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By A. D. Smigelskas, E. O. Kirkendall

THIS is the third paper in a series on the diffusion of zinc in alpha brass.1 At the time of the first-paper it was accepted that diffusion in a substitutional type of solid solution depended upon an equal interchange of solute and solvent atoms across the diffusion interface (or past a given lattice reference point). Discrepancies in the size of the areas under the diffusion curves on each side of the interface, if observed, were explained on some other basis than the fact that the solute atoms might cross the diffusion interface without an equal number of solvent atoms diffusing across the interface in the opposite direction. The second paper presented evidence indicating that zinc atoms in alpha brass diffuse across the interface more rapidly in one direction than the copper atoms diffuse across the interface in the opposite direction. This phenomenon forced the interface to move in the opposite direction of the diffusion of zinc atoms to provide space for the additional zinc atoms dissolved in the alpha brass. That the interface and columnar grain structure on one side would remain intact during this mass movement was not expected; however, it is gratifying that they did. While the evidence was sufficiently satisfying to the author, it was decided that additional experiments were in order to prove that zinc diffuses more rapidly than copper in alpha brass. It is the purpose of this paper to present the results of these experiments. PROCEDURE A bar of 70-30 wrought brass was selected, to avoid the relatively large volume change in going from beta to alpha brass as in the previous investigation. A bar 7 in. (18-cm.)* long and about ¾ in. (1.9 cm.) wide was surface ground and polished with abrasive paper on plate glass to 0.4184 ± .0002 in. (1.0625 ± 0.0005 cm.) thick. Six 0.005-in. (0.013-cm.) diameter molybdenum wires, chosen because of their very low solubility in copper and alpha brass, were stretched lengthwise along each of the two plane surfaces. Glass tubes placed at right angles to the wires every ½ in. held the wires tightly against the brass. The sample was then emersed in an acid copper sulphate plating bath and electroplated to a depth of about 0.020 in. (0.050 cm.) copper on all sides. The glass tubes were no longer necessary to hold the molybdenum wires in place and were removed. The sample was then electroplated to a depth of

Jan 1, 1946

The income of the Institute is derived mainly from dues, advertising in MINING AND METALLURGY and sale of publications. These sources are fortunately supplemented by the interest from invested funds now amounting to over $500,000, a considerable portion constituting endowments for especial purposes. Aside from the medal funds the principal endowments are the James Douglas Fund for support of the Library, the Rocky Mountain Fund and the Seeley W. Mudd Memorial Fund. The income from the two last named is available for the support of research and a variety of other purposes. It is allocated by the Board of Directors upon recommendation of standing committees in each case. An active effort is being made to increase the endowments of the Institute, it being felt that unusual opportunities exist for research and public and professional service through the organization.

Jan 1, 1939

By J. E. Flinn, E. R. Gilbert

Recently, Green reported some high-temperature, 0.60 to 0.89 T3, creep results on unalloyed tantalum. From his study he determined an activation energy of 114 kcal per mole for steady-state creep using the T, differential-temperature method25 for testing. He accounted for the difference between this value and 110 kcal per mole for self-diffusion by the temperature dependence of the elastic modulus, 4 kcal per mole. This reported activation energy is in apparent disagreement with that which can be determined from Green's isothermal data, which we have plotted as log creep rate vs 1/T in Fig. 15. From this figure, it appears that there are two activation energies of -185 kcal per mole at the higher temperatures and -75 kcal per mole at the lower temperatures. It is not obvious that the data can be fitted to a straight line corresponding to an activation energy of 114 kcal per mole. One is led to two possible conclusions regarding Green's study: there are two discrete processes controlling the creep rate from 0.60 to 0.89 Tm or the apparent activation energy is not discrete but continuously increases with increasing temperature. The former speculation would be in closer agreement with the high-temperature creep behavior of tungsten.28 The apparent disagreement between the activation energies determined by the AT and isothermal methods certainly suggests that further study on the high-temperature creep of tantalum is needed.

Jan 1, 1967

By A. F. Frederickson

A MINERAL can best be defined as a phase,' where the term "phase" is described as a homogeneous,* physically distinct, and mechanically sep- arable portion of a system. If one phase develops from another, certain nuclei must first be available.2.394 The manner in which new material is added to these nuclei, and the subsequent structural and other characteristics of the phase, is often markedly influenced by factors other than its temperature, pressure, and gross compositional environment. Rates of growth, presence of impurities, the availability or lack of oxygen, the pH of the system, and percentage of completion of the often determine which modification will develop. Many transitional phases develop when a relatively insoluble precipitate is formed from solution. Different modifications are formed, depending on the speed and percentage of reacting solution added. Some of these "forms" are stable and do not "age" or transform into the so-called stable modifications. These modifications are difficult to treat in terms of equilibrium diagrams for the simple reason that these minerals do not represent an equilibrium situation described by only two (temperature and composition) or three terms (when pressure is considered). Many crystals exist as stable or meta- stable phases in nature in environments much different from those indicated by certain equilibrium diagrams. Cristobalite octahedra grow on zeolite needles in vugs, diaspore develops from a medium that does not appear to have been subjected to high pressures and temperatures, authigenic feld-

Jan 1, 1952

By George Mah, Charles Wert

Internal-friction peaks caused by diffusion of oxygen and nitrogen have been observed in ytterbium. They are thought to be caused by the redistribution, under stress, of strain dipoles around an interstitial oxygen or nitrogen and a neighboring substitutional impurity. With the use of a simple geometrical model, diffusion coefficients for oxygen and nitrogen between special interstitial sites have been calculated. a) APPLICATION OF INTERNAL FRICTION TO MEASUREMENT OF DIFFUSION RATES IN DISSOLVED INTERSTITIAL ATOMS In bcc metals, the interstitial atoms occupy the centers of cube faces (0, 1/2, 1/2), or their equivalents, the center of the cube edges (0, 0, 1/2). An interstitial atom in this position causes an aniso-tropic distortion in the lattice. When stress is applied, mechanical relaxation can take place by the movements of the interstitial atoms. This relaxation has been used to obtain information concerning the movements of the interstitial atoms in the bcc metals. Data for these alloys have been compiled by Stanley and Wert. Other researchers have extended the investigation of interstitial diffusion to the close-packed metals. Gupta and weinig2 found an oxygen peak in a titanium, the height of which is linearly dependent on the oxygen concentration. They assumed, therefore, that they were dealing with movement of atomic ally dispersed oxygen in titanium. KG and wang3 determined that the diffusion coefficients of carbon in fcc steels and in nickel obtained by internal-friction methods were consistent with those obtained by macrodiffusion methods at much higher temperatures. Bisogni found oxygen and nitrogen peaks in hafnium by use of which he deduced the diffusion coefficient of these gases in hafnium. He observed further that the half-widths of these peaks corresponded almost exactly with those of a single-relaxation process; he assumed it to be caused by movement of atomically dispersed oxygen and nitrogen. From these studies, the deduction can be drawn that, in general, diffusion data can also be obtained for the interstitial diffusion in close-packed metals (or more precisely, in slightly impure close-packed metals). One group of such metals for which little data exist for the diffusion of dissolved oxygen and nitrogen is the rare earths. They have great affinity for gases, which enter solution interstitially. In this investigation results were obtained for the Yb-O and Yb-N interstitial solid solutions with traces of substitutional impurities; these solid solutions are of fcc structure. b) MECHANISM OF THE RELAXATION IN FCC CRYSTALS In the fcc structure, an interstitial gas atom is usually situated in the octahedral position (1/2, 1/2,

Jan 1, 1964

By John R. Anderson, Michael B. Bever

CARBON may affect the alloys of copper in several ways. Provided an alloying element does not oxidize preferentially, even minute quantities of carbon dissolved in liquid alloys of high copper content will form insoluble carbon oxide gases under oxidizing conditions. Gas porosity in castings of high-copper alloys can originate in this way. In certain alloys of low copper content carbon may have considerable solubility and may be an effective deoxidizer. In these alloys carbon will tend to suppress porosity. Carbon that is dissolved in the molten alloy is likely to be retained in the solidified metal. The effects of carbon on the physical properties of the metal are determined by the form in which it is present. Depending on the alloying elements and also on the cooling rate, carbon may precipitate as graphite, may form a carbide or may remain in solid solution on cooling. As solid copper does not dissolve a measurable amount of carbon, a carbon-bearing solid solution can occur only if the copper is alloyed with a large excess of an element that forms such a solution. The effect of graphite or of carbides on the properties of an alloy will depend on the size and distribution of the precipitated particles. As Hensel pointed out in discussion,1 the formation of an alloy carbide may interfere with the age-hardening properties of a copper alloy. One would also expect that the presence of carbides or of graphite will under certain conditions promote corrosion or high-temperature failure in nonferrous alloys. Since carbon has an effect on the soundness of castings and affects the structure and behavior of solid copper alloys, its solubility in the liquid alloys is of practical importance. The isothermal change of carbon solubility with alloy composition is of interest from a theoretical standpoint. The binary alloys of copper with manganese and with nickel are used industrially and serve as a base for more complex alloys. The solubility of carbon in each of these metals is known, but its solubility in their alloys has not been determined. EARLIER DATA The solubility of carbon in molten pure copper is about 0.0001 pct at 1100 °C and 0.0004 pct at 1475°C.1 Various authors2-6 have published data on the solubility of carbon in molten manganese. There is agreement on a value of about 6.7 pct in the temperature range 1217° to 1245°C. This solubility value corresponds to the formula Mn3C. It increases very little with increasing temperature. Corson7 states that carbon is soluble in copper-manganese alloys and that the

Jan 1, 1947

By William E. Ford, Edward Salisbury Dana

Secondary Twinning. - When there is reason to believe that the twinning has been produced subsequently to the original formation of the crystal, or crystalline mass, as, for example, by pressure, it is said to be secondary. Thus the calcite grains of a crystalline limestone often show such secondary twinning lamella?. The same are occasionally observed (Ilc, 001) in pyroxene crystals. Further, the polysynthetic twinning of the triclinic feldspars is often secondary in origin. This subject is further discussed on a later page, where it is also explained that in certain cases twinning may be produced artificially in a crystal individual - e.g., in calcite (see Art. 282).

Jan 1, 1922

By J. M. Weehuizen

Complete details are given of the drilling method by which two shafts were sunk at the new Beatm'x mine of Staatsmijnen in the Netherlands. The nature of the rock strata in the Dutch mining district determined choice of the drilling rather than the freezing method. Data for each step and details of the equipment used are given in the illustrations. Staatsmijnen was founded in 1902 with government financial backing, but it is run as a private enterprise, on a commercial basis, with the normal fiscal obligations. The company now has four mines in operation with annual outputs amounting to 7 1/2 million tons of coal. In 1952 it was determined that a new mine—the Beatrix—would be opened. Details of the shaft-sinking operation are described in this paper. SHAFT LOCATION The coal-bearing carboniferous rock in the Dutch mining district is overlain almost completely by soft water-bearing strata, which at the site of the new shafts are about 1600 ft thick. The sinking of the new shafts through this soft water-bearing overburden (Fig. 1) is a costly and time-consuming affair. From the two availaible sinking methods: 1) Poetsch's well known freezing method or 2) the drilling method of Honigmann-de Vooys, the latter was preferred, not only because of its relative cheapness, under the prevailing conditions, but primarily because by using the drilling process, a special type of shaft lining of steel, concrete, and bitumen could be used. The new shafts, located 330 ft apart, have an inner diameter of 18 ft, 4 1/2 in. The boreholes, which have a diameter of 25 ft and which were drilled through nearly 1600 ft of overburden and some 100 ft of carboniferous, each contain more than 29,000 cu yd—by far the largest in the world. DRILLING METHOD The drilling method is based on the use of mud-flush—a thin mixture of clay and water—to keep the borehole filled during the entire drilling period and during insertion of the lining (Fig. 2). The pressure of the mudflush against the borehole wall is greater than that of the water in the surrounding

Jan 1, 1961

By H. W. Fleming, R. R. Brooks

The Clearwater Deposit, a small occurrence of massive-sulphide mineralization enclosed in an envelope of disseminated-sulphide mineralization, was discovered as a result of an aeroelectromagnetic survey in New Brunswick in 1955. Subsequently, additional flights were made over the deposit and various ground follow-up methods were employed to ascertain the nature of their response. All methods proved to be capable of indicating the occurrence with varying degrees of precision. This paper is a presentation and a discussion of the magnetic and electromagnetic data, both airborne and ground, and the self-potential data obtained over this deposit. The attention of Canadian mining exploration companies was initially focussed on New Brunswick by the discovery, in 1953, of the Brunswick ore body. Ground electromagnetic surveys were of considerable assistance in locating and developing this deposit. In the following year, 1954, the Heath Steele base-metal deposits were discovered by employing an airborne electromagnetic device and ground electromagnetic surveys to follow-up the airborne indications. These discoveries demonstrated clearly that both airborne and ground electromagnetic techniques were applicable for locating the near-surface deposits of massive sulphides present in this region. Airborne electromagnetic equipment became available on a contract basis through Aeromagnetic Surveys Limited early in 1955 and was used extensively thereafter throughout a large portion of northern New Brunswick. It was as a result of one of these surveys with Aeromagnetic Surveys Limited equipment in the summer of 1955 that the Clearwater Deposit was detected. The airborne anomaly was located on the ground by means of an electromagnetic survey using a Swedish Slingram unit. During 1956, the region was investigated more thoroughly- in the hope that other sulphide bodies might be located. Airborne electromagnetic coverage was extended and the Clearwater Deposit itself was used as a testing ground for the various methods and types of equipment currently in use in New Brunswick. In this paper com prative data are presented for the airborne magnetic, airborne electromagnetic, ground magnetic and ground electromagnetic surveys over this deposit. The ground electromagnetic instruments used were the McPhar vertical-loop unit and the Slingram and Boliden horizontal-loop units. Self-potential surveys were carried out with a McPhar unit. From the geophysical point of view, all ground electrical methods employed indicated the presence and the extent of the massive-sulphide mineralization with a good degree of accuracy. The horizontal-loop methods however, defined the contacts more precisely as is to be expected when dealing with a flatly-dipping

Jan 1, 1961

By A. D. Smigelskas, E. O. Karenna

This is the third paper in a series on the diffusion of zinc in alpha brass.' At the time of the first paper it was accepted that diffusion in a substitutional type of solid solution depended upon an equal interchange of solute and solvent atoms across the diffusion interface (or past a given lattice reference point). Discrepancies in the size of the areas under the diffusion curves on each side of the interface, if observed, were explained on some other basis than the fact that the solute atoms might cross the diffusion interface without an equal number of solvent atoms diffusing across the interface in the opposite direction. The second paper presented evidence indicating that zinc atoms in alpha brass diffuse across the interface more rapidly in one direction than the copper atoms diffuse across the interface in the opposite direction. This phenomenon forced the interface to move in the opposite direction of the diffusion of zinc atoms to provide space for the additional zinc atoms dissolved in the alpha brass. That the interface and columnar grain structure on one side would remain intact during this mass movement was not expected; how ever, it is gratifying that they did. While the evidence was sufficiently satisfying to the author, it was decided that additional experiments were in order to prove that zinc diffuses more rapidly than copper in alpha brass. It is the purpose of this paper to present the results of these experiments. Procedure A bar of 70-30 wrought brass was selected, to avoid the relatively large volume change in going from beta to alpha brass as in the previous investigation. A bar 7 in. (18-cm.)* long and about 3/4 in. (1.9 cm.) wide was surface ground and polished with abrasive paper on plate glass to 0.4184 0.0002 in. (1.062j + 0.0005 cm.) thick. Six0.00j-in. (0.013-cm.) diameter molybdenum wires, chosen because of their very low solubility in coppcr and alpha brass, were strctched lengthwise along each of the two plane surfaces. Glass tubes placed at right angles to the wires every 1/2 in. held the wires tightly against the brass. The sample was then emersed in an acid copper sulphate plating bath and electroplated to a depth of about 0.020 in. (0.050 cm.) copper on all sides. The glass tubes were no longer necessary to hold the molybdenum wires in place and were removed. The sample was then electroplated to a depth of

Jan 1, 1947

By E. O. Karenna, A. D. Smigelskas

This is the third paper in a series on the diffusion of zinc in alpha brass.' At the time of the first paper it was accepted that diffusion in a substitutional type of solid solution depended upon an equal interchange of solute and solvent atoms across the diffusion interface (or past a given lattice reference point). Discrepancies in the size of the areas under the diffusion curves on each side of the interface, if observed, were explained on some other basis than the fact that the solute atoms might cross the diffusion interface without an equal number of solvent atoms diffusing across the interface in the opposite direction. The second paper presented evidence indicating that zinc atoms in alpha brass diffuse across the interface more rapidly in one direction than the copper atoms diffuse across the interface in the opposite direction. This phenomenon forced the interface to move in the opposite direction of the diffusion of zinc atoms to provide space for the additional zinc atoms dissolved in the alpha brass. That the interface and columnar grain structure on one side would remain intact during this mass movement was not expected; how ever, it is gratifying that they did. While the evidence was sufficiently satisfying to the author, it was decided that additional experiments were in order to prove that zinc diffuses more rapidly than copper in alpha brass. It is the purpose of this paper to present the results of these experiments. Procedure A bar of 70-30 wrought brass was selected, to avoid the relatively large volume change in going from beta to alpha brass as in the previous investigation. A bar 7 in. (18-cm.)* long and about 3/4 in. (1.9 cm.) wide was surface ground and polished with abrasive paper on plate glass to 0.4184 0.0002 in. (1.062j + 0.0005 cm.) thick. Six0.00j-in. (0.013-cm.) diameter molybdenum wires, chosen because of their very low solubility in coppcr and alpha brass, were strctched lengthwise along each of the two plane surfaces. Glass tubes placed at right angles to the wires every 1/2 in. held the wires tightly against the brass. The sample was then emersed in an acid copper sulphate plating bath and electroplated to a depth of about 0.020 in. (0.050 cm.) copper on all sides. The glass tubes were no longer necessary to hold the molybdenum wires in place and were removed. The sample was then electroplated to a depth of

Jan 1, 1947

By V. F. Swanson

At the AIME meeting in Tampa in Oct. 1966, an empirically developed equation was presented which allowed the calculation of free settling velocity for any sized particle: 1 [ ] This equation requires the use of two parameters a and p which are coefficients derived from boundary layer theory.2 It was possible to develop values of a and p for several minerals by back calculation of published data. The original equation had one major flaw. When the fluid density exceeds the density of the solids, the solution to the equation becomes imaginary. A flaw was indicated also by the fact that galena and sylvite both having cubic cleavage, did not have similar values for a and b. Galena gave calculated values of a = 1.082 and g = 3.11, while sylvite gave values of a = 1.870 and p = 2.56. These flaws prompted further study of the equation, resulting in the following empirical modification: [ ] It is obvious a real solution of the equation is possible for all values of ps and p. When PL > PS, V is negative, indicating that the particles will rise against the attraction of gravity. The validity of the modification is borne out by the fact that when values of a and p were back calculated for galena and sylvite using the modified equation, both minerals gave values of a = 1.038 and p = 3.01. With the modification shown in Eq. 2, Newton's friction factor becomes [ ]

Jan 1, 1976

By Takashi Katsura, Avnulf Muan

Equilibrium relations in the system FeO-Fe2O3 Cr2O3 have been determined at 1300°C at oxygen pressures ranging from that of air (0.21 atm) to 1.5 x 10-11 atm. The following oxide phases have stable equilibrium existence under these conditions : a sesquioxide solid solution with corundum-type structure (approximate composition Fe2O3-Cr2O3); a ternary solid solution with spinel-type structure (approximate composition FeO Fe2O3-FeO Cr2O3) and a ternary wüstite solid solution with periclase-type structure and compositions approaching FeO. The metal phase occurring in equilibrium with oxide phase(s) at the lowest oxygen pressures used in the present investigation is almost pure iron. The extent of solid-solution areas and the location of oxygen isobars have been determined. ThE system Fe-Cr-O has attracted a great deal of interest among metallurgists as well as ceramists and geochemists. Metallurgists have studied the system because of its importance in deoxidation equilibria, ceramists because of its importance in basic brick technology, and geochemists because of its importance for an understanding of natural chromite deposits. Chen and chipman1 investigated the Cr-O equilibrium in liquid iron at 1595°C in atmospheres of known oxygen pressures (controlled H2O/H2 ratios). The main purpose of their work was to determine the stability range of the iron-chromite phase. Hilty et al.2 studied oxide phases in equilibrium with liquid Fe-Cr alloys at 1550°, 1600°, and 1650°C. They reported the existence of two previously unknown oxide phases, one a distorted spinel with composition intermediate between FeO Cr203 and Cr3O4, the other Cr3O4 with tetragonal structure. They also sketched diagrams showing the inferred liqui-dus surface and the inferred 1600°C isothermal section for the system Fe-Cr-O. Koch et al3 studied oxide inclusions in Fe-Cr alloys and also observed the distorted spinel phase reported by Hilty et al. Richards and white4 as well as Woodhouse and White5 investigated spinel-sesquioxide equilibria in the system Fe-Cr-O in air in the temperature range of 1420" to 1650°C, and Muan and Somiya6 delineated approximate phase relations in the system in air from 1400" to 2050°C. The present study was carried out at a constant temperature of 1300° C and at oxygen pressures ranging from 0.21 atm (air) to 1.5 x 10-11 atm. The chosen temperature is high enough to permit equilibrium to be attained within a reasonable period of time within most composition areas of the system, and still low enough to permit use of experimental methods which give highly accurate and reliable results. These methods are described in detail in the following. I) EXPERIMENTAL METHODS 1) General Procedures. Two different experimental methods were used in the present investigation: quenching and thermogravimetry. In the quenching method, oxide samples were heated at chosen temperature and chosen oxygen pressure until equilibrium was attained among gas and condensed phases. The samples were then quenched rapidly to room temperature and the phases present determined by X-ray and microscopic examination. Total compositions were determined by chemical analysis after quenching. In the thermogravimetric method, pellets of oxide mixtures were suspended by a thin platinum wire from one beam of an analytical balance, and the weight changes were recorded as a function of oxygen pressure at constant temperature. The data thus obtained were used to locate oxygen isobars. The courses of the latter curves reflect changes in phase assemblages and serve to supplement the observations made by the quenching technique. 2) Materials. Analytical-grade Fe2O3 and Cr2O3 were used as starting materials. Each oxide was first heated separately in air at 1000°C for several hours. Mixtures of desired ratios of the two oxides were then prepared. Each mixture was finely ground and mixed, and heated at 1250" to 1300°C in air for 2 hr, ground and mixed again and heated at the same temperature for 5 to 24 hr, depending on the Cr2O3 content of the mixture. A homogeneous sesquioxide solid solution between the two end members resulted from this treatment. A Part of some of the sesquioxide samples thus prepared was heated for 2 to 3 hr at 1300°C and oxygen pressures of 10-7 or 1.5 x 10-11 atm. Reduced samples (either iron chromite

Jan 1, 1964

By G. A. Crowe, W. T. Bishop

WHILE the literature in the United States on general polarographic technique is extensive, very little appears to be directly applicable to the analysis of flotation tailings. For this reason, it seemed worth while to present a few polarographic methods of ore analysis that have been in constant use in the laboratories of the Hercules Experiment Station for the past few years. At the time of our initial investigation of the polarographic method, there was little or no mention of its specific application to flotation tailings. It was therefore necessary for us to establish suitable conditions for the analysis of our flotation tailings and to consider possible interfering constituents. The polarograph, or dropping mercury electrode, method was discovered in 1925 by J. Heyrovsky and M. Shikata,1 of the Charles University, Prague. This method has since received extensive development and the literature contains many articles on the use of the polarograph for the quantitative determination of metals as well as anions, oxygen in solution, and reducible organic compounds. Kolthoff and Lingane,2 by the publication of their book, "Polarography," in 1941 did much to advance the knowledge and use of the polarograph. In chapter 25 of that book, methods for the polarographic analysis of brass, steel and iron products, alloys, and zinc ore are given. Aluminum,3 cadmium,3.4 cobalt,4 copper,3-9 gold,10 iron,3,11 lead, 3,12,13 molybdenum," nickel,4.8,9 tin,15 and zinc3,4,5,7 in ores have been analyzed by the polarograph. However, most of the work on tailing samples has been published in Russian journals and translations are not yet readily available. In this paper we will describe the method that was developed and used in our laboratory for the determination of copper, zinc, and lead in flotation tailings. PRINCIPLE OF THE METHOD The polarograph is an instrument for applying a potential to a mercury pool and a dropping mercury electrode separated by a solution, and for measuring the resultant electrical current. The procedure is essentially a small-scale electrolysis, in which the voltage required to reduce or oxidize the material identifies it qualitatively and the current measures the concentration quantitatively. Different constituents in a sample may often be determined simultaneously provided they reduce at sufficiently different voltages. An example is the determination of copper and zinc in the same solution. The reduction potentials are quite far apart, as shown in Fig. I. The polarographic method is particularly useful in the range of concentration between those normally determined by spectographic and chemical methods. In

Jan 1, 1946

US 4,185,077 - In the recovery of uranium from a solution produced by leaching uranium ore, the leach liquor is contacted with a polymeric crosslinked vinyl benzyl chloride anion exchange resin and eluted with sulfuric acid to recover uranyl sulfate Such a resin is resistant to attrition and thermal degradation during elution. R.L. Albright, assigned to Rohm & Haas Co Jan. 22, 1980. 6 pp (423-7). Filed: 10-31-75 (627,829).

Jan 1, 1982

By J. A. Lund, A. M. Lawson

THE structures of quenched eutectoid and hypereu-tectoid Fe-Cu alloys have been examined by X-ray diffraction and by optical and electron microscopy. The relevant portion of the Fe-Cu phase diagram is given in Fig. 1. Several values have been reported for the solubility of copper in a Fe at the eutectoid temperature, including 1.4 wt pct by orton' and 2.13 wt pct by Wreidt and Darken.2 Alloys containing 4.8 and 7.5 wt pct Cu have been prepared from two batches of Ferrovac E iron (0.005C and 0.013C) and electrolytic tough pitch copper (99.90 Cu). Specimens of dimensions 0.8 by 0.8 by 0.1 in. were cut from hot-rolled material, austenitized, and quenched into brine at 25°C. Similar specimens were also cooled in the furnace, after a short soaking treatment at 1100°C, at a rate estimated to be 10°C per min in the temperature range of 900" to 500°C. X-ray diffractometry was performed on quenched and on furnace-cooled bulk specimens using iron radiation. Only a bcc phase could be detected in all samples. Lattice parameters were calculated from measurements on four lines, made up of two resolved high-angle doublets. Comparisons were made against a silicon standard. Results are shown in Table I. Based on X-ray diffraction studies of a series of alloys of lower copper concentrations, orton' estimated that the tattice constant of a Fe at 25°C increases 0.0014A per wt pct Cu in solution. Extrapolating Norton's data, it may be concluded that all copper was retained in solution in the brine-quenched 4.8 pct Cu alloy, and that approximately 5 pct Cu was also held in solution on quenching the 7.5 pct Cu alloy. Typical microstructures of brine-quenched specimens, as observed by optical microscopy, are shown in Figs. 2 and 3. Precipitation of the E phase (copper-rich) occurred along the y grain boundaries on quenching the 7.5 pct Cu alloy, rendering them readily detectable in the microstructure, Fig. 3. The original boundaries in the 4.8 pct Cu specimens were gener- ally not discernible, however. This indicates that the z phase which was seen in the higher-copper alloy was probably of proeutectoid origin. Thin foils for transmission electron microscopy were obtained from bulk specimens by spark machining to 0.006 in. thickness, followed by electrolytic polishing. Typical transmission electron micrographs

Jan 1, 1967

By L. Ibagos S., T. Balberyszski

The volumetric flow rate and the initial concentration of the copper sulfate solution influence the rate of reaction and, hence, the precipitation efficiency in a continuous launder cementation system. Using a model of such a system it was found that the precipitation efficiency is related to the two process parameters by the approximate expression [ log [1-n] = -[0.072 co 2.91 e – 0.511c o Q 1.15 ] N Q] where c is the initial concentration, Q, is the volumetric flow rate and N is the number of launders in the system. This expression agrees with an equation developed for the rate of the cementation process if it is assumed that the exponential factor represents the change in the surface area with concentration and the exponents 2.91-and 1.15 relate the hydrodynamic conditions and the surface concentration to co and Q. The experimental results are used to determine the values of a Precipitation Coefficient for any volumentric flow rate and initial concentration of solution. Knowing the Precipitation Coefficient, the total volume of launders that will result in a given precipitation efficiency can be calculated. It is established that maximum precipitation efficiencies are obtained for initial concentrations between 6.0 and 7.0 gpl and volumetric flow rates of approximately 350 m3 /hr Good agreement between calculated and actual launder volumes is obtained for a number of industrial operations for which a comparison is made.

Jan 1, 1973

By George Steintveit

Det Norske Zinkicompani A/S was established in 1924, on the initiative of the Compagnie Royale Asturienne des Mines. Experimental electrothermic zinc production was carried out on industrial scale for a two-year period, but the problems of electrothermic smelting were not solved. A license for the electrolytic zinc production process was then obtained from the Anaconda Copper Mining Co. A plant for electrolytic zinc production was built, near the small fjord town of Odda in Hardanger, West Norway, The production was based on zinc ore from Spain, and cheap local hydro-electric power. The plant came into operation in 1929. Annual capacity, 36,000 tons. In 1964 a long-term agreement was concluded with Boliden AB by which Det Norske Zinkkompani is secured the raw materials basis for an expansion of the annual capacity to 100,000 tons of zinc, Since World War II, the company has been pursuing extensive research and development programs. As a result, various sections have been rebuilt: nev unloading and storage facilities, a 250 ton per day Fluid Bed Roaster with contact plant, new continuous leaching system, integrating the Jarosite Residue Process, new solution purification section - upgrading the solution quality for a 600 Amp/m2 current density Tank Room operation -, installation of induction furnaces for cathode melting with casting machines and automatic stacking of slabs. Simultaneously, instrumentation, and methods of automatic control have been developed and introduced, providing conditions for optimal plant operations.

Jan 1, 1970

By R. F. Mehl, C. S. Barrett, A. H. Geisler

THE complicated nature of the property changes that accompany age-hardening has made it necessary to reconsider and to elaborate the simple dispersion theory.1 It has been apparent for some time that more direct information is needed concerning the atomic mechanism of precipitation from solid solution if the theory of age-hardening is to be developed past a purely qualitative stage.‡ Fortunately, in recent years information has been developed which allows us to trace in detail the lattice changes accompanying the process of precipitation from solid solution. This information relates chiefly to the sequence of the several stages of lattice alteration by which the matrix lattice is transformed to the equilibrium precipitate lattice, and permits reasonable inferences to be drawn concerning the states of internal strain that accompany these stages. This information is most complete for the solid solution of copper in aluminum. The equilibrium precipitate is the ?' phase," CuA12." This forms in plates, parallel to the {100} matrix planes. The atom pattern and atom spacing on the plane in ?' lying parallel to this plane are roughly similar to those opposite it in the matrix.' The formation of ?', however, is preceded by the formation of a transition lattice ?', which again lies parallel to the matrix {100} plane, but in this case the matching of atom pattern and spacing across the matrix-precipitate interface is nearly perfect; thus there is lattice coherency across the interface and the interface is a plane of separation in only a very limited sense.4-8 Particles of ?' may be recognized microscopically and form a well-defined Widmanstätten figure.* The ?' lattice is recognized by the occurrence of diffraction lines on powder photograms or of spots on Laue photograms which may be analyzed in the usual ways to determine the lattice type and the lattice spacings. Very recent research 6.7,1 has shown, however, that streaks occur on the Laue photogram at an earlier point in time during the aging process. These streaks have been attributed to a preferential clustering of copper atoms into small platelike elements of only a few atoms in thickness and a few hundred atoms in diameter, probably of the composition of "CuA12," which may be designated as Guinier-Preston zones or aggregates.1 It is difficult if not impossible to determine the lattice type and lattice spacing in these aggregates. It is possible1 that these aggregates are in fact merely ?' in a high state of dispersion; the inclination to argue this is strong, as we shall see later. Never-

Jan 1, 1941

By Michael B. Bever, John R. Anderson

Carbon may affect the alloys of copper in several ways. Provided an alloying element does not oxidize preferentially, even minute quantities of carbon dissolved in liquid alloys of high copper content will form insoluble carbon oxide gases under oxidizing conditions. Gas porosity in castings of high-copper alloys can originate in this way. In certain alloys of low copper content carbon may have considerable solubility and may be an effective deoxidizer. In these alloys carbon will tend to suppress porosity. Carbon that is dissolved in the molten alloy is likely to be retained in the solidified metal. The effects of carbon on the physical properties of the metal are determined by the form in which it is present. Depending on the alloying elements and also on the cooling rate, carbon may precipitate as graphite, may form a carbide or may remain in solid solution on cooling. As solid copper does not dissolve a measurable amount of carbon, a carbon-bearing solid solution can occur only if the copper is alloyed with a large excess of an element that forms such a solution. The effect of graphite or of carbides on the properties of an alloy will depend on the size and distribution of the precipitated particles. As Hensel pointed out in discussion,' the formation of an alloy carbide may interfere with the age-hardening properties of a copper alloy. One would also expect that the presence of carbides or of graphite will under certain conditions promote corrosion or high-temperature failure in nonferrous alloys. Since carbon has an effect on the soundness of castings and affects the structure and behavior of solid copper alloys, its solubility in the liquid alloys is of practical importance. The isothermal change of carbon solubility with alloy composition is of interest from a theoretical standpoint. The binary alloys of copper with manganese and with nickel are used industrially and serve as a base for more complex alloys. The solubility of carbon in each of these metals is known, but its solubility in their alloys has not been determined. Earlier Data The solubility of carbon in molten pure copper is about o.oooi pct at II00°C and 0.0004 pct at 1475°C.l Various authors2""6 have published data on the solubility of carbon in molten manganese. There is agreement on a value of about 6.7 pct in the temperature range r2170 to 1245°c This solubility value corresponds to the formula Mn3C. It increases very little with increasing temperature. Corson7 states that carbon is soluble in copper-manganese alloys and that the

Jan 1, 1947