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By Klaus Schwerdtfeger

In order to test the performance of ZrO, (CaO) and Tho,(Yz03) electrolytes in the electrochemical determination of oxygen activities in liquid metals at steel-rrzakitng temperatures , electromotive force measurements have been made with the following cells: The oxygen-- activities are calculated from the electmrnotive forces for the investigated systems. The standard free energy of- formation of MnO and the activity of manganese in Fe-Mn melts are derived. Indications are that the Zr 0z(Ca0) electrolyte exhibits little electronic conductivity at oxygen pressures as low as 10'a atnz at 1600°C; however, the partial electronic conductivity may become noticeable at lower oxygen activities. The Tho,(Yz03) electrolyte is found to be an ionic conductor at the oxygen pressure as low as that for the Mn + MnO equilibrium, but exhibits partial electronic conductivity at oxygen pressures higher than 10"1 atm (1500°C). fi. better control of oxidation and deoxidation reactions in steelmaking may be facilitated if the oxygen activity in the steel is known during various stages of the process. In the present work oxygen activities have been measured in liquid iron, manganese, and iron alloys with galvanic cells using ZrOz(CaO) and s solid electrolytes with the object of establishing the range of oxygen pressure in which these materials can be used as electrolytes at steelmaking temperatures. Calcia-stabilized zirconia and Tho2-Y203 solid solutions are oxygen ion conductors. Such electrolytes were first used by Kiukkola and Wagner1 and Peters and ~ann' in galvanic cells for the determination of thermodynamicquantities of oxide systems in the temperature range 700" to 1200°C. At these moderate temperatures calcia-stabilized zirconia has been found to exhibit predominantly ionic conductivity at oxygen pressures as low as those for the Cr + Crz03 equilibrium,394 but at lower oxygen pressures elec- tronic contribution to conductivity becomes significants4 The Th02-Y203 solid solutions are ionic conductors at oxygen pressures lower than those applicable to zirconia base electrolytes.5'6 At high oxygen pressures Thoz base electrolytes exhibit significant p-type semiconduction. At the time the present experiments were carried out several papers1'-* were published on the electrochemical determination of oxygen activities in liquid iron using the ZrOz(CaO) electrolyte. The results of different authors do not agree well. For instance, according to Fischer and ~ckermann" stabilized zirconia can be used to measure oxygen contents in liquid iron larger than 0.02 wt pct, but according to Baker and west1' ZrOz(CaO) cannot be used for the determination of oxygen content in liquid iron because of high electronic contribution to the conductivity. Fig. 1 is a schematic diagram of the apparatus used. About 500 g of liquid metal is contained in a crucible into which a stabilized zirconia or Th02(Y203) tube is immersed. A platinum contact wire is pressed (with a spring mechanism) against the inside bottom wall of the electrolyte tube. The tube is flushed continuously with a stream of air, CO-CO, (or Hz-C02) (at 0.96 atm and at a rate of about 300 cu cm per min), via an alumina tube inserted inside the electrolyte tube. This alumina tube also contains the Pt-Pt/10 pct Rh thermocouple. A capillary alumina tube shielding the other contact wire is immersed in the melt. The molybdenum contact wires were used mostly; in some cases platinum wire was employed. Molybdenum has the advantage that it dissolves more slowly in the melt than platinum. The whole cell was contained in the alumina reaction tube of a resistance furnace with molybdenum winding. The reaction tube was closed gas tight at both ends and flushed continuously with argon. Because of the poor thermal shock resistance of the electrolyte tubes the cell had to be assembled in the cold furnace. The electrolyte tube and alumina sheath

Jan 1, 1968

By E. S. Machlin, Morris Cohen

The isothermal formation of martensite in a 71 pct Fe, 29 pct Ni alloy is found to take place mainly by the nucleation of new plates rather than by the growth of existing ones, and is dependent on the temperature and time of the isothermal hold, the amount of atherrnal martensite present, the state of internal strain, and the application of tensile stress. The conclusion is reached that the isothermal nucleation is activated by thermal fluctuations superimposed on localized regions of very high strain. The reaction-path concept, involving martensite nucleation at strain embryos by athermal activation on cooling, or by thermal fluctuations on holding, reconciles the athermal and isothermal modes of transformation, and offers a unified picture of the kinetics of martensite formation. THE phenomenon of isothermal martensite formation has been the subject of considerable study lately,'-' and its reality has been thoroughly established. The existence of such isothermal transformation has been claimed to confirm the nucleation and growth hypothesis as applied to the martensitic reaction.1 " However, the isothermal formation of a martensitic phase is also compatible with the reaction-pathw escription of the transformation. The purpose of this investigation is to examine the isothermal mode of the martensitic reaction, both theoretically and experimentally, in order to test the likelihood of the above two mechanisms. Material and Methods The alloy used in this study contained about 71 pct Fe and 29 pct Ni. The complete analysis was 29.5 ± 0.2 pct Ni, 0.036 pct C, 0.02 pct N, 0.19 pct Mn, 0.09 pct Si, 0.008 pct P, and 0.006 pct S. The amount of isothermal transformation was determined by electrical resistance measurements using a Kelvin double bridge. The specimens were in the form of rods 1/16 in. diam x 4 in. long. Aus-tenitizing was performed at 1095°C for % hr either in a pre-purified nitrogen atmosphere or in an evacuated Vycor tube, followed by oil quenching to room temperature. After this treatment, the samples were completely austenitic, and the transformation studies were conducted at subatmospheric tempera- tures. Lineal analysis and X-ray determinations of retained austenite were used to calibrate the electrical resistance changes in terms of the percentage of martensite. The martensite range curve for this alloy is given in Fig. 9 of ref. 6. The M, temperature occurs at about -18°C (255°K). Reaction-Path Theory The nucleation and growth description of the martensitic transformation that occurs isothermally has already been given by Kurdjumow.','2 However, no comparable treatment exists using the reaction-path concept." Consequently this section presents the reaction-path description of the isothermal mode of the martensitic transformation. According to the latter theory, there is a reaction path (a strain) which describes the relative motion of the atoms during their transference from the austenitic to the martensitic state. The possibility exists, therefore, that the nucleation of a martensitic plate is accomplished by an embryo that comprises a state intermediate between that of austenite and martensite. This state may be attained within a finite volume by means of a homogeneous strain of the austenitic matrix. There is a free-energy barrier (F.) along the reaction path, corresponding to a critical strain in a critical volume. When activation is achieved, a spontaneous increase in strain and volume of the embryo takes place to generate the full-size martensitic plate. This mode of nucleation is to be distinguished from the more conventional mode involving embryos of the martensitic phase that merely grow in size by an interface motion. There are two ways whereby embryos in the austenitic phase can achieve the critical state of strain for isothermal nucleation: 1—through the formation of internal strains by plastic deformation or by stress; and 2—through thermal fluctuations, preferably superimposed upon existing internal strains. The activation free energy F,, must be supplied either mechanically by internal strains or thermally by energy fluctuations, or by a combination of both.

Jan 1, 1953

By W. B. Stephenson

In the pumping of sands, slurries and slimes, practices developed over the years are the real keystones of 'successful operation. These practices are necessarily based on modifications of familiar theories. Practical methods used in the solution of problems involving the pumping of materials are set forth in the following discussion. Basic Requirements To pump sands and slurries economically, a few basic requirements must be met by the pumping system as a whole. A pipe-line velocity must be established that will move the fluid mixture throughout the entire system without any possibility of the solids settling out. To accomplish this, the velocity of flow must be slightly in excess of the critical velocity of the mixture. The critical velocity of a mixture varies from 3 ft. per sec. to 18 ft. per sec., depending on the screen analysis, concentration, and specific gravity of the solids in the mixture. Most tailings are pumped at a minimum velocity of 4 ft. per sec. if they include slimes, whereas the pipe lines of sand and gravel dredges require velocities as high as 18 ft. per second. A number of articles have been written on the determination of the minimum velocities required to maintain solids in suspension. Studies have also been made on the friction and pumping heads developed when handling solids in suspension.1-4 Our experience so far has shown that, within the normal operating limits of a pumping system, the friction factor follows more nearly the basis described by Howard,' who says, among his conclusions: "... values of f (friction factor) . . . will decrease with an increase in velocity." This conclusion is borne out by our actual experience. When the velocity in a pipe line is not sufficient to keep the solids in suspension, the total friction head' is greater than when the velocity is increased to a point where the solids are in suspension. A slight increase in the volume of feed to the pump and a slight increase in the pump speed are usually all that is necessary to put the system in balance. Maintaining Constant Volume Within reasonable limits, the volume of mixture to be handled through a pipe line should be held constant, so that the required velocity will be provided at all times. There are several ways in which this can be accomplished. The commonest is to provide a sump of sufficient capacity to take care of slight surges in the volume of mixture being fed to the pumping systen]. This sump, however, should not be as large as a settling chamber. The use of a float-controlled, fresh-water make-up valve in a sump will guarantee a constant volume. Where variations in volume are slight,

Jan 1, 1947

By W. B. Stephenson

In the pumping of sands, slurries and slimes, practices developed over the years are the real keystones of 'successful operation. These practices are necessarily based on modifications of familiar theories. Practical methods used in the solution of problems involving the pumping of materials are set forth in the following discussion. Basic Requirements To pump sands and slurries economically, a few basic requirements must be met by the pumping system as a whole. A pipe-line velocity must be established that will move the fluid mixture throughout the entire system without any possibility of the solids settling out. To accomplish this, the velocity of flow must be slightly in excess of the critical velocity of the mixture. The critical velocity of a mixture varies from 3 ft. per sec. to 18 ft. per sec., depending on the screen analysis, concentration, and specific gravity of the solids in the mixture. Most tailings are pumped at a minimum velocity of 4 ft. per sec. if they include slimes, whereas the pipe lines of sand and gravel dredges require velocities as high as 18 ft. per second. A number of articles have been written on the determination of the minimum velocities required to maintain solids in suspension. Studies have also been made on the friction and pumping heads developed when handling solids in suspension.1-4 Our experience so far has shown that, within the normal operating limits of a pumping system, the friction factor follows more nearly the basis described by Howard,' who says, among his conclusions: "... values of f (friction factor) . . . will decrease with an increase in velocity." This conclusion is borne out by our actual experience. When the velocity in a pipe line is not sufficient to keep the solids in suspension, the total friction head' is greater than when the velocity is increased to a point where the solids are in suspension. A slight increase in the volume of feed to the pump and a slight increase in the pump speed are usually all that is necessary to put the system in balance. Maintaining Constant Volume Within reasonable limits, the volume of mixture to be handled through a pipe line should be held constant, so that the required velocity will be provided at all times. There are several ways in which this can be accomplished. The commonest is to provide a sump of sufficient capacity to take care of slight surges in the volume of mixture being fed to the pumping systen]. This sump, however, should not be as large as a settling chamber. The use of a float-controlled, fresh-water make-up valve in a sump will guarantee a constant volume. Where variations in volume are slight,

Jan 1, 1947

By G. W. Brownell, H. T. F. Lundberg, R. W. Pringle, K. I. Roulston

The rapid improvement of the airborne scintillometer and the perfection of its efficiency for counting low energy gamma radiation has made it possible to work out a technique to map in great detail the radiation pattern at the earth's surface. On such maps low radiation over certain areas appears to indicate the existence of oil accumulations, forming a pattern similar to that obtained by the geochemists.

Jan 12, 1953

By Verne D. Johnston

ALTHOUGH the stocks of Lake Superior iron ore on dock or at furnaces at the beginning of the year were about 6,000,000 tons less than at the beginning of 1938, the steel industry was operating at only 52 1/2 per cent of capacity and continued at approximately this rate to about Aug. 1. Consequently the iron mines in the Lake Superior district during the winter and spring period were almost all on a curtailed production basis, governed mostly by the needs of the communities rather than by anticipation of ore demands. Many of these properties gave extra employment by prosecuting heavy strip- ping programs, and the underground mines by shaft sinking and rock development. All underground mines re- turned to full operation in September, mostly two-shift, five days per week. A few operated the sixth day. The ship- ping schedules were increased so that the actual delivery for the year exceeded early expectations by about 20 per cent. Final Lake shipments were slightly in excess of 45,000,000 gross tons.

Jan 1, 1940

By W. A. Knoll

THE sinking of a new shaft at the Newport mine, Ironwood, Mich., was started in May 1931 and completed on Aug. 3, 1932. During this period, 2665 ft. of shaft in granite was completed, at, an average advance of 6 ft. per 24 hr. In November of 1930, experimental work was con-ducted oil 65 ft. of shaft through 22 ft. of overburden where ledge was encountered, and this work convinced the operators that all drilling could be clone with vertical holes with the blasting relief to a 4 ½ -in. hole drilled vertically in the center of the cut. The reason for not adopting the conventional V-cut was to get away from damaging the shaft steel. The blasting in a V-cut naturally tends to throw the broken material upward, but with the cut as adopted the relief was in a horizontal direction to a large extent. The scheme of mucking employed made it necessary to keep the steel shaft sets within 511 ft. of the bottom at all times. This could not be clone without serious damage with a V-cut when blasting in granite. The cut as drilled also broke 10.53 ft. per round of drilling, which was considerably more than the experience with a V-cut in the sane material. The extended cut reduced proportionately the delays for charging, blowing smoke and handling drilling equipment in the shaft. Another advantage was the ease in drilling vertical over inclined holes, and the preservation of the proper spacing of the drill holes at the bottom of the cut.

Jan 1, 1938

By F. G. Jaicks

RECOGNITION of the benefits to be gained from the continuous casting of molten steel into finished or semifinished products has been given by scientific minds since the very beginnings of steel plant technology. In fact, Sir Henry Bessemer is credited with the first of a long list of patents' issued by the U. S. Patent Office for a process which would accomplish this desirable end. None of these early ideas attained practical success and, as a result, the conventional method of teeming into ingot molds became an integral part of modern steelmaking operations. This procedure, although refined to keep pace with the changes which have come about in steelmaking and finishing facilities, is recognized to have inherent shortcomings which adversely affect manufacturing costs and steel quality. Interest in the continuous casting of steel persists because the process is directed toward avoiding some obvious weaknesses of conventional ingot casting. It has been recognized that should it be possible to substitute any of the continuous casting techniques under current development for ingot casting, it would no longer be necessary to make large capital investments in primary rolling equipment, the sole purpose of which is to reduce ingot castings to a form rollable on finishing mills. The results reported in the continuous casting of non-ferrous metals and specialty steels indicate that in addition to avoiding the primary rolling mills there is some basis for expecting significant improvements in yield, surface, and internal quality. Recognizing the shortcomings of the conventional procedures, the Inland Steel Co., in cooperation with Atlas Steels Ltd. and the Freyn Dept. of the Kop- pers Co. Inc., embarked upon a program to evaluate certain aspects of continuous casting in order to determine whether the process could be applied practically to an existing integrated steel plant producing 'large tonnages of carbon steels. TO assist in this evaluation a study was carried out in which several types of low carbon steel were continuously cast in an existing machine. It is the purpose of this paper to review some of the results obtained in the casting studies and to interpret the information that was obtained so as to indicate factors that must be considered in assessing operating limitations and plant capacities. Despite the early interest in the continuous casting of steel, the actual application to the steel industry is relatively recent. At present, there are about 25 operating plants casting steel, most of which have been built in the past decade. None of these plants could be classified as large in terms of the tonnages that are being processed by the major integrated steel plants. In contrast to the situation in the steel industry, there has been widespread adoption of the continuous process in the casting of nonferrous alloys, particularly aluminum and copper. As a result, much of the basic information that was required to apply the process to steel was developed in the nonferrous industries. In this respect, a most important contribution was the development of the Junghans2 system, which was initially designed for the casting of nonferrous metals and later applied to the casting of steel. Alternative methods for casting have also been proposed by Babcock and Wilcox Tube Co.,'" the British Iron and Steel Research Association,5 and the Gebruder Bohler A. G.13 Each of these methods is now being used successfully for the casting of special steels in small experimental plants or in modest sized commercial steelworks. The Original Junghans process was first developcd in Germany. Further application of the process has been made by Rossi in other countries.'*' The experi-

Jan 1, 1958

By Kenneth E. Skiff

INTRODUCTION United Nuclear Corporation and Homestake Mining Company are partners in a major uranium mining and milling venture near Grants, New Mexico. The partnership was formerly called Homestake-Sapin Partners and was recently renamed United Nuclear-Homestake Partners (UN-HP). The mill, originally built in 1958, had a capacity of 1,650 tons per day. With subsequent improvements and the addition of the adjacent Homestake - New Mexico Partners mill, the UN-HP mill is currently rated at about 3,500 tons per day. An alkaline type leach process is utilized by the mill. Milling consists of five basic steps: A. Ore handling and preparation B. Extraction C. Solid-liquid separation D. Precipitation and purification E. Product preparation MILLING Ore Handling and Preparation The primary source of ore for the UN-HP mill is from its four

Jan 1, 1983

By H. H. Kaveler, Z. Z. Hunter

Variation of the horizontal permeability (parallel to the bedding plane) in the vertical section of reservoir rocks has long been observed as a characteristic of a normally heterogeneous system which reservoir rock represent. The use of a recently developed water injection profile device offered opportunity to measure with a high degree of reliability the rate of inflow of water into Burbank sandstone in wells previously cored. Water injection profiles were not correlative with core permeability profiles in such wells. Apparently the vertical permeability substantially influences the flow between strata in a formation in a manner as to void the usual conclusions that have been drawn from consideration of the horizontal permeability measurements alone. The results obtained in comparing water injection profiles with horizontal permeability profiles suggest that many of the usual production operations based upon "selective" behavior or treatment of rock exposed in well bores need to he re-valuated and re-examined. INTRODUCTION Petroleum reservoir rock are heterogeneous systems. Heterogeneity exists in respect to lithologic character insofar as such rock are composed of distinguishable solid phases. Heterogeneity also exists in respect to certain properties, such as porosity and permeability, that vary due to variation of the physi-cal structure of the rock. Except in exceptional cases, both the horizontal permeability (measured parallel to the bedding planes) and the vertical permeability (measured perpendirularly to the bedding planes) exhibit significant variation in any common source of supply. The variation in horizontal permeability. as reflected by con. analyses. has drawn the greatest attention of petroleum technologists probably out of the general notion that the mass movement of fluids in a reservoir is predimonantly in the horizontal direction. Furthermore, in the usual case, the rock permeability measured in the horizontal direction is greater than that in the vertical. The variation of horizontal permeability of reservoir rock has been the basis for developing a number of operating practices and procedures intended to improve the petroleum production operation. Many such procedures are referred to as "selective" in the sense that the practice is intended to control the flow to a more. or less. permeable interval within the common source of Supply. It is often said that such practices are "tailored" to the permeability profile. The practices referred to involve, among others, the following: selective perforation of casing; selective shooting, acidizing and plugging: plugging back to intervals of low permeability; and, regulation of flow to prevent coning of water or gas, or irregular encroachment of water or gas. Certain expressed notions involving a concept of "by-passing," or "trappingl" that are held to be particularly harmful in causing the avoidable loss of recoverable petroleum have grown from observed variations in the horizontal permeability. Oftentimes estimates of the reserve of a common source of supply are tempered by conclusions relating variation in horizontal permeability to recover-ability of the oil-in-place. Certain conclusions attributed to the significance of the variation of the horizontal Permeabilitv often extend to the design and operation of pressure-maintenance projects involving both water flooding and gas-injection. Many advocate increasing the number of injection wells, advocate maintaining uniform and equidistant input-output well patterns, or advocate so-called "dispersed" gas-drive techniques rather than gas-cap injection because the permeability profile of cored wells is supposed to indicate that "by-passing" or "trapping" would otherwise exist. It is important, therefore, to have an opportunity to test whether the variation in the horizontal permeability found through core analyses of a typical reservoir rock is sufficient to establish the paths of fluid flow in a reservoir. It is particularly important to have an opportunity to determine whether flow at the sand face of a well conforms to the permeability profile as established by core analyses. In that manner, the merit of certain 50-called "selective" operating procedures and other notions may be evaluated. The purpose of this paper is to compare horizontal permeability profiles of wells in the Bartlesville (Bur-bank) sandstone with water injection profiles, for the purpose of showing that there is no correlation between the horizontal permeability of a core and the water intake characteristics of a typical sandstone. GENERAL CHARACTERISTICS OF BARTLESVILLE (BURBANK) SANDSTONE The Bartlesville sandstones of Northeastern Oklahoma are off-shore bar deposits.' Although other reservoirs had different processes associated with their deposition or with the formation of their porous, permeable structure, the l!artlesville sandstones on which these field Fields were made are, in every respect. typical petroleum reservoir rock. The permeability of the Bartlesville sandstones shows a typical variation in both the horizontal and vertical direction. Furthermore, the permeability profile logs of wells in any pool are not correlative, even as between wells as close as 660 ft and 330 ft apart.'. The same condition exists in such sand-tones as the Jones Sand at Shuler' and is the ordinary and usual characteristic of reservoir rock. THE FIELD DATA The data reported herein are those obtained from coring of nine wells on the center of ten-acre locations for the purpose of providing water-injection wells in the Bartlesville (Burbank)

Jan 1, 1952

By B. M. Larsen, T. E. Brower

IN two previous papersl,2 dealing with the carbon-oxygen reaction, and the simultaneous content of each, in liquid steel in the furnace, we have made use of the quantity 0[O], defined as the excess oxygen beyond what would be in equilibrium with carbon then present if the pressure of carbon monoxide were I atm,; that is, if [C] X [O] is taken as 0.00222, 0[O] = [O] - 0,00222/[C] where [O] is the percentage of oxygen by weight as measured by the method described earlier.' This quantity 0[O] proves to be substantially independent of carbon content over the range 0.08 to 1.2 per cent, as well as of the basicity of the slag, and is nearly always within the limits 0.015 to 0.025 per cent when the bath is boiling normally and is in what we have termed a steady state. Apparently it must be at least about 0.014 per cent before boiling occurs; but this threshold value seems to depend upon the ease of bubble formation at the metal-hearth interface, hence upon the condition of the surface of the hearth. In any case, 0[O], on the average, changes considerably following any disturbance of the bath, as by addition of ore. The present paper deals with the average changes in ?[O] level following addition of Spiegel or crop ends, or after procedures to promote stirring, or by tapping of the steel from the furnace. The observations were made on a large number of commercial heats, and consequently are subject to the influence of various disturbing factors; the results have the compensating merit of showing the consistency obtainable under the limitations imposed by practical operation. VARIABILITY OF EXCESS OXYGEN IN NORMAL OPEN-HEARTH OPERATION The preceding general statements refer to the average value of ?[O] particularly in heats that are boiling actively; on individual heats, which are less active, there may be a variable time lag between the disturbance and its effect, which complicates the interpretation of what is going on. For instance, if in the normal refining process boiling is sluggish, the slag usually is gaining oxygen from the gas phase above it, or from added ore, faster than it is losing oxygen to the metal; yet when the bath starts to boil vigorously, the opposite condition may prevail for some time. The consequence of this lag is a variation of ?[O], the interpretation of which in a single heat may not be immediately obvious, This condition is illustrated in Figs. I and 2. In Fig, I, ?[O] at the beginning of the test period was near the lower limit of its usual range (dashed lines) in the steady state as a consequence of the lime boil, which had ended about as indicated. The bath is now cold, carbon drop is slow, and the first small ore feed causes only a small rise in 0[O]; as the temperature rises and as lime dissolves in the slag, and the bath becomes more active, the

Jan 1, 1946

By Dale A. Vaughan, Oliver M. Stewart, Charles M. Schwartz

Solid-solubility limits at 1500°, l000q and 500°C for carbon, nitrogen, and oxygen in high-purity tantalum were determined by X-ray lattice-parameter methods. For carbon, the solubility was found to be 0.17 at. pct at 1500°C, and less than 0.07 at. pct at 1000°C. A nitrogen solubility of 3.70 at. pct at 1500° C decreases linearly with temperature to 2.75 at. pct at 1000°C, and 1.8 at. pct at 500°C. In the case of oxygen, the solubility was found to be 3.65 at. pct at 1500°C, 2.95 at. pct at 1000°C, and 2.5 at. pct at 500°C. The phases Ta2C, the low-temperature modification of Ta205, and Ta,N of unknown composition but which has a superlattice structure based upon the original bcc tantalum lattice have been identified as the initial precipitates in the respective systems. Metallographic methods were employed to verify the X-ray analyses. The etching behavior of Ta is discussed in terms of lattice i?rzperfections and precipitate phases. The excellent fabricability, high melting point, and nuclear properties of tantalum are responsible for interest in this refractory metal. Data on the solid solubility of the interstitial elements (oxygen, nitrogen, and carbon) in tantalum and on the precipitate phases are somewhat limited. The significant contributions are discussed below. Because the purity of electron-beam melted tantalum (only recently available) is considerably higher than that used in previous studies, the present investigation was initiated. Gebhardt et all-3 have investigated the tantalum-oxygen and tantalum-nitrogen systems with particular reference to the changes in physical properties and to the rates of reaction between these gases and the metal. The solubility of oxygen in tantalum was reported2 to be 3.7 at. pet at 1500°, 2.3 at. pet at 100O°C, and 1.4 at. pct at 750°C. Schonberg4 reported that several oxide phases (Ta40, Ta,O, TaO and Ta,05) exist while X-ray studies by Gebhardtl showed only two oxides, Ta,05 and an unidentified phase which was associated with a platelet-type precipitate. La-gergren and Magneli,' however, questioned the existence of compounds other than the two allotropic modifications of Ta,05 for the tantalum-oxygen system. In the case of nitrogen, the solubility was estab- lished by Gebhardt3 to be of the order of 7 at. pct at 1800°c. The solubility was reported to decrease rapidly with temperature, and, although no limits were established, a precipitate phase was observed by Gebhardt except when the high-nitrogen specimens were cooled very rapidly from the reaction temperature of 1800c. He reported the initial precipitate phase to be a tetragonal distortion of the bcc tantalum lattice while Schonberg6 reported the phase lowest in nitrogen Jo be a cubic super-lattice with a cell size of 10.11 A. Two other nitride phases, Ta,N and TaN, were reported; these appear to be isomor-phous with the carbides of tantalum. The tantalum-carbon system was investigated by Ellinger7 and by Lesser and Braurer. Two compounds, Ta,C and TaC, were reported to exist, each with a range of composition. The solubility of carbon in tantalum was found to be practically nil at all temperatures. Thus, of the interstitial elements which are present in small amounts in high-purity tantalum, carbon might be expected to form precipitates. The present investigation was initiated to obtain additional data on the solid-solubility limits of these interstitials at 1500°, 1000°, and 500' with particular emphasis on the distribution and the identification of the precipitate phases. EXPERIMENTAL WORK AND RESULTS In the present investigations of the solid solubility and of the precipitate phases in the systems tantalum-nitrogen, -oxygen, and -carbon, high-purity tantalum was reacted with high-purity gases, homogenized at 1800°c, and annealed at and quenched from 1500°, 1000,

Jan 1, 1962

By Robert Glass Cleland

WITH the acquisition of the Nichols Copper Company ' and the development of the large Copper Products manufacturing and selling organization, the Phelps Dodge Corporation had attained two of its important goals. But at that particular time both its immediate and long-range prospects were giving the company serious concern. The financial panic that began late in 1929 was growing worse instead of better. Neither raw materials nor finished products could find a market. In 1932 the price of copper fell to the almost unprecedented figure of four and eight tenths cents a pound. Domestic production of copper in the United States was further threatened by a large low-cost output from the mines of Africa and the Andes. Canadian copper mines, with their large yield of other valuable metals from the same ores, added to the difficulties of the American companies. After a hard-fought campaign, however, the producers of domestic copper finally induced Congress to levy a duty of four cents a pound on copper imported into the

Jan 1, 1952

By George H. Jones

NO STRANGER phenomenon exists in the American mining industry today than the so-called bootleg anthracite industry in Pennsylvania which now produces probably close to 15 per cent of the total hard coal out- put of the State. Instead of being what - was first thought to be a temporary condition, countenanced because of the desperate condition of some of the miners at the depth of the depression. it is thriving now as never before. Re- ports of it have penetrated all over the world, as exemplified by inquiries concerning it in Durban, South Africa mentioned by John C. Cosgrove in his article in the July MINING AND META LURGY.

Jan 1, 1939

By D. A. Elgillani, S. Atak, D. A. Rice, M. C. Fuerstenau, R. B. Bhappu

Quartz and feldspar cannot be floated with sulfonate at any pH; spodumene floats over a narrow acid pH range, while beryl responds moderately over a broad pH range. After wet-grinding in a steel mill, beryl, quartz, and spodumene float well with sulfonate below about pH 7, whereas the improvement in the response of feldspar is not so marked. A mechanism by which iron can be adsorbed on these minerals is presented. Also, the responses of leached, natural, and wet-ground beryl to amine, sulfonate, and oleate flotation are shown and related to the measured zero-points-of-charge of these materials. Earlier work with leached beryl showed that good flotation could be obtained with alkyl aryl sulfonate over a rather wide pH range using a Fagergren flotation cell.' When a similar response was observed with leached quartz, it was decided that unintentional activation was being obtained from the metallic components of the Fagergren cell. To obviate this difficulty, a microflotation cell was designed, and an experimental technique was devised. These have been described elsewhere. Experiments conducted with the small cell showed that leached quartz could not be floated at any pH with any sulfonate addition,3 which is in agreement with the observations of Kraeber and Boppel.4 Similarly, it was also found that leached beryl responded to sulfonate flotation only over a narrow pH range rather than the broad range reported earlier.1 This early work,1 however, revealed the important effect that wet-grinding in a steel mill has on the flotation response of certain silicates. That is, it was found that quartz and especially beryl floated well over an unusually wide pH range after wet-grinding in a steel mill. Microcline, however, floated poorly below pH 4, even though wet-ground under the same conditions. The work of Eigeles6 on adsorption of oleic acid on leached quartz and iron-contaminated quartz at constant pH is in agreement with these flotation data. Other research has shown that ferric iron, added as a salt to the system, functions as an activator in the narrow pH range in which Fe +++ iron hydrolyzes to its hydroxy complexes.3,5 These phenomena indicate that iron functions differently in flotation systems depending on its method of introduction. The object of this paper is to determine the mechanism by which iron is adsorbed on certain minerals, the mechanism of collector adsorption after iron abstraction, and the role that Fe++ and Fe+++ assume in the selective separation of these minerals. EXPERIMENTAL MATERIALS AND METHODS Sodium alkyl aryl sulfonate, mol wt 450,7 pure potassium oleate, and pure dodecylamine were used as collectors. All other chemicals were reagent grade in quality, i.e., n-amyl alcohol as frother; HC1, H2SO4, and KOH for pH adjustment; and ferric chloride as activator. Conductivity water, made by passing distilled water through an ion exchange column, was used in the experimental work. All minerals used in the investigation were hand-picked specimens. Sample Preparation: Each of the minerals was crushed through 8 mesh, and the product was divided into two groups, one to be ground dry and the other wet. Dry grinding was accomplished with an alumina mortar and pestle. The product was dry-screened to 48 x 150 mesh, cleaned magnetically, deslimed in conductivity water, and dried. Preparation of the samples by wet-grinding involved grinding a 200-g charge of the mineral (-8 mesh) at 60% solids with natural water in a mild steel rod mill for four minutes. This charge was then wet-screened immediately with natural water to 48 x 150 mesh, dried, and cleaned magnetically. Some experiments were also conducted with leached beryl and quartz. These products were prepared by leaching the sized sample (48 x 150 mesh) with concentrated HC1 with a percolation technique until no iron could be detected in the leach liquor. Following this step, the sample was rinsed with conductivity

Jan 1, 1967

By William Rawles

THIS report is the first of a series planned by The Mineral Inquiry, organized by the American Institute of Mining and Metallurgical Engineers to make factual studies of the world's mineral resources in their political and international relations. The efforts of The Inquiry are directed toward filling certain notable gaps in available information, without duplication of many other investigations touching this field which" are being conducted by other organizations, public and private. Much of its work is indirect-suggesting topics for study by other individuals and organizations and aiding in their planning and correlation. The present report is designed to show the nationality of the commercial control of mineral resources, in addition to the geographic distribution of production by nation-in other words, the overlapping of political and commercial control. Detailed accuracy cannot be claimed for the figures presented. For some companies division of ownership by nationality has been very difficult to ascertain, as many companies are reluctant to dis-close the extent of their holdings in other corporations, and the impossi-bility of tracing all stock ownership is obvious. Also there are frequent changes in the distribution of stock control. The percentages given rep-resent only the participation that has been identified definitely, even though it is known in some cases with fair certainty that larger interests exist, as, for instance, American participation in foreign chromite companies. In bringing' together these figures we have had the cordial co-operation of the United States Bureau of Mines, the United States Geologi-cal Survey, the Mineral Division of the Bureau of Foreign and Domestic Commerce, the Brookings Institution, and of many specialists connected with the mineral industries covered. The report does not cover the entire list of minerals. Coal, although it is one of the most important minerals, was omitted because not more. than one or two per cent of the world's production comes from mines that are owned by companies foreign to the countries where the coal is produced. Others, such as gold, are omitted because sufficient data have not yet been accumulated. It is hoped that some of these may be covered in subsequent reports. It is not our purpose here to discuss the significance of the figures sub-mitted, but only to point out the general nature of the problems on which they have a bearing.

Jan 1, 1933

By W. D. Forgeng, R. L. Folkman, D. C. Hilty

The solubility of oxygen in molten Fe-Cr alloys has been determined at 1550° , 1600°, and 1650°C for alloys containing up to alloyshasbeenabout 50 pct Cr and found to decrease as chromium increases to 6 pet and then to increase gradually. Phase relations in the Fe-Cr-0 system at steelmaking temperatures have been evaluated and two previously unreported oxides have been identified. OPERATIONS in the melting and refining of chromium steels are dependent to a major degree on the reactions of chromium and iron with oxygen and are primarily directed toward controlling and modifying these reactions to secure maximum advantage in the utilization of chromium. Although fairly effective practices have been developed empirically, understanding of the specific reactions is limited. Moreover, the ability of molten steel to dissolve oxygen that subsequently precipitates as oxide inclusions during solidification is well known, so that clarification of the effect of chromium on the nature and mechanism of formation of these inclusions is desirable. Study of the problem indicated that increased knowledge of the fundamental Fe-Cr-0 system is essential to further technical and economic improvement. Consequently, an investigation of the influence of chromium on the solubility of oxygen in molten iron and of phases and phase relations in the Fe-Cr-0 system was undertaken at the Metals Research Laboratories of the Electro Metallurgical Co. as part of a general program on the effective utilization of chromium in chromium steel production. Experimental Procedure All of the experimental runs made during this investigation were carried out in the rotating crucible induction furnace which has been described in detail in a previous publication.' In review, the principle underlying this furnace is that rotational forces in the crucible cause the molten metal to assume a concave shape in such a manner that the slag is contained in the molten metal cup, thereby minimizing slag/crucible contact and subsequent reaction. Practically all of the heats were melted in commercial-quality magnesia crucibles of the type usually furnished for laboratory induction furnaces. All of the runs were made under an argon atmosphere after the furnace chamber had been degassed. Bath temperatures were controlled by Pt—Pt-10 pct Rh thermocouples. The basic furnace charge consisted of a premelted 12 to 15 lb electrolytic iron slug which had been cast to a shape convenient for fitting into the rotating furnace crucible. A typical analysis of the electrolytic iron slugs is given in Table I. For certain runs, it was desirable to melt down charges containing high initial chromium contents. In these cases the chromium was added to the electrolytic iron during the premelting operations. Chromium was added to the rotating furnace bath in the form of electrolytic chromium of the analysis given in Table 11. In all of the constant temperature runs, the standard procedure was to melt down the electrolytic iron or alloy slug under vacuum, admit argon to slightly greater than atmospheric pressure, and adjust rotational speed to develop a well formed "cup" on the bath surface. The melt was then saturated with oxygen by an addition of ferric oxide and the temperature of the bath adjusted to within +5°C of the desired level. At this point the heat was permitted to come to equilibrium prior to sampling or further addition. This time interval was varied from 15 min to 2 hr but generally was about 20 min. After sampling, the desired chromium addition was made and the bath again equilibrated prior to subsequent sampling. This cycle of addition and sampling continued for the duration of the run which lasted from 4 to 8 hr. At the end of this period, power was shut off and the bath allowed to solidify in the furnace. Quenched metal samples were taken from the equilibrated melts by means of the "Taylor sampler" which has been described by Taylor and Chipman.' Before being submitted to chemical analysis, all samples were carefully examined for surface slag occlusions and cold shuts. Later in the study, each sample was radiographed and examined metal-lographically in cross-section to determine the presence of internal defects. On the basis of these examinations, sound and apparently clean specimens were selected from the Taylor samples for chemical analysis.

Jan 1, 1956

In traversing lately the Sierra Madre, west of Sail Pedro and Guanacevi, I estimated the topographic summit at several points, by aneroid barometer, at about 8,500 ft. Mr. Weed's measurements, 40 miles further north, are from 9,000 to 9,500 ft., and indicate the correctness of the impression I obtained at the time, namely, that the greatest movement in the elevation of the Sierra was between Guanacevi and Guadaloupe y Calvo. This is suggested also by the course of the headwaters of the Rio Conchas and of the Nazas, and by the relative corrasion of the branches of the two streams. Mr. Weed's statements as to the unevenness and great relief of the andesite floor underlying the later dacites and rhyolites are very interesting, and lead me to add that the floor of the andesite breccias and flows is uncovered for several square miles east of Guanacevi. This floor is of reddish, bluish and gray shales, lying horizontal or dipping slightly east. Their age is unknown; but from the interbedded occurrence of copper sulphides, I took it to be Triassic,

Jan 1, 1903

By E. R. Helderman, C. Y. Ang, C. C. Nealey

Beryllium-base alloys have been successfully p7.-epared by the liquid-phase sintering technique. Depending orz the composition and amount of the intended liquid please, microstructures either single -phase or duplex in feature with randomly oriented grains have been obtained. Qualitative and semi-qualitative determination of distribution of alloying elements md microsegregations in some experi)uzental alloys haue been made by electron-micro-probe analysis in conjunction with microliardness testing and standard metallography. Tensile tests reoealed that some conzpositions possess attractive elastic properties with Young's mot1uli greater than 40 X 10' psi. In powder metallurgy, liquid-phase sintering is a process or phenomenon that has proven to be of practical value. For example, the heavy metals such as tungsten-copper-nickel, high-strength heavy gyro alloys,' heavy-duty electrical contacts,' and tungsten carbide tool materials are all products of liquid-phase sintering. Mechanisms involved in liquid-phase sintering, however, are not completely understood. Questions regarding the exact roles played by rearrangement of particles, liquid/vapor surface energy, solution and precipitation, and so forth, have not been completely answered. Evidence has been cited3 that at least volume shrinkage in the densification process is diffusion-controlled. It is possible that the predominant mechanisms for the complete densification and grain growth in a liquid-phase sintered system depend primarily on the alloy systems involved, in addition to processing conditions. Despite the lack of sound understanding of the mechanisms of the process, liquid-phase sintering has been and is being used to advantage either to synthesize microstructures for their special properties or to prepare alloys which are difficult to form by fusion process. Liquid-phase sintering of beryllium alloys was first attempted by Jones and Williams.4 They first tried infiltrating beryllium with magnesium, and then succeeded in preparing the alloy by sintering Be-Mg powder compact in molten magnesium bath. This investigation resulted in the identification of some Mg-Be intermediate phases. Crossley et a1.5 also used liquid-phase sintering technique in an attempt to produce ductile beryllium alloys for structural applications. The major liquid-phase components investigated by Crossley et al. were aluminum and silver with minor additives of germanium, calcium, lanthanum, cerium, and yttrium. The lack of wetting and the bleeding out of liquid phase were the difficulties encountered during experimentation. According to Hodge,6 the two compositions investigated by Crossley, which showed some promise based on compression tests, involved large amounts (over 35 wt pct) of silver, thus making them too heavy to be of practical interest to the aerospace industry and military users. The present investigation was prompted by the search for light-weight (density less than aluminum) beryllium alloys exhibiting small anisotropy in physical properties for precision inertial navigation instrument applications. In addition to isotropy, good structural properties such as high elastic modulus or desirable combination of mechanical and physical properties are also objectives of this investigation. The technique of liquid-phase sintering was chosen for its versatility in producing either duplex or homogeneous microstructures. This report is concerned with the use of copper and aluminum, with or without silicon addition, as the intended liquid phase, and the resultant micro-structures and some physical properties of the beryllium alloys. Qualitative and semiquantitative electron-microprobe analyses of some of the alloys are presented to illustrate the usefulness of this microanalytical technique for the identification of microconstituents and their distribution. EXPERIMENTAL PROCEDURES The beryllium powder used was -200 mesh Brush Beryllium Co. QMV NP-50 grade. Typical chemical analysis of the powder is shown in Table I. Commercial high-purity copper, aluminum, and silicon powders all screened to —100 mesh were used as additions. Mixed powder compositions were ball-milled in ceramic jars for 1/2 hr to ensure thorough blending. Milled powder was loaded either in 3/4-in.-diam button die or in Metal Powder Association flat tensile specimen die and compacted under top and bottom pressure. No lubricant or organic binder was used. Sintering was carried out in a quartz tube under a vacuum of 50 to 100 µ pressure. Surface hardness and some microhardness readings were taken on sintered specimens. Sintered density was

Jan 1, 1965

By W. F. A. Thomae

The Villayet of Aidin is a province in Asia Minor which has a coast line extending from opposite the island of Mitylene to beyond Makri, opposite the island of Rhodes, and embraces almost the entire basins of the two principal rivers, the Sarabat

Jan 1, 1899