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By Ivan E. Goodner, Charles H. Fulton

THE subject of the constitution of copper-iron mattes has received considerable attention in recent years by Keller,1 Bolles,2 Hofman,3 and Gibb and Philp.4 Still more recently Friedrich, Röntgen, Wiedmann, Heyn and Bauer, and Leroux have published, in some instances, elaborate researches on the various systems of the sulphides, and the sulphides and their respective metals, which enter into the constitution of mattes, and have added very greatly to the knowledge of the subject. The work of Friedrich has been especially fruitful. But to date no effort has been made to correlate the data obtained in the latter researches and apply then to the study of the product called " matte," which is made in such large quantities by copper and lead-smelters. In this paper we propose to determine, by metallographic and chemical means, the constitution of copper-iron and copper-lead mattes in the light of the recent data above mentioned. We do not discuss copper-nickel mattes or speisses (artificial arsenides). The paper is divided into three sections I. A review and discussion of the various binary systems of the metallic, sulphides, and the binary systems of various metals and their respective sulphides entering into the constitution of mattes; also a discussion of the physical and chemical properties of these sulphides. II. A description of the results obtained from the chemical and metallographic examinations of the samples of copper-iron and copper-lead-iron matte obtained from various plants.

Nov 1, 1908

By T. Kunitake, H. W. Paxton

The self-diffusion coefficient of chromium in various alloys in the iron-chromium system has been measured. A variation in Dofrom 10-4 for pure chromium to a maximum of 102 near 60 pct Cr appears with a range of activation energy from about 50 to 80 kcal per mol. The general pattern of behavior observed is not consistent with present theories of diffusion by a vacancy mechanism. Suggestions are made for further clarifying experiments. RECENT work on the self-diffusion of chromium,' ?-uranium2-4 and ß-zirconium,23, 26 has indicated that these elements have very low Do (10-3 to 10-4) compared to that conventionally expected for vacancy diffusion. Pound et al.5 have suggested that this may be due to ring diffusion being operative, and have proposed a model which gives Do of the correct order of magnitude. The essential difference between this model and Zener's earlier model6 is that whereas Zener assumes tight coupling between atoms in a ring to establish a vibrational frequency, Pound's model allows the atoms to vibrate essen- tially each in their own normal modes. The probability of each atom moving in the correct direction to cause a ring of n atoms to rotate by 2p/n must then be calculated as a "synchronal entropy" which may be -20 e.u. for a 4 atom ring. In iron, the latest determinations of self-diffusion yield Do in the range 18 to 522.7-9 The most accurate is probably that of Borg and Birchenall8 which is 118 ± 3. This value is not inconsistent with that expected for a vacancy mechanism. Since iron and chromium are very closely similar in size, are both transition metals, and their solution is thermodynamically ideal at temperatures of interest in diffusion, it appeared that a determination of self-diffusion coefficients, Do and Q as a function of composition would be of substantial interest to diffusion theory. The following measurements were made with this purpose in mind.

Jan 1, 1961

Jan 1, 1968

Jan 1, 1968

By C. D. Thurmond

Jan 1, 1968

By H. O. Hofman

Jan 1, 1896

By AIME AIME

WHEN "Chief" Buehler in mid-September set out on his official 10,000 mile swing-around-the-circle visiting Local Sections he decided not to tell his audiences how to organize and operate a state geological survey. As the director for 28 years, of the Missouri Bureau of Geology and Mines (which, he concedes, is the best in existence) lie could have done this to good advantage; but he preferred to discuss affairs of the Institute. In 25 speeches made to member and student groups, he dwelt on sonic or all of the following phases of activities. He stressed the vital importance of the Local Sections in providing the opportunity for members to associate under pleasant auspices with others in their profession. The benefits of Institute membership he classified as tangible and intangible. Of the two lie felt that the latter were more important. A man's progress in his profession depends in large measure upon a broad acquaintance and friendship with others. The Institute is incomparably the best medium for meeting fellow engineers. The primary, function of the new enlarged Membership Committee is to obtain a comprehensive list of engineers eligible to be members, always hearing in mind that the standards of membership must not be lowered in any degree. These men are to be invited by individual letter to apply for membership. Whether they become members or not is of less importance; but it is vital that no qualified man should be outside the fold for the reason that membership had never been suggested to him. Dr. Buehler emphasized repeatedly his feeling that the younger man that had never had Institute membership brought specifically to his attention had been cheated:

Jan 1, 1935

By K. H. Heino

Two 200 T/da Lurgi Turbulent Layer fluid-bed roasters have been in operation at Canadian Electrolytic Zinc Limited since 1966. Zinc concentrate containing 52-54% Zn, 9-11% Fe,31-33% S is treated to produce calcine containing 60-62% Zn,10-12% Fe, .l-.3% S as sulphide and .8-1.2% S as sulphate. Each roaster train comprises a waste heat boiler, two cyclones in parallel and a two-field electrostatic precipitator. Distribution of calcine collected is 10-15 percent from bed overflow, 55-65 percent from boilers, 20-25 percent from cyclones and 2-6 percent from precipitators. A Monsanto designed contact plant produces acid at a rated capacity of 365 T/da (100% H2304 basis) from roaster gases diluted to 7.0-7.5% S02. The process steps are gas cleaning and cooling by weak acid scrubbing, acid mist removal in electrostatic precipitators, gas drying in 93.5-96.5% H2304, conversion of sulphur dioxide to sulphur trioxide in a four-pass converter containing vanadium pentoxide catalyst, and absorption of the sulphur trioxide in 98.1-98.3% H2S04. Product acid is 93.2% H2S04. Conversion efficiency is 97-98 percent and overall sulphur recovery from concentrate is 87-90 percent. The adjacent fertilizer plant has a capacity of 135 T/da of P205. The products are 54 percent phosphoric acid, run-of-pile triple superphosphate, and diammonium phosphate. The plant is of Ugine-Kuhlman design and consists of an air-cooled multiple tank reactor, a tilting pan filter, and a forced circultation vacuum evaporator. Triple superphosphate is made on a continuous belt and partially cured in a rotary dryer. Diammonium phosphate is produced by ammoniating phosphoric acid in a single stage reactor. The slurry of ammonium phosphate is granulated in a blunger and dried.

Jan 1, 1970

By L. V. Wade

Abstract-US Bureau of Mines efforts under longwall research programs to develop the capability to predict support requirements for longwall/shortwall support systems are discussed. Ground control studies are being conducted in conjunction with several longwall/shortwall demonstration projects. Geologic, support performance, and strata behavior are being documented on these projects. A hypothesis is presented for the prediction of support requirements.

Jan 11, 1978

By R. W. Baldwin

On page 309, column 1, the second equation should read: Ma-M1 = dlog_Pa M2-M1 d log P2

Jan 1, 1961

By Barry D. Lichter, Pierre Sommelet

High-temperature heat contents of InAs and GaAs were measured over the temperature range 400°K to temperatures above the melting points using a di-phenyl ether drop calorimeter. Smoothed values of the thermal properties have been derived and tabulated at even temperature interuals . The heats of fusion of InAs and GaAs were determined as, respectively, 8790 ± 200 and 12,590 ± 300 cal per g-atom at the respective melting points of 1210º ± and 1513º ± 1°K, yielding entropies of fusion of 7.26 * 0.16 and 8.32 ± 0.20 cal perºK per g-atom, respectively. A general discussion of the thermal properties of III-V com-pounds is given. THE low-temperature heat capacities of InAs and GaAs have been determined by Piesbergen.1Using a dynamic temperature modulation technique, Miller2 has determined the heat capacities of the compounds as well as GaSb and Ge between room temperature and 650°K; however, it has been observed that values determined by drop calorimetry for GaSb3 and for germanium4 are consistently about 5 pct lower than Miller's results. Cox and Pool10 report values for the heat content of InAs and GaAs and the heat of fusion of InAs. No value for the heat of fusion of GaAs appears to have been previously reported. This paper reports results of high-temperature heat content investigations of InAs and GaAs measured in the range 400" to above 1500°K employing a diphenyl ether drop calorimeter. These results, together with our previous results on III-Sb compounds3 as well as heat-content measurements5 of solid InP and Gap, are used in a general discussion of these compounds. EXPERIMENTAL PROCEDURES High-purity samples of the compounds, stoichio-metric to ±0.1 at. pct, were supplied in the form of crushed crystal fragments by Dr. Carl Thurmond of the Bell Telephone Laboratories. The sample preparation, description of the calorimeter, and details of the heat content measurement have been previously described.3 Samples were sealed in evacuated silica capsules and suspended by a Pt-Rh wire in a Pt-wound vertical tube furnace, heated to temperature

Jan 1, 1970

Jan 1, 1965

Jan 1, 1891

Jan 1, 1961

By Donald Markle

ANTHRACOAL is a mixture of small particles of anthracite coal and a matrix of practically pure carbon, formed from the distillation of coal-tar pitch or other suitable bitumen. It is a hard, dense, homogeneous mass, with a silvery luster and in color varies from silvery to grayish black. When pushed from the oven, it develops only partly the fingerlike structure of coke; but, unlike coke, it has a tendency to remain in blocky masses. When struck with a hammer or passed through crushing rolls, it breaks with an irregular fracture, similar to anthracite, but with very little fines. Due to its density, anthracoal is harder, tougher, and stronger than coke. The results of a test made by the blast-furnace department, of the Bethlehem Steel Co., on two barrels of anthracoal are given in Table 1. TABLE I.-Results of Shatter Tests on Anthracoal and Coke Anthracoal Test Good Blast-furnace Coke First Second Barrel Barrel Moisture, per cent 0.77 0.76 Under 5, variation not over 3 points Sieve test Through 2-in. screen, per cent 7.71 7.29 Under 40 Through 1-in. screen, per cent 1.37 1.56 Through ½ -in. screen, percent 0.93 1.08 Under 8 Over 2-in. screen, per cent 92.29 92.71 Over 60 Shatter test Through 2-in. screen, per cent 10.06 ' 12.40 1 Under 16 Through 1-in. screen, per cent 2.66 2.06 Through ½ -in. screen, per cent 1.80 1.26 Over 2-in. screen, per cent Hardness number 86.40 86.10 Over 81 Analysis Ash, percent 16.64 16.48 Under 11 Sulfur, per cent 1.17 1.10 Under 0.95 Volatile matter, per cent 0.77 0.27 Fixed carbon, percent 82.59 83.25 Over 87

Jan 8, 1921

By Yuri D. Tretyakov, Robert A. Rapp

The stoichiometry ranges ofNiOl+y and LiFe,O,-d were established by high-temperatwe electrochemical meas7rements in a stabilized-zirconia electrolyte cell. The results were consistent with doubly ionized cation vacancies in NiO,+y and interstitial lithium or iron ions in . The defect structure of the ternary ferrite was derived from the consideration of equilibration with respect to oxygen between the solid and the gas phase. The absolute magnitudes of defect concentrations were calculated. Pavtial molar enthalpies of oxygen in the compounds were calculated and interpreted in terms of the enthalpy of defect formation in these crystals. NICKEL oxide (NiO,,?) is a metal-deficient, p-type, extrinsic semiconductor whose properties are consistent with a structural model based on the presence of cation vacancies as the predominant ionic defect at sufficiently high temperatures and oxygen activities. A survey of previously reported conductivity studies and the presentation of some more recent conductivity measurements will be given in a later paper.' The absolute magnitude of the equilibrium vacancy concentration in NiO has been reported from combined conductivity and thermogravimetric data of ' However, disagreement exists concerning the state of ionization of the nickel vacancies in NiO. Some authors3-' have proposed that the predominant defects in NiO are singly ionized nickel vacancies and positive holes (h') formed by the reaction where, accorhng to the notation of Kroger and Vink,6'7 Oq represents an oxygen ion on its normal lattice site. Other authors"27E have proposed that doubly ionized nickel vacancies (V{i ) and positive holes are predominant and are formed by the reaction One purpose of the present investigation was to establish the nature of the predominant defect in NiO,+? as well as its equilibrium concentration and thermo-dynamic properties at elevated temperatures and known oxygen activities. To accomplish this purpose, the coulometric titration of oxygen into and out of NiO was accomplished using a galvanic cell involving the calcia-stabilized zirconia electrolyte. The ternary oxide, lithium ferrite (LiFe50,-6) is ferromagnetic and has the inverse spinel structure LiFe,O,-d Thus, in the ideal stoichiometric XY204 lattice, Fe3 ions occupy one-eighth of the tetrahedral (A) sites, and i' and Fe3' ions share at random one-half of the octahedral (B) sites within the fcc sublattice of oxygen ions.g The structure and thermodynamics of the spinel structures have been comprehensively decribed.'-' A recent compilation of literature for lithium ferrite is also available. 15 Oxygen-excess LiFe50sis not expected to exist because both i' and 17e3& ions are in their highest normal valency states (positive hole formation is not favorable). As will be discussed, equilibration of the ferrite crystal with oxygen of a surrounding gaseous phase will result in the introduction of equilibrium concentrations of ionic and electronic defects. In the Results and Discussion section a defect model for LiFe50,-d is proposed. This defect model is tested by high-temperature coulometric titration experiments. EXPERIMENT The oxygen activities in nonstoichiometric NiOl+, (and also LiFe,O,-d) were measured by means of coulometric titration with the high-temperature galvanic cell The critical characteristic of a suitable experimental cell is the complete isolation of the phase to be investigated in a minimum sized chamber which is free from extraneous sources and sinks for oxygen (leakage). Then oxygen is only admitted to the chamber or removed from it in known amounts by coulometric titration, which involves the passage of oxygen ions through the solid electrolyte with electrochemical oxidation and reduction reactions at the platinum contacts to the electrolyte. The experimental cell is shown in Fig. 1. The cap of the cell was the tip from a closed-end alumina tube, which was found to be leak-free from a helium leak-detector test. This alumina cap was about 1.2 cm OD and about 1.5 cm high. A Zircoa calcia-stabilized zirconia tablet (crucible lid) of 1.5 cm diam and 0.3 cm thickness served as the solid electrolyte. A Pyrex ring of about 0.1 cm thickness was placed between the electrolyte and the cap. The electrolyte tablet was painted with platinum paste on the entire outer face and on that part of the inner face which would be within the enclosure; these electrodes were further prepared by heating in air at 1000°C for 2 hr. Nickel oxide powder, listed as 99.999 pct pure, was purchased from Leico Industries, Inc. Pills of the NiO were cold-pressed and sintered at 1050°C for 3 hr in a platinum crucible. This poorly sintered NiO was crushed, and chunks were wrapped in 52-mesh Pt gauze (to catalyze the solid-gas exchange) for place-

Jan 1, 1970

By George Weaton

Two years ago the general features of the St. Joseph Lead Company's zinc-smelting process were described.1 At that time the discussion was limited to a description of the production of high-purity electrothermic zinc oxide. The present paper will describe the commercial production of electrothermic zinc metal. Since a fairly complete description of the plant of the Josephtown smelter was given in the earlier paper, the brief recapitulation given here will be limited to mention of additional equip-ment recently installed and a bare outline of the preparatory process. The raw material is zinc sulphide concentrate received from the com-pany's mines in St. Lawrence County, New York. An average dry-weight analysis of this material is: Zn, 58.28 per cent; Pb, 0.56; insoluble, 1.6; Si02, 1.12; Fe, 6.4; CaO, 0.47; MgO, 0.27; S, 31.9; Cd, 0.1; Cu, 0.06; Mn, 0.24. Moisture content is usually about 3 per cent. Three 21-ft. 6-in. diameter, 12-hearth Nichols-Herreshoff furnaces roast the concen-trate to a calcine of average composition (first 10 months of 1938) : Zn, 67.69 per cent; Pb, 0.06; insoluble, 1.75; Si02, 1.26; Fe, 7.24; CaO, 0.47; MgO, 0.36; S, 1.88; Cd, 0.1; Cu, 0.07; Mn, 0.27. The sulphur dioxide gas, after passing through a waste-heat boiler, proceeds through a recently redesigned low-resistance gas-purification assembly to the contact sul-phuric acid plant, of which the capacity is 200 tons of concentrates per day. The calcine is mixed with a portion of returned furnace residues and sintered on 42-in. by 44-ft. Dwight-Lloyd sintering machines, gas-fired. Wind-box gases pass through air coolers before filtering in a 1440-bag Dracco unit, and thence to stack. The Dracco fume is mixed with Cottrell dust, from roaster gas cleaning, and sent to the leach plant, where it is roasted (SO2 to acid plant) and leached with sulphuric acid to recover, as end products, lead sulphate, zinc sulphate and cadmium.

Jan 1, 1939

By A. Taylor

NICKEL-RICH alloys hardened with small additions of titanium and aluminum and centered around that region of face-centered-cubic primary solid solution, 7, where the atomic ratio of nickel chromium is about 3 to 1, form an important series of high temperature materials because of their resistance to oxidation, high temperature strength, and excellent creep characteristics at elevated temperatures.' With suitable heat treatment it is possible to precipitate a phase based on the ordered face-centered-cubic y' phase, Ni,,Al, from the randomly ordered nickel-rich y face-centered-cubic primary solid solution. By adjusting the ratio of aluminum to titanium the precipitation of needles of the hexagonal intermetallic compound n-NiaTi may be effected. In the present investigation, the main interest was focused on the interrelationships among the y, y, and 7 phases. By using alloying elements of high purity and a suitable melting technique the presence of carbides and nitrides could be completely obviated, although it is realized that their presence is probably essential in alloys of commercial importance. As a preliminary to the study of the Ni-Cr-Ti-A1 system, it was necessary to establish the constitutional diagrams of the three contiguous systems, Ni-Cr-Al, Ni-Ti-Al, and Ni-Cr-Ti, which together form the nickel-rich corner of the Ni-Cr-Ti-A1 quaternary tetrahedron. Accounts of this work on the ternary systems have already been published by the author. A preliminary disclosure of the author's investigations on the ternary and quaternary systems has been made by Hignett2 and has since stimulated work in the same field by Nordheim and Grant." Before the detailed account of the quaternary system, a brief description will be given of the three contiguous ternary diagrams on which it is ultimately founded. Ni-Cr-Ti System The 750° and 1000°C temperature isothermals of the Ni-Cr-Ti system as determined by Taylor and Floyd' are shown in Figs. 1 and 2. The single phase fields of greatest interest are occupied by the extensive face-centered-cubic y primary solid solution of chromium and titanium in nickel, and the close-packed-hexagonal Daltonide, n-Ni3Ti, from which tie-lines radiate across the very wide y+n two-phase field. The chromium-rich primary solid solution is represented by a. As may be seen from the diagrams, the extent of the y phase field increases quite appreciably as the temperature is raised from 750" to 1000°C. Isoparametric lines for the y phase are shown in Fig. 1. They are interesting in that they are almost parallel to the y/r+n boundary. Thus the determination of the tie-line directions is entirely dependent on the exact stoichiometry of composition of the 7 phase. Ni-Ti-Al System The 750°C isothermal section of the nickel-rich portion of the system Ni-Ti-A1 as determined by Taylor and Floyd is shown in Fig. 3.' The regions of greatest interest are the extensive y primary solid solution of titanium and aluminum in nickel, the y' Berthollide phase field based on the ordered face-centered-cubic structure of Ni3Al, and the hexagonal Daltonide phase, n-Ni3Ti. As may be seen from Figs. 3 and 4 the area occupied by the y phase is substantially the same at 750°C as at 1000°C, but the area of the 7 phase is considerably greater at the higher temperature. The tie-lines radiate from n-Ni3Ti across the y+v and y' + v two-phase fields and are evenly distributed

Jan 1, 1957