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By Klaus Schwerdtfeger

The rate of formation of silicon monoxide from silica spheres has been measured at 1500°C in H2, H2-H2O, H2-He, H2-Ar, and CO-CO2 gas mixtures. Indications are that in the hydrogen-containing gases the reaction rate is mainly determined by convective diffz~sion. In the CO-CO2 mixtures the rate approches a constant value which is independent of sphere diometer (and gas velocity). This suggests that a surface reaction becomes rate controlling in CO-CO2 gas. WHENEVER silica is exposed at elevated temperature to a strongly reducing atmosphere there occurs, inevitably, a volatilization of silica by the formation of gaseous silicon monoxide. Because of the importance of this reaction in metallurgical processes and laboratory experiments, its kinetics were studied in the present work. EXPERIMENTAL The spheres made of vitreous silica were suspended by a molybdenum wire in the hot zone of a gas-tight high-purity recrystallized alumina furnace tube of 3.1 cm internal diam and 100 cm length. Molybdenum wire resistance heating was used. A purified H2, H2-H2O, H2-He, H2-Ar, or CO-CO2 gas mixture was passed through the tube, from top to bottom. The amount of silicon monoxide formed was determined by weighing the silica balls before and after the experiments. The silica balls were made from commercially available translucent fused quartz glass. In experiments with hydrogen-containing gases the silica stayed vitreous during the experiment, whereas in experiments with CO-CO2 mixtures, which were performed over longer times, the balls were always crystallized to cristobalite (as determined by X-ray examination) at the surface. Constant-pressure head capillary flowmeters were used to control the composition of H2-He, H2-Ar, and CO-CO2 gas mixtures. The oxygen and water vapor were removed from the gases containing hydrogen by passage through columns containing platinized asbestos (450°C) and an-hydrone. The CO was purified from O2 and CO2 by passing it through activated copper (200°C) and through ascarite. The H2-H2O gas mixtures were prepared by passing purified Hz through a mixture of oxalic acid dihydrate and anhydrous oxalic acid held at a constant temperature in a water bath. The equilibrium water vapor pressures of oxalic acid dihydrate-anhydrous oxalic acid mixtures were taken from the available data.1 The furnace system was checked for sufficient gas tightness at regular intervals. As an additional check, the H2O and CO2 contents were measured in the exit gas and were found to agree closely with the metered contents when H2-H2O or CO-CO2 mixtures were used. When purified H2 was used, H2O pressures found in the exit gas were always below 0.1 mm Hg. These contents originate either from an incomplete reoxidation of silicon monoxide in the cold part of the furnace or from small leaks which cannot be avoided. If the latter is the case, such small uncontrolled H2O contents decrease the partial pressure of SiO in equilibrium with SiO2 by less than about 7 pct, which is considered small in comparison to other experimental uncertainties. The temperature of the furnace was controlled automatically in the usual manner. The reported temperature was measured with a Pl-Pt/l0pct Rh thermocouple and was accurate to ± 5°C. TRANSPORT-CONTROL LED RATE OF REDUCTION The gaseous convective diffusion from the surface of a sphere can be predicted from the semiempirical relationship obtained by Ranz and Marshall2 in a study of the evaporation of water and benzene drops in air. The following equation applies:

Jan 1, 1967

By H. Biloni, B. Chalmers

Metallographic studies of the segregation of solute in and near the surfaces of chill-cast alloys have shown that, under sufficiently severe conditions, nucleation on the cold mold surface is followed by the formation of a disc of solid of the same composition as the liquid. This disc is surrounded by two concentric rings in which the concentration first decreases and then increases. The discs and rings are surrounded by a region in which arms of low solute concentration separate regions of high concentration. These arms start at the periphery of the outer ring and are initially radial; they make a gradual curved transition from the radial direction to a crystallographic direction. A normal dendritic substrcture is established beyond the position at which the arms have become crystallographically aligned. When the cooling is less severe, the disc becomes less irregular in shape and has a concentration minimum at the center. The term "Predendritic" is proposed for these transitions. A qualitative explanation is outlined for the phenomena observed at the surface and in the equiaxed region of the ingots. It is well-established1-' that the normal mode of solidification for alloys under most conditions is dendritic. A characteristic of dendritic solidification is the growth of rods or plates in specific crys-tallographic directions. The remaining liquid solidifies later, usually with a higher concentration of solute than the original liquid. Very little is known, however, about the transition from a crystal nucleus until the dendritic pattern is established. It is clear that there must be a transition because the nucleus is much smaller than the characteristic spacings found in the "steady-state" structure. And it also seems clear that the initial conditions must be important since the undercooling existing during the nucleation of the grains has a remarkable influence upon the grain size4 and the segregation pattern. The present paper reports a study of the micro-segregation in regions where crystals have nucleated, and the conclusions that can be drawn regarding the early stages of growth, in connection with the details of the solidification process. Aluminum of 99.993 purity, A1-Cu alloys containing 0.5 to 20 wt pct Cu, and Pb-Sn alloys with 5 wt pct Sn were cast and examined metallographically at the as-cast surface, close to the surface, and in the interior after casting. The alloys were cast from controlled temperatures against surfaces at different temperatures ranging from room temperature to approximately the liquidus temperature of the alloy. The surfaces were, in various experiments, graphite, stainless steel, copper, and aluminum. The methods used for metallographic examination were as follows. 1) The Nomarski phase contrast interferometer6 was used to obtain information on the topography of the as-cast surface. 2) The distribution of any solute present in A1 99.993 pct and copper in the A1-Cu alloys was studied by the anodic film technique originated by Lacombe and Mouflard7 and previously applied in the study of the solidification of aluminum by Biloni.8 The electropolished surface of the specimen is anodized under controlled conditions so that the thickness of the oxide film and therefore the interference colors under white light are sensitive to the local composition. This technique was applied to the as-cast surfaces and to metallographically prepared surfaces from the interior. 3) If in Al-Cu alloys, the surface is anodically oxidized for several minutes, instead of seconds as in the color-film technique, the copper segregation is outlined by a different level with respect to the matrix. This method is less sensitive but complementary to that for the color films. 4) The distribution of copper revealed and mapped by the metallographic techniques was confirmed by electron probe. 5) In samples with high concentration of copper, evidence for the copper distribution could be seen optically after electropolishing.

Jan 1, 1965

By H. L. Tedrow

FACED with a scarcity of labor in its operations at Alma, Colo., the London Mines and Milling Co. has been employing women for several months in its sorting and crushing plant. The results so far obtained indicate that women can be used successfully and to good advantage on a number of various jobs around the surface plant of an ordinary mine. Eight women are now employed as sorters to pick waste out of the ore as it passes by them on a sorting belt. After a short period of breaking in they have become adept at their work and are doing better work than that formerly done by the class of labor obtainable. They are continually warned and instructed, particularly from the standpoint of safety and their physical strength.

Jan 1, 1942

By Albert Sauveur

IN an important paper on The Critical Ranges of Pure Iron1 presented at the May, 1913, meeting of the Iron and Steel Institute, Professor Carpenter reports and illustrates the results obtained by him in determining the critical points of some very pure electrolytic iron sheet about 0.01 in. thick. The iron strip was rolled into the form of a cylinder 1; in. long and fn in. wide, weighing 42 g., the thermo-couple being inserted in a small hole in the center. The points Ac3 and Ar3 were readily detected, as well as the point Art, but the point Act was absent from every heating curve. The author concluded from this occurrence that the conception of A2 as an independent allotropic change must be abandoned. At the October, 1913, meeting of the American Institute of Mining Engineers, Dr. G. K. Burgess and J. J. Crowe read a paper on The Critical Ranges A2 and A3 of Pure Iron2 in which they described some extremely important experiments conducted by them at the Bureau of Standards, Washington, D. C. They tested Professor Carpenter's electrolytic iron and detected a sharp and well-defined absorption of heat corresponding to the point Act. Professor Carpenter's failure to detect this point is explained by them on the ground that unless the iron be in a single piece entirely surrounding and in contact with the thermo-couple junction, the thermo-couple will integrate the irregular progress of the heat through the sample and the curves will lose their sharpness. In discussing Messrs. Burgess and Crowe's paper, Professor Carpenter accepted this explanation as probably accounting for the absence of Act in his heating curves.

Jan 2, 1914

By H. A. Wilhelm, P. Chiotti, G. A. Tracy

A summary of analytical, X-ray, thermal, and metallographic data obtained in the study of the Mg-U system is presented. No intermetallic compounds are formed by these two elements, and their mutual solubility is limited at temperatures up to 1255°C. The compositions of the liquids which coexist at 1135°C under a pressure of 3 atm are 0.14*0.05 wt pet U in magnesium, and 0.004 wt pet Mg in uranium. The solubility of uranium in magnesium decreases to 0.0510.03 wt pet at 675OC, and to about 0.0005 wt pet at 650°C. Due to the reactivity of both uranium and magnesium toward crucible materials, the choice of a suitable crucible presented a problem. Crucibles made from high purity magnesia to which 10 wt pet MgF2 was added to reduce porosity proved to be satisfactory. Some observations made with the use of other crucibles are given. THIS investigation was made to establish the phase diagram for the Mg-U system. Ahmann,' formerly of the Ames Laboratory, did some work on the system. He used several methods in an attempt to prepare Mg-U alloys. One of the methods involved the reduction of UF, with a large excess of magnesium. In these experiments, the magnesium wet the surface of the uranium, but there was no evidence for compound formation. The maximum solubility of magnesium in uranium was indicated to be 0.01 wt pet. In another set of experiments, uranium chips as well as uranium powder were heated in contact with molten magnesium in a graphite crucible for periods of time up to 48 hr. A reaction layer was found at the Mg-U interface in several instances. X-ray analysis of the layer material showed the presence of UC and some additional unidentified lines which were interpreted as indicating the possibility of an intermetallic compound of uranium and magnesium. These studies indicated the maximum content of magnesium in uranium to be 0.043 wt pet. One sample of magnesium which had been heated at 1025°C in contact with excess uranium was found by chemical analysis to contain 0.275 wt pet U. Rules, based on empirical or semi theoretical considerations, which attempt to predict the alloying behavior of metals have been presented in the literature. Although these rules are not infallible, they nevertheless serve as useful guides. Using them, several generalizations can be made concerning the Mg-U system. According to Hume-Rothery's' atomic

Jan 1, 1957

By E. G. Leonardon, C. Schlumberger, M. Schlumberger

The object of this paper is to describe the adaptation of electrical resistivity measurements to the particular case of exploration in which the surface is an expanse of water (river, lake, sea). Water in itself does not constitute an obstacle to electrical exploration. It is merely an overburden, which is fluid instead of being solid, and as a consequence the routine of the measurements has to be modified. Also, in many instances, the liquid under consideration is highly conductive (salt water). This introduces an additional difficulty into exploration work, and has to be overcome by the geophysicist. We do not propose to discuss here the basic principles of electrical resistivity measurements, which have been dealt with in various previous papers,' but will simply recall the two fundamental techniques which govern its field application: 1. Horizontal exploration, or method of the resistivity map, in which a series of electrical measurements are carried out at various stations, keeping the same electrode spacing. Thus, a horizontal layer of the subsoil, of a practically constant thickness, is explored. 2. Vertical exploration, or "vertical sounding"2 method, in which a seriesr of measurements is made with increasing electrode spacings at one or several stations. In this way, the apparent resistivity is determined at a given station for various increasing thicknesses of the ground.

Jan 1, 1934

By W. D. Keller

THE high-alumina clays of Missouri are interesting for several reasons. They are the only sedimentary deposits in North America of first grade (over 70 pct A1,0,) diaspore and boehmite sufficiently large to be mined commercially. Mineralogically, they are composed of diaspore and boehmite in intimate coexistence, but gibbsite, the common hydrated alumina mineral in bauxite and laterite, is absent, or is exceedingly scanty if present.* Therefore, the Missouri high-alumina clays do not represent typical laterization. The physical chemistry leading to their mineral genesis, and the geolbgical setting for their formation, present important problems for scientific study. The origin of the Missouri high-alumina clays has been discussed in earlier reports by Allen1 (1935) and McQueen 8, 9 (1929, 1943). These investigations were made under difficult conditions, however, because no diaspore deposit had been opened where a Paleozoic (Pennsylvanian) rock cover lay undisturbed over the high-alumina clay. The relationship of the clay to only the underlying rocks could actually be observed. Lacking the guidance of critical postdepositional geologic evidence, undue and erroneous emphasis was placed on the postdepositional leaching of the deposits in the theories on the origin of diaspore and boehmite from clay (hydrous aluminosilicates) . With new geologic evidence at hand, a clearer picture can be made for the origin of the Missouri high-alumina deposits. In this paper the geology of a diaspore deposit whose original Paleozoic cover had not been eroded will be described and interpreted genetically. The close relationship of boehmite and diaspore (also with kaolinite and a chloritic mineral), will be established. A theory of origin for the high-alumina clays, consistent with the new data, will be postulated.

Jan 1, 1952

By Paul I. Eimon, Byron R. Berger

INTRODUCTION Epithermal silver-gold deposits form at low to moderate temperatures in near-surface environments. These deposits are found in all rock types, but historically, the most important deposits occur as veins in volcanic rocks (e.g., Creede, Colorado; Pachuca, Mexico) and as replacements in sedimentary sequences (e.g., Mercur, Utah; Carlin, Nevada). Increases in the open-market prices for silver and gold in the last few years have resulted in renewed interest in precious metals and the economic viability of large-tonnage low-grade deposits. These bulk-mineable deposits form as replacements in permeable horizons or as stockworks in the up- per parts of otherwise bonanza-type hydrothermal systems and newly recognized systems that erupted onto the surface as hot springs, fumaroles, or geysers. Large tonnage low-grade de- posits were an unconventional resource prior to price increases; however, now they constitute one of the main sources of precious metals in the United States and the importance is growing worldwide. This paper presents conceptual geologic- geochemical models of epithermal precious-metal deposits derived from studies of productive deposits throughout the world. Much of the data presented is not new. However, the interpretation of the data in terms of current concepts of hydrothermal processes is new. This paper deals with idealized and general ore-forming mechanisms, and no attempt is made either to explain the origin of the different chemistries of ore- forming fluids or to examine all of the variations in specific deposits due to local structural controls and host-rock compositions.

Jan 1, 1983

By A. W. Ambrose

The underground losses of oil exceed by hundreds of thousands of barrels all the oil that has been lost in storage, transportation, or refining. The quantity lost is, of course, indeterminate; but when it is considered that the contents of an entire oil field have been excluded from recovery by invading waters, some idea of the amount wasted may be gained. Similarly, enormous quantities of gas have been lost underground. Conservation of the oil, therefore, should start before it is brought to the surface rather than after it is placed in storage tanks. Water is one of the most important causes for underground losses and the operator should give as serious consideration to an underground flood of water as he would to a destructive surface flood. The best insurance, of course, is to have the wells drilled in such a manner that water has no access to the productive oil and gas horizons, and on abandonment the wells should be properly plugged. The encroachment of edge water and the occurrence of waterin;the base of an oil sand present a very serious problem to an oil company sooner or later these waters are bound to cause considerable damage, if they do not entirely destroy the possibilities of further production. Too often, however, a field has been considered to be in a hopeless condition, whereas wells in as bad a condition in other areas have been repaired and the life of the field appreciably lengthened. The corrections are very often suggested by technical study. Very successful results have been accomplished by detailed underground work in the California oil fields, in Cushing, Oklahoma, and in other areas. The purpose of this paper is to outline briefly1 general methods of analyzing oil-field water problems in a producing or in a producing and developing oil field, with a view to suggesting repair work on offending wells. Reference is continually made to producing oil wells; the same general method of procedure, however, should be adopted in a gas field.

Jan 1, 1921

By C. H. Li, R. J. Stokes, S. H. Bendel, J. A. Sartell, T. L. Johnston

The mechanism of the oxidation of high-purity copper has been studied at temperatures from 500° to 981°C employing gravimetric, high-temperature microscopic and inert marker techniques. An investigation of the adhesion of copper oxides was also made. The oxidation of copper is found to be parabolic at all temperatures. It is concluded that the controlling mechanism is the outward diffusion of CU+ ions through the Cu2O layer, but the mechanism of diffusion is modified by the state of compressive stress in the oxide layer at the oxidation temperature. At temperatures below the transition from elastic to plastic behavior of Cu2O the growth stresses reach a value sufficiently high to cause CuO whiskers to be extruded. The extrusion of whiskers results in the injection of a large number of vacancies into the CuO. The Cu20 layer grows by the advance of the CuzO/CuO interface into vacancy-rich CuO. Since there is an adequate supply of non -thermally created vacancies, the activation energy for oxidation is that required to move the Cu+ ion through the appropriate saddle point to a neighboring vacancy, which has been determined to be 20,000 cal per mole. At temperatures at which the Cu20 can deform plastically the stresses are never high enough to cause whiskers to form. thus vacancies must be supplied by themal activation and as a result the activation energy increases to 40.000 cal per mole. ALTHOUGH extensive studies of the oxidation kinetics of pure copper have been made in the past. the mechanism has received relatively little attention. As a result, certain features of the kinetic data have not been satisfactorily explained' For example, several workers1,2 have reported that the activation energy for oxidation in the range from 500° to 700° C was about 20,000 cal per mole whereas that above

Jan 1, 1960

By John L. Boardman

The Anaconda company has never indulged in any employee activities at Butte which might be termed paternalistic, but it has exerted a vast amount of effort in care of its employees during working hours. The reason for this policy is not lack of interest or that the company does not feel the effect of employees' activities while they are "off the job"; it is that the company and the city of Butte have grown up together and each has been adequate in its own sphere, the company in providing employment at the highest possible wage and the city in providing housing, sanitation, commercial services, medical services, schools, churches, amusements and entertainments. The one exception to this independence between the company and the community is the Butte Water Co., which is a wholly owned subsidiary of the Anaconda Copper Mining Co. Mention of this relationship is made here because the water supply of such a city as Butte is one of the principal factors in determining the health of the people. Very early in the development of the Anaconda company an adequate and dependable water supply for the operations became necessary, therefore the company took over this important community function. So well has this activity worked out that during the whole period of time covered, in which the company has expanded to become practically the sole mine operator and the community has grown from a small mining camp to the status of a modern city, there has been no shortage of water or any outbreak of water-borne, epidemic disease. Conditions Leading to Organized Safety Effort A brief sketch of conditions in Butte prior to 1912 is necessary to an understanding of the reasons for placing accident prevention on an organized basis. As early as the year 1884 there were a large number of small independent mining operations depending principally upon the production of silver, although even then copper was becoming prominent in the value of total production for the district. The Butte camp was then just emerging from the log cabin stage to that of a modern city.

Jan 1, 1940

By John L. Boardman

The Anaconda company has never indulged in any employee activities at Butte which might be termed paternalistic, but it has exerted a vast amount of effort in care of its employees during working hours. The reason for this policy is not lack of interest or that the company does not feel the effect of employees' activities while they are "off the job"; it is that the company and the city of Butte have grown up together and each has been adequate in its own sphere, the company in providing employment at the highest possible wage and the city in providing housing, sanitation, commercial services, medical services, schools, churches, amusements and entertainments. The one exception to this independence between the company and the community is the Butte Water Co., which is a wholly owned subsidiary of the Anaconda Copper Mining Co. Mention of this relationship is made here because the water supply of such a city as Butte is one of the principal factors in determining the health of the people. Very early in the development of the Anaconda company an adequate and dependable water supply for the operations became necessary, therefore the company took over this important community function. So well has this activity worked out that during the whole period of time covered, in which the company has expanded to become practically the sole mine operator and the community has grown from a small mining camp to the status of a modern city, there has been no shortage of water or any outbreak of water-borne, epidemic disease. Conditions Leading to Organized Safety Effort A brief sketch of conditions in Butte prior to 1912 is necessary to an understanding of the reasons for placing accident prevention on an organized basis. As early as the year 1884 there were a large number of small independent mining operations depending principally upon the production of silver, although even then copper was becoming prominent in the value of total production for the district. The Butte camp was then just emerging from the log cabin stage to that of a modern city.

Jan 1, 1940

By W. E. Keck

THERE is a considerable tonnage of iron ore in the Menominee Range Michigan that is unsalable only because it has too large a content of sulphur. Beneficiation of such ore is economically desirable, as a rela-tively large quantity of finished concentrate would be obtained (deleteri-ous sulphur mineral content being generally less than 5 per cent) and because large blocks of such ore have been developed incidentally during search for low-sulphur ore. Research on the flotation beneficiation of these high-sulphur ores consisted of: (1) a study of the flotative properties of the principal min-erals in a nearly puree state, (2) flotation of synthetic mixtures of these pure minerals and (3) application of this experimental information to samples of the ores. Gypsum in iron ores is extremely deleterious; but when sufficiently free from impurities it is a valuable commodity. In 1934, the United States produced 1,500,000 tons of calcined and uncalcined gypsum valued at $13,700,000'. Of this quantity and value, Michigan produced approxi-mately 19 per cent4. Thus this investigation may also prove to be of interest in connection with the gypsum industry if minerals separation, such as flotation, becomes necessary in the future processing of gypsum. Data on the flotative properties of gypsum would also be of interest to the science of flotation because such information has been extremely limited. The technical literature reveals one reference to the flotation of gypsum, in which was discussed the use of the mineral, with several others, to determine the relation between the floatability of minerals and the pH of the flotation solution2. This investigation necessarily was not comprehensive in regard to gypsum, but it did show that the mineral could be floated with oleic acid under varying pH conditions.

Jan 1, 1937

By Nelson Severinghaus

AS far back as 40 years ago management made the initial steps toward utilizing the large amount of reject marble produced by the dimension stone quarries in sized products. In 1947 the Calcium Products Div. of the Georgia Marble Co. was organized to manufacture crushed, ground, and screened products from Georgia marble.* It became obvious early in operations that salability of any products of this type was determined by several factors: high calcium carbonate content, whiteness, dryness, and cleanness. Because no reject material could consistently meet these specifications, Calcium Products Div. now operates three underground quarries for raw material feed. In underground operations no stripping is required, surface contamination and trash are eliminated, weather causes no operational difficulties, and the raw material is maintained dry for plant processing.

Jan 12, 1957

By A. Muan

Liquidus data are presented for mixtures in the ternary system FeO-Fe2O3-SiO2 in equilibrium with a gas phase with O2 pressures ranging from 10-10.9 to 1 atm. Data obtained are combined with previously published data to construct lines of equal 02 pressures and lines of equal CO2/H2 mixing ratios along the liquidus surface. Courses of crystallization of selected mixtures under conditions of constant total composition, constant O2 pressures, and constant CO2/H2 mixing ratios are discussed. PHASE equilibrium studies of silicate systems where iron is one component are complicated by the fact that iron readily occurs in three different states of oxidation: Fe3+, Fe2+, and Fe0. Success or failure in work with iron silicate systems is to a large extent dependent on control of the oxidation state of iron and all investigations therefore must be carried out under carefully controlled atmospheric conditions. Silicate systems containing only strongly electropositive metals (like Na+, Ca2+, Mg", etc.) can, for simplicity, be treated as condensed systems, that is, the gas phase can be neglected and the phase relationships discussed in terms of the phase rule written in the well known simplified form P + F = C + 1. In the case of iron silicate systems, however, the composition of the condensed phases varies with the gas composition, and a complete picture of phase relationships can be obtained only by varying the gas composition over a wide range. In order to understand the phase relationships in the more complicated multicomponent silicate systems with iron oxide as one of the constituents, a knowledge of the ternary system FeO-Fe2O3-SiO2 is essential, since it constitutes a bounding portion of all such systems. It was with this in mind that the present study was undertaken. Previous Work A considerable amount of work has been done on various aspects of the chemistry and metallurgy of systems containing silica and iron oxides. The two bounding binary systems FeO-Fe2O3 and FeO-SiO2" The first attempt to obtain information on phase relationships of iron oxide-SiO, mixtures at different 0, pressures was made by Greig.' Darken" determined the melting points of iron oxide on solid silica under various atmospheric conditions. Darken did not determine experimentally the composition of the melts at liquidus temperatures but discussed very ably the principles involved in applying the phase rule to the system. In a recent study Schuhmann, Powell, and Michal8 determined experimentally the liquidus surface of a portion of the ternary system and combined the new information with data in the literature to construct a phase diagram. Their method was briefly as follows: Homogeneous mixtures with various contents of SiO2, FeO, and Fe2O3 were made up by melting together stock mixtures in various proportions. Samples of the homogeneous mixtures, the compositions of which were determined by chemical analysis, were then heated in platinum crucibles in an inert atmosphere until equilibrium among the condensed phases was achieved. The samples were quenched to room temperature and the phases present determined by microscopic examination. Assuming that no change in composition takes place during the equilibration run in inert atmosphere, the liquidus surface can be determined, but no information is obtained regarding the partial pressures of 0, of the gas phase in equilibrium with the condensed phases. The author's method, to be described in the next section, permitted the location of points at the liquidus surface as well as a calculation of the corresponding partial pressures of O2. Experimental Method General Procedure: The standard quenching technique was adapted for a study under controlled variable atmospheric conditions. Premelted mixtures of silica and iron oxides in platinum envelopes were held at constant temperature under chosen atmospheric conditions until equilibrium was reached among solid, liquid, and gas phases. The sample was then quenched to room temperature, the phases present identified, and, for the most significant runs, the composition was determined by chemical analysis. The corresponding partial pressure of 0, was calculated from known equilibrium constants of the gas reactions occuring in the furnace atmosphere. Materials: Starting materials were oxides of commercially highest available purity; cp silicic acid was dehydrated by heating to 1350°C for 6 hr and cp Fe2O3 was dried at 400° C for the same length of time. Samples of 10 g were made up by mixing

Jan 1, 1956

By Nelson Severinghaus

Consolidated Quarries Corp. must conduct operations for an average sales price of $1.25 per ton, about the same price at which stone was sold 25 years ago when the dollar was worth twice what it is now. To maintain success in a competitive business, the company must solve the usual production problems, which will be discussed here in the order they occur in the flowsheet. Most crushed stone quarries must first remove soil and decomposed rock. Although seasons of lower sales sometimes release regular quarry excavating and haulage equipment for this purpose, overburden is often too extensive for this method to be used. In such cases, special equipment must be assigned or the job may be contracted. As many earthmoving contractors have heavy duty specialized equipment well suited to overburden removal, they should be seriously considered before the job is undertaken. Pockets of clay beneath peaks of hard stone sometimes defy mechanized removal. Pick and shovel laborers at this point might be supplanted by more ingenious use of pumps and water or some other mechanical means. Where overburden is extremely heavy or difficult to remove, underground mining must be considered.

Mar 1, 1956

By J. H. Swisher

The solubility of graphite in CaO-S2O2-Al,O3 slags was measured by equilibrating slag samples with graphite crucibles and CO gas. Carbon contents as high as 2 ut pct were obtained in CaO-saturated, CaO-A1,O3 slags, and 1.3 wt pct in slags of the composition CaO.Si0,. Although the observed conditions for Sic formation were in agreement with those predicted from thermodynamic data, CaC, was found to form at a lower temperature than predicted frotn thermodynamic data. From measurements of the equilibrium carbon content as a function of CO Partial pressure, it was found that carbide ions dissolve in CaO-A12O3 melts with a valence of minus two. The carbon content increased with CaO concentration in Ca0-Al,O3 melts and increased with SiO, content along the CaO'AlO3-CaOSi0 join in the ternary system. When solid CaC2 was added to CaO-A12O3 and CaO-SiO2-A12O3 slags, it was found that one of the oxides in the slag was reduced by the carbide (Al2O3 in the forrner and SiOz in the latter). In electric furnace steelmaking, a double-slag practice is frequently used to meet alloy specifications. Initially a flush slag, which is oxidizing in nature, is used to remove phosphorus and carbon from the steel bath. Later in the refining period, the flush slag is replaced by a highly reducing carbidic slag. When calcium carbide is formed in or added to a finishing slag, the slag is effective as a desulfurizing agent and also permits alloying elements such as chromium, vanadium, and tungsten to be added to the slag in the form of oxides. The oxides are readily reduced by calcium carbide, thereby minimizing the use of expensive ferroalloys. More work has been done on the thermodynamics of silicon carbide in slags than on calcium carbide. Baird and alor' and Kay and alor' determined the free energy of formation of Sic by measuring the partial pressure of CO in equilibrium with solid silica, silicon carbide, and graphite. Using a similar technique, they determined SiOz activities in CaO-SiOz and Ca0-Si0,-A1203 slags. Rein and chipman3 also determined the free energy of formation of Sic using slag-metal equilibrium measurements. A literature survey has uncovered only one experimental study of the behavior of CaC, in slag systems. Shanahan and cooke4 report the results of some preliminary experiments on the solubility and stability of CaC, in a CaO-A1,03 and a Ca0-Si0-A1,03 slag at a temperature of about 1500". The carbon solubility as CaC, in a slag containing 50 pct CaO and 50 pct A1203 was reported to be 0.6 pct. They also review earlier work on the binary CaO-CaC, system. A eutectic exists in this system, but various investigators disagree on the eutectic temperature and composition. eal has given an explanation for carbide furnace erruptions in terms of the thermodynamic properties of CaC,; his analysis is not based on experimental data, but on compiled data for the free energies of formation of CaC, and CO.' , These data for steel-making temperatures are all extrapolated from the results of low-temperature measurements. In the experiments described in this paper, slag samples were equilibrated with graphite crucibles and with mixtures of CO and argon or with CO gas at 1 atm total pressure for measurement of the carbon solubility. Most of the work was done on Ca0-A1203 binary slags, although in some experiments CaO-SiO, and Ca0-Si0,-A1,03 slags were used. EXPERIMENTAL Slag samples of the desired composition for the solubility measurements were obtained by blending pre-fused master slags. The master slags were prepared by fusing mixtures of reagent-grade CaC03 with either A1,03 or Si0, in a graphite crucible. The master slags were crushed, then decarburized in air in a muffle furnace at 1200O C. A schematic diagram of the apparatus is shown in Fig. 1. The source of carbon for the solubility meas-

Jan 1, 1969

By Ernest R. Lilley

While American scientific literature contains much information upon geologic conditions controlling the production of oil in Rumania, copper in Chile, and other fuel and metallic resources in many foreign countries, it is singularly lacking in data about the nonmetallics outside of the United States. Thus, though the United States is the outstanding market for European high-quality refined kaolin, and for the chinaware, porcelain, and other products of the European ceramics industries, American literature contains only the briefest references to the deposits from which the raw kaolin utilized is obtained. To the writer, to whom has come in the past year the opportunity of visiting a number of these deposits personally, they have proved of extreme interest both commercially and geologically. It is the latter phase that is discussed in this paper. The older and now largely crystalline rock areas of France, Germany, and other parts of western Europe contain numerous pegmatite dikes of which the upper portions have been subjected to surface weathering and kaolinization in much the same way as those of the eastern portion of the United States. Like the latter, the European pegmatite kaolins have long been known for their freedom from iron and other impurities offensive to the china and porcelain manufacturer. Unfortunately, they are also, like the American deposits, individually of small size and noted for their high costs of production. Deposits of sedimentary clay similar in many respects to the high-quality sedimentary kaolins of Georgia and South Carolina are known and worked, notably in southern Germany and in the Newton Abbott district of Devon and Dorset in England. In general, their relationship to the parent rock from which they were derived is more evident than in the United States and the individual deposits are of smaller areal extent and less regular in outline. While these deposits are of considerable economic importance they did not, because of their similarity to deposits in America, attract and hold the interest of the writer to the extent that several other types of deposits did. It is to the latter, which are so different from the kaolin

Jan 1, 1932

By H. C. Schultz

CERTAIN local conditions were known to govern in large measure the successful adaptation of liquid-oxygen explosives to the large-scale blasting at Chuquicamata. The wide variation in hardness of the rock at this mine makes necessary the use of several types of explosives. A locally manufactured, relatively cheap black powder is used in blasting the softer waste and capping material, where a thorough displacement, breaks the ground sufficiently. Before the introduction of L. 0. X., an ammonia dynamite of about 65 per cent. strength was being used exclusively in the harder underlying orebody, where a strong disruptive as well as a displacement effect is required for breaking the ore. The L. 0. X., as developed for quarry work in the United States, has a practically pure carbon cartridge material, and the explosive has an extremely high rate of detonation, which should therefore cause it to usefully develop its full disruptive effect in hard ground. The individual blasts at Chuquicamata are large, black-powder shots which dislodge masses of rock averaging 250,000 tons each, and dynamite shots which dislodge masses averaging 80,000 tons each. It was desirable, therefore, to attempt to displace with L. 0. X. the faster, higher-cost ammonia dynamite used in the smaller blasts. It was not considered practical to attempt to displace the low-cost black powder with L. 0. X., as estimated costs showed no probable saving if this were accomplished. Since it was desirable to continue shooting relatively large blasts for effective operation, it was recognized that larger storage facilities than had been in use would be needed for the liquid oxygen. Because of the difficulty of transporting and discharging large storage containers of efficient design, the better plan appeared to be storage and discharge of the liquid at the place of manufacture, and transportation of the filled soaking boxes to the blast.

Jan 1, 1928

By W. A. Backofen, G. Y. Chin, W. F. Hosford

The effect of machine stiffness on discontinuous flow and fracture of the 2024 aluminum alloy was studied in tension at 4.2OK. An increase of machine stiffness was found to decrease the amount of elongation and drop in load during discontinuous flow, thereby postponing fracture to larger strains and higher stresses. The possibility of utilizing stiffened tools in deformation processing to suppress shear fracture originating from unstable flow was indicated. The problem of nucleating discontinuous flow and the role of the effective mass of the system in discontinuous flow were also considered. AT low temperatures the plastic flow of metals is often discontinuous, with sudden load drops and elongations.1,3 Basinski1,4 has presented strong evidence that discontinuous flow, at least in aluminum alloys, occurs under nearly adiabatic conditions. During testing the load may drop suddenly and flow become localized when the thermal softening, due to heat generated in plastic straining, is greater than the strain and strain-rate hardening. This instability criterion is more easily satisfied at low temperatures because 1) the volume specific heat is reduced so that relatively large temperature increases are possible in straining, and 2) the flow stress is relatively temperature-dependent. The important role of adiabatic shear in ductile fracture processes has been emphasized,5-1 and consideration has already been given to the influences of thermal and mechanical properties on the tendency of a material to undergo adiabatic shear.17677 By focusing attention on how the mechanical loading system influences low-temperature discontinuous flow, additional insight into adiabatic shear and its effect on fracture may be gained. EXPERIMENTAL PROCEDURE Because of its low thermal conductivity, the 2024 aluminum alloy exhibits a highly consistent discon- tinuous-flow behavior at 4.2°K and was therefore chosen as the material for study. Machined specimens of 0.113 in. diam and 1.125 in. gage length were solution heat-treated at 490°C for 3 hr, quenched into cold water, and immediately immersed in liquid nitrogen until just before testing. Testing was done at 4.2°K by immersion in liquid helium at a crosshead drive rate of 0.03 in. per min. As normally used (hard-machine basis), the spring constant of the testing machine was k = 25,000 lb per in. By inserting beam springs in series with the specimen, this value could be lowered by a factor of about 100. Details can be found elsewhere.? As a result of variable machine stiffness, the actual strain rate ranged from about 3 x 10 5 to 3 x 10-4 per sec from one test to another, as well as within any one test. However, preliminary tests had established that the tensile curves were not altered significantly by this strain-rate variation. Fig. 1 shows a typical load vs plastic-elongation curve for a solution heat-treated 2024 aluminum alloy specimen pulled in the standard hard machine (k = 25,000 lb per in.) at 4.2"K. The elastic extension has been subtracted. Plastic flow proceeded smoothly from yielding at approximately 22,000 psi (load = 220 lb) to a strain of about 4 pct at which point the flow became discontinuous. The magnitude of the load drops as well as the plastic elongation per drop increased with increasing strain until the specimen finally broke abruptly. The load-elongation behavior of a sample tested with a relatively soft machine under otherwise identical conditions is given in Fig. 2. In general, there

Jan 1, 1964