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By Harold W. Aldrich, Walter G. Scott

The leaching process of the Inspiration Consolidated Copper Co. is based upon the solubility of oxidized copper in sulfuric acid and the solubility of sulfide copper, largely in the form of chalcocite, in ferric sulfate solution. This necessitates the carrying of a rather large amount of iron in solution. The ferric sulfate is regenerated from ferrous sulfate by the oxygen given off at the anode during electrolytic precipitation of the copper. In September, 1924, excavation was started at Inspiration, Arizona, for the construction of a plant to treat 7500 tons of ore per day. When the plant was begun, the fact developed that by a minor change in the height of the overflow on the leaching tanks, 9000 tons could be charged into each tank and treated satisfactorily. This determined the maximum capacity of the plant as 9000 tons per day. The first ore was charged in October, 1926, and there are now available the records of five complete years of operation; namely, 1927 to 1931, inclusive. The original estimate of copper content of the ore to be mined for this plant was 1.19 per cent, of which 0.77 per cent was as oxide and 0.42 per cent as sulfide. From the metallurgical results obtained at the 35-ton pilot plant, it was estimated that a 90.0 per cent extraction of the oxide copper and a 75.0 per cent extraction of the sulfide copper could be made. It was estimated that the tailing would carry 0.182 per cent total copper, resulting in a

Jan 1, 1934

By E. A. Gulbransen, A. Pebler

Pressure-composition isotherms have been determinedfor the systems ZrMo2 -H2 between 0" and 900°C at hydrogen pressures between 10-4 and 760 Torr. Tkese studies plus X-ray diffraction analyses of selected compositions show that these intermetallic compounds form a complete series of hydrogen solid solutions within this temperature and pressure range. The partial molar enthalpies and entropies of solution of hydrogen in the three intermetallic compounds were calculated. The solubility of hydrogen in these Laves phases can be related to their free electron concentration. ThE reaction of hydrogen with inter metallic compounds of zirconium with Laves phase-type structure has both theoretical and practical interest. The in-termetallic compounds have structures different from any of the pure metals. In addition the electron to atom ratio of the intermetallics varies appreciably. In the nuclear materials field, these materials are of interest since intermetallic compounds may exist as precipitates in commercial zirconium alloys with transition metals. From studies on the hydrogen reaction, one can establish the stability of the intermetallic compounds relative to the hydrides of the component metals. The intermetallic compounds may also be used as getters for hydrogen and as materials for hydrogen storage. This paper will present the results of equilibrium and structural investigations of the ZrCr2-H2, the ZrV2-H2, and the ZrMo2-H2 systems for the temperature range of 0" to 900°C and the pressure range of Torr to 1 atm. A complete thermochemical analysis will be made of the measurements. Some of the results have been referred to in a survey paper' covering the types of hydrogen behavior observed in zirconium alloys. LITERATURE ZrCr2 is the only intermetallic phase in the Zr-Cr system.' It exists in two allotropic modifications. Between 900" and 1000°C the hexagonal MgZa (C14) structure transforms into the cubic MgCu2 (C15) structure. Beck4 has previously shown that the intermetallic ZrCrz takes up hydrogen into solid solution up to a composition H/ZrCr2 = 1.14 at room temperature and 1 atm hydrogen. A ZrCr2 hydride was stated to have a fcc structure. The binary Zr-V system has been investigated by williams5 although Rostoker and Yamamoto 6 had given earlier a partial phase diagram. ZrV2 was the only intermediate phase found in the system. wallbaum7 reported earlier that the compound ZrV2 hp the MgZm (CJ4) type structure with a = 5.288A and c = 8.664A. This was not comfirmed by Elliot8 nor by Matthias, Compton, and corenzwit9 who reported that ZrV2 has a cubic MgCua LC15) type structure. The latter authors gave a = 7.429A. Also, several authors do not agree on the temperature of the peri-tectic horizontal. It appears that ZrV2 may exist in several modifications. A high capacity for occluding hydrogen was reported by Beck4 who found H/ZrV2 = 1.38 at room temperature and 1 atm of hydrogen. ZrMoz is the only intermetallic phase in the Zr-Mo system.10 ZrMoa is formed by a peritectic reaction of the melt with a molybdenum-rich solid solution. ZrMo2 has the C15-type structure with a = 7.59A. MATERIALS High-purity chromium, vanadium, and molybdenum were used together with grade 1 crystal bar zirconium to prepare the alloys. Table I lists the chemical analysis and the sources for the metals. Ten-gram alloy compacts were levitated and melted in an inert argon

Jan 1, 1968

By W. Rostoker

Single isothermal sections were constructed for the titonium-rich corners of the systems Ti-Fe-O, Ti-Cr-O, and Ti-Ni-0 with a view to locating the shape and disposition of the ternary intermediate-phase fields for the compounds isomorphous with Fe3W3C. IN a previous note,' it was reported that a group of ternary intermediate phases existed which occurred in the general composition range Ti,X,O-Ti&O where X was one of the following elements: copper, nickel, cobalt, iron, or manganese. In two instances, binary intermediate phases occurred (Ti²Cu and Ti²Ni) which appeared to be isomorphous. The X-ray diffraction patterns of the phases could be indexed on a cubic lattice whose cell edge was of the order of 11 kX. Karlsson2 stated that the line extinctions and line intensities indicated that these phases were isomorphous with Fe³W³C and therefore belonged to the space group Oh. This author also noted that no unique phase of this type occurred at the composition Ti,Cr,O. This latter statement was accepted as true at the time the previous technical note was written.' However, work continued along these lines and that reported here has shown that a phase isomorphous with Fe³W³C does exist in the vicinity of the composition Ti³Cr³O but not at or near Ti4 Cr²O. The lattice parameter of this phase was found to be 13.01 kX. Metallographic examination of both as-cast and annealed specimens of these supposed ternary oxide phases disclosed structures which were far from single phase in many instances. It was considered a point of some interest to locate more positively the composition coordinates of the single-phase fields. To this end, single isothermal sections for the systems Ti-Fe-O (1000°C), Ti-Cr-0 (1000°C), and Ti-Ni-0 (900"C) were constructed. Phase relationships were studied by both X-ray diffraction and metallotrra~hic methods. Allovs were prepared as 10 g buttons by melting in a noncon-sumable electrode, water-cooled copper crucible arc-melting furnace using a helium atmosphere. Oxygen was introduced quantitatively by the use of weighed amounts of TiO² or TiO. Iodide titanium and the purest available alloying metals were used. All results are discussed in terms of the nominal composition of the melts. Previous experience with making oxygen-rich alloys had shown that oxygen losses were not significant if a homogeneous melt was produced. Weight-loss measurements were used to check loss in metallics during melting. Anneals were conducted in evacuated Vycor bulbs, and annealing times ranged from 24 hr at 1000 °C to 48 hr at 900°C. To achieve equilibrium in certain sluggish alloys, seven-day anneals were used. Debye-Scherrer powder patterns were taken in a 14 cm diam camera using filtered CuK radiation (K² = 1.541232 kX; K., = 1.53739 kX). Specimens were prepared by crushing and screening previously annealed buttons. In general, the X-ray diffraction results were used to identify the major phases, while the metallographic examinations were more useful in indicating the number of phases present. By the use of the combined results and general fundamental rules governing ternary equilibrium, it was possible to construct isothermal sections in good detail. In some instances where auxiliary lattice-parameter data were available, it was possible to lay down tie lines and to locate more positively corners of three-phase fields. Isothermal Section of the System Ti-Fe-O at 1000°C The binary systems Ti-O³ and Ti-Fe4 have been published. Binary phases, TiO, TiFe, and TiFe2, are likely to be encountered in the titanium-rich corner of the system. The structures are NaCl (Bl), CsCl (B2), and MgZn, (C14) types, respectively. Although preliminary X-ray diffraction studies indicated the presence of a ternary phase in the composition range Ti,Fe,O-TiJ?e,O, metallographic examination of two specimens at these compositions revealed the presence of other phases. Thirty-eight alloys were used to delineate the phase boundaries of the isothermal section illustrated in Fig. 1. The five almost single-phase ter-

Jan 1, 1956

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

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,' 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

Application of technology to the search for new deposits went on apace in 1963. Traditional methods, aided by modern communications, were successful in some out-of-the way corners of the world that had not been adequately prospected, but the co-ordination of several mutually supporting techniques is necessary to define exploration targets in most areas today. Although these obviously include geophysics and geochemistry, which are treated elsewhere in this issue, geology continues to play a major role. As the search focuses on less and less obvious targets there will be more need than ever to "pull out all the stops." Any anomaly may have significance and must be evaluated as a possible lead. Ability to detect them increases as the laboratory workers refine techniques for measuring physical, chemical, and isotopic properties; it will be increasingly the responsibility of the exploration geologist to understand and apply these to economic problems. Simple propecting, the search for outcrops of recognizable ores of traditional types, was perhaps most successful for iron. Potentially large deposits of high-grade magnetite-specularite-hematite ore have been found in the Mary River area near the north end of Baffin Island. The ore holds up four hills that stand some 1500 ft above the surrounding country; obviously they were ripe for discovery by the first person to come across them, in this case Murray Watts, president of British Ungava Explorations, Ltd, As preliminary examination indicates a lump ore averaging 68 to 70% iron, these deposits may be commercial in spite of the unfavorable climate and their isolation from world markets.

Jan 2, 1964

By N. J. Grant, K. M. Zwilsky

A series of copper-alumina dispersion strengthened alloys were prepared using three different copper and two different alumina powder sizes. Improvements in strength of up to ten times that of pure copper were found in room-temperature as well as elevated-temperature stress-rupture tests. Conductivity values remained from 70 to 90 pct that of pure copper. The best alloys were based on the finest metal powder (1 p) and contained from 7.5 to 10-0 vol pet of 0.018 or 0,033 p alumina. DISPERSION strengthening of metals consists of strengthening a metal matrix by the addition of oxides or other refractory constituents, followed by strain hardening, in order to reinforce the base material and extend its temperature range of application. Since the discovery of SAP by lrmannl and Von zeerleder2 in 1949, many investigators have reported data obtained on a variety of metal-inert oxide alloys.3-7 The present work deals with the mechanical mixing of copper and alumina powders. While several techniques of introducing the second phase have been investigated to date, mechanical mixing so far has been recognized as the simplest, least expensive, and most universally applicable technique that can be used to obtain an ultrafine dispersion of inert particles. In the present case, the effects of changing the metal particle size, the oxide particle size and the volume percent of oxide were investigated. This work is an extension of a previous study.6 EXPERIMENTAL PROCEDURE The starting materials were three different grades of copper powder and two different alumina powders. The three metallic powders were -74 µ(- 200 mesh) electrolytic copper powder consisting of irregular equiaxed particles having a normal screen distribution and analyzing 99.5 pct Cu, and two powders having a 5-µ and 1-µ particle size, average, respectively. The latter powders were produced by the hydrogen reduction of purified sulfate solutions at elevated temperature and pressure and were furnished by the Sherritt Gordon Mines, Ltd. The alumina used was obtained from Godfrey L. Cabot Co., under the trade name of Alon C, one batch of powder having a particle size of 0.018 µ, the other a particle size of 0.033 µ. The crystal structure of these alumina powders was found to be cubic gamma. Each batch of powder was mixed in a Waring Blendor for a total of 15 min, followed by a low-temperature reduction in hydrogen and vacuum compacting in cylinders which were hydrostatically pressed at 35,000 psi to give a compact that could be handled conveniently. Six of the compacts were hydrogen sintered at 900°C while the remaining four were sintered at 1000°C. Subsequently, all compacts were hot extruded at 760°C with a reduction of area ratio of approximately 20 to 1. Evaluation of alloys included density and resistivity measurements, room-temperature tensile tests, stress-rupture tests at 450°C plus one other temperature per alloy, hardness tests, microstruc-tural examination, X-ray analysis of the dispersed phase after dissolving the metal phase, and oxidation studies on two of the alloys. A vacuum-melted, wrought copper rod was tested together with these alloys for comparison purposes. RESULTS Table I is a summary of the compositions, sintering temperatures, densities and conductivity values of the ten alloys prepared. All alumina additions are given in volume percent, and will be referred to as

Jan 1, 1962

By J. R. Long, R. S. Dean, F. S. Wartman, E. T. Hayes

The production of titanium in I5-lb. lots and with a purity sufficient to be consolidated into ductile metal, as described in a previous paper,' has provided adequate material for a study of the physical properties of titanium and a more thorough examination of its working qualities. Data on the physical properties reported in that paper were obtained on metal fabricated by a fixed procedure, standardized for the purpose of control of the reduction, and are representative only of material fabricated under those conditions. There are many possible variables in the working schedule, which will have significant effects on the properties of the finished material; and since the previous working methods were not necessarily the best, an investigation of the fabrication of titanium by other methods was undertaken. In this work the consolidation of the powder by pressing and sintering was conducted essentially as outlined in the report cited' and all efforts were centered on fabrication methods for those powders and the proper- ties produced by them. Hardness, density, microstructure, and tensile properties were determined at various stages in the working and annealing; and resistivity measurements were made on a few bars and drawn wire. Consolidation of the PowdeR The screen analysis of the available titanium powder is given in Table I. No attempt was made to alter the size distribution from that noted because this powder, although coarse by normal powder-metallurgy standards, produced acceptable compacts suitable for the present work. Because of their large specific surface, finer powders are more contaminated by oxygen and produce harder compacts, which are difficult to work. The powder as produced is soft, compresses in a normal fashion, and exhibits very little tendency to adhere to the die surfaces. Unlike aluminum and magnesium powders, it can be readily pressed without the use of die lubricants. When compacted at 50 tons per

Jan 1, 1946

By J. R. Long, E. T. Hayes, R. S. Dean, F. S. Wartman

The production of titanium in I5-lb. lots and with a purity sufficient to be consolidated into ductile metal, as described in a previous paper,' has provided adequate material for a study of the physical properties of titanium and a more thorough examination of its working qualities. Data on the physical properties reported in that paper were obtained on metal fabricated by a fixed procedure, standardized for the purpose of control of the reduction, and are representative only of material fabricated under those conditions. There are many possible variables in the working schedule, which will have significant effects on the properties of the finished material; and since the previous working methods were not necessarily the best, an investigation of the fabrication of titanium by other methods was undertaken. In this work the consolidation of the powder by pressing and sintering was conducted essentially as outlined in the report cited' and all efforts were centered on fabrication methods for those powders and the proper- ties produced by them. Hardness, density, microstructure, and tensile properties were determined at various stages in the working and annealing; and resistivity measurements were made on a few bars and drawn wire. Consolidation of the PowdeR The screen analysis of the available titanium powder is given in Table I. No attempt was made to alter the size distribution from that noted because this powder, although coarse by normal powder-metallurgy standards, produced acceptable compacts suitable for the present work. Because of their large specific surface, finer powders are more contaminated by oxygen and produce harder compacts, which are difficult to work. The powder as produced is soft, compresses in a normal fashion, and exhibits very little tendency to adhere to the die surfaces. Unlike aluminum and magnesium powders, it can be readily pressed without the use of die lubricants. When compacted at 50 tons per

Jan 1, 1946

By Don L. Kendall, Martin G. Buehler

A simple physical model has been developed to fit carrier-removal data in silicon irradiated near room temperature with reactor spectrum neutrons. Commonly observed donor and acceptor defect energy levels are assumed to be introduced linearly with neutron fluence. The donor levels (in ev) are Ev + 0.16, Ev + 0.27, and Ev + 0.31 and the acceptor levels are Ec - 0.55, Ec - 0.40, and Ec - 0.1 7, where Ev and Ec are the valence and conduction band energies, respectively. The introduction rates of each level are adjusted to fit literature initial carrier-removal rate data. When normalized with respect to the Ev +0.27 level, the relative values of introduction rates are 5.3, 1.0, 3.1, 1.0, 2.0, and 20.0, respectively for the six levels indicated above. To fit p-f (hole concentration vs neutron fluence) and n-f (electron concentration us neutron fluence) data, the introduction rates are multiplied by a factor which preserves the relative values given above. This factor depends upon irradiation temperature, reactor energy spectrum, neutron fluence calibration, and oxygen content of silicon. An extensive study of the effect of neutrons on carrier-removal in silicon irradiated with reactor spectrum neutrons (E > 10 kev) has been given by Stein and Gereth1 (SG) and Curtis, Bass, and Germano' (CBG). They measured initial carrier-removal rates for both p- and n-type silicon over an impurity range typical of silicon devices. In this work, we attempt to fit a simple theory to this data to establish a usable relationship between hole and electron concentration, p and n, respectively, and neutron fluence f. The p-f and n-f relations are needed to assist in the design of neutron tolerant silicon devices and are needed to clarify presently used empirical resistivity-fluence relationships.3 Neutron damage in silicon produces a variety of defects ranging from simple point defects to defect clusters. For the purpose of this treatment, we assume that simple point defects dominate carrier-removal effects. In contrast to this view, stein4 has proposed that defect clusters are responsible for a significant portion of carrier-removal effects. In the following section, it is shown that the carrier-removal effect in n-type silicon with an electron concentration less than 1015 cm-3 can be explained adequately by assuming that the divacancy is the dominant defect and that its introduction rate is independent of the electron concentration. For electron concentrations greater than 1015 cm-= an additional acceptor defect center is needed, and for simplicity the A-center (vacancy-oxygen pair) has been chosen. Although the E-center (vacancy-phosphorus pair) can account for some of the results, the A-center was chosen because the E-center requires a more involved treatment which the presently available data do not justify. In p-type silicon three radiation-induced donor levels are assumed, namely the divacancy and two other centers of unspecified nature located at Ev + 0.16 ev and Ev to 0.31 ev. The donor divacancy at Ev + 0.27 ev is assumed to be introduced at the same rate in p-type as in n-type. However, this rate is too low to fit p-type initial carrier-removal data. The dominant centers in p-type silicon are assumed to be the Ev + 0.16 ev and Ev + 0.31 ev levels where the latter is not the divacancy. The introduction rates are chosen to fit initial carrier-removal rate data. Assuming that the introduction rates are independent of Fermi level, the ratio between them is fixed for subsequent p-f and n-f calculations. Using the same ratios, the initial carrier-removal rate data1,2 as well as p-f and n-f data1,5 can be fit provided the absolute value of the introduction rates are adjusted to account for irradiation temperature, reactor energy spectrum, neutron fluence calculation, and the oxygen content of silicon. THEORETICAL ANALYSIS This analysis is basically the same as that used by Hi116 to analyze electron damage in silicon except we express the degree to which an impurity level is ionized not in terms of the Fermi level, but in terms of carrier concentration. Landis and pearson7 have used the latter approach to analyze y-damage in silicon. Neutron-induced defects responsible for carrier-removal at room temperature are assumed to be simple point defects with no interaction between defects so that they may be represented by discrete energy levels. It is also assumed that no constituent of a defect complex is used up and defects stabilize shortly after irradiation. Defects are assumed to be introduced linearly with fluence according to the product Rtf where Rt is the defect introduction rate and f the neutron fluence. Taking into account the ionization of defects according to Fermi statistics, and considering charge neutrality where minority carriers are neglected, the n-f relation is where no is the preirradiation electron concentration. The parameter Nt is the electron concentration at which the ionized defect concentration is one-half the total defect concentration (Rtf) or where Et is the defect energy level. For silicon at 300°K, ni = 1.45 X 1010 cm-3 and Ei = Ev+ 0.542 ev which was determined using Ec — Ev = 1.11 ev and me* = 1.07 mo and mh* = 0.558m0. The spin degeneracy factor, which usually appears as a number multiplying the Nt/n term of Eq. [1], is taken as unity. In effect, this factor has been incorporated into the defect en-

Jan 1, 1970

President-Mrs Robert D Coombs, 375 Paramus Road, Paramus, N J First Vice-President-Mrs Howard R Norsworthy, 333 East 53 Street, New York 22, N Y Second Vice-President-Mrs Arthur Notman, Circle Road, Dongan Hills, Staten Island 4, New York Third Viee-President-Mrs David Eugene Park, 30 Sutton Place, New York 22, N Y Fourth Vice-President-Mrs Cony T Brown, 211 East Abeyta Avenue, Socorro, New Mexico Fifth Viee-President-Mrs J A Carpenter, 245 University Terrace, Reno, Nevada Recording Secretary-Mrs W McG Peirce, 7 Lexington Avenue, New York 10, N Y Asst Recording Secretary-Mrs Arnold H Miller, 601 West 115 Street, New York 25, New York Corresponding Secretary-Mrs Theodore Nagel, 76 Remsen Street, Brooklyn 1, New York Treasurer-Mrs Robert W Rowen, 116 East 68 Street, New York 21, N Y Assistant Treasurer-Mrs Samuel H Dolbear, 11 Broadway, New York 4, N Y Assistant Treasurer-Mrs H A Kursell, 12 Murray Hill Road, Scarsdale, New York

Jan 1, 1955

By P. Somasundaran, I. J. Lin

There are several methods described in the literature for the determination of the order and the rate constant for the flotation of minerals. These often involve some type of computational or graphical procedures. A relatively simpler method developed on the basis of a technique used by Chang" in chemical kinetics is described in this paper. Chang's technique, like most others in chemical kinetics," is based on the law of mass action which states that the rate of a chemical reaction is proportional to the active masses of the reacting substances at any given time. Application of this law to the flotation of minerals would involve the adaptation of the terms "flotation" for "chemical reaction" and "floatable amount of the minerals" for "the active masses of the chemical reactants." There are indeed a large number of physical processes controlling the actual flotation rate. The most inefficient one of these could be considered equivalent to the slowest reaction in a series of chemical reactions. If variables such as aeration rate and agitation are kept at constant levels, the rate of flotation under free flotation conditions (i.e., conditions under which the suspension is dilute) will be given by the following equation: where C is the concentration of the floatable minerals in the pulp at any given time t, K is the rate constant, and n is the order of the reaction. If we represent the floated fraction of the floatable mineral at time t as m (0 m - 1) and C at t = 0 as Ca, integration of Eq. 1 yields

Jan 1, 1974

By H. B. Hunter, F. G. Stone, F. J. Dunkerley

Introduction and Literature Survey This is the second in a series of papers coming from this laboratory on the correlation of the low temperature tensile properties of tin-binary alloys with microstructure. These engineering data and those of the previous paper1 were obtained as the initial part of a long-range program to determine the changes in the fundamental mechanical properties accompanying the beta to alpha phase change in tin and its binary alloys below 13.2°C. Since it appears now that the more fundamental studies will be delayed,* and since no summary of the low temperature properties of these tin-base white bearing alloys was found in the literature, it was decided to publish all the engineering data thus far obtained. Accordingly, the tensile properties of thirteen binary alloys containing from 0.1 to 60 pet cadmium and 0.1 to 10.43 pet antimony measured at six temperatures from —196 to +23°C are presented here and their variations rationalized in terms of microstructure. A literature search showed that these systems had not been investigated at low temperatures, although both the tin-cadmium and tin-antimony2,3,4,5 and the tin-rich corner of the ternary system67 have been studied at room temperature. Hanson and Pell-Wal-pole5 and Homer and Plummer4 determined the tensile properties of alloys containing from 0 to 10 pet cadmium. The same authors3 determined the tensile strength and elongation in the tin-antimony system from 2 to 18 pet antimony at room temperature while Pell-Walpole et al.6,7 studied the properties of high tin and tin-antimony-cadmium alloys. Since there were many variables besides composition in these tests, it was difficult to make a valid comparison with the room temperature data of the present study, but in general the tensile strength and ductility values are in reasonable agreement. Pell-Walpole2 also determined the effect of grain size on the tensile strength of pure tin and 1 pet alloys of both antimony and cadmium. The true maximum stress was found to decrease exponentially as the number of grains in the cross-section increased. This effect of grain size was strikingly revealed in the present work, as indicated in a later section. Hanson and Pell-Walpole8 placed the solid solubility limit of antimony in tin at 3.5 pet at 20°C, increasing to 4 pet at 190°C, and then sharply increasing to 10.3 pet at 246°C (the latter being a peritectic point). Their results are in disagreement with those of previous investigators,9 and the discrepancy seems to lie in the micro-graphic observation of the second phase

Jan 1, 1950

By Hugh O?Neill

IN PREVIOUS papers,1 the author has reported the results of experiments on the straining in tension of a single crystal test piece, about 0.6 in. long, of vacuum-melted electrolytic iron containing 1.8 per cent. of silicon. The crystal was originally in the "as cast" condition, and was stressed slowly along a tetragonal axis so that slipping along conjugate gliding planes finally transformed the original cylindrical portion into a pair of fracture wedges. One of these fracture wedges was sectioned along the stress axis in a plane at right angles to the edge of the wedge. A metallographic study of this plane of -section led to the conclusion that slip had taken place in the (111) direction along (112) planes making a V shape with the stress axis. The present paper describes the results of scratch-hardness tests conducted on the same section, in order to determine the distribution of strain hardness therein, followed by annealing, and considers the resulting variations in hardness. These observations supplement those made by Krivobok2 on similar material reduced 25 per cent. by hammering (i. e., by impact) in the cold. In order to investigate ageing effects, two small crystals of the same alloy were also tested.

Jan 1, 1928

By H. J. Morel-Seytoux

Methods of predicting the influence of pattern geometry and mobility ratio on water flooding recovery predictions are discussed. Two methods of calculation are used separately or concurrently. The analytical method yields exact solutions in a convenient form for a unit mobility ratio piston-like displacement. A few typical pressure distributions, sweep efficiencies and oil recoveries are presented for various patterns. For non-unit mobility ratio, one may resort to a numerical method, such as that of Sheldon and Douherty. 1,2 Because the domains of applicability of the analytical and numerical techniques overlap, the exact solutions provide estimates of the errors in the numerical procedures. The advantages of the analytical and numerical methods can be combined. To develop a numerical technique as independent of geometry as possible, the physical space is transformed into a standard rectangle. The entire effect of geometry is rendered through one term, the "scale-factor", derived from mapping relations. The scale factor can be calcu-lated from the exact unit-mobility ratio solution for the particular pattern of interest. By this means recovery performances for arbitrary mobility ratio con be obtained for many patterns. A sample of tesults obtained in this manner is presented. INTRODUCTION Pattern geometry and mobility ratio are two major factors in making a waterflood recovery prediction. Because assisted recovery has become increasingly important to the oil industry, pattern configuration and mobility ratio also assume a greater significance in the assessment of the economic value of recovery projects. The influence of pattern geometry and mobility ratio in shaping a recovery curve and on the other quantities of interest to the reservoir engineer is the main subject of this paper. Much effort has already been spent on estimating quantitatively the influence of either pattern or mobility ratio or both on oil recovery. The literature reports many investigations of this nature. 3-9 However, many results or methods of recovery prediction presented in the literature cannot be considered fully satisfactory. Even for unit mobility ratio and piston-like displacement, where analytical solutions are available, the literature shows discrepancies. For non-unit mobility ratio, the divergence in the results is extreme. For infinite mobility ratio in a repeated five-spot, depending on the investigator, the sweep efficiency ranges from 0 per cent to 60 per cent. With respect to the influence of pattern on recovery, only the repeated five-spot has received much attention. Other confined patterns and pilot configurations have received very little attention. Two calculation methods are presented in this paper, either separately or concurrently: the analytical method of potential theory and the numerical method of finite-difference approximation. The analytical method is more restricted in scope than the finite-difference method, but it has the definite advantage of providing exact solutions within its range of applicability. If a unit-mobility ratio piston-like displacement is assumed, the analytical approach is possible. A few typical results are reported in this paper; the detailed description of the general method and of a great variety of results will be the subject of other articles. Fornon-unity mobility ratio, we must resort to a numerical scheme. The numerical technique is that which was described by Sheldon and Dougherty.l,2 It is not limited to piston-like displacement. However, mainly single interface results will be presented here. Because the respective domains of applicability of the analytical and the numerical method overlap, useful comparisons of exact and numerical solutions can be made for a variety of patterns. The advantages of the analytical and numerical approaches can be combined. The reason for the success of this analytical-numerical approach can be summarized in the following two points: 1. The numerical solution for arbitrary mobility ratio can be programmed most efficiently when the physical space in which the displacement actually takes place is transformed into a standard shape; and 2. This can be done with remarkable simplicity whenever an analytical expression for the pressure

Jan 1, 1966

By Walter H. Bruckner, George B. Clark

SINCE the end of World War II interest has been increasing in the use of shaped charges in the mining industry and in other industries using explosives for blasting purposes. Shaped charges employ the principle known as the "Munroe effect," which was discovered by Charles E. Munroe more than 50 years ago (in 1888). Details of their design have been explained e1sewhere.l,2,3 Fig I shows the essential features of design of two types of shaped charges (with conical and hemispherical cavities) and a schematic sketch of their action upon detonation. The following discussion deals with the behavior of the metal in the cavity liners when they are subjected to intense pressures exerted when the explosive charge is detonated. Among the conclusions reached in research on shaped explosive charges, the following have been established concerning cavity liners: 1,2 I. The optimum wall thickness of a conical cavity liner is dependent upon the apex angle of the cone as well as on the base diameter of the charge. Acute apex angles require thinner walls for optimum performance and more obtuse angles require thicker walls for the same base diameter. 2. Cones were more effective in forming a penetrating jet when the walls were tapered; i.e., the thickness of the wall of the cone increased from the apex down. 3. The physical and mechanical proper- ties of metals have a marked effect upon their performance as cavity-liner material. Boiling point, ductility, malleability, tensile strength, and hardness are among the properties that influence the effectiveness of a metal used as a cavity liner. Lead, for example, makes a wide, flat crater in steel plates. Aluminum makes a deeper crater than lead, and an aluminum alloy having a high tensile strength makes a deeper hole, but slightly smaller in diameter. Cast iron makes a deep, narrow hole. These findings, together with the following analysis under Metallographic Survey of Slug, offer solutions to many of the problems involved in solving the mechanism of the formation of Munroe jets. It has been fairly well established that cavity liners collapse in a manner similar to that indicated in Fig 2. Conical liners are known to collapse upon themselves while hemispherical liners are believed to turn inside out in the process of jet formation. The first has been definitely proved by recovery of collapsed portions of cones, while liners from partly detonated charges show that hemispheres may turn inside out. Fig 3 shows a sketch of a recovered slug from a 6-in. shaped charge using a 45° cone made of cast iron. (This size of charge drilled holes up to 3 ft in depth in solid granodiorite.)

Jan 1, 1947

By C. Baldwin Sawyer

During the last half century, much time has been devoted to investigations of the effect of nitrogen on the physical properties of steel, but in all discussions of results there is considerable doubt as to the accuracy and interpretation of analyses. No conclusions concerning the effects of nitrogen on the physical properties of steel can be more reliable than the methods used for determining the quantities of nitrogen present. The work described in this paper endeavors to establish some additional conditions required by the customary distillation method for reliable and nccurate determinations. Results by a combustion method of analysis for total nitrogen content are presented; these indicate that all of the nitrogen in steel, exclusive of that contained in blowholes, may be determined by the distillation method. Based on these more sound and more reliable analyses, results havc been obtained that bear on the following divisions of the general subject, nitrogen in steel: Nitrification of steel by melting in nitrogen, nitrification of steel by heating in ammonia, decomposition of nitrified steel by heating, and thermal analysis of nitrified steel. Consideration of Two Methods of Analysis and Some Results The details of the distillation and combustion methods are chemical in character and of little interest to most readers. They are therefore described in an appendix. The distillation method is essentially that described by Hurum and Fay1 and was generally used throughout this work. It is capable of the greatest accuracy and all results given are significant to the last, figure. Where analyses do not check, the samples

Jan 1, 1923

By C. Baldwin Sawyer

During the last half century, much time has been devoted to investigations of the effect of nitrogen on the physical properties of steel, but in all discussions of results there is considerable doubt as to the accuracy and interpretation of analyses. No conclusions concerning the effects of nitrogen on the physical properties of steel can be more reliable than the methods used for determining the quantities of nitrogen present. The work described in this paper endeavors to establish some additional conditions required by the customary distillation method for reliable and nccurate determinations. Results by a combustion method of analysis for total nitrogen content are presented; these indicate that all of the nitrogen in steel, exclusive of that contained in blowholes, may be determined by the distillation method. Based on these more sound and more reliable analyses, results havc been obtained that bear on the following divisions of the general subject, nitrogen in steel: Nitrification of steel by melting in nitrogen, nitrification of steel by heating in ammonia, decomposition of nitrified steel by heating, and thermal analysis of nitrified steel. Consideration of Two Methods of Analysis and Some Results The details of the distillation and combustion methods are chemical in character and of little interest to most readers. They are therefore described in an appendix. The distillation method is essentially that described by Hurum and Fay1 and was generally used throughout this work. It is capable of the greatest accuracy and all results given are significant to the last, figure. Where analyses do not check, the samples

Jan 1, 1923

By J. E. Crawshaw, Francis B. Foley

In the first report1 disks of steel of known composition and history were exposed, under carefully prescribed conditions, to impacts of explosion products resulting from the explosion of 50-gm. charges of explosives having well-determined rates of detonation, or to impacts of a weight of known mass, falling through measured distances. There were available at the Bureau of Mines Experiment Station five explosives, having rates of detonation of 5716, 4470, 3190, 2296, and 1523 meters per second. It being desired to continue this exposure downward, and no explosives with a lesser rate of detonation being at hand, resort was had to the impact of a falling weight, the differences in the velocity of impact being attained by varying the height from which the weight was allowed to fall. It was expected by this means to demonstrate experimentally that the development of Neumann bands was determined by the suddenness of the deformation of the metal in which they were produced. But while progressive deformations were obtained with the explosive charges, the falling-weight method failed because the tup was progressively deformed, also the disks were so flattened as to be unfit for metallographic examination. A return, therefore, has been made to the use of explosives as the source of energy, an air-gap being interposed between the charge of explosive and the disk, as the effect diminishes as the function of the distance between the charge and the object on which the products of its explosion, or the shock wave from its detonation, impinge. The details of the arrangement of the tests by the air-gap method were the same as those described by Foley and Howell,2 except that after the system had been set up and the desired apparent specific gravity for the explosive attained by tamping it, the small lead block, with the steel disk adhering

Jan 1, 1926

By N. P. Goss

ASTERISM appearing in X-ray Laue dia-grams is an extremely sensitive index of changes in the internal structures of indi-vidual grains of polycrystalline metals. It indicates the existence of various forms of subboundary structure or subdivision within the grain. The present viewpoint is that the grain is made up of lattice blocks having substantially the same size and shape.1-4 When these blocks all assume exactly the same orientation, the crystal is perfect and asterism is absent. Cleaves and Thompson5 observed that the hardness of iron is virtually constant over a range of grain sizes. It is quite possible that the subboundary structure caused this, and that the latter is just as important as grain size itself. While the experiments reported here are not con-clusive, they do support this viewpoint. Metals can, under certain conditions, be prepared entirely free from asterism, but this preparation does not necessarily require long heating or slow cooling, as will be shown here. In this paper a distinction is made be-tween mosaic and distorted grain struc-tures but the difference is only a matter of degree. In a previous paper9 it was shown that the grains can become distorted even during heat-treatment. The block structure exists inherently, even in a perfect crystal; the size and shape of these crystallites, or lattice blocks, varies, depending upon a number of factors. Goetz, for example,7 has shown that a metal before crystallizing from the molten state must go through a paracrystalline phase with oriented groups of atoms about 10-14 to 10-15 c.c., or 10-5 cm. in size.

Jan 1, 1940