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By J. F. Elliott

PRESENT knowledge of the usual metallurgical slags indicates that they are, for the most part, rather complex in behavior and as yet there is no ready means for describing, in a simple manner, the behavior of any one of them. One of the best known slag systems is the iron oxide-silica-lime ternary which is the basic "solvent" in a number of important metallurgical refining operations, the basic open hearth being one of the most important. In this operation, the slag dissolves such components as sulphur, phosphorus, manganese oxide, and magnesia. Considerable study of this slag system and the behavior of these additions has been carried out in the past by a number of authors, as has been summarized in several critical reviews.','2 However, except for determination of the activity of iron oxide, only a limited amount of effort has been directed towards developing, from these data, an understanding of the general behavior of the basic solvent. Reported here are the results from a series of calculations based on data from the literature which permit a semiquantitative evaluation of the activities of iron oxide, silica, and lime (plus magnesia) in the ternary system at 1600°C. The preliminary results, which were reported briefly at a symposium held by AIME in 1953, have been revised and are completed. The steps in the calculation are as follows:* I—establish the activity curves and the curve of the excess molar free energy of mixing at 1600°C for each of the binary systems, 2—construct the activity surface of iron oxide for the ternary from the data on the binary systems and information available in the literature for the ternary area, 3—determine the surface of excess molar free energy of mixing for the ternary system from the activity surface of iron oxide and from the molar curves obtained for the binary system, and 4—differentiate the ternary surface of the molar excess free energy of mixing to obtain the ternary surfaces for the logarithm of the activity coefficients for silica and lime (log rslo, and log rc.~). Si0,-Fe,O: Schuhmann and Ensio have measured the activity of iron oxide in simple iron oxide-silica slags when in equilibrium with y iron. Their data recalculated to 1600°C are shown in Fig. 1. Also included is a point representing a measurement by Gokcen and Chipmana of the activity of iron oxide at 1600°C at the point of saturation with solid silica. For convenience and in accordance with other treatments,' the calculations are based on the hypothetical component, FelO, which is obtained by converting all the analyzed iron in the slag to FeO. In spite of Schuhmann and Ensio's conclusion that the activity of iron oxide in the system does not vary with temperature over the experimental range of 1258" to 1407"C, the data are corrected to 1600°C assuming that temperature does have an effect. It was felt to be most reasonable to assume that the term log rr.10 is a linear function of the reciprocal of the temperature. Reyu has indicated that an effect of temperature on the activities in this system is to be expected from the Schuhmann and Ensio data. In essence, the correction consists of multiplying the experimental value of log rf,,o by the ratio of the experimental temperature in Kelvin to 1873°K. The magnitude of the correction is not large, being approximately 11.5 pct of the experimental value of log rve10. A very minor correction was necessary to compensate for the fact that the slags were in equilibrium with y iron in the experiment, while at steel-making temperatures they would be in equilibrium with liquid iron. Data for the correction were obtained from Darken and Gurry. The standard states established are pure liquid iron oxide (FelO) in equilibrium with pure liquid iron (with the appropriate amount of oxygen in solution) and pure liquid silica. The method of plotting in Fig. 1 is convenient for the calculation of the activity of liquid silica and permits a reasonable extrapolation for the activity of Fe,O in the ranges where no experimental data are available. The uncertainty in the extrapolation to infinity at one terminal where Nvelo = 1 for the usual Gibbs-Duhem integration is reduced considerably by this method. The region of two coexisting liquid phases is estimated to range from 1.8 to 41.7 mol pct Fe,O. The nature of the activity curve for the single-phase region indicates that the activity of iron oxide across the two-phase region is very close to 0.39. Computation of the function log ~F,,o/(1— NF,,o)' for this region (dashed line) in conjunction with the curve through the adjusted experimental data indicate the best probable value of 0.382 for alPe,o in the two-phase area. The line from 0 to 0.018 Nf~~o is obtained by assuming that the component follows Henry's law. In this range, the value for log rveto is 2.59. Appropriate mathematical manipulation of the plotted linet yields the activity curves for the The curve AF", the excess molar free energy of mixing (actual minus ideal), as shown in Fig. 3 is also computed from Fig. 1. This curve is required for subsequent calculations. CaO-Fe,O: The phase diagram for the lime-iron oxide system when in equilibrium with liquid iron is not well known but there appears to be no intermediate compound present. This fact as well as the activity values for Fe,O extrapolated to the CaO-Fe,O binary from Taylor and Chipman' tend to indicate somewhat negative deviations from ideality for the activity curves for the two components. Strong indication of this is evident in Fig. 1 where are plotted the points computed from the estimated activities of Fe,O for the binary system.' It appears that the best line through the data is a horizontal straight line. Because of the general indication of the slight negative departure from ideality, the line is extrapolated horizontally to NF~,o = 0. It is con-

Jan 1, 1956

By J. J. Gilman

The data presented indicate that the critical shear stress and strain-hardening Thedatapresentedrate of a zinc monocrystal depend on the orientation of its slip direction with respect to its external boundaries. The tendency of a crystal to form deformation bands also depends on its shape. THE plastic behavior of pairs of zinc monocrystals in which both members of the respective pairs had the same orientation with respect to the longitudinal axis, but each had different orientations with respect to their rectangular external shapes, were compared in this investigation. The purpose of the investigation was to see what influence the shape or surface of a zinc crystal has on its mechanical properties. In a previous investigation of triangular zinc monocrystals,1 anomalous axial twisting was observed which seemed to be related to the triangular shape of the crystals. Wolff,' in 400°C tensile tests of rectangular rock-salt crystals bounded by cubic cleavage planes, found that, of the four equivalent slip systems, the two with the "shorter" slip directions yielded and produced slip lines at lower stresses than the other two. This observation and the work of Dommerich³ as formulated by Smekal4 as a "new slip condition" for rock-salt: "among two or more slip systems permitted by the shear stress law, with reference to the formation of visible slip lines by large individual glides, that slip system is preferred which has the shortest effective slip direction." More recently, Wu and Smoluchowski5 reported essentially the same effect for ribbon-like (20x2x0.2 mm) aluminum crystals at room temperature. Experimental Chemically pure zinc (99.999 pct Zn), purchased from the New Jersey Zinc Co., was the raw material. Glass envelopes, containing graphite molds and zinc, were evacuated while hot enough to outgas the graphite but not melt the zinc. At a vacuum of about 0.2 micron the envelopes were sealed off and then lowered through a furnace at 1 in. per hr so as to melt and resolidify the zinc and produce mono-crystals. One-half of one of the molds is shown in Fig. la. Each mold consisted of four pieces from a cylindrical graphite rod that was split longitudinally and transversely at its midpoints. Rectangular milled grooves 0.050 in. deep and % in. wide formed the mold cavity when the split halves were assembled with twisted wires. Fig. lb shows the specimen shape obtained when the top and bottom mold-halves were rotated 90" with respect to each other. Good fits prevented leakage and excess zinc was necessary to provide enough liquid head to fill the mold completely. In removing soft crystals from the molds it was impossible to avoid small amounts of bending. However, manipulations were carried out whenever possible with the crystals protected by grooved brass blocks. All specimens were annealed prior to testing. From the top and bottom sections of each crystal, X-ray specimens and tensile specimens 7 to 8 cm long were sawed. The tensile specimens were annealed inside evacuated tubes for 1 hr at 375°C. Next the crystals were cleaned and polished by 2-min dips in a solution of 22 pct chromic acid, 74 pct water, 2.5 pct sulphuric acid, and 1.5 pct glacial acetic acid.' Cleaning was followed by a 10-sec dip in a 10 pct caustic solution, then washed in water and alcohol, and dried. This treatment results in a bright surface covered by an invisible oxide film. The testing grips were a slotted type with set screws and were supported in a V-block during the mounting operations in order to avoid bending the crystals. A schematic diagram of the recording tensile-testing machine is shown in Fig. 2. The machine has been described elsewhere.' The head speed was 0.3 mm per sec for all tests. The crystal orientations were determined by the Greninger X-ray back-reflection method with an estimated accuracy of 1. Description of Crystal Geometry A schematic picture of a rectangular zinc mono-crystal is shown in Fig. 3. ABD designates the front edge of a basal plane (0001) of the crystal, the only active slip plane for zinc at room temperature. Of the three possible (2110) slip directions, the active one is indicated by an arrow. Cartesian coordinates are taken parallel to the specimen edges. The normal, n, to the basal plane (n is parallel to the hexagonal axis) has the direction cosines a, ß and ?. X0 = 90 — y is the angle between the longitudinal axis and

Jan 1, 1954

By Earl Bardwell

(Butte Meeting, August, 1913.) THE structural relations existing between cuprous oxide and copper were first systematically studied by Heyn1, who suggested that a study of the microstructure of refined copper might be substituted for the analytical methods in vogue for determining the oxygen content of copper coming .;from the refining furnace. Hofman, Green and Yerxa,2 in their paper A Laboratory Study of the Stages in the Refining of Copper, working along the lines suggested by Heyn, showed that a study off the microstructure could be made to yield a correct estimate of the oxygen content of the specimen of refined copper under examination. In order to determine the oxygen content of the specimen of refined copper under examination a photomicrograph was first made. From the relative areas of copper and eutectic, the percentage of cuprous oxide and the corresponding percentage of oxygen were then readily calculated. It was found that the values for oxygen thus obtained corresponded closely with the analytical results. With the idea of utilizing, this method of determining the oxygen content of each charge dipped from the refining furnaces at the Boston & Montana Reduction Plant, the physical testing laboratory was equipped with suitable apparatus for carrying out the work. It may be of interest to describe certain of the methods which have been worked out in, this connection and give such data as have been obtained bearing on the effect of the oxygen content of refined copper upon its conductivity.

Jan 7, 1913

By Carl Scholz

Discussion of the paper of Carl Scholz, published in Bi-monthly Bulletin, No. 22, July, 1908, pp. 551 to 559. HOWARD N. EAVENSON, Gary, W. Va. (communication to the Secretary*) :-For some time before the publication of Mr. Scholz's paper, I had been collecting data bearing upon its subject, and I now take pleasure in presenting my results to the Institute in the form of a discussion. It has long been a matter of common opinion among mining-men that mice-explosions are, more frequent during the colder, or winter months, than during the warmer ones, and it is a matter of common knowledge among them that the air-ways and road-ways in most mines are much drier and are more in¬clined to be dusty during the winter than during the summer. In many mines, places which are wet and sloppy in the summer are dry and sometimes dusty during the winter. These changes, of course, can only be due to atmospheric conditions, and are caused by differences in temperature and humidity. Until recently, however, very little attention has been paid to the part that atmospheric conditions may play in mine-explosions, or, rather, to the effect they may have in rendering mine-conditions peculiarly dangerous, and in spreading and rendering more disastrous the effects of what would otherwise probably have been .small explosions. To show the difference in mine-conditions during sunnier .and winter months, I have tabulated in Table I. the results of 24 observations of hygrometric conditions in several different mines at different times of the year. Mines Nos. 1, 2, and 6 are located in the Pocahontas.coal -region, in McDowell couuty, W.Va., the first one being a shaft-mine shaft mine and the others drift. Mines 1A and 2A are drift-mines located in Logan county, W. Va. All of these are mines of fair size, but none of them has been in operation more than six years,

Jun 1, 1909

By E. L. Anders

The Mile Six pool is located on the La Brea-Parinas Cullcession of International Petroleum Co., Ltd., in northwestern Peru on the west coast of South America. The reservoir pressure in this pool has been maintained within 200 psi of its initial value throughout its history, and gravity drainage has played an important role in the production behavior. It has now produced 95 per cent of its estimated ultimate recovery. It is estimated that this interesting oil pool will ultimately produce 67 per cent of the initial oil in place and that the resulting residual oil saturation may be as low as 19 per cent of the pore volume (29 per cent of the hydrocarbon pore volume). An evaluation of reservoir rock and fluid characteristics and ultimate oil recovery is presented. INTRODUCTION This study of Mile Six pool was made to evaluate its performance according to latest available information. The production performance of this pool has been discussed in various articles in the past. and the reported behavior has been used as an example for application of computation procedures for gravity drainage depletion' and as an illustration of field behavior under gravity drainage or expanding gas cap drive. There have been wide variations in reported values of initial oil in place, reservoir oil volume factor. connate-water sauration, volume of effective sand, and ultimate recovery because of the paucity of reliable basic data. These various factors have been determined as accurately as practicable with the latest available information, and this evaluation is presented herein. The production history of Mile Six is an excellent example of gravity drainage depleion with effective pressure maintenance by gar injection. GENERAL Mile Six pool was discovered by cable-tool drilling in November. 1927. when well 1996 was completed in the Parinas sand. After slow development with cable tools and sporadic production. the pool was opened to continuous pro(iuction in November. 1933. and develpment was completed with rotary rigs. Pressure maintenance was started in December, 1933. by returning gas to upstructure wells. Most of the development was 'completed by 1937, but some additional wells were drilled in the period 1939-1947. and several old wells were deepened. A total of 46 oil and gas wells and 4 dry holes were drilled on approximately 7-acre spacing. Of the producers. 21 are now flowing. 2 are pumping. 44 are gas input wells. 3 are abandoned. I is a gas well shut in. and 15 are shut in because of non-commercial production or high gas-oil ratio. The locations of all wells are shown on the map of Fig. I. Total oil production on Dec. 31. 1952, was 30,867,373 bbl: cumulative gas production was 22,023,777 Mcf; and 26,410,946 Mcf of gas had been returned to the reservoir. These figures do not include oil and gas lost ill a blowout in January. 1940. GEOLOGICAL DESCRIPTION Mile Six pool is located on the northern end of a structural spur projecting from the La Brea-Negritos uplift.' The spur is probably a reflection of a basement structure. It plunges gently to the north, i broken into a complex series of fault blocks. and contain.; the Verdun Alto. Section Sixteen. and Mile Six pools. The Parinas handstone (lower Eocene!. which is the producing formation in Mile Six. occurs at an average depth of 2,200 ft in the pool and dips north and east at from 15' to 20". The pool covers an area of approximately 350 acres. Mile Six is downfaulted about 600 ft from Section Sixteen pool to the soutb. and a major fault forms its western boundarv. The north and east boundaries are formed by the intersection of the sand top with the water-oil contact which occurs at approximately 2.440 ft subsea. An original gas-oil contact probably existed at about 1.875 ft subsea. Fig. 1 presents the latest structural interpretation of the pool. and Fig. 2 is an isopach map showing thickness of the total Parinas formation above the original water-oil contact. The heavy lints of Fig. 1 are contours on the sand top, and the fine lines are contours on the fault planes. This type of straight-line structural map was developed 1)) International's geologists to reflect structural conditions where the bedding planes dip and have no curvature. 'The La Brea-Parinas Concession is highly faulted by normal fault.. The beds are flat wherever exposed. The Parinas formation is approximately 635 ft thick. and it is etimated that 62 percent II the formation is effective sand. The original oil zone was about 565 ft thick. Fig. 211 presents an electric log showing typical Parinas sand development ill Mile Six pool. The Parinas band in Mile Six i. a well-sorted. medium- to-coal-se-grained. cross-bedded sand with minor lenses of shale and small lenses and pockets of pebble conglomerate. The sand grains are subangular to rounded and consist chiefly of quartz with feldspars. biotite hornblende, and augite as accessory minerals. Because of faulting of the Parinas- formation to the east and north of the pool. there is probably l possibility of a significant, natural water drive in Mile six. The faults within the pool. as indicated in Figs. 1 and 2. are of smaller disI,laceInent and seem to act only , partial barriers to fluid movement within the reservoir. RESERVOIR CHARACTERISTICS Core analysis data are available from five wells. The data were obtained from three wells (Nos. 3401. 3586 and 3719) at the time of their completion and from well 1996 when the original liner was sidetracked and the well was deepened ill 1946. Data from well 2779 were obtained in 1943 from old cores taken when the well was deepened in 1934. From these core analyses. the average porosity was estimated to be 22.6 per cent. and the average permeability to dry ail. was estimated to be 780 and Measured productility indices varied from 3.1 to 71.4 B/D per psi differential. Specific productivity indices varied approximately from 0.1 to 0.3 B./D per psi per ft of sand.

Jan 1, 1953

By T. D. Guldem, J. L. Kaae

ALLOYS with nominal composition of 45-Fe 35-Ni 20-Cr, ASTM-B-163, known under the commercial names of Incoloy 800 and Sanicro 31 (Alloy 800), are often employed at elevated temperatures for extended periods. Therefore, knowledge of the aging behavior of these alloys is of considerable importance. Significant decreases in ductility and increases in yield strength have been observed in the 45-Fe 35-Ni 20-Cr alloys containing about 0.4 pct Ti and 0.4 pct A1 after long-term aging at 540" to 700"~."~ However, no direct evidence has been presented for precipitation phenomena that might result in such changes. Strengthening effects have been attributed to the effects of local or-dering.3 Since y' precipitation (Ni3A1, Ti) is known to occur in similar alloys which contain more titanium and aluminum,4-7 it was decided to explore the possibility that y' might precipitate in these alloys and might be responsible for the changes in mechanical properties on aging. This note reports some observations of two distict types of matrix precipitates made by means of transmission electron microscopy, in a 45-Fe 35-Ni 20-Cr alloy containing 0.31 pct Ti and 0.4 pct Al. The steel used in this investigation was obtained from the Sand-vik Steel Works; it is designated Sanicro-31 (Alloy 800). The chemical composition of the alloy is given in Table I. Aging of solution-treated material at 700" and 800°C for 130 and 100 hr, respectively, produced the matrix precipitates shown in Figs. l(a) and l(b). It is apparent from these micrographs that the precipitate particles occurred in the form of thin square plates parallel to the matrix cube planes. Extraction replication and selected-area electron diffraction showed that the precipitates were M23C6. Coherency strains, consistent with the semicoherent nature of small M23C6 precipitates,' were evident for certain imaging conditions. In addition to matrix precipitation, preferential precipitation of M23C6 on dislocations was common, as has been reported previously for austenitic stainless steels.'" Specimens aged for longer times (-300 hr) at 700°C exhibited a different type of coherent matrix precipitate in addition to the M23C6. An example is shown in Figs. 2(a) and 2(b). In addition to the few large M23C6 precipitates, small precipitates exhibiting strain contrastl0,ll are present. The "line of no contrast" of the strain field of a given precipitate lies along differ-

Jan 1, 1970

By T. G. Digges, M. R. Achter

ALTHOUGH zone melting has found favor in recent years because of its convenience and its faster rate of production of single crystals, the older technique of strain annealing still has a number of advantages. It has been reported1 that the lattice of a crystal prepared in this manner has fewer defects than one grown from the melt and, of course, the control of the external geometry is easier. Also, the diameter of the crystal which can be grown by zone melting has a theoretical limit determined by the surface tension, thermal conductivity, and specific gravity of the material, while the size of that which can be grown in the solid state is limited only by practical considerations. In a program for the study of the structure-sensitive properties of niobium and its alloys it was desirable, for ease of handling, to have available single crystals of large diameter. This requirement dictated the choice of the strain-anneal technique. Induction heating was chosen in the present work in preference to other methods because of its deep penetration of large-diameter sections. A five-turn coil, powered by a motor generator operating at 10,000 cps, is contained in a vacuum chamber. The work is lowered through the coil for both the recrystallization and the crystal-growth steps. Starting with electron-beam melted material, the bars are cold-swaged, recrystallized, strained in a tensile machine, and then subjected to the growth step. Single crystals have been grown under the following conditions: Reduction in area during swaging— 79 to 99 pct, recrystallization temperature—1500o to 1667°C at the rate of 1.25 in. per hr, strain—1.0 to 2.5 pct, growth temperature—1600o to 2400°C at rates from 0.15 to 1.25 in. per hr. Starting grain sizes achieved after the recrystallization step varied from 0.6 to 1.55 mm. The starting grain size was found to be critical; if it is too fine and has any residual cold work, as shown by the presence of a fiberlike texture, a single crystal cannot be grown. Using this technique niobium single crystals have been grown from 0.250 in. diameter and 12 in. long to 1.00 in. diameter and 5 in. long as shown in Fig. 1. The 1-in. crystal is the largest to be reported for a refractory metal as compared to 0.500 in. for molybdenum grown by zone melting.2 As with zone melting, control of orientation is possible by the use of special procedures. Other investigators, see for example Williamson and Smallman,3 have reported that orientation control may be achieved by a bending technique. In the present work the strained rod is partially lowered through the coil to start the growth of the crystal. Then it is removed and bent at a point ahead of the interface between the single and polycrystalline portions. Finally, it is returned to the chamber and growth is continued "around the corner". The amount of bending which can be imparted to the rod is limited by coil geometry which up to now has been 10 deg. However, by repeating the bending and growing operations it should be possible to attain any desired orientation. The perfection of these single-crystal specimens as a function of process variables is being measured by X-ray and metallographic techniques and the results will be reported in a forthcoming paper. This work was partially supported by the Advanced Research Projects Agency.

Jan 1, 1964

By Jean Howard

ALTHOUGH zone melting has found favor in recent years because of its convenience and its faster rate of production of single crystals, the older technique of strain annealing still has a number of advantages. It has been reported1 that the lattice of a crystal prepared in this manner has fewer defects than one grown from the melt and, of course, the control of the external geometry is easier. Also, the diameter of the crystal which can be grown by zone melting has a theoretical limit determined by the surface tension, thermal conductivity, and specific gravity of the material, while the size of that which can be grown in the solid state is limited only by practical considerations. In a program for the study of the structure-sensitive properties of niobium and its alloys it was desirable, for ease of handling, to have available single crystals of large diameter. This requirement dictated the choice of the strain-anneal technique. Induction heating was chosen in the present work in preference to other methods because of its deep penetration of large-diameter sections. A five-turn coil, powered by a motor generator operating at 10,000 cps, is contained in a vacuum chamber. The work is lowered through the coil for both the recrystallization and the crystal-growth steps. Starting with electron-beam melted material, the bars are cold-swaged, recrystallized, strained in a tensile machine, and then subjected to the growth step. Single crystals have been grown under the following conditions: Reduction in area during swaging— 79 to 99 pct, recrystallization temperature—1500o to 1667°C at the rate of 1.25 in. per hr, strain—1.0 to 2.5 pct, growth temperature—1600o to 2400°C at rates from 0.15 to 1.25 in. per hr. Starting grain sizes achieved after the recrystallization step varied from 0.6 to 1.55 mm. The starting grain size was found to be critical; if it is too fine and has any residual cold work, as shown by the presence of a fiberlike texture, a single crystal cannot be grown. Using this technique niobium single crystals have been grown from 0.250 in. diameter and 12 in. long to 1.00 in. diameter and 5 in. long as shown in Fig. 1. The 1-in. crystal is the largest to be reported for a refractory metal as compared to 0.500 in. for molybdenum grown by zone melting.2 As with zone melting, control of orientation is possible by the use of special procedures. Other investigators, see for example Williamson and Smallman,3 have reported that orientation control may be achieved by a bending technique. In the present work the strained rod is partially lowered through the coil to start the growth of the crystal. Then it is removed and bent at a point ahead of the interface between the single and polycrystalline portions. Finally, it is returned to the chamber and growth is continued "around the corner". The amount of bending which can be imparted to the rod is limited by coil geometry which up to now has been 10 deg. However, by repeating the bending and growing operations it should be possible to attain any desired orientation. The perfection of these single-crystal specimens as a function of process variables is being measured by X-ray and metallographic techniques and the results will be reported in a forthcoming paper. This work was partially supported by the Advanced Research Projects Agency.

Jan 1, 1964

By G. Donald Emigh

Nothing is more important to life-plant and animal-than phosphate. Its compounds are essential to the energy functions of all living systems and for the formation of bones and teeth. Animals get their phosphate from eating plants and other animals, or domestically from feed supplements. Plants get their phosphate from the soil. Man's most important use of phosphate is for fertilizer; however, he is also a heavy user of many industrial phosphate chemicals. Phosphate occurs in all igneous and sedimentary rocks, and in all fresh and saltwater. The average content in rocks is 0.1 to 0.2% P2O5, as documented recently by McKelvey (1973). About 200 minerals contain more than 1 % P,O,. However, the important one in igneous rocks is fluorapatite, (Ca,(PO,) ,F) containing about 42% P,O, and 3.8% F,; in sedimentary rocks the one important mineral is francolite, a carbonate fluorapatite containing up to 2% molecular CO,. Both are in the apatite family of minerals. The mineralogy of phosphate minerals was reviewed recently by Altschuler (1973). Although phosphate occurs in nearly all rocks, economic recovery is limited to deposits where natural concentration of the phosphate mineral has occurred. Occasionally natural concentration is great enough that the material can be used as mined; generally, however, the ore is low grade and must be concentrated.

Jan 1, 1975

By B. Ball, C. H. Cox, S. N. Yap

Electrokinetic measurements on cassiterite were made in the presence of sodium di-hydrogen phosphate, mono-hydrogen arsenate, bisulfite, and sulfate. Flotation studies were also conducted using sodium dodecyl sulfonate in the presence of these salts. It was found that the anions specifically adsorb on cassiterite in the order H2AsO-4 H2PO4 HSO3 SO4 and consequently cause flotation depression. The adsorption mechanisms of the various inorganic anions are discussed in detail.

Jan 1, 1980

Asarco's Sacaton unit, located near Casa Grande 45 miles southeast of Phoenix, Arizona, was brought into production in February 1974. Ore reserves are estimated at about 48 million tons at 0. 95% copper. Mineralization of the orebody comprises both sulfides and oxides, with minor amounts of gold and silver. Preproduction stripping of 40 million tons of overburden was accomplished in less than two years. Mining is done at the rate of 9,000 stpd ore with a waste-to-ore ratio of 4.6 to 1. 0. The mine is developed on 40 ft benches, and by 1979 underground block caving methods will be phased into the operation at a depth of 1900 ft. Ore is mined in the pit two shifts per day, seven days per week, and is hauled with 85 ton trucks to the primary crushing plant. Trucks dump their loads into a 165 st capacity pocket equipped with a chain curtain which controls the ore flow to the 6 ft 6 in. wide by 24 ft long (2. 0 m by 7.3 m) vibrating feeder grizzly. Grizzly bars are inclined at a 5º slope on the first half of the 0 feeder and 10 on the last half. Grizzly bars have 6 in. (13 mm) spacings which pass 60 to 70% of the mine-run ore. Grizzly oversize drops into a 48 in. by 60 in. (1. 22 m by 1.52 m) primary jaw crusher. Both the grizzly undersize and crusher discharge are collected on a 42 in. (1.07 m) conveyor belt operating 398 fpm (121 mpm) for transport to the 4,750 live st intermediate storage area ahead of the fine crushing plant. Capacity of the Sacaton primary crushing plant is a nominal 1150 stph (1043 mtph). It operates fourteen shifts per week with an effective crushing time of four hours per shift. An economical open-air design was used, but an enclosed operator control room is located on the upper level where the dump truck, feeder, and crusher can be observed. Oversize rocks are removed from the feeder or crusher by the 10-ton bridge crane. Direct operating costs for this well-designed primary crushing plant, including labor, power, supplies, and maintenance, are only 3.5 cents per short ton. An interesting feature of the Sacaton orebody is that the non-sulfide copper minerals, which are less prevalent than the sulfides, occur intimately with the sulfide minerals; for this reason, all ores as mined are treated in a flotation circuit using sulfidizing methods for oxide recovery.

Jan 1, 1978

By George A. Morrison

A deposit Of limestone Was known to exist at a depth of 2000 ft under the property of the Columbia Chemical Division of the Pittsburgh Plate Glass Co. at Barber-ton, Ohio. A 662-acre site was selected for the projected mine, some two miles northwest of the plant and near the main line of the Erie Railway. An electric railway 8800 ft in length connects the mine and the plant. The deposit is overlain by 18 ft of un-consolidated (sand and gravel), 100 ft of water-bearing sandstone, and finally 2080 ft of shale into which thin layers of sandstone are embedded. The limestone bed itself is 345 ft thick and overlies 200 ft of gypsum. A 300-ton-per-hour capacity mine was decided upon. Two shafts were deemed advisable, one for production and the second for service; and these were sunk 550 ft apart, one to a depth of 2323 ft and the other to 2258 ft. Each is 16 X , ft in the clear and timbered with 6-in. steel H-sets on 8-ft centers, using 3/8 X 4 X 4-in. angles as studdles. Twelve inch I-beams were used at 160 ft intervals as bearers set in deep hitches and concreted to a vertical depth of 8 ft. Wooden sheathing was first employed but sloughing of the shale created a pressure on this lining and finally concrete was deemed necessary. Water was encountered only within the first 315 ft, flowing at 60 gpm and by grouting this was reduced to 15 gpm. Temporary wooden sinking headframes were installed with 300 cu ft capacity storage pockets and with doors automatically controlled by air cylinders by hoistmen. Each shaft was operated on four 6-hr shifts. The usual V-cut was drilled at the center of the shaft and the round consisted of 34 holes- A 40 pet gelatin dynamite was employed with some 60 pet in the cut holes. Drilling crews consisted of four to six men. Shale drilled easily but became more bed in depth and sandstone wore away the gauge Of the bits rapidly. A room-and-pillar mining system was adopted whereby rooms turned off on 80-ft centers, each room 40-ft wide and 50-ft high. Rib pillars between rooms were cut into 100 ft lengths by frequent holes. Ventilation is achieved through the two shafts, the down-draft through the service shaft, and the return through the pr0duction shaft. The hoist has a a Of 300 tons per hour and is equipped with 10-ton balanced skips requiring. a 2-min cycle Or 30 trips Per hour- Hoisting is designed to Operate by automatic loading and no hoistman is required for normal Operation. The 48 X 60 in. jaw primary crusher is underground. It is fed through chute and chain feeders and is flood-oil lubricated and cooled. An inclined belt conveyor returns oversized material to the crusher. Tramming is by Diesel-powered trucks.

Jan 1, 1948

By George A. Morrison

A deposit Of limestone Was known to exist at a depth of 2000 ft under the property of the Columbia Chemical Division of the Pittsburgh Plate Glass Co. at Barber-ton, Ohio. A 662-acre site was selected for the projected mine, some two miles northwest of the plant and near the main line of the Erie Railway. An electric railway 8800 ft in length connects the mine and the plant. The deposit is overlain by 18 ft of un-consolidated (sand and gravel), 100 ft of water-bearing sandstone, and finally 2080 ft of shale into which thin layers of sandstone are embedded. The limestone bed itself is 345 ft thick and overlies 200 ft of gypsum. A 300-ton-per-hour capacity mine was decided upon. Two shafts were deemed advisable, one for production and the second for service; and these were sunk 550 ft apart, one to a depth of 2323 ft and the other to 2258 ft. Each is 16 X , ft in the clear and timbered with 6-in. steel H-sets on 8-ft centers, using 3/8 X 4 X 4-in. angles as studdles. Twelve inch I-beams were used at 160 ft intervals as bearers set in deep hitches and concreted to a vertical depth of 8 ft. Wooden sheathing was first employed but sloughing of the shale created a pressure on this lining and finally concrete was deemed necessary. Water was encountered only within the first 315 ft, flowing at 60 gpm and by grouting this was reduced to 15 gpm. Temporary wooden sinking headframes were installed with 300 cu ft capacity storage pockets and with doors automatically controlled by air cylinders by hoistmen. Each shaft was operated on four 6-hr shifts. The usual V-cut was drilled at the center of the shaft and the round consisted of 34 holes- A 40 pet gelatin dynamite was employed with some 60 pet in the cut holes. Drilling crews consisted of four to six men. Shale drilled easily but became more bed in depth and sandstone wore away the gauge Of the bits rapidly. A room-and-pillar mining system was adopted whereby rooms turned off on 80-ft centers, each room 40-ft wide and 50-ft high. Rib pillars between rooms were cut into 100 ft lengths by frequent holes. Ventilation is achieved through the two shafts, the down-draft through the service shaft, and the return through the pr0duction shaft. The hoist has a a Of 300 tons per hour and is equipped with 10-ton balanced skips requiring. a 2-min cycle Or 30 trips Per hour- Hoisting is designed to Operate by automatic loading and no hoistman is required for normal Operation. The 48 X 60 in. jaw primary crusher is underground. It is fed through chute and chain feeders and is flood-oil lubricated and cooled. An inclined belt conveyor returns oversized material to the crusher. Tramming is by Diesel-powered trucks.

Jan 1, 1948

By J. C. Mertz

ACCURATE knowledge of the solid solubilities of the elements that dissolve in the important base metals is needed for guidance in the preparation and heat-treatment of the alloys derived from these compo-nents. While there is still difference of opinion concerning the merits of the X-ray and microscopic methods of determining such solubilities, it is certainly true that the recent extensive use of X-ray diffraction to review the existing constitutional data has revealed many glaring inaccu-racies and has brought about a much improved knowledge of phase-boundary locations, which will inevitably come to include all of the important alloy systems. When the work is done with all necessary precautions it appears that in the majority of cases where the solubilities extend beyond a few tenths of a per cent the X-ray back-reflection technique is capable of furnishing the best of information in this field. For the most prolonged and thorough studies it is obviously advisable to combine the results of several methods, in particular, to obtain an agreement between X-ray and microscopic data. This paper reviews the work previously done on the solubilities of phosphorus, arsenic, antimony and bismuth in copper and, in considera-tion of the uncertainties thus made apparent, presents, new X-ray data obtained with the first three members of this group.

Jan 1, 1936

By Kenneth Cottingham

The number of wells completed in Ohio during I940 was about 20 per cent more than during the preceding year, the comparative totals being 1020 and 1228. Of the 1940 completions, 327 were oil wells, 491 gas wells, and 410 dry. The completions for the past five years, divided into oil wells, gas wells, and dry holes, are shown in Table 2. Wells drilled deeper and input wells in water-flood areas are not included in the tabulation. The annual production of oil has decreased steadily in Ohio from the maximum of 23,941,000 bbl. produced in 1896. Table 3 shows the quantities of oil produced in the last five years. In 1940, the total was 3,052,000 bbl., produced by about 25,500 wells. The number of wells and the approximate quantities by grades are shown in Table I. Table i ,—Tabulation by Grade Grade 1 2 Barrels __________________________________________________________________________________________ Pennsylvania ............. . 1,198,000 Lima.................... . 325,000 Corning................... 3,730 1,159,000 Lodi...................... T,040 350,000 Cleveland................. 30 1:1,000 Total................... 25,500 3,052,000 The prices paid for Ohio crude oil in 1940, together with dates of changes in posting, are shown in Table 4. The production of natural gas in 0hio has declined from a maximum of 79,510,032 M cu. ft. in I9I5 S to 36,469,000 M cu. ft. in 1939, the most recent year for which a figure is available. Consumption reached its peak in Ohio in the year 1916, when it was 169,480,01r M cu. ft., declining to 114,720,ooo M CU. ft. in 1939. The produc-tion and consumption of natural gas in Ohio for the past five years are shown in Table 5. TAble 2.—Completions in Ohio during Past Five Years Numbs of Wells Drilled during Year YearI, ] Oil Gas Dry Total 1936............. 263 570 324 1,157 1937............. 317 503 45I 1,271 1938............. 189 433 288 gro 1939............. I70 501 349 1,020 19391940............. 327 491 410 1,228 Total.......... 1,266 2,498 1,822 5,586 Table 6 shows the number of oil wells and the number of gas wells completed by sands during 1940, with the average initial production per well for each sand. Table 7 shows the total number of wells drilled—oil, gas and dry—by sands. Development during 1940 Szth-Trenton.—For several years, considerahle interest has been shown in a horizon lying some 500 to 700 ft. below the top of the Trenton, known to the driller in western Ohio as the "green sand," and in eastern Ohio as the St. Peter. In 1939, ten 'lgreen sand" tests were drilled, all in western Ohio and all dry- In 19401 eight wells were drilled to this horizon, one of which was a small oil well (one barrel) in Men county- Of the remaining seven—all of which were dry-—one in Franklin County, in central Ohio, was drilled to a depth of 2903 ft. .Another was in Medina

Jan 1, 1941

By Kenneth Cottingham

The number of wells completed in Ohio during I940 was about 20 per cent more than during the preceding year, the comparative totals being 1020 and 1228. Of the 1940 completions, 327 were oil wells, 491 gas wells, and 410 dry. The completions for the past five years, divided into oil wells, gas wells, and dry holes, are shown in Table 2. Wells drilled deeper and input wells in water-flood areas are not included in the tabulation. The annual production of oil has decreased steadily in Ohio from the maximum of 23,941,000 bbl. produced in 1896. Table 3 shows the quantities of oil produced in the last five years. In 1940, the total was 3,052,000 bbl., produced by about 25,500 wells. The number of wells and the approximate quantities by grades are shown in Table I. Table i ,—Tabulation by Grade Grade 1 2 Barrels __________________________________________________________________________________________ Pennsylvania ............. . 1,198,000 Lima.................... . 325,000 Corning................... 3,730 1,159,000 Lodi...................... T,040 350,000 Cleveland................. 30 1:1,000 Total................... 25,500 3,052,000 The prices paid for Ohio crude oil in 1940, together with dates of changes in posting, are shown in Table 4. The production of natural gas in 0hio has declined from a maximum of 79,510,032 M cu. ft. in I9I5 S to 36,469,000 M cu. ft. in 1939, the most recent year for which a figure is available. Consumption reached its peak in Ohio in the year 1916, when it was 169,480,01r M cu. ft., declining to 114,720,ooo M CU. ft. in 1939. The produc-tion and consumption of natural gas in Ohio for the past five years are shown in Table 5. TAble 2.—Completions in Ohio during Past Five Years Numbs of Wells Drilled during Year YearI, ] Oil Gas Dry Total 1936............. 263 570 324 1,157 1937............. 317 503 45I 1,271 1938............. 189 433 288 gro 1939............. I70 501 349 1,020 19391940............. 327 491 410 1,228 Total.......... 1,266 2,498 1,822 5,586 Table 6 shows the number of oil wells and the number of gas wells completed by sands during 1940, with the average initial production per well for each sand. Table 7 shows the total number of wells drilled—oil, gas and dry—by sands. Development during 1940 Szth-Trenton.—For several years, considerahle interest has been shown in a horizon lying some 500 to 700 ft. below the top of the Trenton, known to the driller in western Ohio as the "green sand," and in eastern Ohio as the St. Peter. In 1939, ten 'lgreen sand" tests were drilled, all in western Ohio and all dry- In 19401 eight wells were drilled to this horizon, one of which was a small oil well (one barrel) in Men county- Of the remaining seven—all of which were dry-—one in Franklin County, in central Ohio, was drilled to a depth of 2903 ft. .Another was in Medina

Jan 1, 1941

By G. M. Gordon, J. W. Spretnak, R. Speiser

AT present, considerable research is being directed toward the development of high-temperature, oxidation-resistant columbium alloys. Columbium. along with molybdenum and tungsten, exhibits good high-temperature strength. Unlike molybdenum and tungsten. however. columbium does not form a volatig oxide below 1375°c.l Although the outermost oxide formed on pure columbium, Cb2O3 is stable in air at elevated temperatures, it is not of a protective nature. It is porous and voluminous, and

Jan 1, 1959

By R. J. Fruehan, F. D. Richardson

Electrochemical measurements have been made of the activity of oxygen in copper and its alloys with silver and tin at 1100" and 1200°C. The galvanic cell used was Pt, Ni + NiO/solid ellectrolyte/[O] in metal, cermet, Pt The results do not support any of the equations so far designed for predicting the activities of dilute solutes in ternary solutions from activities in the corresponding binaries. If, however, a quasichemical equation is used with the coordination number set to unity, agreement between observed and calculated activities shows that this empirical relationship can be useful over a fair range of conditions. SEVERAL solution models have been proposed for predicting the activity coefficients of dilute solutes in ternary alloys from a knowledge of the three binary systems involved. Alcock and Richardson1 have shown that a regular model, and a quasichemical model,' in which the dissolved oxygen is coordinated with eight or so metal atoms, can reasonably predict the behavior of both metal and nonmetal solutes when the heats of solution of the solute in the separate solvent metals are similar. But when this is not so, neither model gives useful predictions unless coordination numbers of one or two are assumed. Wada and Saito3 subsequently adopted a similar model to derive the interaction energies for two dilute solutes in a solvent metal. Belton and Tankins4 Rave proposed both regular and quasichemical type models in which the oxygen is bound into molecular species, such as NiO and CuO in mixtures of Cu + Ni + 0. However, their models have only been tested on systems in which the excess free energies of solution of the solute in the two separate metals differ by a few kilocalories. Ope of the reasons why more advanced models have not been proposed is because few complete sets of data exist for ternary systems in which the solute behaves very differently in the two separate metals. For this reason measurements have been made of the activities of oxygen dissolved in Cu + Ag and Cu + Sn. Measurements on both systems were made by means of the electrochemical cell, Pt, Ni + NiO/solid electrolyte/O(in alloy), cermet,Pt [1] The activity of oxygen was calculated from the electromotive force and the standard free energy of formation of NiO, which is accurately known.5 Before investigating the alloys, studies were made of oxygen in copper to test the reliability of the cell and to check the thermodynamics of the system. Of the previous studies those by Sano and Sakao,6 Tom-linson and Young,7 and Tankins et al.8,7 have been made with gas-metal equilibrium techniques; those by Diaz and Richardson,9 Osterwald,10 wilder," Plusch-kell and Engell,12 Rickert and wagner,13 and Fischer and Ackermann14 have been made by electrochemical methods. EXPERIMENTAL The apparatus employed was the same as described previously,9 apart from slight modification. The molten sample of approximately 40 g was held in a high grade alumina crucible 1.2 in. OD and 1.6 in. long. The solid electrolytes were ZrO2 + 7½ wt pct CaO and ZrO2 + 15 wt pct CaO; the tubes 4 in. OD and 6 in. long were supplied by the Zirconia Corp. of America. They were closed (flat) at one end. In one experiment with Cu + O, both electrolytes were used in the cell at the same time. The reference electrodes inside the electrolyte tubes consisted of a mixture of Ni + NiO. They were made by mixing the powdered materials and pressing them manually into the ends of the tubes, with a platinum lead embedded in them. The tubes were then sintered overnight in the electromotive force apparatus at 1100°C. By sintering the powders inside the tubes (instead of using a presintered pellet9) better contacts were obtained between the electrolyte, the powder, and the platinum lead. Troubles arising from polarization9 were thus much reduced. The electromotive force was measured by a Vibron Electrometer with an input impedence of 1017 ohm; the temperature was measured with a Pt:13 pct Rh + Pt thermocouple protected by an alumina sheath. The couple was calibrated against the melting point of copper. The cermet conducting lead of Cr + 28 pct Al2O3, previously found to be satisfactory9 for use with Cu + 0 was also found satisfactory with Cu + Ag + 0 and Cu + Sn + 0. Superficial oxidation was observed, but it did not interfere with the working of the cell. The reaction tube containing the cell was closed at each end with cooled brass heads and suspended in a platinum resistance furnace. The tube was electrically shielded by a Kanthal A-1 ribbon which was wound round it, and the ribbon was protected by a N2 atmosphere between the furnace and the reaction tube. The cell was protected by a stream of high purity argon which was dried and passed through copper gauze at 450°C and titanium chips at 900°C. All the metals used were of spectrographic standard. Procedure. In studies of the system Cu + 0, be-

Jan 1, 1970

By E. O. Kirkendall

The investigation reported herein was undertaken to obtain data to supplement those presented in an earlier paper,l particularly for longer times at a higher temperature. This information may further develop our knowledge of the mechanism of diffusion in substitutional solid solutions. Diffusion of solute atoms interstitially dissolved is not difficult to visualize: it can take place without much disturbance of the solvent atoms. The mechanism of diffusion of solute atoms substitutionally dissolved is not so easily understood. Many theories have been advanced. Rosen-hain,2,3 Frenkel,4 Smekal,5 Langmuir,3,6 Steigman, Shockley and Nix,' and Johnson8 all proposed theories to explain diffusion. Langmuir's proposed mechanism consisted of a simple cyclic interchange of atoms involving an interchange in lattice positions of four or more atoms. This mechanism, accepted by the author at the time of his previous publication,1 and apparently quite generally accepted, required a net exchange in positions of both solute and solvent atoms in equal numbers. In other words, the rate of diffusion of the solvent and solute atoms would be the same. That this cyclic interchange in lattice positions of solute and solvent atoms in equal numbers is the only true mechanism of diffusion is denied by the evidence presented in this paper. Experimental Procedure This modification of similar procedure1 will be outlined briefly. The method consisted of the following steps: I. A pure Muntz metal (60.6 per cent Cu, 0.1 per cent total impurities) that was almost all beta brass at 780°C. was chosen. 2. The brass was turned between centers in a lathe to a diameter of 0.5965 inches. 3. After the brass was cleaned, it was electroplated with pure copper to a diameter of about one inch. 4. The sample was heated slowly to 400°C. under reduced pressure and held at that temperature for 4 hr. to remove occluded gases. It was then cooled to room temperature. 5. The sample was heated to 780°C. ± 3°C. and held at that temperature for different lengths of time; then quenched. Samples were cut off each time after quenching. Metallographic samples 1/4 in. thick were removed at I hr., 6 hr., 24 hr., 96 hr. and 701 hr. After 96 and 701 hr. samples of about I in. were removed for X-ray analysis. 6. The metallographic samples were polished on the cross section and photomicrographs were taken. 7. The I-in. samples were polished and etched on both ends. With the aid of a microscope each was carefully mounted in a four-jaw chuck in a lathe, so that they could be accurately bored for an arbor. 8. Turnings were taken for each X-ray sample. After each set of turnings, the sample was heated in an oil bath for about 1/2 hr. at 300°C. It was then etched in 25

Jan 1, 1942

By E. O. Kirkendall

The investigation reported herein was undertaken to obtain data to supplement those presented in an earlier paper,l particularly for longer times at a higher temperature. This information may further develop our knowledge of the mechanism of diffusion in substitutional solid solutions. Diffusion of solute atoms interstitially dissolved is not difficult to visualize: it can take place without much disturbance of the solvent atoms. The mechanism of diffusion of solute atoms substitutionally dissolved is not so easily understood. Many theories have been advanced. Rosen-hain,2,3 Frenkel,4 Smekal,5 Langmuir,3,6 Steigman, Shockley and Nix,' and Johnson8 all proposed theories to explain diffusion. Langmuir's proposed mechanism consisted of a simple cyclic interchange of atoms involving an interchange in lattice positions of four or more atoms. This mechanism, accepted by the author at the time of his previous publication,1 and apparently quite generally accepted, required a net exchange in positions of both solute and solvent atoms in equal numbers. In other words, the rate of diffusion of the solvent and solute atoms would be the same. That this cyclic interchange in lattice positions of solute and solvent atoms in equal numbers is the only true mechanism of diffusion is denied by the evidence presented in this paper. Experimental Procedure This modification of similar procedure1 will be outlined briefly. The method consisted of the following steps: I. A pure Muntz metal (60.6 per cent Cu, 0.1 per cent total impurities) that was almost all beta brass at 780°C. was chosen. 2. The brass was turned between centers in a lathe to a diameter of 0.5965 inches. 3. After the brass was cleaned, it was electroplated with pure copper to a diameter of about one inch. 4. The sample was heated slowly to 400°C. under reduced pressure and held at that temperature for 4 hr. to remove occluded gases. It was then cooled to room temperature. 5. The sample was heated to 780°C. ± 3°C. and held at that temperature for different lengths of time; then quenched. Samples were cut off each time after quenching. Metallographic samples 1/4 in. thick were removed at I hr., 6 hr., 24 hr., 96 hr. and 701 hr. After 96 and 701 hr. samples of about I in. were removed for X-ray analysis. 6. The metallographic samples were polished on the cross section and photomicrographs were taken. 7. The I-in. samples were polished and etched on both ends. With the aid of a microscope each was carefully mounted in a four-jaw chuck in a lathe, so that they could be accurately bored for an arbor. 8. Turnings were taken for each X-ray sample. After each set of turnings, the sample was heated in an oil bath for about 1/2 hr. at 300°C. It was then etched in 25

Jan 1, 1942