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By Paul H. Johnson

Heap leaching is a simple means of recovering copper from oxide and oxide-sulfide ores. Although this method requires relatively low capital investment, it suffers from low copper recoveries and relatively high acid consumption. The objectives of this study were (1) to determine what factors influence these shortcomings, and (2) to establish a basis of correlation. between laboratory and field testing. The principal methods of leaching copper ores at the present time are heap, dump, in-place, and vat. A number of references are presented in the bibliography on the theoretical and practical aspects of these methods. In the heap-leaching method, crushed or uncrushed oxidized copper ore is placed on a prepared drainage pad. Acid leach solutions are dis¬tributed over the top of the heap, caused to percolate downward through the ore bed by gravity, and are drained from its base. The leach duration is generally a matter of a few months. Dump leaching is used to recover copper from very low-grade oxide-sulfide pit-waste materials. Here again, leach solutions are, percolated downward through a heap. However, in this method, little or no acid is added to the leach liquors, prepared drainage pads are not used and the leaching cycle is generally measured in terms of several years. Leaching agents are usually autogenously generated by the breakdown of sulfide minerals within the dump.

Jan 1, 1970

By R. B. Fermor

"The tyndalloscope is used in Europe for dust-hazard assessments in both coal and metal mines. Dust-hazard conditions can be directly evaluated by the tyndalloscope in many underground working situations, once the basic standard table or tables have been prepared from representative mine-rock samples.The tyndalloscope is excellent, in many cases, for diagnostic dust sampling during a working shift, because individual readings can be taken to within three-minute intervals. The limitations of the tyndalloscope are also discussed.The author suggests that a combination of both the tyndalloscope and gravimetric sampling methods would be an ideal match for most mine dust-hazard assessments."

Jan 1, 1970

By M. Murakami, Y. Murakami, O. Kawano

The formation and growth of Guinier-Preston zones in Al-Zn alloys containing 4.4, 6.8, 9.7, and 12.4 at. pct zn have been studied by the X-ray small-angle scattering method. Particular attention was paid to the effects of small amounts of third elements silver, silicon, and magnesium on the formation and growth of G.P. zones. It was noticed that an appreciable number of G.P. zones were formed during the course of rapid cooling and that the size, volume fraction, and number of these G.P. zones were influenced by the existence of the third elements. During subsequent aging it was also found that the addition of both silver and silicon lowered the temperature for the growth of G.P. zones, whereas the addition of magnesium raised it. These results were explained in terms of the mutual interactions among zinc atoms, vacancies, and the third elements. A number of studies on the formation and growth of Guinier-Preston zones in Al-Zn alloys have been reported.1-4 Panseri and Federighii have found that the initial stages of zone growth take place at temperatures as low as around -100°C. For investigation of the mechanism of the initial stages of zone growth, growth studies must be carried out at low temperatures. In order to investigate the possibility of the formation of G.P. zones by the nucleation mechanism or the spinodal decomposition during quenching which was reported by Rundman and Hilliard,5 the examination of the as-quenched structure must be performed. In this paper the investigation of the early stages of the formation and growth were determined by means of the X-ray small-angle scattering method. With this technique, change of X-ray scattering intensities was measured while quenched specimens were heated slowly from liquid-nitrogen temperature to room temperature. At as-quenched state and after heated to room temperature, investigation of zone size, volume fraction, and zone number per unit volume was carried out. Measurements on these specimens yielded information on the early stages of zone formation and growth. Measurements were made also on specimens quenched to and aged at room temperature. From these measurements the previously reported model6 for the later stages of growth is confirmed; namely, the larger zones grow at the expense of smaller ones. Three elements, silver, silicon, and magnesium, were chosen as the third elements for the following reasons: Silver. In the binary A1-Ag alloy the spherical disordered 77' zones were observed immediately after quenching.7 Therefore, in the Al-Zn-Ag alloys, it is suggested that silver atoms might induce cluster formation during quenching. Also, since the migration energy of the zinc atoms was found to be raised by the addition of silver atoms,' silver atoms may have a great effect of the zinc diffusion, especially during low-temperature agings. Silicon. The effects of the addition of silicon atoms were found to be marked, especially at low-tempera-ture aging. In the binary Zn-Si system, no mutual solid solubilities between silicon and zinc9 and no in-termetallic compounds10 are reported to exist. Shashkov and Buynov11 investigated the behavior of silicon atoms in Al-Zn alloys and showed that silicon was not in the G.P. zones. The interaction between silicon atoms and vacancies is strong enough to increase the quenched-in vacancy concentration.* Magnesium. Magnesium atoms are reported to trap quenched-in vacancies and after much longer aging times these trapped vacancies will become free and act as diffusion carriers.13 Therefore at intermediate aging times, the diffusion of zinc atoms in Al-Zn-Mg alloys will be slower than in the binary Al-Zn alloys, whereas at longer times zinc diffusion will become faster. EXPERIMENTAL PROCEDURE The alloys used in this investigation had compositions of 4.4, 6.8, 9.7, and 12.4 at. pct Zn with or without 0.1 and 0.5 at. pct Ag, Si, or Mg. The alloys were prepared from high-purity aluminum, zinc, silver, silicon, and magnesium, with each metal having a purity better than 99.99 pct. The analyzed composition of the specimens is given in Table I. The measurements of the X-ray small-angle scattering were carried out with foils of 0.20 mm thick. The change of the scattering intensity was always measured at the fixed scattering angle of 20 = 2/3 deg. This angle exists nearly on the position of the intensity maximum. The value of the interparticle interference function14 which has large effect in this range of angles may not change abruptly in the case of the spherical shape of small zones. Therefore, from the above considerations, it is concluded that an increase of the intensity measured at this constant angle corresponds to an increase of the average radius and volume fraction of G.P. zones. The specimens were homogenized at 500°, 450°, and 300°C for 1 hr in an air furnace. For the study of the formation and growth at low temperatures, the foil

Jan 1, 1970

By N. S. Bornstein, M. A. DeCrescente

ThE nickel and cobalt base superalloys employed in gas turbine engines under some conditions' oxidize at an accelerated rate when exposed at elevated temperatures to atmospheres containing minor quantities of sea salt. It is generally agreed by investigators in the field that the major steps comprising this phenomena of accelerated oxidation, also called hot corrosion or more commonly, sulfidation, are a) a slag composed primarily of Na2S04 is formed on turbine components, b) the protective oxide scale is rendered ineffectual, c) the slag reacts with. the substrate to form metal sulfides, and d) the substrate is rapidly oxidized. Sodium sulfate, a minor constituent of sea salt, is formed within the gas turbine engine from the reactions between NaC1, the major constituent of sea salt, and the oxides of sulfur.' Depending upon concentration, engine compression ratio, and temperature, the Na2S04 will be present in the gaseous or condensed state. It has been determined that in order for sulfi-dation to occur the Na2S04 must be present in the condensed state.' Although a number of sulfidation mechanisms have been postulated, there is no consistent explanation of oxide scale breakdown and subsequent catastrophic oxidation. Some investigators believe that after oxide scale breakdown, the Na2SO4 reacts with the substrate to form lower-valent sulfur compounds. The accelerated rate of oxidation is due to oxidation of a nickel-sulfide phase." Other investigators believe that sulfur from the fused salt reacts with chromium in the alloy to form chromium-rich sulfides; thereby depleting the alloy of an element which imparts oxidation resistance.3,4 This publication will demonstrate that the accelerated rate of oxidation associated with sul-fidation is due to interactions between Na20, a con-stituent of NazSO.,, ancl the substrate. The aim of this study was to separate and determine the effect of compounds of sulfur and sodium on the oxidation kinetics of various nickel-base superalloys, in order to elucidate the sulfidation mechanism. The work reported herein is sponsored in part by the Naval Ship and Development Center-Investigation of EXPERIMENTAL PROCEDURE The nickel base alloys B-1900, U-700, and Waspaloy were chosen for this study. The nominal compositions are presented in Table I. The specimens, approximately 1 in. by 1 in. by 0.060 in. received in the "as cast" condition were polished with 600 grit emery, washed, and rinsed with acetone immediately prior to oxidation experiments. Sulfida-tion attack was duplicated in the laboratory by apply-ing a saturated aqueous solution of Na2S04 onto the al loy substrate and subsequently exposing the specimens in oxygen at elevated temperature. The method of Na2S04 application is described elsewhere in detail.6 In another set of experiments the affected substrate microstructure associated with sulfidation was reproduced free of the normal oxide scale, by reacting and diffusing elemental sulfur into the alloy. The experimental procedure is also described elsewhere in detail. All oxidation studies were performed using an Ainsworth thermobalance type RV-AU-1, which is readable to 0.01 mg and is reproducible to ±0.03 mg. The specimens, introduced into a heated furnace, were exposed in the temperature range 800" to 1000°C

Jan 1, 1970

By R. H. Adams, A. M. Khan

The Huntington Beach oil field is on the Pacific Coast, southeast of the City of Los Angeles (Fig. 1). It lies both onshore and offshore. Most of the onshore section is operated by Standard Oil Co. of California, WOI. The Tar reservoir is of upper Pliocene age, about 200 ft thick, and consists principally of fine-grained, unconsolidated, somewhat shaly sand, with thin inter-bedded shale stringers throughout (Fig. 2). The reservoir is a broad, highly faulted, elongated anticline, with an areal extent of about 370 acres. Most of the faults bisecting the structure are normal, trend north-south, and are the main cause of reservoir discontinuity (Figs. 3 and 4). From 1964 to Dec., 1967, 259 steam stimulations were performed on a total of 125 Tar sand wells. Eighty-six new wells were drilled and steam stimulated. Of the total, 96 have been stimulated twice, 34 three times and 3 four times. During this same period, a two-injector steam drive pilot has been in progress. The response obtained from this project has been compared with the response to cyclic stimulation. This paper presents an analysis of the field observations for the two methods of thermal recovery. History of Development Drilling to the Tar pool commenced in 1924 with an initial well production of 40 to 50 B/D of 12o API gravity oil. Complete primary development of the pool has been spread over several years. Approxi- mately 40 wells were drilled during the first phase of development, which was completed in 1945. The subsequent primary development started in 1960 with initial well productions of 30 to 40 B/D oil. Thirty-seven wells were completed in the Tar pool during this phase. For the most part, slotted, gravel flow packed liners have been used in the wells in this pool. A cyclic steam stimulation pilot was initiated in March, 1964. Based on the very successful stimulation in the pilot area, the cyclic stimulation project was expanded to include all of the Tar pool wells producing at the end of 1965 (Fig. 5). Also, a development drilling program was begun at this time. To date, 86 new wells have been drilled under this program. The number of wells drilled each year in this secondary phase of development is also shown in Fig. 5. New Well Completion Practices Most of the new wells have been completed to produce from both the Upper and Lower Tar zones. Generally, a casing stub is cemented from the top of Lower Tar to the base of clean Upper Tar sands to exclude intermediate water-bearing sands. The water string is then cemented from the top of Upper Tar to about 1,500 ft with neat cement and 30 percent silica flour. The annulus from 1,500 ft to surface is then filled with a petroleum-based gel through a high-temperature port collar. Once again, a history of sand-free production dictated the use of 60-mesh gravel flow packed liners. The Upper and Lower Tar

Jan 1, 1970

By Carl L. Bieniewski

U.S. molybdenum production increased fivefold from 18.2 million pounds in 1946 to 90.5 million pounds in 1966, and constituted 87.3 percent of the total free world supply in the 1946-66 period. Mining development in other free world countries in the next few years may reduce the magnitude of the U.S. position, although similar development planned for the United States may counteract some of the relative gains by those countries. In 1966 two-thirds of the reported molybdenum consumption in the United States by end uses was as an alloying element in steel. Molybdenum also has important use as an alloying element in iron and high-temperature alloys. Consumption of molybdenum metal for making fabricated parts has increased in the past few years, especially in the space and nuclear industries. Molybdenum compounds are used mainly for making pigment, catalysts, and lubricants. Based on producer reports of shipments of primary products to domestic customers, U.S. consumption of molybdenum increased from 16.5 million pounds of molybdenum in 1946 to 65.6 million pounds in 1966. U.S. molybdenum reserves are now estimated to be 5.9 billion pounds of recoverable molybdenum, an increase of 2.1 billion pounds above previous estimates. Molybdenum ores account for 71.4 percent of the reserves, copper ores for 22.3 percent and copper-molybdenum, tungsten, and uranium ores for 6.3 percent. Several methods for predicting future demand are illustrated and estimates of demand using these methods were made for 1975. Based on present capacities and announced company plans for future developments, estimates of annual production were made for 1967 through 1975 for the United States, Canada. Chile, Peru, and the free world. These data indicate that molybdenum production in 1975 for the free world is expected to be 246 million pounds with the United States producing 68.2 percent and Canada, Chile, and Peru 30.3 percent.

Jan 1, 1970

By Alfred E. Schwaneke

A new high-temperature soft soldering system has been developed by the Bureau of Mines for use on copper, copper alloys, and low-carbon steel; the method is applicable to automobile radiators and home appliances. The system uses a unique sacrificial metal coating method to promote spontaneous wetting and spreading of zinc and zinc alloy solder: on metallic substrates. The 10-5 to 10-6 cm thick, electroplated or sputtered, sacrificial nickel coating is absorbed by the molten filler alloy during soldering and produces a direct solder-substrate metallic bond. Preliminary measurements on butt joints with copper members give tensile strengths up to 22,000 psi at room temperature using 95 Zn-5 Al alloy as solder. Spontaneous wetting, spreading, and capillary penetration are extremely rapid and produce joints as easily as 50-50 tin-lead solders. Recrystallization or annealing of the wrought copper joint members is negligible at the soldering temperatures of 450° to 490° C and lower. A list of fluxes and solder alloys is included in the report.

Jan 1, 1970

By E. B. Wilson

"Although the Operations Research technique of Reliability Theory has been applied with marked success in many fields, including the Apollo spaceship programs, the concept of reliability has not been generally adopted in mining and other heavy industries. Of course, reliability, or the probability that a system will be able to operate without a failure for a given interval of time, does not require the same emphasis in mining as in the aerospace industries. Nevertheless, certain aspects of Reliability Theory can be followed advantageously. For example, reliability calculations can determine the best time to overhaul and whether to retain stand-by units.The usefulness of the pseudo-operations research technique known as Replacement Theory is more readily re-cognized by the maintenance engineers in mining and other heavy industries. One of the least complex models enables the optimum Lifetime of an asset to be determined."

Jan 1, 1970

By P. S. Kotval, H. Hahell

PRECIPITATION of M23C6 carbides at grain boundaries in austenitic steels and nickel base superalloys has received considerable attention. Hatwell and Berghezan,1 in a study using carbon extraction replicas, observed that dendritic growth of the M23C6 carbide phase occurred at grain boundaries in austenitic steels. Merrick and Nicholson2 have observed that in thin foils of "Nimonic 75" alloy the precipitation of M23C6 carbide was discontinuous at grain boundaries. Lewis and Hattersley3 have suggested that the type of M23C6 precipitation observed in Ni-Cr austenites represented the early stages of discontinuous precipitation. In a more recent study, Singhal and Martin4 have concluded that grain boundary M23C6 precipitation involves the migration of an austenite grain boundary by a mechanism very similar to that proposed by Tu and Turnbull.5 Tu and Turnbull's suggestion essentially involves grain boundary migration under the driving force arising from the difference between the surface free energies of the opposite sides of the plate. Thus, Singhal and Martin's observation4 implies that the first stage of discontinuous precipitation has taken place and that the grain boundary has provided a diffusion short circuit for the sub-stitutional solute atoms (principally chromium) which assist the preferential growth of the M23C6 plate in contact with the grain boundary. However, no evidence of the characteristic cellular morphology typical of discontinuous precipitation was found in Singhal and Martin's studies. Presumably, this is due to the low volume fraction (i.e., low supersaturation of solute) of the precipitating carbide reported by Singhal and Martin.4 Recently, Raymond6 has studied precipitation of the M23C6 carbide in Incoloy alloy 825 and shown that the growth of this phase is perpendicular to grain boundaries at 1400°F and in the plane of the grain boundary at 1700°F. The former aging condition resulting in discontinuous or "cellular" precipitation. Raymond has suggested an explanation for this behavior based on the relative rates of chromium diffusion by volume and grain boundary diffusion at the two different aging temperatures. In the course of a recent investigation on precipitation behavior in several ' strengthened superalloys, precipitation of M23C6 carbide at grain boundaries was studied. Under conditions of a high degree of supersaturation, the M23C6 carbide precipitates in the discontinuous or cellular morphology in Waspalloy (Ni-18.51 Cr-2.0 Fe-3.53 Mo-1.16 Al-2.78 Ti-0.09 C). This note presents electron microscopy observations of this mode of precipitation and its effect on mechanical properties. Specimens of Waspalloy after "solution" heat treatment at 1950°F show essentially single phase matrix with a few residual particles of "primary" MC carbide. In normal commercial heat treatments, precipitation of Ni3(Al,Ti) ordered fcc r' phase occurs throughout the matrix and M23C6 precipitates as globular particles at the grain boundaries. In these commercial heat treatments the degree of supersaturation during precipitation is low. However, if specimens of Waspalloy are quenched from the solution heat treatment temperature of 1950°F and then aged at an aging temperature where the degree of supersaturation is high, discontinuous precipitation of M23C6 occurs. Figs. 1 and 2 show thin foil micrographs of Waspalloy, solution heat treated at 1950°F, water quenched, and aged at 1292° and 1598°F, respectively, for 500 Fig. 1—Thin foil of Waspalloy, solution heat treated at 1950°F for 1 hr, water quenched, and aged for 500 hr at 1292°F. Magnification 15,500 times. Fig. 2—Thin foil of Waspalloy, solution heat treated at 1950°F for 1 hr, water quenched, and aged for 114 hr at 1598° F. Magnification 13,000 times.

Jan 1, 1970

By B. J. Dalton

Several relationships between coexisting phases for analytical binary solutions near the critical point are given. These relationships were developed from a consideration of a (G u, P) surface at constant temperature and a (G u, T) surface at constant pressure, where G is the molal Gibbs free energy, u is the concentration of component 1 expressed as a mole fraction, G is the pressure, and T is the temperature. These formulas should facilitate the calculation of some of the quantities useful in making thermodynamic consistency checks on phase equilibria data about the critical point.

Jan 1, 1970

By Franklin H. Persse

Domestic bismuth supply was projected from production figures for the ores in which it occurs--copper, lead, zinc, and tungsten. Published and unpublished data concerning host ores were examined to determine bismuth reserves and resources, and mine production. Potential recoverable bismuth occurring with reserves and resources of copper, lead, and zinc was estimated to be 36.3 million pounds. A bismuth availability diagram was developed from quantity estimates and ratios of production cost to value for these host ores. Additional recoverable bismuth occurring with domestic tungsten reserves was estimated to be 1.5 million pounds. Domestic byproduct production of bismuth will approximate 1.3 million pounds annually by 1980. This quantity will provide about 37 percent of the 3.5-million-pound estimated requirement for that year. Known world supply of bismuth appears to be sufficient for world demand to the end of this century. The study indicates that bismuth reserves and potential resources in the rest of the world have not been adequately reported.

Jan 1, 1970

By A. H. Larson, R. J. McClincy

The activity of Sb,03 in PbO-Sb,03 slags containing less than 50 mol pct Sb,03 was determined by the inert-gas saturation method at 700°C. In this composition range, the activity gf SbzO3 shows a strong negative deviation from ideality. The activity of PbO in these slags was calculated by application of the Gibbs-Duhem iniegration to the Sb203 activity data. The calculated activity of PbO in slags containing more than 63 mol pct PbO was found to deviate in a positive direction from ideality uthile a negative deviation was found for slags containing less PbO. The standard Gibbs free energies of formation of Sb,03 and PbO. Sb203 have been calculated and compared with existing data in the literature. The activity of Sb203 in PbO-Si0,-Sb203 (PbO/SiO, = 2) slags containing less than 25 mol pct Sb,03 was also determined by the inert-gas saturation method at 700°C. In this composition range, the activity of Sbz03 shows a very large negative deviation from ideality. VERY little experimental work has been published in the past to determine equilibrium data in the oxide systems connected with the refining of lead. These data are of value since impurities such as antimony, arsenic, and tin must be removed from lead and recovered for further treatment. Equilibrium studies on antimony and arsenic systems are also of interest for the design of new processes for lead refining and lead dross treatment. Maier and ~incke' first determined the liquidus curves for the PbO-Sb203 system and identified the compound PbO . Sb203. They found the phase diagram for this system to be two simple eutectics located on either side of the congruent melting compound. They also determined a very limited amount of vapor pressure data for Sb406 abbve PbO-Sba3 melts at 697"~. A second phase diagram investigation on this system was reported by Hennig and Kohlmeyer' who confirmed the existence of the compound PbO . Sb203 as well as the form of the diagram. A disagreement was noticed, however, in that their liquidus temperatures over nearly the entire composition range were higher than those reported by Maier and Hincke. Barthel~ and pelze14 redetermined the liquidus curve at the PbO-rich end of the PbO-Sb@, system and agreed very closely with the results of Maier and Hincke. None of the investigators mentioned above reported any mutual solid solubility in the PbO-SbD3 system. Zunkel and Larson5 have determined the phase diagram for the PbO-rich end of the PbO-Sb203 system by slag-metal equilibrium studies in the Pb-PbO-Sb203 system and by thermal analysis studies in the PbO-Sbz03 system. A maximum solid solubility of 5.6 mol pct Sb203 in PbO was observed at the eutectic temperature of 604°C. Their results for the phase diagram agree favorably with those of Maier and Hincke. The vapor pressure of Sb2O3 in the temperature range from 470" to 800°C has been determined by Hincke, using a modification of the transportation meth~d.~ His results for temperatures below the melting point of Sba3 are the only data reported in the published literature. The predominant vapor species has been shown to be Sb,06 by Norman and staley.? Myzenkov and Klushin,8 using the boiling-point method, have determined the pressure of Sb406 above liquid SbD3 in the temperature range from 715" to 1025°C. The agreement between these two studies is not very close. A portion of the discrepancy lies in the fact that Hincke used silica crucibles, which were attacked by the liquid Sbz03 at high temperatures. This fact does not account, however. for the large difference observed at the melting point. ~aier' gives a brief summary of vapor pressure data for Sb,O, above pure liquid Sbz03 which agree quite well with the data of Myzenkov and Klushin at temperatures near the melting point. This paper describes the determination of Sb2O3 activity data in the PbO-Sb203 and Pb0-Si02-Sb203 (PbO/SiOz = 2) systems by the inert-gas saturation method. These activity data are compared with the data calculated by Zunkel and arson. EXPERIMENTAL Materials. The materials used in this investigation were analytical reagent-grade PbO (99.8 pct PbO, 0.14 pct insoluble in CHsCOOH, 0.02 pct not precipitated by HB, 0.1 pct CaO, and 0.08 pct SiOz), Sbf13 (99.6 pct Sb203, 0.004 PC~ C1-, 0.005 PC~ SO;-, 0.15 p~t AS, 0.001 pct Fe, and 0.03 pct other heavy metals such as Pb), and SiOz (chromatographic grade). Apparatus for Vapor Pressure Determinations. The apparatus used in this investigation consisted of a transportation reaction system with two separate gas trains. The argon transporting gas was first mixed with a small amount of hydrogen, metered, and dried by passage through silica gel and anhydrone drying tubes arranged in series. After this preliminary drying, the argon was passed through copper wool at 500°C to convert the residual oxygen to water vapor which was removed by three anhydrone drying tubes. A second stream of argon was metered and dried and then passed around the outside of the alumina reaction tube to flush away the volatile species to pre-

Jan 1, 1970

By Richard J. Lewandowski

Corrosion and product contamination have been difficult problems for extractive metallurgy industries in the U.S. because of the highly active chemicals used. During the past twelve years, other industries, particularly the chemical and paper segments, began to combat this problem with some degree of success using newer materials of construction, including reinforced plastics. These materials are made by combining a corrosion resistant thermosetting resin with a glass fiber reinforcing material and are used to con¬struct hoods, stacks, blowers, tanks, towers, pipe, and equipment of the most complex configurations. For service in contact with aggressive chemicals, the equipment is most often fabricated with the bisphenol-A fumarate polyester resins because of their resistance to corrosive attack. Data from both laboratory work and case histories of field applications are presented-for many common chemicals found in extractive processes. Information is also presented concerning design standards and recommended construction procedures

Jan 1, 1970

By R. V. Lundquist

Past reports by the Bureau of Mines have described the extraction of alumina from numerous aluminum silicate materials by the lime-soda sinter process. The results from pilot-plant investigations of six materials, with alumina-to-silica mole ratios from 0.3 to 8.7, indicated a relationship between the alumina-silica ratios and the processing characteristics of the sinter. A series of laboratory tests was conducted to define this relationship. Sinter and leach tests determined that an alumina-to-silica mole ratio of 0.90 or greater resulted in the best alumina and soda recoveries while leaving the leach slurries practically free from any tendency toward gelation. The widely different chemical and mineralogic properties of the various aluminous materials used in compounding the mixes had no perceptible effect on the leaching characteristics of the sinter. The blending of low-cost, high-alumina materials with aluminum silicate materials to give an alumina-to-silica mole ratio of 0.90 or greater would improve alumina and soda extraction and minimize operating problems in the lime-soda sinter process.

Jan 1, 1970

By R. F. Lynch, J. D. Wood

The Al-1.0 pct Mg alloy 565 7 was studied using optical microscopy and electron microprobe X-ray analysis. Constituent particles were found to exist inter-dendritically in the as-cast material in a region of precipitate free a -aluminum. Five phases besides a fine precipitate and a-Al were identified in the cast structure: Fel3, Fe2Al7, Mg2Al3, CUMgAl2, and Cu2FeAl7. Thermal treatments conducted for 100 hr at 1180°, 1130°, 1080°, 1030°, 980°, and 880° F revealed a general dissolution and spheroidization of the in-terdendritic constituent network observed in the cast structure. The principal constituents present in the thermally treated structures were FeAl3 and Fe2Al7 with the relative amount of Fe2A17 to FeAl3 increasing with a decrease in the treatment temperature. The phases Present in the wrought structure were identical to those observed after the thermal treatments, with the constituent particles strung out in the direction of rolling. ALLOY 5657 is a nonheat-treatable commercial purity Al-1.0 pct Mg alloy utilized extensively because of its bright finishing characteristics. This investigation was conducted to determine the constituents present in 5657 alloy, and to study the effect of extended thermal treatments on morphology. Numerous studies have been carried out to establish the equilibrium diagrams for various aluminum systems,1-3 with phase identification based on X-ray analysis, morphology, and the etching response of relatively large particles. Phragmen4 conducted a study of the phases in aluminum eutectic systems and compiled a "corrected" table of etching responses, drawing on his work plus that of Schrader,5 Keller and Wilcox,6 and Mondolfo.7 A review of the original work of Keller and Wilcox, and Mondolfo, which was concerned with the constituents found in commercial alloys, reveals that in numerous cases their etching responses differ from those reported by Phragmen and from each other. These inconsistencies may occur because a specific constituent will react to a given etch in a varying manner depending upon its size, the elements dissolved in the phase, the other constituents surrounding a phase, and the solute content of the matrix. Work with a commercial orientation was conducted on alloys 2024 and 3003 by Sperry8,9 and on alloy 3003 by Barker,10 where the relationship between the phase diagram and the nonequilibrium structure of an alloy was examined. Backerud11 investigated the A1-Fe binary system and found that at high cooling rates the equilibrium eutectic reaction forming a-A1 and FeA13 is replaced by another lower temperature eutectic reaction forming a-A1 and metastable FeAl6, a constituent first identified by Hollingsworth et al.12 Most of the above mentioned studies were conducted on materials having a significantly greater alloy content than 5657 alloy, where the relatively small size and sparse distribution of second phase particles hinders the process of identifying constituents. EXPERIMENTAL PROCEDURE Material with a composition as given in Table I was examined in the as-direct chill cast, hot rolled and cold rolled conditions, and after thermal treatment of the cast structure. Thermal treatments were terminated by a water quench. Microscopic examination was conducted under various lighting conditions following the application of standard etchants as specified in Table 11. A semi-quantitative electron microprobe X-ray analysis was conducted for Al, Mg, Fe, Cu, Si, Zn, and Ti. RESULTS AND DISCUSSION Microstructure of the As-Cast Material. Particles of second phase material were found to exist inter-dendritically, principally in regions of precipitate free a-Al, as illustrated in Fig. 1. Adjacent to the ingot edge was a region of inverse segregation, resulting in an increased amount of second phase material containing large sized particles which aided in phase identification. Phase Identification. Cast Structure. Five phases besides a-Al and a fine precipitate were identified using optical microscopy and electron microprobe X-ray analysis, as presented in Tables II and III, respectively. FeA13 and Fe2A17 are often found with Fe2A17 forming a sheath around the core of FeAl3, resulting from an incomplete peritectoid reaction. These phases have a nearly identical appearance under white light, although they are easily differentiated under crossed polarizers, as characteristically illustrated in Figs. 2(a) and 2(b), respectively. Microprobe analysis con-

Jan 1, 1970

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. Gaucher, M. St-Amant

"Among the electromagnetic surveys performed by SOQUEM in the last three years, a certain number of the more instructive cases have been chosen to illustrate the theory of electromagnetism by field examples of: (a) The depth penetration of the TURAM as compared to the SLINGRAM (Ronka) method. (b) The limitations of the TURAM as compared to the SLINGRAM method when a conductor dips the wrong way, or when it is small in size. (c) The expression of a shallow-dipping conductor in a SLINGRAM survey. (d) The effect on the SLINGRAM survey of deep ditches or reef structures.(e) A comparison between the CRONE and the SLING-RAM method in the Abitibi clay belt, by means of field and model studies, indicating a usually better signal-to-noise ratio for the SLINGRAM method. From the above and from other experiments, different electromagnetic methods are now being used by SOQUEM, depending on field conditions."

Jan 1, 1970

By Gary A. Kingston

Chromium resources in the United States are estimated at 1.8 million tons of recoverable chromium contained in 22.5 million tons of chromite-bearing material. Additional resource is presumed existent in large, but as yet undetermined, quantities of material containing less than 10 percent Cr203. No domestic resources are being mined presently (1969). Excluding transportation charges to domestic consuming areas, the total 1.8 million tons of chromim is estimated to be available, in ore or concentrate, at costs up to $0.64 per pound; 63 percent of the total is available under $0.11 per pound; and 38 percent under $0.08 per pound. It is judged that transportation from the resource areas to the existing market centers would add nearly $0.05 to the cost of a pound of chromium contained in ore or concentrate. Technically effective beneficiation methods have been developed for much of the known domestic resource, and further development might reduce costs of processing these materials. However, at present, domestic chromium resources are noncompetitive with foreign sources.

Jan 1, 1970

By Albert J. Forney

A process for the manufacture of high-Btu gas from coal has been developed by the Bureau of Mines. The process consists of fluid-bed gasification of the coal, followed by the gas treatment steps of gas purification and methanation. Advantages of the system are that caking coals can be used directly, and more than half of the ultimate methane is made in the gasifier.

Jan 1, 1970

By Hsun Hu, B. B. Ruth

The rates of migration of high-angle boundaries in zone-refined aluminum crystals rolled 20 to 70 pct in the (110)[i12/ orientation were studied. Following a recovery anneal at an appropriate temperature to stabilize the polygonized structure, boundary migration rates of artificially nucleated grains were measwed isothermally at several temperatures. Results indicate that the rate of boundary migration depends strongly on the amount of deformation and on the cell size of the polygonized matrix, and is related to the driving free energy by a power function. The degree of anisotropy in growth 0.f the re crystallized grains nn&apos;th preferred mientation is independent of deformation; the migration rates of the fast-moving and the slow-moping boundary segments of a gowing grain differ by as much as one order of magnitude. The actir\ation energy fm a grain boundary migration, although nearly the same for both the fast-moving and the slow-moving boundaries for a given deformalion, decreases from 45 to 30 kcal per mole with an increase in deformation from 20 to 70 pct reduction. Re crstallization by the growth of the artificially nucleated grains results in preferred orientation. The Percentuge of&apos; grains favorably oriented for growth increases with increasing deformation. None of these grains corresponds to the ideal Kronberg-Wilson orientation relationship. The observed growth aniso-tropy is discussed in terms of boundary structure. The boundary velocity as a function of the cell inter -facial area, or the driving free energy, is discussed in the light of current theories of boundary migration. It is well established that recrystallization with re-orientation occurs by the migration of high-angle boundaries of strain-free grains. The driving force for this process is provided by the free energy stored in the metal during deformation. A quantitative study of the effect of varying driving force on grain boundary migration in deformed metals has not been possible heretofore, primarily because of: 1) concurrent recovery steadily decreasing the available driving free energy for boundary migration, &apos;-3 and 2) in-homogeneity of strain in the deformed metal.4 Aust and Rutter3 studied grain boundary migration in striated single crystals of zone-refined lead. Although the driving free energy in such crystals remains unaltered during annealing, this method does not provide a range of driving free energies over which measurements of grain boundary migration can be made. In the present investigation, the rates of migration of high-angle boundaries in deformed aluminum zone- refined single crystals were studied at various temperatures, after deformation ranging from 20 to 70 pct reduction by rolling at -78°C in the (ll0)[i12] orientation. The boundary migration rates along different crystallographic directions were determined under steady-state conditions, i.e., in the absence of competing recovery processes or impingement of recrystallized grains growing into the deformed single crystal matrix. Simultaneous recovery was eliminated by suitable anneals prior to the boundary migration measurements. The recrystallized grains, which grew a ni so tropically into the homogeneously polygonized matrix, developed flat boundary segments during early stages of growth. These boundary segments subsequently migrated along a direction approximately normal to the boundary plane into the matrix rystal. Increasing deformation over the range employed was estimated to increase the driving free energy for boundary migration by about five times. The kinetics of the boundary migration process, examined under these conditions, indicate that the boundary velocity is greatly affected by a small change of the driving free energy in the matrix crystals. These results were examined in the light of the current theories of grain boundary migration. EXPERIMENTAL PROCEDURES Single crystal strips (9 by 1 by 0.125 in.) of zone-refined aluminum, were seed-grown by the Bridgman method in a high-purity graphite mold (<lo ppm ash) at 1 in. per hr. Precautions were taken to minimize contamination of the metal during crystal preparation and subsequent handling. Spectrographic analysis of the metallic impurities in the grown crystals is Qven in Table I. The crystals were rolled in the (110)[112] orientation at -78°C to various reductions in thickness, ranging from 20 to 70 pct, in 10 pct increments. The desired reduction was achieved by many rolling passes, each being no more than 0.002 in. To minimize surface friction, the crystal was rolled between two thin layers of teflon. For those crystals rolled more than 40 pct, it was necessary to remove the disturbed surface layers by electropolishing at -5" to -10°C at an intermediate stage of rolling. The edges of deformed crystals were removed by a jeweler&apos;s saw while submerged in alcohol at -78° C to obtain samples of about ? by i in. The distorted metal at the cut edges and the surface layers were then removed by electropolishing, with removal of a minimum of 0.004 in. from each surface. The thickness of the crystals prior to rolling was chosen so that the final thickness was 0.025 in. for all samples. These deformed single crystals were each prean-nealed for 1 hr at an appropriate temperature in the range of 130" to 280°C, depending upon the amount of deformation. The purpose of this preannealing was to

Jan 1, 1970