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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 T. F. Witherbee

On .the 22d of November, 1879, white, iron unexpectedly ap peared while working the Cedar Point Furnace, Port Henry, N Y., on the following burden, calculated to turn out mill and foundry iron: Anthracite coal,. ., .. .. 8000 pounds. Connellsville coke,. ..1500 " Total,..4500 " Old Bed ore,........ 3750 " New Bed fine ore,. ..2000. " New Bed chunk ore,. .. 1000 " Kearnev hematite ore,.750 " Total,..... 7500 " Magnesian limestone,. 1665 " Common limestone,. ...835 " Total,........ 2500 " The production per week since making mill iron-—from September 1st, 1879, to date, seven weeks—was 412 gross tons. Ore was not immediately taken off, as nothing serious was looked for. The iron for the next week graded from No. 4 to white, and in six days the make was 2741/2 tons. At 10 p.m., Friday, the 28th, a slip of -14 feet occurred, and on Saturday, at 5 A.M., another of 3 feet on the south side and 7 feet on the north side took place. At this time it was found that the south side had been hanging for over a week—a fact which had not been reported. Throwing off the wind, to produce slips and reduce pressure, had been tried with no effect. The stock, as seen through the tuyeres, seemed to consist almost entirely of coal, with just enough infusible cinder to cement it into a mass through which the blast could not be forced. At 3.50 A.M., Sunday, the 30th, the first cinder seen in seventeen hours came into tuyeres Nos. 1, 2, 3, and 6. At 9.30 A.M. No. 3 was taken out to see if the stock

Jan 1, 1881

By M. C. Manderson

Abstract-The sharp drop in world phosphate demand that took place in 1975, due to temporarily high prices, now seems to be reversing itself. And prices for both phosphate rock and phosphate fertilizers, which declined dramatically from their 1975 highs, now appear to be bottoming out. This recent price weakness has delayed new mining ventures that had previously been planned for completion by around 1980. While there is ample capacity to supply near-term rock needs, the stage seems to be emerging for a better supply-demand and price environment in the late 1970's and early 1980's.

Jan 1, 1978

By E. A. Gulbransen, W. S. Wysong

The behavior of tungsten and its surface oxides in oxidizing and reducing atmospheres and in high vacua at elevated temperatures is a question of considerable technical importance. The use of tungsten as a a Or as an important component in alloys in high temperature Oxidizing atmospheres has been limited because of the unprotective nature of its oxide film and the volatility of its oxide. This paper will present results of a micro-balance study of the following problems: (1) the oxidation behavior in the ternperature range of 25 to 550°C (') the reduction with pure hydrogen Of thin Oxide films formed On tungsten, and (3) the volatility Of thin Oxide films On tungsten. Tungsten is an interesting metal to study for the following reasons: (1) although the Oxide to to ratio is greater than one, the oxide is not considered protective, ('1 the meta1 readily Oxidizes at temperatures from 30" to 55o°C (3) the oxides WO² and WO³ are reduced at temperatures as low as 500°C. by hydrogen, and (4) the Oxide WO3 is volatile at temperatures from 800 to 1100°C. Literature The oxidation of tungsten in its thin film range has not been studied critically. In the thick film range Dunn3 has made the only systematic study. He found the oxidation rate to obey the parabolic rate law in the temperature range of 700 to 900°c. The temperature variation of the oxidation rate constant was found to follow an exponential law of the Arrhenius type. An inflection was noticed in the temperature plot of the rate law constant at 850 to 900°C. This was attributed to a phase change in the oxides, Schei14 has studied the oxidation rate at 500 and 700°C over long periods of time and found a linear rate law. This result was interpreted as evidence for the presence of a nonprotective film. Pilling and Bed-worth's5 analyses of the oxide volume to metal volume ratio would indicate that a compact protective film should form. McAdam and Geil6 have studied the oxidation of tungsten in the thin film range using the interference color method. A parabolic rate law was found. Their curves showed that tungsten oxidizes faster than nickel but more slowly than iron. The lattice structures found in the oxidation of tungsten surfaces have been studied by Hickman and Gulbransen.? They have reported that WO3 is the stable oxide in contact with the metallic substrate up to approximately 600°C while wo³ forms first at 7oo°c. Hagg and Magneli8 have recently reported a study of the lattice structures . observed in the tungsten oxidcs using the X-ray diffraction method. In addition to an a-phase WO3 and a '-phase WO2, they reported the existence of two new phases. A 8' phase, homogeneous between

Jan 1, 1949

By Richard McCaffery

CONTENTS PAGE 1. Research on Blast-furnace Slags (A Progress Report). By Richard S. McCaffery 5 2. Determination of Viscosity of Iron Blast-furnace Slags. By Richard S. McCaffery, Clarence H. Lorig, Ira N. Goff, Joseph F. Oesterle and Oscar O. Fritsche 27 3. Effect of Magnesia on Slag Viscosity. By Richard S. McCaffery, Joseph F. Oesterle and Oscar O. Fritsche 55

Jan 1, 1931

By W. Geo. Waring

THE growing need of better methods for the recovery of zinc and other elements from complex sulfide ores has suggested an inquiry respecting a possible group separation of the elements by the aid of volatilization at more or less elevated temperatures. It 'is evident that if the zinc content of such ores can be completely separated, for instance, as pure oxide, by a volatilization 'method, there should be no difficulty in recovering the other elements by smelting and refining. Zinc burning" as applied to zinkiferous ores has advanced but little in practice since the invention of the wetherill grate-furnace process in 1852, as may be seen by reference to papers on the subject.' In other words the thermochemical reaction employed in effecting the volatilization of the zinc is essentially one of reduction by means of carbon, whether the ores treated contain their zinc in an oxidized form, or as the sulfide. The zinc vapors, liberated from the ores at a temperature above that required for the reduction of ZnO by C (about ,1100° C.) or for the volatilization of ZnS per se, (about' 1300°-1400° C.) are subsequently burned to ZnO or to ZnO + SOz, by contact with' atmospheric ,oxygen in the upper or posterior parts of the furnace chamber, or in a so-called "combustion chamber" after leaving the .furnace proper.

Jan 1, 1925

By S. Beatty

RECENT experimental results' on the superconductive properties of vanadium indicate that the magnetic behavior of the metal is greatly affected by internal strains caused by mechanical work, and particularly by oxygen and nitrogen impurities. These result in an increase in the hardness of the metal such that metallurgists' have used hardness as a measure of the impurities. An increase in the impurities should also be reflected in a change of lattice parameter with increasing impurity content. The lattice parameter of vanadium prepared by the thermal decomposition of the iodide has been determined by two workers. Neuburger3 obtained a value of a, =3.0338 ± 0.0003A for the body-centered cubic lattice by means of the powder method. The work of Katelaar is referred to by van Arkel4 in which a value of a0 = 3.025 is given. Four samples were used for this investigation. Sample A, the vanadium of the highest purity in the group, was obtained by means of the thermal decomposition of vanadium diiodide and deposited on a 3 mil diam tungsten filament in the form of crystals. The second sample, labeled B, was obtained by the calcium reduction of the pentaoxide at a sufficiently high temperature to give a melt. A third sample, C, was obtained in the same manner as B but remelted in a pure argon atmosphere. The last sample, D, was prepared by the calcium reduction method and the fine powdered vanadium was then sintered by means of applied heat and pressure. Samples A, B, and C were thus essentially free of mechanical strain in their preparation. Sample D was annealed in a high vacuum at 800°C. The samples were prepared for X-ray diffraction analysis such that all additional strain by cold work or by contamination with oxygen and nitrogen was kept at a minimum. Powder obtained from filings was deemed unsuitable since this would require annealing to get rid of the cold work. A heat treatment up to 1000°C at 10-6 m pressure might still increase the impurity content by means of adsorbed oxygen from residual gas in the vacuum chamber. The most satisfactory samples were prepared for back-reflection film techniques. Samples were cut to size, etched with hydrobromic acid, and mounted in Bakelite. They were then lightly polished on 3-0 paper and lightly etched. Chemical and Hardness Analysis of Samples Spectrographic analyses were made of the four samples and indicated similar metallic impurities for the group. The major metallic impurity in each sample was iron, which was less than 0.01 pct. The sum of the other metallic impurities was approximately 0.1 pct. The carbon content was assumed low by virtue of the methods of sample preparation. The principal impurity difference between the samples was in the oxygen and nitrogen content.

Jan 1, 1953

(Members are urged to send in for this column any notes of interest concerning themselves or their fellow-members.) Members and guests who called at Institute headquarters during the period Jan. 10, 1916 to Feb. 10, 1916: William Rettie, Yonkers, N. Y. Wallace E. Pratt, Manila, P. I. R. V. Norris, Wilkesbarre, Pa. T. Skewes Saunders, El Oro, Mex. Fred MacCoy, El Oro, Mex. M. L. Requa, San Francisco, Cal. Reno H. Sales, Butte, Mont. R. W. Schultz, Ravenna, O. R. T. White, Batourn, Russia. H. J. Brown, Chester, Pa. David T. Day, Washington, D: C. A. M. Van Rensselaer, New Rochelle, N. Y. H. M. LaFollette, LaFollette, Tenn. Norman C. Stines, Russia. F. N. Speller, Pittsburgh, Pa. Howard R. Hughes, Houston, Tex. Robert W. Hunt, Chicago, Ill. C. F. Schnepp, Ridgefield Park, N. J. B. E. Fernow, Toronto, Ont., Can. George L. A. Thomson, Elizabeth, N. J. A. F. Bennett, New York City. Jasper T. Robertson, Chicago, Ill. J. C. Ralston, Spokane, Wash. J. B. Tyrrell, Toronto, Ont., Can. George J. Lyon, Schenectady, N. Y. H. G. Officer, New York Cty. Jesse C. Porter is now superintendent of the San Fernando Mine, Hoyo de Manicaragua, Santa Clara Province, Cuba.

Jan 3, 1916

By Huey-Lin Luo, T. R. Anantharaman, William Klement

Two new metastable phases have been obtained in Au-Ge alloys by rapid cooling from the melt. One is of the hep structure with near-ideal axial ratio and may be considered a Hume-Rothery phase. The other has a complex tetragonal structure (a = 11.627Å and c = 22.191Å for the Au60Ge40 alloy) and may be looked upon as a superlattice made up of forty-four fee unit cells. Alloys with the tetragonal phase are charactevized by marked preferred orientation. The metastable constitution of the Au-Ge alloys is discussed with reference to the rate of cooling from the melt. THE Au-Ge equilibrium diagram features a rather deep eutectic near 27 at. pet Ge with a maximum solid solubility of 3.2 at. pet Ge in gold and is similar to the Ag-Ge, Ag-Si, and Au-Si diagrams.' The present study of the effects of rapid cooling from the melt on the structure of Au-Ge alloys constitutes an extension of similar investigations2-8 in this laboratory on alloys of noble metals with germanium and silicon. Nonequilibrium hep structures have so far been obtained by quenching Ag-Ge2, 3 and Ag-Si4, 5 alloys from the melt; an Au-Si alloy of approximately eutectic composition has been found6 to solidify in a noncrystalline state. EXPERIMENTAL PROCEDURES Twenty-nine alloys prepared from gold of 99.9+ pet and germaium of 99.999 + pet purity were investigated. The method of alloy preparation, the technique of rapid quenching from the melt, and the X-ray diffraction procedures were similar to those described previously.3, 4 Essentially, small sections (-20 mg) of thin alloy rods (-1 mm diam) were rapidly heated up to 1200°C in a graphite crucible under argon and the liquid alloy ejected by a helium blast onto a polished copper strip held on the inner periphery of a rotating wheel. The resulting thin foils were examined with or without the copper substrate in a G.E. X-ray Diffractometer or in a 114.6-cm-diam Debye-Scherrer camera. RESULTS Table I gives the constitution of liquid-quenched Au-Ge alloys, as estimated from intensities of X-ray reflections from the corresponding phases, viz., a (fee solid solution), ß (hep phase), ? (tetragonal phase), and diamond-cubic (dc) germanium. Despite unavoidable variations in the quenching rates, the proportions of the phases in different alloys were generally reproducible and stable at room temperature. There was no evidence of quenching strain, since the a doublets were well-resolved in high-angle Debye-Scherrer reflections in all cases except where stacking faults in the a fee and ß hep structures contributed to X-ray line broadening. The ß and ? metastable phases showed signs of decomposition to the equilibrium a phase and germanium only after a few hours annealing above 100°C. A few alloys around the eutectic composi-

Jan 1, 1965

By G. B. Gould

FROM the very inception of the price-control experiment in the bituminous-coal industry, the problem of price differentials was of major importance. In fact, assuming that there will be no legal or Govern- mental obstacles to price control, the successful maintenance of the present or any other method designed to control bituminous-coal prices will depend upon the discovery of some satisfactory way to determine these differentials in price, among: individual mines and groups of mines. Being of organic origin, bituminous coal is a commodity that presents an almost infinite variety of qualities. It is inevitable, therefore, that a work- able price-control system must attempt

Jan 1, 1935

[Appalachian Petroleum Section: James M. Kimbrough, chairman; John H. Adair, first vice-chairman; Walter L. Diddle, second vice-chairman; Byron M. Finch, secretary-treasurer. Balcones Section: Robert V. West, chairman; Frank W. Jessen, first vice-chairman; Zane V. Morgan, second vice-chairman; Brantley G. Myers, secretary-treasurer. Meets 4th Wed., Petroleum Club (San Antonio) or Terrace Dining Room (Austin) Billings Petroleum Section: Charles B. Evans, chairman; L. M. Lyon, first vice-chairman; Gordon E. Lansford, second vice-chairman; Fred. A. Haddenhorst, secretary-treasurer. Meets 3rd Tues., Billings Petroleum Club. California Coastal Section: Robert L. Richardson, chairman; David K. Hayward, first vice-chairman; W. Jackson Bransford, secretary; William N. Harwell, treasurer. Meets 3rd Thurs., Pierport Inn, Ventura. Caracas Petroleum Section: Edwin A. Moo re, chairman;. Jose Cirigliano, vice-chairman; Frank B. Davis, secretary; Robert N. Powers, treasurer. Meets 2nd Tues., Caracas Theater Club.]

Jan 1, 1961

By DOOLITTLE E. M.

(Canal Zone Meeting, November, 1910.) The following notes are contributed, not with the idea of offering a complete history of the development of this very important process as applied to the Leadville district, but with the hope that the practice, as it was carried out in the Bi-Metallic Smelter, may still be of interest to others. The Bi-Metallic Smelter, at Leadville, Colo., was the first to make a commercial success of the process described in the following pages, which consisted essentially of smelting raw silver- and copper-bearing sulphide ores in blast-furnaces to form a matte, which was generally re-smelted with siliceous ores for a second high-grade matte. Robert Sticht, in his excellent monograph on the subject,1 has outlined briefly the plant belonging to this company. He says, in effect: The Boulder, Mont., enterprise set the example for others with whom the patentee (w. L. Austin) had been negotiating, and the old La Plata lead-smelter at Leadville, Colo., was fashioned into a crude, temporary experimental plant for the Bi-Metallic Company, and the feasibility of the process demonstrated by a trial run. Subsequently, the plant was considerably improved, and, being supplied with very favorable ores, continued to run without interruption from August, 1892, to June, 1893. In September, 1893, smelting was resumed in a completely remodeled establishment, some $200,000 having been expended upon the new work. Thus, aside from the Montana experiments, which, under the direction of W. L. Austin, began as early as- 1885 2 at Toston, and continued with indifferent success for six or seven years, the Bi-Metallic plant at Leadville may be said to have * Formerly Superintendent, Bi-Metallic Smelting Co. + Formerly Chief Assayer and Chemist, Bi-Metallic Smelting Co. 1 Modern Copper Smelting, E. D. Peters, 7th ed., p. 415 (1895). 2 Trans., xvi., p. 259 (1887-88).

Dec 1, 1910

By George F. Kunz

THE recently discovered occurrence of diamonds near Murfreesboro, Pike county, Ark., was brought to. our attention by Mr. Samuel W. Reyburn (Trustee for Messrs. C. S. Stifft, A. D. Cohn, August Zinsser, Jr., and himself, owners of the property), through whose courtesy we investigated the locality of the deposit. Prospecting with the diamond-drill is now in active progress ; but mining operations on a large scale have not yet been ordered. Geology.-The geology as well as the petrography of this interesting locality has been well described by Messrs. J. C. Branner and R. N. Brackett.1 Briefly summarized, the igneous rock in which the diamonds are found is a vitreous peridotite, forming a stock or volcanic neck, which has broken up through the Carboniferous and Cretaceous quartzites and sandstones. After an extensive period of erosion, during which an unknown portion of the neck and presumably a previously existent volcanic cone have been removed, the surface was covered with thin beds of Post-Tertiary conglomerate. The volcanic intrusion was accompanied by the formation of several small dikes of a rock much like that of the main body. One of these dikes cuts across the stock, while another cuts the Cretaceous sandstone, but is overlain by the conglomerate, thus giving a datum for the period of intrusion. So far as known, there was little, if any, metamorphism of the country-rock by the igneous magna, which probably followed an approximately vertical course, so that a more or less vertical extension downward of the igneous body to indefinite depths may be expected.

Mar 1, 1908

By J. L. Schroeder, W. G. Talman

EXPERIENCE has shown that certain known natural conditions and other indefinite characteristics combine to make a mining area vulnerable to mountain bumps. Some of the known conditions are heavy overburden, an overlying stratum of strong non-elastic rock, a structurally strong coal seam that does not crush easily and yet is the weakest stratum in the series, and a floor stratum of more than ordinary firmness. The indefinite characteristics could include resistance of top or bottom of a coal seam to lateral flow, effect of immediate top and bottom strata, nature of the coal seam, and other factors about which very little is known. It is in this area that exhaustive study is needed to achieve positive control of the dreaded mountain bump hazard. In the Gary district, West Virginia, two of the five operating mines have areas known to be vulnerable to mountain bumps.These are the No. 2 and 6 mines, which are working the Pocahontas No. 4 coal seam. In this area the seam is overlain at a zero to 10-ft interval by the massive Eckman sandstone, which is about 100 ft thick in the vulnerable areas. Total overburden, consisting of shale, coal seams, and sandstones, ranges from 700 to 1400 ft where bumps have occurred (Fig. 1). The coal seam is 4 to 8 ft thick and has a weak columnar structure of very soft and spongy or woody coal. The immediate top is either the Eckman sandstone or hard shale, both of which provide generally good roof conditions for mining operations. The bottom ranges from medium to hard gray shale. The incidence of bumps in the Gary district dates from about 1930 and can be correlated to some degree with the increased rate of extraction attained with mechanical mining. During early years of operation at the No. 2 and 6 mines, most of the work was development and under comparatively light cover. As overburden became heavier, together with an increasing percentage of coal coming from pillar extraction, mountain bumps began to occur. Before 1945 they were much less severe than in later years, and because there were no injuries or fatalities, no records were kept. But by 1951 the incidence of bumps had increased to such extent that it became evident a mining system would have to be designed to eliminate or at least minimize these occurrences. Drawing on experience with modified versions of old systems and certain characteristics peculiar to the Pocahontas No. 4 coal seam, the district mining engineer, Martin Hayduk, outlined the essential factors for bump control in the Gary district. These control factors indicated: 1) The highly stressed area, which lies within the limits of convergence effects, moves at approximately the same rate as the retreating pillar line. 2) There is a decided softening of the periphery of blocks which is greatest and deepest on the gob side. 3) Blocks less than 45 ft wide never have been known to bump in the Pocahontas seams. Fig. 2 shows the mining plan based on these observations—a thin-pillar system with a minimum of secondary development. It was recognized from the start that the Hayduk system had certain limitations. When pillar work backed up to an inevitable surrounded block it was no longer applicable; also, burnt bottom and/or unknown factors reduced the system's effectiveness in certain headings. Since there was no way to eliminate the loaded block, it was decided to experiment with auger drilling to attain controlled release of this stored-up energy. The decision to auger was made after consideration of three separate plants, which were: 1) To cut the solid block into pillars of maximum size by driving away from the fracture line and at such a distance outby that development

Jan 1, 1959

By H. A. MEGRAW

THE meeting of the A. I. M. E. at Wilkes-Barre, Pa., Sept. 12 to 15, inclusive, celebrated the fiftieth anniversary of the Institute. It was at Wilkes-Barre, in 1871, that the foundation was laid for the great institution that now includes in its roster the greatest names. in mining engineering in every civilized country of the world. The founders of the Institute, with rare prescience, established a common ground upon which all mining engineers, whatever particular branch they might consider most pertinent, could stand securely, assured of a deep-seated interest from their brethren similarly minded in other localities. So wise and clear was the vision of the founders that every engineer connected with mining has found it beneficial, not to say indispensable, to maintain his connection with the Institute and to increase his technical enthusiasm through the medium of the valuable technical publications. The little coterie of 1871 has grown to a strong body of more than 10,000 members in 1921, reflecting the glory of the founders in the record of the accomplishments written on the pages of the fifty years of the

Jan 1, 1921

By D. Weinstein

The high temperature mechanical properties of stainless steels after fast neutron irradiation are discussed in the light of effects caused by lattice dattmage and effects caused by helium generated from n,a transmutations. Embrittlement at high temperatures is due to helium accumulation at grain boundaries and to cavity formation and proPagation along grain boundaries. Following from the embrittlement mechanism, it is suggested that when deformation occurs by mechanisms associated with super plasticity, helium ac-curnulation at boundaries should be attenuated and cavities, if formed, should be nonpropagating. As the mean free Path between interphase boundaries of a two-phase Fe-Cr-Ni alloy was decreased, the degree of superplastic deforrnation at 870°C increased, as vneaszired by total elongation and by the expottent m = a log 'a/a log 'i. This alloy and type 304 stainless steel were cyclotron irradiated in an a-particle beam to a helium concentration of -1 x 10 atom He per atom. The stainless steel specimen was embrittled, but the ductility of irradiated two-phase Fe-Cr-Ni alloys correlated with the values of. m during 'defor-malion. The .finest grained, helium-injected specimens that deforrned with highest m values exhibited the largest elongations to ,fracture. These results could be correlated with metallographic observations of cavity behavior: the propensity for intergranular propagation was lessened as the m value increased. It is concluded that superplastic deformation is ef-fectizle in attenuating helium embrittlement at elevated temperatures. One of the principal problems associated with development of fast breeder reactors is application of alloys such that suitable fuel cladding results. Stainless steels and other Fe-Cr-Ni alloys, because of highly acceptable nuclear characteristics, represent the primary materials for this component, and an exhaustive research and development effort is being conducted. The main deficiency of these materials has been a severe loss of ductility at high temperatures after fast neutron irradiation. An extensive body of mechanical property data and microstructural observations has provided an adequate phenomenological description of embrittlement; in conjunction with transmission electron microscopy studies, a reasonably acceptable embrittlement mechanism has been obtained. Following from this mechanism, it is suggested in the present work that ductility would be enhanced if deformation could occur by mechanisms associated with the phenomenon of superplasticity. Experiments to test this hypothesis have been conducted, and the results are presented and discussed in this paper. IRRADIATION EMBRITTLEMENT AT HIGH TEMPERATURE Austenitic stainless steels have been irradiated to accumulated fast neutron fluences of 1020 to 1022 nvt at temperatures between 60" and 600°C. Specimens that have been exposed to these conditions and subsequently tensile tested at temperatures between 600" and about 900°C exhibit approximately 5 pct total elongation to fracture.'-3 For unirradiated specimens receiving a nearly identical thermal exposure, total elongation at these test temperatures is about 45 pct. Examination of irradiated specimens has shown that fracture propagation is entirely intergranular. These phenomenological aspects of irradiation embrittle-ment at elevated temperatures are well known and are not generally disputed. Although the explanation of this phenomenon has been controversial, a mechanism for ernbrittlement has emerged that accounts reasonably well for the observed mechanical behavior. The controversy resulted primarily from an indeterminate role of neutron-in-duced lattice damage, if any, and a presumed, but experimentally unverified, contribution to embrittle-ment from helium generated by n,a transmutations. Recently, Holmes and coworkers4 have conducted experiments that separate these effects, and the results are instructive in formulation of the ernbrittlement mechanism. Holmes el al.4 irradiated type 304 stainless steel in EBR-I1 to a fluence of 1.4 x 1022 nvt (E > 0.18 mev); the irradiation temperature was 538" * 48°C or, in terms of absolute melting point, 0.49 * 0.03 T,. After irradiation, tensile tests were conducted at temperatures of 21" to 870.C, the specimens first being annealed for 30 min at each test temperature. In addition, thin sections of irradiated specimens were annealed for 1 hr at identical temperatures, electro and examined by transmission electron microscopy. Thus, for a given temperature, it was possible to correlate mechanical properties with the defect structure. At room temperature, the yield stress of irradiated specimens was a factor of 2.5 higher than unirradi-ated specimens exposed to an equivalent thermal history. Electron microscopic examination of the irradiated specimen revealed a high density of lattice damage in the form of Frank sessile dislocation loops and polyhedral voids. Holmes et al.4 concluded that the presence of this defect substructure caused the increase in yield stress and that after irradiation in a fast neutron flux at 0.49 Tm, substantial lattice dam-age persists. Annealing at progressively higher tem-

Jan 1, 1970

By G. A. Deitz, J. Halpren

The kinetics of dissolution of silver in cyanide solutions under oxygen pressure have been investigated over a wide range of conditions with a view to establishing the reactions involved and the factors which influence the rate. The results indicate that the rate is determined principally by the transport of reactants in solution to the silver surface. The thermodynamic features of the reaction with particular reference to the influence of pH and CN- are also discussed and summarized in the form of potential-pH diagrams. METALLIC silver is readily attacked and dissolved by cyanide solutions in the presence of oxygen. This reaction has long been recognized and extensively applied1 in the well-known cyanide process for the extraction of silver from its ores. While this process has been subjected in the past to a number of investigations2,3 both of a practical and fundamental nature, some features relating to the chemistry of the reactions involved, the role of oxygen, the nature of the rate-controlling step, and the effects of pH and certain reagents such as lime, are still not fully understood. It was felt that this situation justified a further investigation of the reaction, made with a view to obtaining a better understanding of its kinetics and mechanism. In the present investigation rate curves for the dissolution of silver were determined over an extensive range of carefully controlled reaction conditions. By carrying out the reactions in a pressure vessel, the partial pressure of oxygen, and hence its concentration, could be varied widely. The influence on the reaction of other variables including temperature, pH, and the concentrations of cyanide, peroxide, and other salts was also examined. The results of these kinetic studies are presented and discussed in this paper, together with a summary of available thermodynamic information relating to the possible reactions which can accompany the attack on silver by aqueous solutions of cyanide and oxygen. Chemistry and Thermodynamics of the Reaction The chemistry of the reactions of gold and silver with aqueous cyanide solutions has been the subject of several recent reviews.'." It has been proposed' that the following reaction occurs when silver dissolves in cyanide solutions in the presence of oxygen: 4Ag + 8CN- + 0, + 2H.0 -t 4Ag(CN); + 40H- [la] An equation of this form, for the corresponding dissolution of gold, was first suggested by Elsner." Bodlaender5 proposed a similar overall reaction, but suggested that it took place in two steps, 2Ag + 4CN- + O2 + 2H2O ? 2Ag(CN),- + 2OH- + H2O2 [2a] followed by 2Ag + 4CN- + H2O2? 2Ag(CN); + 20H- [3a] On the other hand, Janin- suggested that the dissolution of gold can occur with the liberation of hydrogen, rather than by reduction of oxygen. The corresponding equation for the dissolution of silver is 2Ag + 4CN- + 2H20 -t 2Ag(CN); + 20H + H2 [4a] All these reactions represent oxidation-reduction processes and may be resolved into the corresponding separate oxidation and reduction components. The oxidation step involves the formation of the argentocyanide ion and is the same for all the reactions, i.e., Ag + 2CN? Ag(CN)2 + e [51 However, reactions la, 2a, 3a, and 4a differ in the nature of the reduction steps which are, respectively, O2 + 2H2O + 4e ? 4OH- [lb] O2 + 2H2O + 2e ? H2O2 + 2OH- [2b] H2O2 + 2e ? 2OH- [3b] 2H2O + 2e? 20H- + H2 [4b]

Jan 1, 1954

By Theodore B. Counselman

Of all natural resources, iron ore made into steel is the most important both in tonnage and value. The primary reason for the prosperity of the United States in the last century has been its pre-eminence in domestic supplies of iron ore and steel. The depletion of these reserves by two world wars and by the demand for richer blast furnace charges, as well as the constantly growing world- wide demand for steel, has fostered the recent quest for new iron ore mines around the globe. These developments have made a dramatic change in the iron ore picture of the world. It is the purpose here, however, to look briefly at the development of the United States iron ore industry, which has played such an important role in the events leading to the modern day boom in iron ore exploration.

Jan 7, 1965

By Mark L. Requa

(San Francisco fleeting, October, 1911.) DURING the past two years California has developed a new and important oil-field : I refer to Midway. This field produced the famous Lake View gusher, which is credited with a total production in excess of 8,000,000 barrels. Fortunately for the oil industry of the State, this well is now a thing of the past, and nothing save a great crater-like opening marks its location. The pipe is entirely worn away and gone ; and it is a matter of serious doubt if there can be anything done that will cause the well to produce again. Fortunately, also, there have been no, other wells in that field or elsewhere throughout the State that in any way compared with the Lake View. Midway is noted for large wells, of from 500 to 2,000 barrels production; but the decline is rapid, and a few months serve to bring the output down to a few hundred barrels. In the oil-territory heretofore blocked out as proved and probable, there have been, during the year, many changes. Some areas which were expected to be fairly productive have apparently failed; others, more strictly "wild-cat," have come in; while in some of the older fields there are properties which are beginning to show evident signs of exhaustion. The total area of proved territory will therefore probably suffer but small increase, when balances are struck off. The increase of new area has come from extensions of the Midway field, the development of a field in Lost Hills and Belridge, and extensions of the Fullerton-Whittier field in southern California. In these later developments, down to date, the fresh area absolutely proved is not much in excess of 3,000 acres. Recent developments in Coalinga indicate the possible extension of that field to the south, but at great depth. Coalinga is still the most northerly field of any consequence in the State. The Kettleman Hills have hitherto brought in nothing, although a

Apr 1, 1912

By Nicholas J. Grant, Hanna Ibach, Bill C. Giessen

The system Ta-Rh was investigated over the entire comnposition range using metallogvaphic and X-ray techniques as well as thermal analysis. Terminal solubility limits, solidus temperatures, and the crystal structures of two new intermediate phases were determined. There are five intermediate phases: o, tetragonal, isostructural with o(Fe-Cr); a1, orthorhomnbic : a2, orthorhombic, isostructural with CozSi; 0 3, a high -temperature phase of unknozun structure; and a TaRh3, cubic, AuCu3 structure. a, aL, a,, and a melt peritectically; and a TaRh, has a maximum melting point. Five peritectic and one eutectic reactions occur. THE Ta-Rh phase diagram has not been fully treated in the literature; however, two inter metallic phases have been described.&apos;-&apos; This study attempts to work out the diagram covering the details of phase boundaries as well as the crystallography of the intermediate phases. EXPERIMENTAL METHODS Starting materials were tantalum powder of 99.8 pct purity, supplied by National Research Corp., Cambridge, Mass., and rhodium powder of 99.9 pct purity, supplied by Bishop Co., Malvern, Pa. Analyses as given by the manufacturers are presented in Table I. In addition to the spectroscopic analysis, an oxygen analysis has been made of the tantalum powder. After preliminary trials, the standard procedure employed in making the alloys was as follows (see Ref. 4 for further details). The powders were weighed, mixed manually, compacted under 16,000 psi, and arc-melted at not more than 500 amp under thoroughly titanium gettered welding-grade argon of 400 mm Hg pressure. The gettering process was repeated after each melt. It had been shown previously5 that under these conditions no oxygen pick-up exceeding 0.001 pct in a hafnium button could be detected. The buttons, ranging from 5 to 10 g in weight, were inverted or, if possible, crushed and remelted three times. Melting presented no difficulty, except for tantalum-rich al- loys, which showed considerable spashing during melting. The average weight loss of 1 wt pct rose to 2.5 wt pct in these cases. Subsequent melting, however, resulted in losses of less than 0.1 wt pct. The melts obtained frequently showed small in-homogeneities, mostly in the tantalum-rich part of the system below 25 at. pct Rh. This was not due to insufficient blending of the elements, but to crystallization taking place from the cooled bottom. This condition was not improved by further re-melting; therefore the following precautions were taken. Cross sections of as-cast buttons were made. For the investigation only buttons were used where these inhomogeneities did not exceed 1 at. pct (estimated from the amounts of haSeS resent). In addition, only the center portions of such buttdns were utilized to minimize errors. Smaller buttons showed smaller concentration gradients and were used as a check. Finally, all alloys were homogenized to eliminate coring (see below). After this, the error in alloy composition due to inhomogeneity was cl at. pct. In order to confirm the concentrations of the alloys and to provide an impurity check, wet-chemical analyses and oxygen-fusion analyses of four key alloys were carried out. The results, together with the concentrations as calculated with the weight balance method, are presented in Table 11. It was found that for three alloys the agreement is very good (< 0.2

Jan 1, 1964