Search Documents

By R. P. Aikman, F. G. Miller, J. M. Podgursky

As part of a larger study of the mechanism of froth flotation of coal, the rates at which coal particles of various size and specific gravity react to froth flotation were investigated. Results of this study show that in flotation: I) recovery rate increases, but selectivity decreases with a decrease in particle size down to 100 mesh, and 2) recovery rate is constant for all sizes between 100M and 325M. n response to the growing demand for low-sulfur coking coal for iron making, the coal industry is continually striving to perfect methods for cleaning coal to acceptable ash and sulfur levels while maintaining maximum product yield. By present standards the industry has adequate processes for cleaning coarse coal, i.e., + 28 mesh, at almost any desired specific gravity. However, in the case of fine coal, i.e., —28 mesh, neither of the two existing processes - froth flotation or hydrocycloning — in its present state of development yields products that are comparable in ash and/or sulfur content to products normally obtained from coarse coal processes. The work outlined in this paper is part of a larger study directed toward maximum exploitation of froth flotation for fine coal processing. The concepts and data presented are now serving as a basis for designing fine-coal circuits in which improved efficiency is obtained by optimum use of froth flotation with other fine-coal processing methods. The paper includes: 1) A discussion of the value of a detailed wash-ability study as a method of assessing the problems associated with fine coal processing, 2) A general discussion of hydrocyclone principles, included to serve as a basis for understanding the mechanism of coal flotation, and 3) A detailed discussion of the mechanism of coal flotation, as well as the research leading to the optimum use of froth flotation in combination with other fine-coal cleaning methods to provide efficient fine-coal processing. Our study of the rates at which coal particles of various size and specific gravity react to flotation shows that in flotation: 1) recovery rate increases but selectivity decreases with a decrease in particle size down to 100 mesh, 2) recovery rate is constant for all sizes between 100 mesh and 325 mesh, and 3) the flotation process effectively rejects only those extremely fine particles which do not contain surface carbon. (Because of this feature, froth flotation is an excellent method for rejecting clays - the only extreme fines in - 325-mesh coal that are always carbon free.) Washability studies of flotation products are used to assess flotation efficiency. These studies show that: 1) the increase in percent sulfur in flotation products above the theoretical sulfur content as defined by the washability study is due almost entirely to flotation of fine high-specific-gravity particles that are part coal and part pyrite, and 2) in a given size range particle floatability decreases with an increase in particle specific gravity. Error curves are explained and are used to compare the mechanisms of coal flotation and hydrocycloning. These comparisons show that hydrocyclone performance is affected primarily by particle mass, i.e., particle specific gravity and size, whereas coal flotation performance is dependent on both the particle mass and the coal surface available for bubble attachment. Since the error curve is a basic tool for rating the efficiency of any coal processing system, it will be useful to quickly review the principles of error curve construction. RATING COAL-PROCESSING EFFICIENCY BY THE ERROR CURVE The organic component of coal is of lower specific gravity than its impurities, and the most effective principle for coal concentration is therefore separation on the basis of specific gravity. However, since there is no sharp dividing line between pure coal and pure ash components, specific gravity must be closely controlled if the product is to have acceptable quality at maximum yields. In turn, the basis for close control in any coal processing system is the reference standard provided by precise laboratory washability studies. In these studies, coal is carefully separated into a series of progressively higher specific gravity fractions to establish a relationship

Jan 1, 1968

By E. P. Sadowski, L. P. Trudeau, C. R. Cupp

The apparent high radiation resistance of two varieties of maraging steel is described and an indication is given of some phenomena that require further study. Two aspects were included in this work: a) effects of neutron irradiation on the room-ternperature tensile properties of 18 Ni (250) maraging steel; b) effects of neutron irradiation on the room-temperature tensile properties and on the impact resistance of 12 pct Ni-5pct Cr-3 pct Mo maraging steel. Subsize tensile and impact test specimens were used. The 18 pct Ni steel was irradiated to a neutron fluence of 3.3 x 10 n per sq cm (>1 mev). The 12-5-3 variety was irradiated to two neutron fluence levels: 1) 1.5 x 10 per sq CTTL (>I mev) 2) 3.1 x 10'9nper sq cm (>1 mev) In all respects both varieties showed unusually high resistance to change in strength and ductility after neutron irradiation. There was no noteuorthy over-aging in fully aged specimens. The aged 18 pct Ni variety showed a 4 pct drop in yield strength upon irradiation with little or no decrease in ductility. The aged 12-5-3 variety showed a 5 pct increase in yield strength on irradiation with a very slight decrease in ductility. The impact transition of the 12-5-3 variety only increased 35 to 45 Co upon irradiation, and the shear energy fracture value for the subsized specimens decreased only half as much as expected frorn experience with conventional steels. THE development of new reactor concepts and nuclear technology now depends to a large extent on the availability of new alloys capable of operating in stringent reactor environments. One of the most important new types of metallurgical material that has been developed in recent years is the maraging steels. This type of alloy is notable for its remarkable retention of toughness at high strength levels. In the course of a research program which incorporated ambient temperature radiation effects studies to determine the mechanisms of strengthening of 18 pct nickel maraging steel,' it became evident that the resistance of the alloy to neutron-induced changes in mechanical properties should be studied. This paper is to present evidence for the apparent high radiation resistance of maraging steel. The experimental program was in two parts: a) Effect of neutron irradiation on the room-temperature tensile properties of 18 Ni (250) maraging steel. b) Effect of neutron irradiation on the room-temperature tensile properties and on the impact resistance of 12 pct Ni-5 pct Cr-3 pct Mo maraging steel, a cobalt-free alloy. EXPERIMENTAL PROCEDURE 18 Ni (250) Maraging Steel. Tensile test specimens were machined to the dimensions shown in Fig. 1 from $-in.-diam hot-rolled bar of the composition shown in Table I. All specimens were austenitized for 1 hr at 1500°F (815°C) in argon and water-quenched. Half of the specimens were then mar aged for 3 hr at 900° F (482°C) in argon. The specimens were irradiated in a fast neutron transformer rod at approximately 120°F (50°C) to a neutron fluence of 3.3 x 10 10 n per sq cm (>1 mev). The irradiation was performed in the NRX reactor of Atomic Energy of Canada, Ltd., at Chalk River, Ontario, Canada. In all cases, the thermal neutron flux was three times as high as the reported (> 1 mev) fluxes. The room-temperature tensile tests were performed with an Instron tensile testing machine operating at a crosshead speed of 0.05 in. per min. The loading frame of the machine, mounted in a hot cell, was remotely controlled. The specimens were tested either

Jan 1, 1968

By G. V. Sirianni, G. E. Viens, R. A. Campbell, G. N. Banks, R. L. Sachdeva

"A combined shaft-electric furnace for the smelting of ores and the melting of metallized iron pellets is being developed. The materials are preheated, and in some cases pre-reduced, in the shaft before being transferred to the electric furnace, where melting or smelting is completed. It has been demonstrated that this combination of equipment will enable much of the relatively expensive electrical energy to be replaced by cheaper energy in the form of oil or natural gas, and preliminary experiments indicate that the total energy requirements for a melting or smelting operation are significantly reduced. Projections based on results obtained from the preliminary experiments indicate that further improvements will be possible when certain modifications to the equipment are completed."

Jan 1, 1968

By Frank W. Dickson, George Tunell

Five hot spring areas of the western United States show evidences of present day deposition of HgS; two also show evidences of accompanying Sb2S3 deposition. Sulfide minerals are depositing at or near the surface from hot waters that differ for each spring ai:ea in amount and kinds of dissolved matter. All the springs contain dissolved substances that act as buffering agents and that cause increased alkalinity with increasing temperature. Transport of Sb2S3 is possible in H2O and in boron and sulfide solutions. Increasing alkalinity and temperature enhance stibnite solubility. Quantitatively important transport of HgS appears restricted to alkaline sulfide solutions that contain HgS2=. Elemental mercury probably forms in deep hot waters because HgS breaks down into mercury and sulfur above 200°C, and free S is removed by reaction with water. Elemental mercury should accompany HgS2= in solutions that were at 200°C or higher. Cinnabar deposits from saturated alkaline sulfide solutions because of combinations of temperature decrease, dilution, oxidation, and reactions with wall rock: Amedee Hot Springs, Boiling Springs, and Coso Hot Springs are areas in which HgS is the only sulfide deposited. Hot waters at Amedee and Boiling Springs are supersaturated with HgS or transport colloidal HgS. Steamboat Springs waters deposit mainly silica and stibnite, but they have deposited HgS recently. Sulphur Bank waters deposit mostly stibnite and some HgS. The hot-spring waters of all springs represent highly modified deep water. Field and laboratory studies support the concept of transport of HgS in moderately alkaline sulfide solutions as HgS2=. Fluctuating deposition of stibnite and cinnabar reflects availability of sulfide or variations in deep-source HgS and Sb,S,. Silica and HgS dissolve mutually in alkaline sulfide solutions, and cinnabar and quartz would be expected to deposit simultaneously. Free mercury given off by hot-spring waters would impregnate country rocks.

Jan 1, 1968

By E. Miller, J. M. Eldridge, K. L. Komarek

Aclivilies of magnesium in liquid Alg-Si alloys have been delermined between 5 and 60 at. pcl Si, close to the melling point of Mg2Si, by an improved isopieslic melhod. Silicon specinrens, held in alumina crucibles and graplrile conlainevs of special design, were healed in a letrlpevalure gvadient and equilibrated with mag-nesilcrrl rapor in a closed lilanium system. The ther-madynamic Junctions were calculated and compared with the thermodyuamic properties of the other three mg- Gvoup IVB systems. Lattice paramelers of three Mg2X compounds were measured. The bonding in the Mg2X compounds is largely covalent with small and uarying amounts of metallic and ionic conlvibutions. The Mg-Si phase diagram1 has one congruent melting compound, Mg2Si, of essentially stoichiometric composition, two eutectics, and very limited terminal solid solubilities. Little information is available on the thermodynamic properties of this system. The free energy of formation of Mg2Si has been determined by the Knudsen cell technique2 in the range 572" to 680oC, by the transportation method3 between 858" and 950oC, and by the electromotive-force method4 in the range 400o to 600°C. Kubaschewski and villa5 and caulfield6 have measured the heat of formation of Mg2Si. An electromotive-force study of magnesium-rich liquid alloys was recently published by Sryvalin el al.7 The present investigation was undertaken to complete a general survey of the thermodynamic properties of the homologous series of Mg-Group IVB systems, i.e., Mg-Pb,a9,Mg-Sn,10,11 mg-Ge,12and Mg-Si. An isopiestic technique, previously developed for similar measurements on liquid Mg-sn11 and Mg-Ge alloys,12 was modified for the Mg-Si system. Specimens of the nonvolatile component, silicon, were contained in dense alumina crucibles placed inside covered graphite crucibles which were heated in a temperature gradient in an evacuated and sealed titanium reaction tube and equilibrated with magnesium vapor of known vapor pressure. The alumina crucibles prevented contact between the highly corrosive liquid Mg-Si alloys and graphite. The graphite cruci- bles effectively preserved the high-temperature equilibrium composition of the liquid alloys containing highly volatile magnesium on termination of the experiments during the quench to room temperature. EXPERIMENTAL PROCEDURE Silicon of semiconductor-grade purity (E. I. du Pont de Nemours and Co., Brevard, N.C.) and 99.99+ pct Mg (Dominion Magnesium Ltd., Toronto, Canada) were used. Graphite crucibles with press-fitted lids were machined from high-density (1.92 g per cu cm) rods (Basic Carbon Corp., Sanborn, N.Y.) which had a maximum ash content of less than 0.04 pct. The alumina crucibles had a purity of 99.7+ pct (Triangle RR grade, Morganite, Inc., Long Island City, N.Y.). In preliminary runs the liquid alloys were contained in graphite crucibles following the exact procedure developed for the Mg-Ge system.'2 These runs failed due to appreciable reaction between the molten Mg-Si alloys and graphite, and the results have been discarded. The procedure was then modified and the Mg-Si alloys were subsequently held in alumina crucibles. For most of the runs alumina crucibles of known weight and approximately 6.3 mm ID, 12.5 mm height, 1.0 mm wall thickness were loaded with weighed amounts of silicon and encapsuled in tightly covered weighed graphite crucibles 5/16 in. ID, 2 in. helght, 3/32 in. wall thickness). The graphite crucibles were machined from rods which were 85 pct of the theoretical density. These crucibles were therefore sufficiently porous so as to permit magnesium vapor to effuse through the silicon under the experimental conditions of approximately 970O to 1220°C and 1 day equilibration time. However, negligible magnesium was lost from the crucible during the quench due to the slow effusion rate through the pores of the graphite. The inner alumina crucible prevented the liquid alloys from contacting the graphite, and the very tightly fitting graphite crucible lids served to retain any magnesium vaporizing from the alloys inside the crucibles during the quenching step.12 The loaded silicon-alumina-graphite cells were positioned, one above another, on a 16-in.-long titanium thermocouple well and tied securely to the titanium tube with thin molybdenum wires held in grooves around the circumference of the graphite crucibles. A thin (0.005-in.) molybdenum strip prevented contact between the graphite crucibles and the titanium. This assembly was lowered into a titanium reaction tube (la in. ID, 16 in. long, $ in. wall thickness) closed on one end which contained a 11/2-in.-long cylinder of magnesium at the bottom. The inner titanium thermocouple well was positioned eccentrically in the large tube because of the eccentric mounting of the cells on the well. Appropriate modifications of the titanium cap"'12 were made to join the inner and outer titanium

Jan 1, 1968

By Wilbur S. Burbank, Robert G. Leudke

The impressive western San Juan Mountains of Colorado were carved by Pleistocene and Recent erosion from a thick blanket of Tertiary volcanic rocks that rests upon a basement of metamorphic, sedimentary, and igneous rocks ranging in age from Precambrian to Tertiary. These rocks record a long, complex, and fairly complete sequence of geologic events that have affected the region through much of geologic time. The geologic history of the region includes several periods of deformation, erosion, and igneous activity; closely associated with two of these periods were two periods of mineralization. The older of these was related to Late Cretaceous-early Tertiary (Laramide) intrusive activity, and its deposits occur in the older sedimentary units. The younger, of later Tertiary age and related to the widespread middle Tertiary extrusive and intrusive activity, is the chief concern of this paper. Tertiary volcanism built a great plateau surrounding the San Juan volcanic depression, a complex of subsided crustal blocks in the vent areas. The Silverton and Lake City cauldrons, nested within the larger depression, were domed by resurgent magma that created keystone grabens along the distended crests of the domed floors and many postcauldron radial and concentric fractures, dikes, and intrusive plutons within and marginal to the cauldron sites. The postvolcanic evolution of large quantities of gases, chiefly carbon dioxide and water, propylitically altered the rocks in and around the volcanic depression prior to the younger period of ore deposition. The ore deposits, localized mainly in the radial and concentric fractures about the cauldrons and in the associated graben faults, include fissure veins, chimneys, replacements, and disseminations in volcanic and underlying basement rocks. Fissure veins, constituting the major economic source, yielded precious- and basemetal ores. Most veins are compound with sphalerite, galena, and chalcopyrite; some veins contain silver-bearing arsenical sulfosalts and free gold. These minerals occur in predominantly quartz gangue. However, gangues composed of several manganese silicates and carbonates and relatively· barren of metals are abundant locally and probably originated by alteration of rocks at roots of faults and fissures during evolution of carbonatic solutions. The bulk of the ores are hypogene and probably had their source in deep parent magmas of the shallow eruptive rocks. Total production since the early 1870's has exceeded half a billion dollars in recovered metals, with a ratio of precious- to base-metal values of about 3 to 2. Since 1930, improvements in metallurgical treatment and mining techniques have increased the base-metal yield.

Jan 1, 1968

By Paul F. Kerr, Donald M. Hausen

Fine colloidal gold near Carlin, Nevada is disseminated in leached carbonate strata of the Roberts Mountains Formation in the Lynn "window" of the Roberts Mountains thrust fault. The ore body is generally stratiform and is more or less conformable to altered beds near the top of the formation, underlying Devonian limestones. Two sequences of mineralization are recognized: ( 1) an earlier base metal-barite assemblage related to early Cretaceous intrusives (121 ± 5 m.y.), and (2) a later low temperature Au-As-Hg-Sb assemblage of near surface emplacement. The earlier sequence consisting of sparse galena and sphalerite in barite with anomalous amounts of zinc, lead, nickel and copper, associated with dikes of dacitic composition, is of little economic importance. The later sequence of gold, realgar, cinnabar, and stibnite associated with extensive silicification and argillic alteration of limestone beds, has resulted in important deposits of gold. Argillic alteration of hydrothermally leached carbonate strata has provided the environment in which the most prominent gold deposition took place. Carbonate minerals in the limestone host rock have been replaced by microcrystalline quartz and chalcedony to form stratiform silica masses and recrystallized lenses of euhedral quartz. Zones of porous silicification are light gray to white, elliptical in shape, and more or less follow bedding. Silicification is bordered by argillic alteration and pyritization. Deposition of gold usually lies in a zonal pattern that encircles chimney areas of silicification.

Jan 1, 1968

By P. Chiotti, R. J. Hecht

Vapov pressure data of solid and liquid alloys along with phase diagram data WERE employed in calculating the thermodynamic properties for the Ca-Zn system. The relative excess partial molal free energy for zinc in the liquid alloys was fitted to the relation wnvre i is we tvmpvrutiirc in ucgrees neivtu ana in is the tr~ole fvaction. Relations for the standard free energy of fortnation for the eight cornpounds were developed. ThE phase diagram for the Ca-Zn system as determined by Messing et a1.' is reproduced in Fig. 1. Earlier work on the phase diagram has been summarized by Hansen and Anderko2 and the very limited thermodynamic information for this system has been reviewed by Hultgren et a1.3 The heat of fusion for the compound CaZn2 has recently been determined to be 9260 cal per mole.4 Solubility data for calcium in zinc for the temperature range of 650" to 725°C were fitted by the relation and reported by Johnson and Dilloon5 In the present investigation zinc vapor pressure data were obtained by both the dewpoint and Knudsen methods in order to calculate the thermodynamic properties for liquid and solid alloys. The dewpoint method as employed in this work requires that only one of the components be significantly volatile, in this case zinc, and that the vapor pressure of pure zinc be known. For calculation purposes the vapor pressure data for pure zinc3 were fitted to the relations; for temperatures below 692.7K, the melting point of zinc. The corresponding free-energy relations for vaporization and sublimation of pure zinc are respectively. Some of the calculations also required knowledge of the free energy of fusion of zinc and calcium and the free energy for the 721°K allotropic transformation of calcium. The free energy of fusion of zinc was taken to be the difference between Eqs. [4] and [5], or The free energy of fusion and transition for calcium were based on the enthalpy values of 2040 and 222 cal per g-atom, respectively, as reported by Chiotti et al. 4 and the heat capacity data given by Hultgren et a1.3 and are represented by the relations, In the latter expression the difference in heat capacity between the a and 0 forms of calcium was neglected. MATERIALS AND EXPERIMENTAL PROCEDURES The metals used in preparing the alloys were Bunker Hill slab zinc, 99.99 pct pure, and Ames Laboratory calcium. The average impurities in the calcium in parts per million by weight, ppm, were N-17, H—77, Ba—216, Mg-15, Si—7, C—157, and Fe—9. The zinc was cleaned in dilute nitric acid and the calcium was used as received. The calcium was stored and handled in an argon-filled glove box and when removed from the dry box it was kept in an argon-filled desiccator. Tantalum was found to be a suitable alloy container. The alloy components were contained in a 1-in.-diam cylindri-

Jan 1, 1968

By R. R. Brown

The Bureau of Mines undertook a limited feasibility study to determine the practicality of removing copper from automobile scrap by thermal treatment. Test specimens, prepared by wrapping bare and insulated copper wire around small steel coupons, were heated at 600° to 1,150° C in various atmospheres for different lengths of time under both static and dynamic conditions. The tests indicated that adequate removal of copper cannot be effected by thermal treatment of scrap above the melting point of copper. Tests showed that copper present in scrap as insulated wire is embrittled by thermal treatment at 800° to 900° C if the insulation contains lead, and that the embrittled copper is almost completely removed by a mechanical action such as tumbling. Also chemical pretreatment of specimens to effect embrittlement of copper and the magnetic separation of oxide scale were studied. Tests showed that bare copper can be embrittled by depositing waterglass (Na, Si409) on copper prior to thermal treatment.

Jan 1, 1968

By J. L. Reuss

The Bureau of Mines derived information on the softening characteristics of both unfired and indurated iron ore pellets as measured by hot compression strength in a laboratory study. A surprisingly high hot strength (240 1b per ½ -inch spheroid) was developed by unfired magnetite pellets near 900° C; lesser maxima were developed by pellets made from hematite and specularite concentrates near 1,000° C. Those from goethite remained weak throughout the pre induration heating. Fully indurated commercial pellets retain a high resistance to softening when heated in air. On the contrary, in a hot reduing atmosphere their high cold crushing strength dissipates rapidly. At 1,000° C, for example, the average compression strength of seven different commercial pellets was 110 lb; at 1,100° C, the hot strength was only 60 lb. After a rather sharp initial drop, the loss of strength with increase of temperature was gradual. There was no sudden collapse, nor any significant difference, in behavior of commercial pellets whether made from magnetite or hematite concentrates.

Jan 1, 1968

By Raymond F. Gray, Victor J. Hoffman, Richard J. Bagan, Harold L. McKinley

The first indication of tungsten in the Bishop area was the discovery of scheelite concentrations in a gold placer operation in the ( since named) Tungsten Hills in 1913. After early intermittent production, the deposits of the district were slowly discovered and developed. The Pine Creek mine, located in 1916 and under the direction of Union Carbide Corporation since 1935, became the principal producer in the district. By the end of 1965, the total production of the district had reached 3,450,932 units of WO3, 17,071,242 pounds of molybdenum, and 19,599,110 pounds of copper. The topography of the district is characterized by its extreme relief, ranging in elevation from 13,986 feet to about 4400 feet in the Mount Tom quadrangle. The present topography is the result of the uplift and erosion of the Sierra Nevada and the great subsidence of the Owens Valley with its related deposition and volcanism. The general structure of the pre-Tertiary rocks consists of a series of tightly-folded metasedimentary and metavolcanic rock remnants surrounded by exposed plutons ranging in composition from hornblende gabbro to alaskite. The metasedimentary rocks consist of low- to intermediate-grade metamorphic equivalents of fine-grained sediments deposited during the Paleozoic era in a miogeosynclinal environment. Later volcanics were deposited in a eugeosyncline. The ore bodies in the Bishop district consist of scheelite-bearing tactite formed by the pyrometasomatic replacement* of calcareous sediments along the contact with an acidic granitic intrusive. A number of the metasedimentary remnants have had tungsten deposited along their edges.

Jan 1, 1968

By David W. Wisecarver

Kennecott Copper Corporation and the U. S. Bureau of Mines cooperated in a full-scale slope stability research project at the Kimbley Pit near Ely, Nevada. The west wall of the Kimbley Pit was mined from an over-all slope angle of 45° to an over-all slope angle of 57° and the pit was deepened nearly 50 feet. Mining was begun February 10, 1966, and completed October 30, 1966. Approximately 2.55 million tons of ore and waste were mined. The project was designed and carried out to learn more about the behavior of a pit wall as its slope angle is steepened and to obtain a possible insight into engineering parameters for use in design of future slopes. Data from this project are presented as obtained from (1) instruments installed in two adits for deformation and displacement measurements, (2) a subsidence network installed on the surface above the steepened wall, (3) pre- and post-mining observations of stress in rock, (4) sonic-velocity measurements, and (5) seismic and microseismic investigations. Changes occurred in measured quantities as the slope was steepened but stopped when mining was completed. Agreement was noted between the measured changes and predicted changes obtained from calculations using the finite element technique. Subsidence surveys and microseismic studies show the steepened pit wall to be stable.

Jan 1, 1968

By R. V. Mrazek

The heat of formation of vanadium trichloride was determined at 298.15° K. Measurements were made in a solution calorimeter in which an aqueous hydrochloric acid-potassium dichromate solvent was employed. Data are presented for the heats of solution of vanadium trichloride and the vanadium trioxide "backup" compound, and for appropriate dilution reactions needed to preserve stoichiometry. The resulting heat of formation of vanadium trichioride (VCI3) at 298.15° K was found to be ?H°298.15° K = -138.89 ±0.37 kcal/g mole.

Jan 1, 1968

By E. A. von Hahn, T. R. lngraham

Cementation rates ulere studied by rotating an elec-tropolished or etched copper strip in aqueous solutions, of either perchloric acid or alkaline cyanide, containing silver ions. The rates of cementation were more rapid in acidic media than in cyanide media. In both, the rates varied with the rate of rotation of the copper strip. The deposits formed in the acidic solutions were finely divided, loosely adhering powders. Those formed in the cyanide solutions were dense and adherent. The presence of the deposits influenced the cementation rates. In the acidic solutions the rate was enhanced, possibly because of the increased cathodic area. In the alkaline solutions the rates were decreased in the presence of the deposits. This has been attributed to restricting the diffusion of the copper ion from the rnetal outward into the bulk of the solution. In an earlier paper1 the authors described a kinetic study of the cementation of palladium on copper in perchloric acid solutions. That work indicated that there were two stages in the palladium cementation process. The first, more rapid stage was consistent with rate control by the diffusion of Pd11 ions to the copper surface and/or by chemical reaction at the surface. The second stage was consistent with rate control by the diffusion of copper ions from the copper surface, through the deposit, out into the main body of solution. The effect of the type of deposit on the rate of cementation is of particular interest because it may be one of the primary features involved when large quantities of metal are to be cemented from solution. No substantial investigations of the effect seem to have been made. Accordingly, an extension of the previous work was arranged to study the cementation of silver on copper. This system was selected because of the convenience of the analytical methods, the previously established technology with copper, and the fact that the system could be studied in both acidic and alkaline media. By selecting perchloric acid and alkaline cyanide solutions as the media, it was hoped that some assessment might be made of the effects, on cementation, of having the silver ion present in a virtually uncomplexed state and in a highly complexed state. EXPERIMENTAL The cementation rates were studied, as previously described,' by rotating a copper strip (1.0 by 23.2 cm) clamped to the peripheral surface of a lucite cylinder. The solutions were kept at constant temperatures (±0.05°C) under an atmosphere of purified nitrogen, and samples were taken periodically for analysis. The initial solution volume was 1000 ml and the sample volume 5 ml. The initial silver(1) ion concentrations were made low (0.5 to 1.0 x 10-4 moles per liter) to minimize the influence of the cemented deposit on rates. The solutions were prepared by dilution of suitable aliquots of silver perchlorate and silver cyanide stock solutions. Both stock solutions were prepared from purified silver powder (Johnson, Matthey, and Mallory Ltd.) with redistilled deoxygenated water, and they were kept under an atmosphere of purified nitrogen. To prepare the stock solutions, weighed amounts of silver powder were dissolved with nitric acid. For the AgC104 stock solution the silver nitrate solution was evaporated twice to near dryness with perchloric acid and then made up to volume: For the NaAg(cN)2 stock solution, the silver ions were precipitated with sodium hydroxide solution. The precipitate was filtered, washed thoroughly with redistilled water, dissolved with 1.1 times the required stoichiometric amount of sodium cyanide solution, and made up to volume. The small amounts of free perchloric acid and sodium cyanide present in the stock solutions were disregarded in the preparation of the solutions. The copper strips were cut accurately from 0.025-in. sheet (American Metal Climax OFHC brand) and annealed for 1.5 hr at 470°C in a stream of nitrogen. Analyses of the solution samples for silver and copper were done with a Techtron Model AA-3 atomic absorption spectrophotometer. Calibration standards of the same composition as the experimental solutions were prepared and analyzed simultaneously with the samples. No difficulty was experienced in the analyses, and the reproducibility was within 1 to 2 pct in both alkaline cyanide and perchloric acid solutions.

Jan 1, 1968

By Paul W. Zimmer, Carl E. Dutton

Iron ore in the Menominee district is mined from two iron-formations of middle Precambrian age. The older formation is present in the northeastern part; is composed mainly of hematite, magnetite, quartz, and minor silicates; and contains about 34 per cent iron. The rock has been so coarsened by meta- morphism that concentration of magnetite and hematite is feasib!e, and pellets containing more than 60 per cent iron are being produced. The older formation is also present in the southeastern part where it has 1:een only slightly metamorphosed. Ore containing more than 50 per cent iron was formerly mined from local residual concentrations of iron oxides from which silica had been sufficiently leached, or replaced by iron oxide, or affected by combinations of these processes. The younger iron-formation occurs in the western part of the district and, if unaltered, is interlayered siderite and chert. The ore in this area also contains more than 50 per cent iron and formed as local residual concentrations but in two stages. The siderite was converted to iron oxides (hematite and "limonite"), and silica was contemporaneously or subsequently removed by leaching, or replacement, or combinations of these processes.

Jan 1, 1968

By M. D. Banus, M. B. Bever, A. K. Jena

The heals of formation at 78", 195, and 273°K of the ternary compound h3SbTe2 based on the elements and based on the binary compounds In Sb and [inTe have been measured. The heats of formation at these temperatlcres of the binary compounds In Sb and In Te based on the elements have also been determined. Heal contents and free energies of the three compounds have been calculated from 0° lo 80I)°K. The free energies of joyrrzalion, heats of formations, and entropies of formation at 298°K have also been calculated. The results shown that the tertnary compound is metastable with vespecl to InSh and ln Te below 696 °K. bul is slable above that temperature. The weaker bonding of results in a positice entropy of formation which with incrensirzg temperature makes increasing negative conlvihtclions to the free energy and above 696°K renders the compound slable. THE ternary compound In3SbTez occurring in the quasi-binary system In Sb- In Te' forms on cooling at 829°K by a peritectic reaction.' Observations at 673" and 573 K have shown that this ternary compound decomposes slowly into the binary compounds InSb and1n~e.l'' It has not been possible to analyze the metastable behavior of the ternary compound because up to the present time data on its thermodynamic properties have been lacking. Some information on the binary compounds, however, is available. The heat of formation of InTe at 273°K and its free energy at 673°K are kn~wn.~'~ The heats of formation of InSb at 78", 273', 298", and 723°K have been measured5-' and its heat capacity between approximately 12" and 300"Kg9l0 is also known. In the investigation reported here the heats of formation at 78% 195% and 273°K of the ternary compound In3SbTez have been measured. The heats of formation of the binary compounds InSb and InTe at these temperatures have been obtained by combining new calorimetric results with previously published data. The heat contents and free energies of the three compounds at various temperatures from 0" to 800°K have been calculated. Against the background of this information, the metastability of the ternary compound will be discussed. 1) EXPERIMENTAL 1.l) Preparation of Specimens. The materials used consisted of the elements indium, antimony, and tellurium, the binary compounds InSb and InTe, and the ternary compound In3SbTez. The elements, obtained from American Smelting and Refining Co., had a nominal purity of 99.999+ pct. The compound InSb was Cominco semiconductor grade; the compound InTe was prepared from the elements by melting under a vacuum of 10-h m Hg followed by slow cooling. Three batches of specimens of the compound In3SbTez were used. One batch was prepared by melting appropriate amounts of the elements in an evacuated and sealed Vycor tube. The melt was held at approximately 100°K above the liquidus for about 8 hr, shaken repeatedly, and quenched into a mixture of ice and water. The specimen was annealed in vacuum at 760°K for 4 weeks. In preparing a second batch, a mixture of the component elements was melted and quenched in water. The resulting ingot was powdered. The powder was pressed into pellets, which were annealed in vacuum at 748" to 773°K for 4 weeks. A third batch was prepared in the same manner as the second, except that the starting materials were InSb and InTe rather than the elements. Metallographic examination of samples of the three batches and X-ray diffraction examination of a sample of the second batch did not reveal evidence of microsegregation or a second phase. The results obtained with the three batches showed no systematic differences. 1.2) Calorimetry. The calorimetric method has been described in detail." Samples of the compound In3SbTez, mechanical mixtures of InSb and InTe in the proportion of 1:2, and mechanical mixtures of indium, antimony, and tellurium in the proportion of 3:1:2 were added to a bismuth-rich bath at 623°K in a metal-solution calorimeter. These additions were made from 78°K (liquid nitrogen), 195°K (dry ice and acetone), and 273°K (ice and water). The heat effects of the additions were measured. The difference in the heat effects of the additions of a compound and the additions of the mixtures of its constituents, adjusted for differences in the concentration of the bath, is the heat of formation of the compound. In the concentration range not exceeding 1.5 at. pct solute, the heat effect of the additions was a linear function of concentration. The heat of formation refers to the temperature from which the additions were made, namely, 78", 195", or 273°K. Several calibrating additions were made in each calorimetric run. The calculated heat capacity of the calorimeter and hence the calculated heat effects of the additions of samples depend upon the values adopted for the heat contents of the calibrating substance. In this investigation bismuth at 273°K was used and a value of 4.96 kcal per g-atom was taken for (HGZ3"k . 2) RESULTS AND DISCUSSION 2.l) Heats of Formation. The heats of formation of the ternary compound In~SbTez from the component elements indium, antimony, and tellurium and from

Jan 1, 1968

By Donald L. Ball

The equilibrium of boron nitride, gaseous nitrogen, and solute boron was investigated in Fe, Fe-C, and Fe-Si rnelts by the Sieverts technique. The free ellergy of dissociation of boron nitride, involving -the implied standard states, was evaluated in the range 1400" to 1600°C as: ?Fo = 38,000 - 23.5T, cal ber mole The solute-solute interaction coefficients eBB, ecB , and eg were determined as 0.058, 0.22, and 0.078, respectively. BORON is an important ingredient in some types of steel and cast iron. It was employed at a particularly high level, 0.01 wt pet, in the as-cast malleable iron "CentraSteel".1 In this material, the boron concentration was critical in order to assure graphite, and avoid primary cementite, in the as-cast structure. One possible function of the boron in this alloy was the nucleation of graphite through the agency of boron nitride, which, conceivably, precipitated from the melt during cooling. A research program was instituted to assess the validity of this proposed mechanism. The first undertaking, reported here, was a determination of the thermodynamic possibility of boron nitride precipitation. Data available in the literature on the activity coefficient of solute boron in iron-base melts are inadequate for the present purpose. They will be reviewed briefly, however, so that comparison can be made, when

Jan 1, 1968

By R. B. Walker, R. Palmer, L. C. Bryner

The purpose of this investigation was to further study some of the factors affecting the air oxidation of sulfide minerals. Data obtained from laboratory studies on the effect of temperature, concentration of iron salts, pH, and other catalysts on the biological and nonbiological oxidation of sulfide minerals are presented. The oxidation of copper sulfide minerals and subsequent leaching of the soluble copper has long been a profitable operation. The chief oxidizing agent is oxygen from the air. This reaction is influenced by a number of different factors such as temperature, light, hydrogen ion concentration, oxidizing agents, and various catalysts. Sullivan1 found that copper sulfide minerals are slowly oxidized by the air and that dilute sulfuric acid and iron (111) increased their solubility. At that time it was not known that bacteria were involved in the oxidation of the sulfide minerals. It has been shown that pyrite, molybdenite, free sulfur, and the copper sulfide minerals found in the waste rock dumps in Bingham Canyon, Utah, are largely oxidized by chemosynthetic autotrophic microorganisms found in the leaching streams.2-6 Similar organisms have been isolated in other mining areas7,8 and from the effluents from coal rnines.9 The following are some of the questions that have arisen regarding the mechanisms of the reactions involved in the leaching process. How dependent is the leaching operation upon the biological reactions? How does the temperature effect the biological and non-biological reactions? How does the concentration of iron (II) and (111) effect the rate of oxidation of copper (II) sulfide? Does the iron act as a catalyst? Does activated carbon act as a catalyst on the oxidation of sulfide minerals? What effect does the hydrogen ion concentration (pH) have on the above reactions? The purpose of this paper is to report the results of laboratory studies on these problems. EXPERIMENTAL The apparatus used in this investigation was an air lift percolator described in our earlier work.' The percolator consisted essentially of an air lift which enabled the leaching solution and microorganisms to pass freely through a suspension of mineral (substrate) in Ottawa sand. The air lift served the additional purpose of maintaining an ample concentration of oxygen and carbon dioxide in the nutrient (leaching) solution. (See Fig. 1.) The percolators were so constructed that they could be immersed in liquid constant temperature baths for temperature studies. The thermostats were controlled to +0.5°C. The reactions were all run in the dark. The percolators were charged with one to three g of mineral, dispersed in 100 g of Ottawa sand and 100 ml of nutrient or leaching solution. The sand was purified to remove traces of iron by digesting with concentrated hydrochloric acid and washng with distilled water until free from chloride. After drying, the sand was ready for use. The compressed air supply was regulated to 5 psi and bubbled through an aerator containing distilled water, which was maintained at the same temperature as the bath used. The air was filtered through cotton plugs to maintain sterile conditions. The tops of the

Jan 1, 1968

By Perry N. Halstead

This report describes two goniometers that, by simple manipulation, can be used to ascertain the attitude of a joint, vein, or fracture plane observed on the planar projection of a borehole photograph taken with an NX borehole camera of the type developed by the U.S. Army Corps of Engineers. One goniometer was designed to interpret photographs taken in vertical drill holes and the other for photographs taken in inclined drill holes. In practice, several measurements are made on each photograph with the goniometer. These data are then substituted into mathematical equations, which are derived in this report and the attitudes of fracture planes are determined.

Jan 1, 1968

By J. M. Réjean Gagnon

"Quebec Cartier Mining Company is currently mining a low-grade iron ore deposit in northeastern Quebec. The Company is producing some 8,000,000 dry gross tons of concentrates per year, grading about 66 per cent iron. The pit, which is located on the keel or hinge line of a fold, will eventually be about 1,000 feet deep with a surface area of 8,000 by 2,600 feet. The most significant structural discontinuities in the mine are the natural bedding planes and secondary perpendicular joints. The exposed walls are subjected to a sub-Arctic climate and heavy blasting occurs approximately six times a month.QCM utilizes design and operating techniques to control rock fall. Steps are also being taken to analyze the ultimate over-all pit slope stability."

Jan 1, 1968