjustable parameters. The agreement found between calculated results and the observations reported in the literature constitutes powerful evidence in favor of the mechanism of martensite formation proposed. The theory is applicable to systems other than steel (as is discussed later in this paper) which exhibit a diffusionless phase change but because of the wide-spread interest in the austenite-martensite transformation, particular attention will be given to the iron-base alloys. For other systems which undergo a similar face-centered cubic to face-centered tetragonal transformation, the mathematical treatment is identical with that presented here. Hence the theory successfully describes the transformation in the indium-thallium alloy.'" Homogeneous Transformation to Martensite The distortion which any homogeneously transforming volume of austenite undergoes in order to become martensite is shown in Fig. 1, as was first suggested by Bain.' (This distortion will hereafter be referred to as the "Bain distortion.") This specification of a contraction along one cube axis ;ombined with an expansion in all directions perpendicular to this axis describes what is properly called the "pure" distortion associated with this transformation. The distinction between a "pure" and an "impure" distortion plays an important part in the discussion which follows. A "pure" distortion is characterized by the existence of at least one set of orthogonal axes fixed in the body which are not rotated by the distortion. (These are called the "principal axes" of the distortion.) No such set of axes exists in the case of an "impure" distortion. On the other hand, an impure distortion can always be represented as the result of a pure distortion combined with the rotation of the specimen as a rigid body. For a given impure distortion the corresponding pure distortion

Jan 1, 1954

By Claude H. P. Lupis, John F. Elliott

The classic Siez~erts' technique has been employed to determine the solubility of oxygen in liquid pure silver and the effect on the oxygen solubility of solute metal additions to liquid silver. The results indicate that oxygen deviates slightly from Sieverts' law in pure silver as = 3.9. Gold, platinum, md palladium decrease the solubility of oxygen in silver. First-order free energy, enthalpy, md entropy interaction coefficients are determined from the data. An important aspect in the establishment of the formalisms to be applied to represent the thermody-namic behavior of components of solutions is the accuracy of the experimentally determined thermody-namic properties. Wagner developed the first-order free energy interaction coefficient.' Recent papers2'3 extend the treatment formally to other thermodynamic properties and define the second- and higher-order interaction coefficients. A current communication4 considers in some depth the requirements and limitations imposed because of experimental error on the use of several formalisms now under active consideration in the field. This communication reports the results of an experimental study of the behavior of oxygen in liquid silver alloys that was carried out concurrently with the development of Refs. 2 and 3 with the hope of providing sufficiently precise information so that enthalpy and entropy interaction coefficients could be determined. THE EXPERIMENTS The Sieverts technique was employed using an improved design of the reaction bulb over that developed originally by Humbert5 and subsequently improved by pehlke6 and Weinstein.7 The Vycor reaction bulb as shown in Fig. 1 was air-cooled and contained a port for the thermocouple angling off to one side and a vertical port for connections to the gas supply and

Jan 1, 1969

By D. L. Katz

The Oklahoma City Wilcox sand, discovered on March 26, 1930, has produced 394 million barrels of crude oil and 819 billion cubic feet of natural gas as of July I, 1941. The 100,000-bbl. wells, pressures of 2600 lb. per sq. in., and flows of "Wilcox" sand caused exciting moments in the early life of the field. Today the reservoir is substantially at atmospheric pressure and produccs 75,000 bbl. of crude oil daily through 466 pumping wells. Early estimates of the initial crude-oil content of the "Wilcox" sand1 indicated that about 600 million barrels of crude oil would remain after the pumping wells ceased to produce economically. The Oklahoma City Wilcox Secondary Recovery Association was organized in March 1939, to study the possibilities of recovering a portion of this oil. Only a very brief summary of the information available can be presented in a paper of this nature. Some simplifications and generalizations are necessary to give the over-all picture in SO short a space and statements made may not apply to a specific well or small area. Since the area under consideration by the Association is that north of the south line of section 22-11-3, some information will be presented for areas A, B, C, 1, 2, 3 and part of 4 of Fig. 2, and some will be for the entire Wilcox zone west of the fault. This paper is essentially an abstract of an engineering report made by A. D. Small, B. T. Murphree, M. C. Sons and the author for the Oklahoma City Wilcox Secondary Recovery Association on Sept. 5, 1940. Some information is taken from a report to the Association by C. V. Sidwell on March I, 1940, and some data are from a recent report by A. D. Small. It gives a brief history of the Wilcox zone, estimates of the initial oil contents of the reservoir, present conditions in the reservoir, and probable results from several programs of "secondary recovery." History of Wilcox Zone The Wilcox sand lies on the flank of the general structure, as shown by cross section of Fig. I2,3,4 and areal map of Fig. 2. The sand is of Ordovician age and is composed of well assorted, rounded sand grains with no apparent cementing material. The loose texture of the sand is shown by the enormous quantities of sand production from the wells and from the soft cores. The productive sand varies from zero thickness on the east to 220 ft. maximum and to zero thickness on the west because of water. The development of the pool4 as dependent upon drilling restrictions within the city limits, which accounts for the spacing of drilling operations listed in Table I by years. In 1931, areas I through 7 of Fig. 2 were open for drilling with the exception of some west-edge properties, and all wells drilled before Feb. I, 1935, were in this portion of the field. Nearly all wells drilled from 1933 to 1037 were in areas A, B and C. Since 1939, the newly drilled wells have gradually enlarged the producing area toward the west in the northern portion.

Jan 1, 1942

By D. L. Katz

The Oklahoma City Wilcox sand, discovered on March 26, 1930, has produced 394 million barrels of crude oil and 819 billion cubic feet of natural gas as of July I, 1941. The 100,000-bbl. wells, pressures of 2600 lb. per sq. in., and flows of "Wilcox" sand caused exciting moments in the early life of the field. Today the reservoir is substantially at atmospheric pressure and produccs 75,000 bbl. of crude oil daily through 466 pumping wells. Early estimates of the initial crude-oil content of the "Wilcox" sand1 indicated that about 600 million barrels of crude oil would remain after the pumping wells ceased to produce economically. The Oklahoma City Wilcox Secondary Recovery Association was organized in March 1939, to study the possibilities of recovering a portion of this oil. Only a very brief summary of the information available can be presented in a paper of this nature. Some simplifications and generalizations are necessary to give the over-all picture in SO short a space and statements made may not apply to a specific well or small area. Since the area under consideration by the Association is that north of the south line of section 22-11-3, some information will be presented for areas A, B, C, 1, 2, 3 and part of 4 of Fig. 2, and some will be for the entire Wilcox zone west of the fault. This paper is essentially an abstract of an engineering report made by A. D. Small, B. T. Murphree, M. C. Sons and the author for the Oklahoma City Wilcox Secondary Recovery Association on Sept. 5, 1940. Some information is taken from a report to the Association by C. V. Sidwell on March I, 1940, and some data are from a recent report by A. D. Small. It gives a brief history of the Wilcox zone, estimates of the initial oil contents of the reservoir, present conditions in the reservoir, and probable results from several programs of "secondary recovery." History of Wilcox Zone The Wilcox sand lies on the flank of the general structure, as shown by cross section of Fig. I2,3,4 and areal map of Fig. 2. The sand is of Ordovician age and is composed of well assorted, rounded sand grains with no apparent cementing material. The loose texture of the sand is shown by the enormous quantities of sand production from the wells and from the soft cores. The productive sand varies from zero thickness on the east to 220 ft. maximum and to zero thickness on the west because of water. The development of the pool4 as dependent upon drilling restrictions within the city limits, which accounts for the spacing of drilling operations listed in Table I by years. In 1931, areas I through 7 of Fig. 2 were open for drilling with the exception of some west-edge properties, and all wells drilled before Feb. I, 1935, were in this portion of the field. Nearly all wells drilled from 1933 to 1037 were in areas A, B and C. Since 1939, the newly drilled wells have gradually enlarged the producing area toward the west in the northern portion.

Jan 1, 1942

By P. Marier, T. R. lngraham

The kinetics of the sulfation of MnO,, MnzO3, and Mn3O4 in SO,, SO3, and O, mixtures was examined and the descending order of sulfation rates at temperatures near 400°C was found to be Mn,O3 > MnO, > Mn3O4. The respective activation energies for the thermal decomposition of MnO, and Mn,O, are 39 and 47 kcal. At 900°C, the thernzal decomposition of MnSO, to MnzO3 is slower than that to Mn3O4. The respective activation energies are 62 and 51 kcal, respectitely. MANGANESE is used to improve the hot workability of steel in the proportions of approximately 13.5 Ib of ferromanganese per ton of steel produced. This requirement accounts for about 95 pct of its large industrial market in North America. The remaining 5 pct is used in the battery and chemical industries. In most North American ores, the percentage of manganese and the manganese-to-iron ratio are not suitable for the direct production of ferromanganese. Hence, most of the North American requirements for manganese are satisfied by importing ore. Typically, many of the studies done on native low-grade manganese resources have been directed toward the production of ore substittes" and the recovery of manganese from open-hearth slags.3 Of the wide variety of processes which have been proposed, the most popular involve compounds in the Mn-S-O system. The thermodynamic properties of manganese and its compounds were reviewed by ah' in 1960 and, more recently, lngrahams discussed the thermodynamics of some of the reactions involved in the Mn-S-O system at normal roasting temperatures. The conditions for producing manganese sulfide during the reduction roasting of manganese sulfate are discussed by Fuller and Edlund.9 A novel scheme was proposed recently by zimmerley7 for utilizing waste sulfur dioxide from stack gases to recover the manganese from ocean-mined manganese nodules. Very little of the work published on manganese compounds has been related to reaction rates. Singleton et 1.' studied the rates of reaction on the MnO-C and Mn7C3-3MnO systems and observed linear and parabolic kinetics respectively in the systems. Tatievskaya et a1.' studied the low-temperature reduction of Mn&, MnO,, and Mn& in HZ and CO, and reported activation energies in the range 1628 kcal. In this paper, the rates of some of the decomposition and formation reactions involving MnSO4, MnOz, MnzO3, and Mn3O4 will be examined after the conditions for the thermodynamic stability of the individual compounds have been designated. CONDITIONS FOR STABILITY OF MnSO4, MnOz, MnZO3, AND Mn3O4 The areas of stability for h'hSO4, MnOz, MnzO3, and h3O4 were established from the data of Mah4 and Ingrahams and are shown in the predominance area diagram,10 logpq- logpsq, in Fig. 1. The diagram is drawn for two temperatures, 700°K, solid lines, and 1100°K, dotted lines. The sketch for the lower temperature includes the conditions likely to prevail in the Zimmerley patent7 when manganese nodules react with sulfur dioxide and that for the higher temperature indicates the conditions for recovering MnzO3 or Mn3O4 from MnSO4 during a roasting reaction. From the fact that the boundary between the areas of stability of MnOz and hSO4 at 700°K is parallel to the abscissa, it is evident that MnOz and SO2 should react together to produce MnSO4, irrespective of the oxygen pressure in the system. If the source of sulfur for sulfation were from waste flue gases, it is likely that the oxygen content of the gas stream would be more than sufficient to oxidize any MnsO4 to MnzO3, 107 atm of O2 required, or even to convert any Mnz03 to MnOz, 0.02 atm OZ required, prior to sulfation. At 1100°K, the diagram indicates that MnSO4 may be converted directly to either MnzO3 of Mn3O4, depending upon the prevailing partial pressure of oxygen. When the gas stream contains more than 1 pct Oz, logpq = -2, only MnzO3 would be recovered from an experiment done under equilibrium conditions. At oxygen partial pressures of less than 1 pct, one would expect to bring about a reversible exchange between MnSO4 and Mn3O4 by appropriate adjustment of the partial pressure of SOZ. These various reactions will be described in the subsequent kinetic experiments.

Jan 1, 1969

By W. O. Philbrook, R. H. Spitzer, F. S. Manning

A generalized mathematical model has been developed to describe the kinetics of the gaseous, topo-chemical reduction of porous hematite spheres. Gas-solid reduction is permitted at each of three advancing interfaces and is controlled by a complex series-parallel sequence of chemical and transport steps. Despite the fact that transport resistances are significant to the advance of each interface, little deviation from linear advance is predicted for the first 98 pct of reduction. Calculations to predict the movement of magnetite /wustite interface by a solid-state diffusion mechanism have been incorporated into the earlier dense-pellet model.' The porous-pellet model is found to give a better description than the dense-pellet one for McKewan's measurements2 of interface movements in dense polycrystalline hematite reduced in hydrogen-water vapor mixtures. THIS paper reports a continuation of work"3" directed toward the better understanding of gas-solid reactions and the development of mathematical models that may be helpful in the design or control of ore-reduction processes. Laboratory studies of the reduction of single oxide samples in tube furnaces normally employ an abundant excess of pure reducing gas. Reduction may appear to be adequately described by a model assuming gas-solid reaction solely at the iron/wustite interface.''' However, when iron ore is reduced in either a fixed bed or an efficiently operated counter-current column, there are portions of the bed where the partially spent gas is no longer capable of reducing wustite to iron. Nevertheless, the formation of the intermediate reaction products, wustite or magnetite, can and does continue. In order to account for this aspect of the reduction of beds of particles, three semiempirical mathematical models were devised.' One of these was for the limiting case of completely dense particles, and two alternatives were provided for porous particles. For purposes of the analysis, a dense pellet was defined as one in which the wustite and magnetite layers were impervious to the reducing gas when the atmosphere was capable of forming iron. In a porous pellet, the intermediate product layers were assumed to be sufficiently permeable to allow reducing gas to penetrate beyond the iron/wustite interface to form wustite and magnetite by removal of oxygen as a gaseous product rather than by a solid-state redfiction mechanism. Further progress required a better understanding of the reaction of the individual particles with the gas stream. A comprehensive mathematical treatment was developed' to describe the continually changing interplay of transport and reaction steps

Jan 1, 1967

By J. M. Callow

THe results obtained by pneumatic flotation throughout the country on all classes of ore, and the tonnage now being treated by this particular method, speak for themselves. Its advantages over the so-called agitation process are now established by facts and data from practicc. The comparative efficiency of a rapidly revolving paddle, as a means for aerating an ore pulp, and of a cyeloidal or turbine blower for the same purpose, would seem to be so obvious as to leave no room for discussion. Practitioners in this art are to be congratulated on the acquisition of the valuable literary contributions that have recently been made on the theory of flotation by Messrs. Ralston, Van Arsdale, Taggart and Beach, and others, and the very valuable and able articles by Messrs. Laist and Wiggin on "Flotation Concentration at Anaconda, Mont.," by Dr. Rudolf Gahl on the "History of Flotation at Inspiration," and by David Cole on "The Advent of Flotation in the Morenci District." It is not within the province of this article to attempt an answer to the various issues raised in regard to the theory, or to defend the one advanced by me a year ago. But since discussion usually benefits the profession, a reply will be made to some of the statements made by the last-named writers. CoMPABATIVE SENSITIVENESS AND ATTENDANCE Concerning the article, "Flotation Concentration at Anaconda, Mont.," by Laist and Wiggin, a little explanation is in order. It should be stated that, with the exception of about 24 days at the end of the testing period, the Callow experimental plant at Anaconda was not run under my direction. This perhaps accounts for some of the concIusions drawn on page 499 of the descriptive paper. The conclusion that the use of acid seems to be of considerable advantage, calls for some comment. While the tests conducted by the Anaconda Copper Co. do show acid to be of considerable benefit, this is a consequence of using acid sludge as a flotation agent. My belief has always been that the Anaconda

Jan 1, 1917

By M. A. Grossmann

THE hardenability of most steels can be predicted within 10 to 15 per cent provided the complete chemical composition is known, including "incidental" elements; and provided the as-quenched grain size is known; and provided, finally, that the composition and heating temperatures for hardening are such as to result in austenite free from carbide particles. In method proposed herein, the steel is considered as having a base hardenability due to its carbon content alone (the hardenability of a ''pure steel" of the given carbon content, without any other elements), and this base hardenability is multiplied by a multiplying factor for each chemical element present. After multiplying all these together, the final product is the hardenability. Grain sue may be taken into account either in the base hardenability or after the multiplication. Hardenability is stated in terms of "ideal critical diameter"; namely, the diameter of bar, in inches, that will just harden all the way through (absence of un- hardened core) in an "ideal" quench, and the calculation may also be related to the Jominy test. The data bring out certain features rather clearly. For example: I. It is quite useless to attempt to predict hardenability unless all elements, including "incidentals," are known; thus an "incidental" chromium content of 0.20 per cent increases the hardenability by about 50 per cent. 2. The relative effectiveness of different alloys is sometimes unexpected; thus molybde- num when calculated in this way appears to be of the same order of effectiveness as manganese, rather than much more powerful as wouldappear to be common experience; observe that an increase from no manganese to 0.20 per cent Mn provides a multiplying factor of 1.67, and an increase from no molybdenum to 0.20 per cent Mo provides a factor of 1.63, an increase of over 60 per cent in each case. However, if to a steel containing 0.50 per cent Mn there is added " 20 points of manganese," the factor is raised from 2.65 (for 0.50 per cent Mn) to 3.35 (for 0.70 per cent Mn), or an increase of only 26 per cent. Thus the first small addition of an element has a much more powerful percentage effect than an equal further addition when some is already present, and in most cases the effect of molybdenum is considered in relation to a steel in which molybdenum is absent. 3. If two elements are equally effective, a greater hardenability will be obtained by using, for example, 0.5 per cent of each than by using 1.0 per cent of either of them alone. 4. A knowledge of the as-quenched grain size is essential for precise work, since a difference of only one grain size number (say No. 7 instead of No. 6) makes a difference of almost lo per cent in hardenability (in these units); this, however, does not apply to certain steels of high hardenability. It should be emphasized that in chromium steels (over 0.30 per cent Cr) and chrome- molybdenum and chrome-vanadium steels, undissolved carbides are likely to be present in the steel as quenched, and that in such cases the charts can indicate only a maximum possible hardenability, whereas the extent of hardening actually obtained may be much less. Thus tests on a number of chrome-molybdenum steels have indicated a degree of hardening amounting to only 50 to 65 per cent of the maximum possible, and in chromium steels from full hardening (100 per cent) down to as low as 70 per cent. On the other hand, when the amount of such elements is small (Cr under 0.30 per cent, Mo up to 0.25 per cent in the absence of Cr, and V up to 0.04 per cent), the charts provide reasonable approximations. The precise figures on the charts are suggested as tentative, subject to some modification as more data accumulate, but the fundamental concept appears to be supported by tests made on a wide variety of steels, a few of the correlations being shown in Fig. I.

Jan 1, 1942

By Howard N. Eavenson

From the Pittsburgh coal bed in the four states of Pennsylvania, Ohio, Maryland and West Virginia has been produced an output that, at mine prices, represents a greater value than any other single mineral deposit in the world has yielded.12 While this distinction may in a few years pass to the gold reef of the Witwatersrand, it is possible that eventually, owing to the tremendous reserves still remaining, the ultimate yield of the Pittsburgh bed will be greater than that of any other known single deposit. Considering its importance, not a great deal has been written of its early history and development as a whole; most of the accounts have been of limited localities, or, at the most, of the area within a single state. In "Coal through the Ages" the writer mentioned some references to its early history, but this study will deal not only with its history but with the character of the bed, where and why it was first developed, and its effect upon the states in which it is found. It has not been the intention to write a detailed history of the development of the seam in each locality, as neither time nor inclination were available for doing such work, but only to show the influences that tended to hasten or retard such development. In general the historical matter ends about 1830, when geological surveys began to be made. Some of the maps show data available only since that time, and the sections about coal preparation and coking have been extended to the present time to show the changing conditions. It is believed that the early history includes all published records, and many more sources than those shown in the bibliography were consulted. It is quite likely that some references to coal in this area may be found in the unpublished papers of some of our early soldiers and colonizers, which exist in several libraries, and it is hoped that some future * Dedicated to Dr. Thomas S. Baker, President Emeritus, Carnegie Institute of Technology, whose labors in promoting the International Coal Conferences and in establishing the Coal Research Laboratory have done much in showing the industry how science can be of help to it. Manuscript received at the office of the Institute Feb. 15, 1938.

Jan 1, 1938

By Howard N. Eavenson

From the Pittsburgh coal bed in the four states of Pennsylvania, Ohio, Maryland and West Virginia has been produced an output that, at mine prices, represents a greater value than any other single mineral deposit in the world has yielded.12 While this distinction may in a few years pass to the gold reef of the Witwatersrand, it is possible that eventually, owing to the tremendous reserves still remaining, the ultimate yield of the Pittsburgh bed will be greater than that of any other known single deposit. Considering its importance, not a great deal has been written of its early history and development as a whole; most of the accounts have been of limited localities, or, at the most, of the area within a single state. In "Coal through the Ages" the writer mentioned some references to its early history, but this study will deal not only with its history but with the character of the bed, where and why it was first developed, and its effect upon the states in which it is found. It has not been the intention to write a detailed history of the development of the seam in each locality, as neither time nor inclination were available for doing such work, but only to show the influences that tended to hasten or retard such development. In general the historical matter ends about 1830, when geological surveys began to be made. Some of the maps show data available only since that time, and the sections about coal preparation and coking have been extended to the present time to show the changing conditions. It is believed that the early history includes all published records, and many more sources than those shown in the bibliography were consulted. It is quite likely that some references to coal in this area may be found in the unpublished papers of some of our early soldiers and colonizers, which exist in several libraries, and it is hoped that some future * Dedicated to Dr. Thomas S. Baker, President Emeritus, Carnegie Institute of Technology, whose labors in promoting the International Coal Conferences and in establishing the Coal Research Laboratory have done much in showing the industry how science can be of help to it. Manuscript received at the office of the Institute Feb. 15, 1938.

Jan 1, 1938

P. L. Pratt (University of Birmingham, Birmingham, England)—The author has measured the hardening effect of isolated edge and screw dislocation boundaries in a remarkably elegant manner, and he proposes that the detailed structure of the boundary determines its effectiveness as a barrier to slip although "there are still unknown details of the distribution which may be extremely important." On p. 678 the author states "that for a good crystal (one having a yield of about 30 psi) a change in annealing temperature from 300" to 400 °C resulted in a negligible shift in the level of the stress-strain curve." Is this in agreement with the results of the earlier paper by Li, Washburn, and Parker8 in which such a change of temperature produced notable hardening in crystals with a yield of about 30 psi? Or were these earlier crystals, of the same nominal purity, less perfect than those used in this work? The experiment illustrated in Fig. 15, p. 681, shows that the boundary has sharpened after annealing at 400 °C, the temperature at which the hardening effect first becomes apparent. Did the author verify that no sharpening of the boundary occurred at, say, 300 °C where no hardening was found? This would seem to be an important check on the proposed mechanism, especially since zinc of this purity should polygonize at temperatures well below 400 °C within the annealing times used here. There seem to be at least two alternative explanations which could fit these facts: 1—The boundary may sharpen at 300 °C or even lower temperatures but be unable to contribute greatly to the hardening until jogged by thermal vacancies and other impurity atoms after 400 °C anneal. This mechan- ism, discussed in the earlier paper,' is believed to account for the thermal hardening observed by Blank'" in NaCl, as stated elsewhere: and by results from recent experiments which tend to confirm this view. 2—The dislocations in the diffuse boundary may be locked by impurity atoms at 300 °C and thus only sharpen the boundary at 400 °C with the aid of thermal vacancies. In this case it would be difficult to distinguish between the two sources of hardening (sharpening or jogging), using metal of this purity. Jack Washburn (author's reply)—The author wishes to thank Dr. Pratt for his discussion. In connection with his first comment, it should be pointed out that the temperature of testing in the present series of experiments was —196°C, whereas, in the earlier experiments he referred to,' it was 20°C. Therefore, the yield values should not be directly compared. It is likely that the crystals used in the present work were initially more perfect macroscopically than the large shear specimens used previously. The small size of the test section in the kink specimens made it possible to select regions of the large crystals, from which they were acid-cut, that were free of observable small angle boundaries. The sharpening of a microscopically diffuse boundary such as that in Fig. 15 begins in zinc of this purity well below 300°C. However, it is probably not justified to conclude that because a boundary looks sharp under the microscope it has attained the ideal structure. The author agrees with Dr. Pratt that jogging of dislocation lines is one of the structural features of a small angle boundary that should be important in determining its strengthening effect. More detailed information concerning the changes in boundary structure as a

Jan 1, 1956

By Roger L. Beals, George A. Tweedy

I. INTRODUCTION. THE results of the cyanide-operations, given in detail in the following paper, show the progress that is being made at the Minas del Tajo. The old pan-amalgamation process, in operation up to and including 1905, while paying a profit on high-grade ores, was no longer able to treat profitably the ores in sight at that time, hence an alteration in the process was imperative. The success of this alteration is eloquently expressed by the following data Pan- Amalgamation. Cyanidation. 1905. 1907. 1903. Tons treated, . . 51,387 53,983 69,300 Value per ton (U. S. currency),. $10.75 $8.39 $8.28 Extraction, per cent., 65.00 88.50 S7.45 Extraction, per ton. .- $7.00 $7.4.; $7.24 Total cost, per ton treated, 6.50 4.311 4.01 Profit, per ton treated, . . 0.50 3.07 3.23.;

Feb 1, 1910

By T. D. Murphy, G. V. Henderson

The element silicon, with its usual partner, oxygen, plays the same role relative to inorganic materials as carbon and hydrogen play with respect to living organisms. The crystallographic structure of silicon dioxide (SiO2) consists of one atom of silicon well-nigh inseparably bonded to four contiguous atoms of oxygen, a gas of but slightly more than half its atomic weight, forming a three-dimensional network of SiO4 tetrahedra (Dietz, 1968). This wispy arrangement is the fabric of the mineral quartz which is one of the harder, more abrasive, and chemically stable raw materials to be found in Mother Nature's cupboard. Most of us are vaguely familiar with the observation that nearly 60% of the lithosphere to an approximate depth of 10 miles is composed of these two elements, which proportion actually rises to about 75% if the atmosphere, hydrosphere, and biosphere are included (Parker, 1967). Elemental silicon is a brittle steel-gray metalloid with a density of 2.42 and does not occur in nature. In its limited commercial form, which is still brittle and metallic in appearance, its density drops to 2.33. It combines with oxygen to form the gaseous oxide SiO, or the solid dioxide Si02 (analogous to its congener carbon in CO and CO2); a tetrachloride SiCI4 (analogous to CC14); or, combining with oxygen and one or more metal ions, forms the largest rock-making family of all, the silicates. Further, next to the feldspars, quartz is the most abundant known mineral and, in some form or another, accounts for roughly 12% of surficial terrestrial rock. It is this so-called "free silica" to which your attention is chiefly directed in this chapter. In any such consideration of silica, its several crystalline phases with their attendant differing physical properties appear worthy of delineation. Alpha quartz is the only one of this interesting polymorphic family that is thermodynamically stable at normal pressures and temperatures up to about 573°C. The low phases of tridymite and cristobalite can exist in the so-called metastable state below 117° to 200ºC but seldom occur in nature in these two different crystal forms (Sosman, 1965). Opaline silica, now considered by most researchers to be a variety of cristobalite, occurs in abundance and is the only exception. The three remaining polymorphs, keatite, coesite, and stishovite, also are metastable under ambient conditions. Keatite, however, is not known to occur naturally and has only been synthesized in the laboratory. The other two have been identified in submicron sizes and in microscopic amounts, occurring naturally as a result of high order shock-wave pressures generating quite elevated temperatures --such as might accompany the impact of a large meteorite on a hard sandstone terrain (Chao et al., 1962). An intriguing characteristic of these silica minerals, and one which has very practical applications, is their extremely variable densities. The classic 2.65 specific gravity of alpha quartz drops to 2.20 in tridymite, cristobalite, and lechatelierite (natural silica glass), as well as in many man-made glasses of commerce which are merely noncrystalline or amorphous solids in the form of super-cooled liquids which can no longer change their shapes (Pauling, 1950). It rises again to 2.50 and 2.93 for keatite and coesite, respectively, and finally becomes a reported 4.35 for stishovite-nearly a 50% range in density for the known physical combinations that silica naturally assumes (Frondel, 1962; Konnert et al., 1973; Pecora, 1960). Pursuing its esthetic aspects, briefly, silica is well-represented among gem stones which, to qualify as such, must have the attributes of beauty, durability, and rarity (Jahns, 1983). As quartzose gems usually have but one or, at

Jan 1, 1983