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NEW MEMBERS The following list comprises the names of those persons who became members during the period July 10, 1919, to August 10, 1919. BALL, C. LEONARD.. Cons. Engr., Suffern Co., Inc., 135 Broadway, New York, N. Y. BARRY, CHARLES W Box 502, Idaho Springs, Colo. BATTLE, JOEL ALLAN, JR., Min. Engr., U.S. Bureau of Mines, Room 2114, Interior Bldg., Washington., D. C. BEER, GUIDO, Compagnia. Italian, Dir Bronzi Speciali, C. I., B. S. La Direzione, Italy. BITLER, WILLIAM F., Management of Coal Properties, The Provident Life & Trust Co. of Philadelphia, 409 Chestnut St., Philadelphia, Pa. BLOOM, SETH W., Chief Engr,, Northwestern Min. & Exchange Co., 130 E. Sribner Ave., Du Bois, Pa. BOYDELL, W. Guy B., Min. Engr., Tul Mi Chung Mine, Care Seoul Min. Co. Whang Hai Do, Chosen. Korea. BRYAN, RUSSELL R.., Met., Sunnyside Min. & Mill. Co., Eureka, San Juan Co., Colo. CHIAPELLA, STEPHEN EUGENE 323 W. 30th St., Los Angeles, Cal. CONWAY, EDMUND JOHN, Exploration Engr., Granhy Consolidated Min., Smelt & Power Co., Ltd., Anyox, B. C., Canada. DEMOREST, DANA J Prof. of Met., The Ohio State Univ., Columbus, Ohio. EIDEMILLER, H. N., Geol., Benjamin C. Neely, Min. Lands & Leases, Crystal Falls, Mich.

Jan 9, 1919

By Cyril Wells, Robert F. Mehl

The two earlier papers in this series1,2 presented data on the rate of diffusion of carbon and of manganese in gamma iron. Apart from their scientific interest, these data are needed chiefly in order to treat data on carburization, on rate of formation of pearlite, and on rate of austenit-izing in a quantitative way.1'2'9'10 In the present investigation rates of diffusion of nickel in ?-Fe over wide temperature and concentration ranges have been determined, and the effects of carbon, of im- purities, and of grain size on these rates have been studied. Claussen,3 using the data of Fry,4 has calculated the diffusion coefficient of nickel in y-Fe as 9.2 X 10-11 sq. cm. per sec. at 1200ºC., but had no data from which to calculate the variation of D with concentration, temperature, and percentage of carbon. Method and Materials Method.—Nickel was diffused along the axis of a cylindrical specimen across a concentration gradient, concentration-penetration curves were determined and D values calculated from Grube or Matano solutions.5 Details of the method are given

Jan 1, 1941

By Cyril Wells, Robert F. Mehl

The two earlier papers in this series1,2 presented data on the rate of diffusion of carbon and of manganese in gamma iron. Apart from their scientific interest, these data are needed chiefly in order to treat data on carburization, on rate of formation of pearlite, and on rate of austenit-izing in a quantitative way.1'2'9'10 In the present investigation rates of diffusion of nickel in ?-Fe over wide temperature and concentration ranges have been determined, and the effects of carbon, of im- purities, and of grain size on these rates have been studied. Claussen,3 using the data of Fry,4 has calculated the diffusion coefficient of nickel in y-Fe as 9.2 X 10-11 sq. cm. per sec. at 1200ºC., but had no data from which to calculate the variation of D with concentration, temperature, and percentage of carbon. Method and Materials Method.—Nickel was diffused along the axis of a cylindrical specimen across a concentration gradient, concentration-penetration curves were determined and D values calculated from Grube or Matano solutions.5 Details of the method are given

Jan 1, 1941

NEW MEMBERS The following list comprises the names of those persons who became members during the period June 10, 1919, to July 10, 1919. ANDERSON, JOHN EDWARD, Min. Engr., Lehigh Valley Coal Co., 121 N. Laurel St., Hazleton, Pa. BENBOW, B. L., Mgr., Cleveland Wire Division, National Lamp Works, General Electric Co., 1770 E. 45th St., Cleveland, Ohio. BLAIR, CHARLES S., Geol., Tennessee Coal, Iron & R. R. Co., Birmingham, Ala. BOLAND, FRED L., Chief Draftsman, Mine Dept., Chile Exploration Co., Chuquicamata, Chile, South America. COLLIER, OTTO L., Civil & Min. Engr., Secretary, Ernest M. Merrill Engrg. Co., Mullens, Wyoming Co., W. Va. DELAMATER, GEORGE RICHMOND, Asst. Supt:, By-product. Coke Oven Dept., Steelton Plant, Bethlehem Steel Co., Steelton, Pa. DOELL, WILLIAM R Chief Engr., Mahuomen Iron .Co., Crosby, Minn. ENDO, SHINZO 365 Komagome Shimmeicho, Hongo, Tokio, Japan. EVANS, CHARLES E., Chief Draftsman, American Smelt. & Refin. Co., Murray, Utah. FISCHER, OSCAR A 62S First National Bank Bldg., Denver, Colo. FISHER, GEORGE KINGSBURY, Met. Engr 47 Baker St., Saranac Lake, N. Y. FRAZEE, VERNE, Min. Engr Moweaqua, Ill. FURNICHI, ROKUZO, Supt. of Min. Dept., Besshi Copper Mine, Baron Sumitomo Co. Ehime Japan

Jan 8, 1919

By Charles Hart

THE art of electric smelting came with the turn of the present century and owes its existence to the introduction of alter-nating current, which found its first wide use in the establishment of the great power plants at Niagara Falls, N, Y. Prior to that time current was largely direct. The fur-naces were electrolytic in nature and found their first metallurgical use in the produc-tion of aluminum, and this process still prevails. The normal production of pig iron up to that time was carried on in blast furnaces in which charcoal, coke and anthracite were used as the fuel. This new electric process called for sufficient carbonaceous material to reduce the oxides and impregnate the pig iron with sufficient carbon, but the remainder of the energy was to be supplied by electric power. The chemical reactions are essentially the same in electric smelting as obtains in the older blast furnace. All of these data are so well known in both methods as to need no discussion at this time, for they can be found in scientific publications and books written during the first two decades of this century.

Jan 1, 1940

By Persifor Frazer

General Geology of the Northern Black Hills. The " Black Hills of Dakota," to the northern part of which the following observations apply, occupy a position on either side of the boundary between Wyoming and South Dakota, approximately between 103" 15' and 104" 48' of west longitude and 43 15' to 43" 50' of north latitude. The area is roughly 4160 square miles.* (See Plate I.) As has been pointed out by Profs. H. O. Hofman, I?. R. Carpenter and others, and illustrated by Mr. Newton in the publications of the United States Geological Survey, these hills are made up of a large number of the known formations from the Archean to the Tertiary, which latter constitutes the border of the region. The mining operations are largely confined to the interior of this area, and the centers from which they are conducted (Deadwood, Lead City, Galena, etc.) are situated near the line of junction of the Archean schists and quartzite, supposed to represent the Potsdam Sandstone of the N. Y. series, or the lowest of the Paleozoic measures. The Archean or pre-Paleozoic rocks consist mainly of a mica-schist in which hornblende and garnet are frequently

Jan 1, 1898

Bethlehem Steel Co. has just brought an all-new iron ore mine into production at Marmora, Canada, about 120 miles east of Toronto. High grade pellets produced at the mine from open-pit magnetite ore travel 64 miles by rail to the port at Picton, then go by Lake boat to help supply Bethlehem's Lackawanna, N. Y., plant. At full production about half a million tons of pellets a year will be shipped, and mining will be at a scale of more than a million tons per year of ore. Aeromagnetic surveys carried out in 1949 by the Ontario Dept. of Mines and the Canadian Geological Survey revealed an anomaly that interested Bethlehem geologists. By 1951 the company had put down some 40 diamond drillholes ranging from 460 to 1800 ft to block out the magnetite replacement deposit which lies in pre-Cambrian limestone below about 130 ft of Paleozoic limestone. The orebody, roughly 2100 ft long and up to 400 ft wide, averages about 37 pct iron, too low for direct shipment. Not only construction of concentrating and pelletizing facilities, but 20 million tons of stripping lay ahead before production could start

Jul 1, 1955

By R. J. Wysor

Discussion of the paper of R. J. WYSOR, presented at the New York meeting, February, 1916, and printed in Bulletin No. 106, October, 1915, pp. 2161 to 2170. LEONARD WALDO, New York, N. Y.-Will Mr. Wysor kindly give us more information as to the pyrometers used and the temperature measurement? R. J. WYSOR, So. Bethlehem, Pa.-We used standard Bristol pyrometers with bare fire ends. These were standardized both before and after the tests with salt and pure aluminum. We also interchanged the pyrometers. J. W. RICHARDS, So. Bethlehem, Pa.-Did you attain any results which gave you approximately the value of the heat insulation at any of the furnaces? R. J. WYSOR.-In the first installation we were afraid to put in the insulation throughout the hot-blast main for the reasons mentioned in the paper, but we used the insulating brick in two 8-ft. sections in straight lengths of our hot-blast mains. Owing to the high conductivity of the steel shell, the temperatures which were taken on the outside were not representative of the two temperatures resulting from heat flow through the insulating brick. I believe that when a hot-blast main is insulated

Jan 5, 1916

BOSTON SECTION ALFRED C. LANE, Chairman, GEORGE A. PACKARD, Vice-chairman, E. E. BUGBEE, Sec'y-Treas., Mass. Inst. of Technology, Cambridge, Mass. R. L. AGASSIZ, FRED W. DENTON. Forty-sixth Meeting The forty-sixth meeting of the Boston section was held at the University Club on Monday evening, Jan. 28, 1918. Thirty-six members and guests were present, which is a record for this Section. After a good dinner, President Philip N. Moore, of the Institute, was introduced, and spoke of the many problems of the Institute. The topics covered were the progress and growth of the Institute during the administrative year, the efforts to stimulate the local sections and to bring them more in touch with the policies and problems of the parent body and, last but not least, of the constructive results and patriotic work of the Institute in the national service of the war. The other guest of the Section, Mr. Thomas Nelson Perkins, Counsel for the Priority Board, spoke most entertainingly of recent experiences in Russia, England and France. After considerable discussion during which Mr. Perkins most obligingly answered innumerable questions, the meeting adjourned at about 10 p. m.

Jan 7, 1918

Jan 1, 1952

The following is an incomplete list of members and guests who called at Institute headquarters during the period July 11, 1918 to August 11, 1918. John Carter Anderson, Tucson, Ariz. Edson S. Pettis, San Francisco, Cal. Lieut. Frank A. Ayer, Tyrone, N. M. Wm. H. Rettie, Yonkers, N. Y. W. R. Canton, McGill, Nev. J. T. Robertson, Port Richmond, S. I. Alden Crankshaw, Palmerton, Pa. Harry O. Robinson, Margarita, John Davenport, W. Norfolk, Va. Venezuela. A. Faison Dickson. C. K. Seng, Gilbert, Minn. F. A. Fahrenwald, Cleveland, C). E. S. Sheffield. L. Hall Goodwin, New York. H. G. Smith. W. H. W. Hamilton, Baker, Ore. Harry M. Spoor. Floyd D. James, St. Louis, Mo. H. H. Stoek, Urbana, Ill. George A. Laird. Arthur L. Tuttle, Copperhill, Tenn. J. W. McBride, Spokane, Wash. Thor Warner, Phoenix, Ariz. Arthur Notman, Bisbee, Ariz. Christopher G. Atwater, Manager Agricultural Dept., The Barrett Co., is in Washington serving the U. S. Navy Bureau of ordnance in connection with the Navy nitrate plant recently authorized by Congress. Edward Ludlam Blossom announces his marriage to Mabel Townsend, daughter of Mr. and Mrs. George Comings Mills, on Wednesday, July 17, 1918, at New York City.

Jan 9, 1918

By C. R. Simcoe, T. J. Koppenaal

The effect of direct and alternating currents on the quench aging behavior in an Al-4 pct Cu alloy has been investigated by use of resistivity measurements. The reaction rate increases with direct current density in the investigated range of 1000 to 3000 amps per sq cm. Alternating current of a specific frequency is observed to decrease the reaction rate by a factor of about two. ErDMANN-JESNITZER et al.,1,2 investigated the effect of direct and alternating current on the quench and strain aging behavior of low-carbon iron. In both cases they observed that direct current accelerates the aging reaction and that an alternating current can completely inhibit the aging process. The purpose of the present research was to investigate these phenomena in the quench aging behavior of an Al-4 pct Cu alloy and to determine the correlation, if any, between the increase in the observed reaction rate and possible heating effects accompanying the aging with direct current. EXPERIMENTAL PROCEDURE The aluminum-base alloy used in this investigation contained 3.98 wt pct Cu (1.72 at. pct) with impurities of 0.003 pct Si, 0.002 pct Fe, and 0.001 pct Mg. The alloy was rolled into a ribbon about 0.36 mm thick and 3.7 mm wide. The ribbon was split end from end with the ends being used as electrical contacts and the central unsplit section, about 5.3 cm in length, serving as the specimen. Solution treatment was accomplished by quenching from a salt bath at 520° ± 2°C into water at 25° ±0.5°C; the specimen was immediately transferred to a liquid nitrogen bath. All aging was done at 75° ± 0.2°C in a rapidly stirred ethylene glycol bath. Resistivity measurements were made by the double potentio-metric method employing a standard resistor; for purposes of convenience, the resistance measurements were made at 77°K. The transfer of the specimen from the aging bath to a liquid nitrogen dewar was accomplished in less than 1 sec. The aging kinteics were studied with the specimen being aged under the influence of direct current, alternating current, and without any type of current. The amount of heating caused by direct currents was investigated by soldering a thermocouple on the specimen surface and measuring the temperature change after applying various current densities. The temperature was observed to increase (from 75°C, the aging temperature) about 0.8°, 3.0°, and 8.5°C with direct currents of 1000, 2000, and 3000 amp per sq cm, respectively. When employing alternating current, the circuit was monitored with an oscilloscope and adjustments made to produce a normal sine-wave pattern. RESULTS Prior investigations3'4 in the aging characteristics of A1-4 wt pct Cu have shown that the resistivity initially increases, reaches a maximum, and then decreases to values significantly lower than the as-quenched resistivity. This type of behavior is seen in Fig. 1 which shows the resistivity at 77°K as a function of aging time at 75°C observed in this investigation. At this aging temperature, the resistivity maximum is seen to occur in about 1 to 1-1/2 min and it further decreases to the as-quenched value in about 24 min. The behavior observed with the application of direct currents of 1000, 2000, and 3000 amp per sq cm during aging is shown in Fig. 2. With increasing current densities, (+) ?pmax decreases and the rate of the aging process increases. The time necessary to reach the as-quenched resistivity value decreases from 24 min for aging without current to about 16, 10, and 7 min for aging with 1000, 2000, and 3000 amp per sq cm direct current, respectively. Fig. 3 shows the results obtained when two changes were made during the aging with 2000 amp per sq cm

Jan 1, 1963

J. A. Mathews,* Syracuse, N. Y. (written discussion?).-It is interesting to note how frequently we hear of some process that is going to revolutionize the tool-steel business. I don't know why it is, but every one seems to have it in for us poor tool-steel men. About 15 years ago, a good-sized plant was built in Syracuse for the manufacture of cast tools of malleable iron. The promoter of the scheme claimed to have a secret, process that had been given to him by a tramp to whom he gave a lift along a dusty road. The widows and orphans invested liberally in the securities of the company without consulting the men established in the machine-tool business in Syracuse. About two years later, when the sheriff's sale occurred, the secret, which was carried on the books of the company as an asset valued at $2,000,000, brought $15 at auction. A little later another concern started on the theory of replacing scrap high-speed steel with new high-speed steel tools made therefrom. All the tool-steel companies have made a practice of purchasing high-speed

Jan 5, 1919

Albert R. LEdoux, New York, N. Y.—I can add a little to the information which has been given, by saying that it has been our business for some years, among other things, to inspect outgoing copper from some of the works here in the East, and to find out why there are variations not only in the conductivity of the wire-bars, but also in the character of the cathode-copper shipped; and we have found two things: These impurities which have been mentioned are largely upon the surface of the cathode. Samples taken of the inside, even of the nodules or " berries " which grow on the outside of the cathode, show that they do not contain more impurities than the denser material in the interior. In other words, it is a superficial deposit or contamination. There is still another reason for impurity in some of the copper which finds its- way to the manufacturers, namely, carelessness in the handling of molds or in casting. We have found copper which was comparatively pure, as far as the copper itself was concerned, but contained, mechanically intruded in the interior of the ingots,

Jan 1, 1913

By Robert I. Kingman

SUFFICIENT testing has been performed with the Dutch State Mines Cyclone for thickening and desliming flotation feed at the concentrator of the National Lead Co., Tahawus, N. Y., to prove its application for this work. It is the purpose of this article to present some of the test results, operational details and advantages of cyclone thickening and classification. The metallurgy of the mill operation was described by Frank R. Milliken, assistant manager of the titanium division.l The present flowsheet for the recovery of ilmenite consists in grinding the crushing plant product in four open-end rod mills in closed circuit with mechanically vibrating screens to approximately -20 mesh. The screen undersize is treated in Crockett magnetic separators which produce three products: magnetic concentrate, nonmagnetic tailing containing ilmenite and gangue, and a Crockett slime overflow. The non- magnetic tailing is classified into eight sizer spigots products and a classifier overflow. The spigot sand products are tabled separately to produce a rough ilmenite concentrate, a middling product and a tailing. The table middlings are returned to Crockett feed. The table concentrate is dewatered and dried and further concentrated on Wetherill magnetic separators to produce the finished ilmenite concentrate.

Jan 8, 1950

(Members are urged to send in for this column any notes of interest concerning, themselves or their fellow-members.) Members and visitors who registered at institute headquarters during October A. Adiassewich, St. Petersburg, Russia. Charles W. Merrill, San Francisco, Cal. A. F. Lucas, Washington, D. C. Carl J. Trauerman, Butte, Mont. Allan J. Clark, Lead, S. D. Herbert B. Cox, Boston, Mass. Prof. Loewinson-Lessing, St. Peters- James W. Malcolmson, Kansas City, Mo. burg, Russia. A. E. Sunderhauf, Paramaribo, Dutch F. Maury Gillespie, Abangarez, Costa Rica. Guiana, S. A. M. Gardner Talcott, Irvington-on-Hudson, N. Y. D. W. Brunton, Denver, Colo. A. P. Watt, Newark, N. J. Dwight E. Woodbridge, Duluth, Minn. S. A. Taylor, Pittsburg, Pa. Alexander Fyfe, Boston, Mass. Ralph Wilcox, Miami, Ariz. Robert A. Seip, Wilkes-Barre, Pa. William J. Cox, Denver, Colo. A. J. Eveland, Boston, Mass. E. P. Ross, Duquesne, Pa. M. F. Sayre, Brewster, N. 1. H. Mortimer-Lamb, Montreal, Canada. Albert Sauveur, Cambridge, Mass. F. L. Grammer, Leesburg, Va. Robert H. Leach, Brockton, Mass. R. R. Moore, Mexico City, Mex. Steinar Foslie, Kristiania, Norway. Charles E. van Barneveld, San William A. Wong, Honolulu, Hawaii. Fran¬cisco, Cal.

Jan 11, 1913

By Howard S. Strouth

SINCE the days of the Conquistadores, people have told exaggerated tales of the wealth and possibilities of Mexico and Central and South America, and the mining fraternity has never been known to exaggerate any less than any other professional group known to man or beast. However, during a short stay in Mexico one can probably hear more whoppers than at any other time, when dozens of mining propositions are thrust across the desk, and it is not necessary to remind anyone that a listing of the do's and don't's for Mexico requires special mention of the fact that most mining propositions offered south of the border eventually turn out to be a beautiful fairy tale. The following is not suposed to be either an exact description of Standard Mining Corp.'s operations in Mexico by its mining associate, the Corporacion Minera y Beneficiadora Anahuac, S.A., or the last word as to the most economical way to start such an operation. But rather it is the sum total of the recent experiences of the writer while commencing such an operation in 1951-52 with the help of many qualified gentlemen.

Jan 6, 1953

By T. S. Lundy, R. E. Pawel

Effects of short-circuiting paths on observed diffusion behavior in real crystalline systems are considered. It is concluded that experimentally measured diffusion coefficients may vary widely from values associated with true lattice diffusion to those appropriate for short-circuiting paths alone depending upon the conditions of the experiment and the sensitivity and completeness of the data. IN 1961 Harrison1 classified experimentally observed diffusion behavior in systems involving both lattice and dislocation-enhanced atomic transport into three categories. His types A and C were limiting cases where the measured diffusion coefficients using the usual serial sectioning techniques were representative of lattice diffusion (with only slight effects of dislocations) and dislocation-network diffusion (with only slight effects from lattice diffusion), respectively. In both cases A and C for a sectioning experiment in which the diffusion couple has the semi-infinite geometry and unidirectional diffusion takes place from a plane source located at the origin of the coordinate system, he pointed out that Gaussian penetration behavior should be observed. For case A the lattice coefficient should be slightly enhanced by dislocation contributions, and the model of Hart2 can be used to predict the amount of this enhancement. For case C the observed coefficient should be that for the dislocation network and have little or nothing to do with lattice diffusion. Hart's model in its general form is still applicable, but the apparent diffusion coefficient for this case is virtually independent of dislocation density. Harrison's case B is that for which non-negligible contributions exist for transport by both mechanisms and "the concentration distribution does not approximate to any simple form." With the possible exception of very low temperatures where diffusion distances approach atomic dimensions, any real diffusion specimen will in general show non-Gaussian behavior provided the data are complete enough to uncover it. Thus, a "complete" set of data for any real system cannot be expected to be totally amenable to treatment by a simple mathematical model which does not take into account the relative distribution of transport by the various modes or submodes. For a particular sensitivity of specimen analysis and at a given temperature of annealing if the concentration profile could be observed as a function of time, "the behavior will initially be type C, and will develop into type B. and ultimately type A".1 Thus, it appears that the type of diffusion behavior which is experimentally observed in a given system depends very much upon the particular experimental conditions and the particular tools available to obtain the data. Interpreted in this fashion, Harrison's classification refers not to the diffusion behavior as a whole but to the relative sensitivity of the method of examination and completeness of the data. In the present paper we will: 1) assume that the measured penetration behavior follows the same general classification as that proposed by Harrison; 2) give, for diffusion in tungsten, examples of the range of diffusion coefficients that it is possible to obtain in a single experiment; and 3) speculate that some arguments which consider the possibility of short-circuiting effects being responsible for "anomalous" diffusion in several bcc metals may have been discarded prematurely.3 Both monocrystalline and polycrystalline tungsten were used in this work. The former was obtained as triple-pass, electron-beam zone-refined 6.0-mm-diam rod from Materials Research Corp.. Orange-burg. N.Y. The latter was swaged, high-purity bar stock which was annealed for 2 hr at 2200°C and 10-9 torr to yield an average grain diameter of about 25 /i. The tracer Nb95 was received in oxalate solution from the Isotopes Division, Oak Ridge National Laboratory. Experimental procedures of specimen preparation, isothermal diffusion annealing, serial sectioning by anodizing-and-stripping, and y counting of the individual sections to determine the tracer penetration profile after a given diffusion anneal have been described elsewhere.4 However, it should be noted that the anodizing-stripping sectioning technique has the particular advantage for this research of permitting sectioning to be accomplished over a wide range of

Jan 1, 1970

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

R. W. NEWCOMB, New York, N. Y. (written discussion *).-This paper is particularly interesting to me, because it gives data on a much mooted question, viz., the serviceability of Le Chatelier (platinum-platinum-rhodium) thermocouples under severe industrial conditions. It has always been supposed that platinum-platinum-rhodium thermo-couples, used at high temperatures under strong reducing conditions, would not give long service and were subject to rapid volatilization. The fact, however, that the carefully kept records indicate that a little more than 3 gm. out of more than 830 gm. was lost over this considerable period, shows what kind of service can -be obtained from platinum-platinum-rhodium thermocouples,, when properly installed, and well cared for. While the writer has no actual figures on the loss of weight, etc. of platinum-platinum-rhodium thermocouples under service, he was told, by the man in charge of pyrometers at a large industrial plant in which over 400 platinum-platinum-rhodium thermocouples were installed in furnaces doing various kinds of heat-treating work, that the average maintenance cost, for materials alone, including platinum-platinum-rhodium wires and protecting tubes, was 27 c. per furnace, per month:

Jan 12, 1919