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Discussion of the paper of W. R. SHIMER, presented at the New York meeting, February, 1915, and printed in Bulletin No. 99, March, 1915, pp. 557 to. 585. WILLIAM R. WEBSTER, Philadelphia, Pa.-I would like to ask Mr. Shimer how the finishing temperature of the H-beams and other beams rolled on the Gray mill at Bethlehem compare with the rolling temperatures of the rails referred to in this paper. Also, how the reductions in the rolling of the beams compare with the reductions in the rolling of the rails. I would also like to know if any drop tests were' made on the rails referred to as having been allowed to cool and then annealed; in other words, what results, if any, were obtained from tests on rails after the internal strains of rolling had been removed; and in the matter of the rail blooms, I would like to ask if they are not often heated to a higher temperature than is desirable on account of the thin flanges in order to carry the heat through to the finishing pass. The tensile strength of the steel in these rails is given as 125,000 lb. per square inch, which is almost as high as tire steel. If some of these blooms were rolled into rounds of about the same section as the head of the rail, would you not get better results from tension tests than those from the head of the rail? In other words, in rolling rounds, whether you would not be able to control the rolling and finishing temperatures better than is possible in the rail, owing to thin section of the rail flanges. Some years ago I had experience with the rolling temperatures of tire steel, running from about 127,000 to 133,000 tensile strength. These tires had the tensile strength and the deflection specified. One of the manufacturers had no trouble whatever, after a little experimenting, in meeting the conditions of the specification. Another manufacturer who made some of these tires came to the office and stated that he had tried tires from three heats of steel and could not meet the specifications and

Jan 5, 1915

By R. W. Raymond

Alexander Brinton Coxe was born in Philadelphia, Pa., Jan. 19, 1838, the second of five sons of Hon. Charles Sidney Coxe and Ann Maria Brinton. A more extended history of his family and its important relations to the development of the United States will be found in my Biographical Notice of his younger brother, Eckley B. Coxe, published in 1895. It is therefore sufficient to say here that Dr. Daniel Coxe, a clis-

Jan 1, 1907

By Charles A. Stetefeldt

This treatise is the sequel of a paper on "Russell's Improved Process for the Lixiviation of Silver-ores," etc., read at the Chicago meeting, in May, 1884, and published in the Transactions, vol. xiii., page 47. The facts it presents are principally compiled from Mr. Russell's notes on his practical experience gained in various places where the Russell process has been introduced. For a complete understanding of this paper a perusal of my former one is desirable, as can be seen from the frequent references here made to it. All silver-ores that do not carry a large percentage of lead or copper can be treated by Russell's process with success and economy. I do not mean to create the impression that from ores containing considerable quantities of lead and copper a high percentage of the silver cannot be extracted by this process. Such ores, however, will, in many localities, be reduced to better advantage by smelting. In case lead-bearing silver-ores are suitable for concentration, it may be profitable to concentrate the ore by Krom's dry system, obtaining a smelting-product high in lead, and to lixiviate the tailings and the dust. This plan has been adopted in a mill recently erected in Cortez District, Nevada. The dry system of concentration deserves the preference because it delivers the tailings and the dust in a condition ready for chloridizing-roasting. In wet concentration the drying of the tail ings would be expensive, and there would be a considerable loss of silver in slimes. Oxidized ores, containing silver chloride and lead minerals, may be lixiviated after crushing, and the tailings may be concentrated for lead. In this case wet concentration would be most suitable. This has been done at the Old Telegraph Mine, Utah. I would give, however, the preference to dry concentration in all cases which, of course, requires that concentration should precede lixiviation. The Russell process is also adapted to the treatment of tailings resulting from ores which have been worked either by the old

Jan 1, 1887

By Thomas T., Read

TWO American students entered the Ecole des Mines in 1856, Joseph Lesley of Philadelphia and Thomas Egleston of New York. Lesley remained there only one year, but Egleston completed the whole 'curriculum and received, in 1860, the certificate given to foreign students .in lieu of the official appointment and degree. awarded French students. Returning home he received, in 1861, an appointment by Secretary Henry of the Smithsonian Institution to sort, label, and arrange the collections of mineralogical and geological specimens which had been brought to Washington by the various government exploring expeditions in the West. Thomas Egleston, born in New York City on Dec. 9, 1832, was the son of Thomas Jefferson Egleston, who came to New York from Massachusetts some time before 1829. The first American ancestor of the family had settled near Dorchester. in 1630. T. J. Egleston and Joseph Battell established an iron-merchandizing business* at 166 South St., New, York, which prospered exceedingly; so much so that when Thomas J. Egleston died, July 12, 1861, his estate had a book value of over $500,000. Since an older brother was expected eventually to take over this business, Thomas, who had a liking for science, went to Yale,, where he completed the regular four-year course in 1854, and then remained another year for advanced work in chemistry under Silliman. I One biographer says he went to Europe, . early in 1-856, on account of his health. It was the custom at that time for wealthy young men to make a tour of Europe after completing their academic education. Whatever the precise reason, he began scientific work at the Jardin des Plantes in Paris but soon trans* It still operating as Egleston Bros. Inc., though no direct descendants of its founder are now living.

Jan 1, 1941

By K. A. Natarajan, I. Iwasaki

The influence of dissolved oxygen and the Pt - Pt-O reaction on the measurement of redox potentials in solutions containing ferrous-ferric couple was examined. Current-potential curves were used to illustrate the shift in measured potentials toward the oxygen potential in oxygenated and deoxygenated systems at low concentrations of ferrous and ferric ions. The ranges of concentrations of the ferrous-ferric couple, in which the interference from oxygen and the platinum-oxygen reactions becomes significant, are illustrated through the mixed potential mechanism.

Jan 1, 1975

[EXECUTIVE COMMITTEE OF THE BOARD OF DIRECTORS LOUIS S. CATES, Chairman DONALD H. NCLAUGHLIN, Vice-Chairman JOHN L. CHRISTIE JOHN R. SUMAN CLYDE E. WEED]

Jan 1, 1946

The following officers were elected by the Pennsylvania Anthracite Section of the A. I. M. E. on the evening of June 28th. Chairman, R. V. Norris; vice-chairmen, C. F. Huber, W. G. Whildin, W. J. Richards, Eli Conner; executive committee, Douglas Bunting,. W. W. Engle, Chas. Enzian, J. M. Humphrey, A. B. Jessup, R. A. Quinn; secretary and treasurer, Paul Sterling.

Jan 9, 1919

ALBERT SAUVEUR, Chairman. A. A. STEVENSON, Vice-Chairman. HERBERT M. BOYLSTON, Secretary, Abbot Bldg., Cambridge, Mass. John Birkinbine, William Kelly, J. S. Unger, William H. Blauvelt, Charles Kirchhoff, Felix A. Vogel, James Gayley, Richard Moldenke, Leonard Waldo, Henry D. Hibbard, Joseph ANT. Richards, William R. Walker, Henry M. Howe, C. F. W. Rys, William R. Webster, Robert W. Hunt, E. Gybbon Spilsbury, Frederick W. Wood. J. E. Johnson, Jr., For the meeting of the Institute which is to be held in New York City, Oct. 16 and 17, 1913, the following program has been arranged: October 16, 1913, 10 A. M W. A. Forbes, Blast Furnace Gas Cleaning. W. H. Blauvelt, The Slagging Producer. Prof. F. Peter (Leoben, Austria), The Generation of Steam by Waste Heat from Furnaces. G. C. Stone, The Generation of Steam by Waste Heat from Regenerative Furnaces. W. R. Shinier, Over-Oxidation of Steel.

Jan 10, 1913

By W. A. Backofen, G. Y. Chin, W. F. Hosford

The ductile fracturing process was studied in single-crystal and poly cvystalline aluminum deformed in tension over a temperature range from 295° to 4.2°K. At temperatures as low as 77°K, the fracture of "inclusion-free" material, including zone-refined aluminum, was by rupture (-100 pct RA). At 4.2 OK, fracture was brought on by adia-batic shear. Metallographic examination did not disclose any voids or slip-band microcracks, thus negating for inherently ductile metals any mechanism of void nucleation by vacancy condensation or of cracking due to dislocation pile-ups. In Izigh-purity aluminum not treated to be inclusion-free, fracture at temperatures as low as 45°K was of the double-cup type and a result of void formation. The reduction-of-area decreased as temperature was lowered, corresponding to the earlier appearance of voids. Such behavior was rationalized in terms of a larger increase, with decreasing temperature, in the .flow stress relative to the strength of the inclusion-matrix interface. Evidence for low-temperature adiabatic shear was found in discontinuous flow at 4.2"K, in the transition to a localized shear fracture at low temperatures, and in the suppression of shear fracture with an elastically hard pulling device. A simple analysis for the initiation of adiabatic shew permitted a general correlation of the various contributing factors. It has been pointed out that the duration of shear depends upon effective mass and elastic stiffness of the deformation system. IT has long been recognized that fracture* may Throughout this paper, the term "fracture" is taken to mean any process that results in the separation of a material into two (or more) parts. Thus rupture as it may be encountered in a tension test leading to 100 pct reduction-of-area is included in this category. occur in a ductile mode, and that the process can be of great practical as well as general interest. Much information about ductile fracture has also been accumulated over this period, but only recently has an understanding of mechanism begun to appear. Ludwik,' in 1926, first reported fracture in a tensile specimen starting with a central crack in the necked section. Since then, other studies have disclosed that such cracks may form by the coalescence of voids nucleated in this region where hydrostatic tension is highest.2-4 Rogers and Crussard et al.' have emphasized void formation and reori-entation along localized shear bands as a mode of crack propagation. pines6 has considered the tensile rod as a bundle of fibers joined by weak interfaces, which subsequently separate to allow individual fiber contraction. The notion of cavity growth and coalescence by purely plastic processes was discussed by Cottrell: who added that the tensile reduction-of-area ought not to be sensitive to temperature. On the other hand, it has been observed that the reduction-of-area is greatly increased if tests are carried out at high temperaturesa or under high hydrostatic pressure.' Fracturing anisotropy in wrought products lends support to the idea of void formation from preexisting flaws strongly aligned by earlier processing.''-l2 There is evidence that many voids result from the fracturing of inclusions or separation at the inclusion-matrix interface Another possibility is that voids grow out of pore volume produced in the initial solidification and never fully removed in later working. In general, a structure 3f particles, pores, and weak interfaces can be expected, at least in materials of engineering interest. Vacancy condensation has been suggested as an alternative mechanism of void formation for materials considered to be inclusion-free.13 Yet experience has shown that tensile reduction-of-area increases with purity, to the extreme of rupture as so often observed in single crystals. Adiabatic shear has an important bearing on ductile fracture. It occurs when the decrease of flow stress, as a result of local temperature rise from heat generated during straining, becomes larger than the increase due to strain and strain-rate hardening. As demonstrated by experiments on punching of plates,14 a large temperature rise may be brought about by rapid straining. Adiabatic flow as a result of the high strain rate reached in an ordinary tensile specimen just prior to separation may account for the cone formation in cup-and-cone fracture;14 evidence of such local heating has been presented.15 For geometrical reasons, however, pure sliding along the conical surfaces is unlikely, and separation under tensile forces is probably an important accompanying feature of the shear.7 In deformation processing operations, a high shear-strain rate may exist at boundaries between plas-

Jan 1, 1964

Geology, by O. D. Von Engeln and Kenneth E. Caster, McGraw Hill Book Co., Inc., $7.00, 730 pp., 1952.The authors desired to write a book which would supplement the work of the teacher. The effort presents the facts of historical geology as an outgrowth of the understanding of physical geology-a method in keeping with the fundamental law of geology that "present agencies and forces, acting through enormous time, have shaped the world as we see it-the law of uniformitarianism." Narrative continuity is maintained throughout the text. Each historical geology period is made distinctive, provided with an identity, and shown to have particular characteristics. Elementary Heat Power, second edition, by Harry L. Solberg, Orville C. Cromer, and Albert R. Spalding. John Wiley & Sons, 1952. $6.50, 624 pp. The authors attempt to develop an understanding of the functions, principles of construction, and actual performance of heat-power machinery as a preliminary to the study of engineering thermodynamics. Matter and energy, fuels, and combustion are considered first, followed by chapters on internal combustion engines, fuel burning equipment, and steam engineering and utilizing installations. Pumps, compressors, gas turbines and refrigeration are also dealt with.

Jan 1, 1952

By J. A. Bownocker

THE Pittsburgh is one of the most important coal beds of Ohio. It was the last of the great coal beds to be worked extensively in that State, has the largest area of virgin coal, and will in all probability be the last of the great deposits to be exhausted. The line of outcrop sweeps nearly southwest in a sinuous line from Jefferson County on the north to Lawrence on the south, a distance on a bee-line of at least 150 miles. (Fig. 1.) The maximum width of the area under which this coal is due is about 55 miles, but in most places it is less than half that and in the two southern counties it is in places restricted to narrow ridges. Here as elsewhere the Pittsburgh coal forms the base of the Monongahela formation, and the following section taken from Condit shows the position of this bed with reference to certain higher ones in this field:1 FEET INCHES Shales and thin beds of limestone 24 5 Coal, Meigs Creek, No. 9 4 0 Shale, sandy 11 0 Coal 0 8 Shale, clayey 6 0 Coal, Lower Meigs Creek 3 0 Shales,clayey 2 0 Limestones and thin layers of clay 25 0 Unseen 11 0 Coal, Redstone 2 0 Unseen 11 0 Coal, Pittsburgh, No. 8 8 0 Clay 5 0 Limestone 4 0 From the standpoint of continuity the Pittsburgh coal of Ohio must be classed with the patchy type. As the map shows, the coal is thin or wanting along many miles of the line of outcrop. The large deposits form three separate areas, which, in order of their importance, are generally known as (1) the Belmont, (2) the Federal Creek, and (3) the Gallia fields.

Jan 10, 1926

By H. S. COOLEY

TO talk about a "factor of economy" in connection with the wire ropes used in mining practice may be coining a new phrase. If such be the case it needs no other apology than that economy in wire rope usage is so bound up with the factor of safety as to justify a similarity in naming that makes one suggest the other. At the latest Wire Rope Research Conference, held under the auspices of the A. S. M. E., Re- search Committee and Engineering Foundation, data were introduced covering mine ropes working under

Jan 1, 1930

By D. E. Thomas

Oxidation rate constants were determined for Cu-Pd and Cu-Pt alloys as a function of alloy composition and temperature. Reaction products were identified. Relationship between oxidation rate constants and diffusion constants in the reaction zones is discussed. THE mechanism of oxidation of alloys is consider--'¦ ably more complex and not so well understood as that of pure metals. The oxidation of a one-phase binary alloy of which one component is a noble metal should logically be the simplest case of alloy oxidation, for in this case one is concerned presumably only with the oxidation of the base metal and the diffusion process by which it reaches the reaction site. This had led a number of investigators to study such systems. Probably the earliest work was that of Tammann and Rienacker' on the tarnishing of Cu-Au alloys at temperatures up to 300°C. These alloys oxidize according to the logarithmic law, that is, the film thickness is proportional to the logarithm of the time. The rate of film formation was found to decrease with increasing gold content. Raub and Engel² investigated the oxidation of Au-Cu, Cu-Pd, Au-Ag-Cu, Au-Pd-Cu, and Ag-Pd-Cu alloys at 750°C in air. These alloy systems form a continuous series of solid solutions at the temperature of oxidation with the exception of those containing silver. Au-Cu alloys oxidize parabolically, the rate constant decreasing slowly with increasing gold content up to about 15 atomic pct* Au, and more rapidly thereafter. An alloy with 14 pct Cu forms only a very thin layer of CuO on the surface and probably also a subscale.† Alloys containing more than 14 pct Cu have scales consisting of CuO and subscales of Cu,O embedded in nearly pure gold. The Cu-Pd alloys obey the parabolic law except for slight deviations for alloys containing 53 and 84 pct Cu. The overall oxidation rate decreases rather smoothly with increasing palladium content. A scale consisting of a thin layer of CuO and a thick layer of Cu²O and a subscale of Cu²O embedded in nearly pure palladium was observed for alloys containing 84, 53, and 30 pct Cu. An alloy with 19 pct Cu formed only a subscale of CuO embedded in nearly pure palladium, and an 8 pct Cu alloy formed only a thin film which was presumed to be PdO. The ternary alloys considered by Raub and Engel oxidized in much the same way as did the binaries. Wagner and Grunewald³ found that Ni-Au alloys, oxidized at 900°C in oxygen, formed a scale of NiO and a subscale containing NiO and gold. The overall oxidation rate increases with increasing gold content, passes through a maximum and then decreases to zero for pure gold. The fact that gold increases the oxidation rate was attributed to "pores" in the scale. Kubaschewski' investigated the air oxidation of alloys of platinum or gold with up to 10 pct Cu or Ni at temperatures in the range 300" to 1550°C. Parabolic behavior was noted for all alloys except Au-Ni, with rates decreasing in the order Au-Cu, Au-Ni, Pt-Ni, Pt-Cu. The diffusion coefficients for the latter three systems are known, and they decrease in the same order. However, activation energies for the oxidation of these alloys do not agree with the activation energies for diffusion in the respective alloy systems. Kubaschewski and Goldbeck7 nvestigated the oxidation of Ni-Pt alloys in air at temperatures of 600"

Jan 1, 1952

By C. P. Proctor

WESTERN Pennsylvania, eastern Ohio, and Illinois are carrying out experiments wherein much more slate and other impurities are loaded with the coal in the mine and hauled to the surface preparation plant for removal. In general everything is sent to the cleaning plant although there may be some gobbing in the mine. No conclusions have been announced as to the effect of such a mining system on clean coal costs. Such factors as ability of the surface plant to handle the impurities, land and facilities for disposing of the impurities, and the transportation facilities underground should be considered.

Jan 1, 1942

By Y. L. Yao

A scale based on existing data for the mutual solid solubilities of metals in binary systems has been compiled. This scale is useful for estimating the relative magnitude of two solubilities, provided that these two metals do not form a continuous series of solid solutions. In his classic work on the theory of metallic solid solutions, Hume-Rothery proposed that, other things being equal, a metal of lower valency should be regarded as more likely to dissolve one of higher valency than vice versa. He called this the "relative valency effect". Later he found that the application of this general principle was limited to the three univalent metals: copper, silver, and gold. In dealing with alloys of these metals with metals of higher valency, Hume-Rothery stated, it is usually found that the solid solution of the univalent metal is of the greater extent.&apos; The question of whether there is a systematic trend in comparing the relative magnitude of mutual solubilities, if valency is not considered a criterion, naturally arises. The present paper proposes a "mutual solid solubility" scale on an empirical basis. The order of its arrangement is determined by the relative magnitude of mutual solid solubilities. Some applications of and inferences from this scale are given. ORIGIN AND SCOPE OF THE SCALE An extensive survey of over 400 binary phase diagrams shows that, with certain exceptions and within certain limitations, metals can be arranged in the following order: Na Zn Cd Ga Bi Ge Sb As Hg Sn Si Mg Li Ba In Tl Pb Al Ca Be Mn Cr Re W Mo Cu V Ta Fe Ru Cb Co Ti Hf Ni Os Zr Ir Pt Au U Rh Ce Pd Ag Th so that a metal higher on the scale tends to have a higher solubility in a metal lower on the scale than vice versa. some experimental solubility data are given in Table I. These data, unless otherwise specified, are taken from Hansen and Anderko.6 Throughout this paper, the term "solubility of A in B" is taken to mean the maximum solid solubility of A in B in atomic percent, while the maximum solid solubility of B in A in atomic percent is called "reciprocal solubility". The exceptions found in the above-mentioned survey are: Al-Ag system, 20.34 at. pct Al in Ag, 23.8 Ag in Al; Mg-Pb system, 5.9 Mg in Pb, 7.75 Pb in Mg; As-Sn system, vanishingly small amount of As in Sn, a large As primary solid solution; Cd-Hg system, Cd in Hg <Hg in Cd; Mg-T1 system, 5(?) Mg in ßT1, 15.4 T1 in Mg; W-Ti system, -21 W in ßTi, -25 Ti in W; Zr-Ag system, probably small amount of Zr in Ag, 20 Ag in ßZr.7 Considering the large number of examples, the exceptions are few. It is remarkable that metals may be so arranged without considering other factors such as size, crystal structure, electronic structure, and so forth. A limitation to the use of the scale is the fact that it cannot be tested for two metals forming a continuous series of solid solutions. It is interesting to point out that when the continuous solid solutions have a miscibility gap the critical composition is

Jan 1, 1961

By J. R. Long, C. E. Armantrout, A. H. Roberson, T. R. Graham, R. S. Dean

THE general program of the Federal Bureau of Mines on the study of alloys made with electrolytic manganese has been extended to copper-manganese-aluminum alloys. The initial results of the work are presented in this report and concern a determination of the mutual solubilities of these three metals to form the alpha solid solution. The principal studies of this system, reported in the literature, have been focused on the Heusler alloys containing 10 to 30 per cent Mn with 9 to 15 per cent Al. These investigations concern the ferromagnetic properties and the determination of the crystallization contours, with little emphasis on the phases present in the solid state outside of this area. Heusler1 recognized a breakdown of the beta solid solution of the magnetic alloy, which he says decomposes into the alpha, beta, and gamma phases of the copper-aluminum system, somewhat modified by the presence of manganese. Rosenhain and Lantsberry2 examined alloys ranging up to 10 per cent Mn and io per cent Al but were unable to reach definite conclusions concerning the phase boundaries in that area. Krings and Ostmann3 made magnetic studies and examined the system by thermal analysis. They present contours of the liquidus surface but do not place any of the phase boundaries. Corson4 [ ] has drawn a hypothetical boundary for the alpha field with few data to support such construction. The binary systems involved have received considerable attention by numerous investigators, and their general features are well established. The hopper-aluminum system (Fig, I) has been thoroughly examined by Stockdale,5 who places the limit of solubility of aluminum in copper at 7.4 per cent at the liquidus and 9.5 per cent at room temperature. Smiths established the eutectoid temperature at 570°C. by a study of isothermal decomposition of the beta phase. The copper-manganese system (Fig. 2) has been recently reviewed by Dean and co-workers.7 Using high-purity alloys, they place the solubility of alpha man-

Jan 1, 1946

By O. G. Lellep

IN every country economic circumstances prescribe the method used to produce a commodity at lowest cost. In Pennsylvania a man&apos;s wages for working 4 hr buys a ton of coal wholesale; in Germany a laborer must work 40 hr, or ten times as long. In western Europe, therefore, conservation of fuel is of primary importance, and recent practices of burning lime and cement differ from those employed in the United States. This paper presents data collected during a trip through western Europe in 1953. Considered uneconomical, shaft kilns for burning cement disappeared in the United States two generations ago. But because required capital investment is low and operation greatly improved, shaft kilns are still used to some extent in Europe, where fuel costs are high, and are even included in designs for plants under construction. During the last 50 years shaft kilns have been maintained at the same physical size, while their output has been increased at least four times.

Jan 7, 1954

By N. C. Fick, R. L. Rickett

DESPITE the large volume of literature on alloys of iron and silicon,1 there is little published information dealing specifically with the constitution, at various temperatures, of the alloys containing less than 0.10 per cent carbon and from 0.5 to 4.5 per cent silicon that are used extensively in the electrical industry. Because such information was needed by those engaged in the production of these alloys in, sheet and strip form, the constitution was determined of a series of commercial silicon steels containing 0.05 to o.08 per cent carbon and 0.20 to 4.31 per cent silicon, over the temperature range 1300° to 2500°F. These alloys were all from regular production heats and of commercial quality. The results of, the tests are given in Fig. I and for comparison the constitution diagram of iron-silicon alloys with 0.01 to 0.02 per cent carbon, taken from the literature, is also presented. MATERIAL AND PROCEDURE All steels were hot-rolled to a thickness of 0.060 to 0.080 in. and used in this condition. Their chemical compositions, including over-all check analysis, and "center" analysis for carbon and silicon, are given in Table I. The so-called center analysis was determined on samples pickled to remove the outer surface and leave only the center third of the gauge thickness-the portion of the sample on which metallographic ratings were based. In most, but not all, of the alloys, slightly higher carbon was found at the center than when the whole strip was sampled; the two methods of sampling show relatively little difference in silicon. Two of the steels, A and E, contain relatively high phosphorus, while I and K are somewhat higher in manganese than the others. [ ] The procedure consisted essentially of heating specimens (about 1/16 by 3/8 by 3/4 in.), protected from oxidation or change in carbon content, at a temperature in the desired. range and for a selected period, after which they were quenched in iced brine; the degree of transformation that had then occurred was determined by metallographic examination. The soaking periods were selected after preliminary investigation had shown that a con-

Jan 1, 1946

By T. S. Lundy, R. E. Pawel, F. R. Winslow, C. J. McHargue

The volume-diffusion coefficients of Nb-95 and Ta-182 in niobium have been measured over the temperature range 878° to 2400°C. High-temperature specimens (T 21500°C) were sectioned by conventional lathe and grinding techniques while low-temperature specimens were sectioned by an anodizing and stripping technique previously described. Over a range of more than ten orders of magnitude in diffusivity, the self-diffusion data is well-represented by the equation: D = (1.1+ 0.2) exp [- (96,000 * 900)/RT ] cm2/sec Upward deviations from this line are explained by short-circuit diffusion in combination with the loss of resolution of the sectioning techniques. Oxygen contamination within the range 100 to 450 ppm was found to have little or no effect on the self-diffusivitj 01 niobium. In a limited number of measurements, the diffusivity of Ta-182 in niobium was found to be about half that of Nb-95 in niobium. These data may be described by D = (I.0+0.90.5)exp [- (99,300 * 2400) /RT ] PREVIOUSLY reported studies of self-diffusion in niobium were by Resnick and Castleman1 and Peart, Graham, and Tomlin.2 The data of Resnick and Castleman over a temperature range 1585" to 2120°C show considerable scatter but. can be represented by D = (12.4 *0.8) exp [-(105,000+3OOO)/RT] cm2/sec The limited data of Peart, Graham, and Tomlin follow the equation D = 1.3 exp (-95,00O/RT) cm2/sec In view of recent diffusion data for ß zirconium3 and 0 titanium4 in which Arrhenius-type plots do not yield straight lines and of the potential high- temperature uses of niobium and its alloys, we thought it important to investigate the diffusion behavior of this bcc refractory metal over a large temperature range. This has recently been done for molybdenum,5 chromium,6 vanadium,"" and tantalum.9 Niobium was a particularly suitable material for this study largely because of the development of an anodizing and stripping sectioning technique which enables diffusivities as small as l0-19&apos; sq cm per sec to be determined accurately.10 In addition to self-diffusion data, data were obtained for the diffusion of Ta-182 in niobium and for the effect of varying oxygen content on self-diffusion. I) EXPERIMENTAL PROCEDURE Materials. The niobium was obtained from three sources: 1) melting stock from Shieldalloy Corp., 2) electron-beam melted single crystals, 1/2 in. diameter, from Semi-Elements, Inc., and 3) oxygen-doped, electron-beam melted single crystals from Materials Research Corp. The melting stock was electron-beam melted and specimens 5/8 in. diameter by 1/2 in. long were machined from the center of the bar. The analysis supplied by the vendor and an interstitial analysis of one of the specimens are given in Table I. The single crystals (type 2 above) were cut with a jeweler&apos;s saw to specimens about 3/8 in. long. The interstitial analysis of this material is given in Table 11. This material was used

Jan 1, 1965

By Klaus Schwerdtfeger

In order to test the performance of ZrO, (CaO) and Tho,(Yz03) electrolytes in the electrochemical determination of oxygen activities in liquid metals at steel-rrzakitng temperatures , electromotive force measurements have been made with the following cells: The oxygen-- activities are calculated from the electmrnotive forces for the investigated systems. The standard free energy of- formation of MnO and the activity of manganese in Fe-Mn melts are derived. Indications are that the Zr 0z(Ca0) electrolyte exhibits little electronic conductivity at oxygen pressures as low as 10&apos;a atnz at 1600°C; however, the partial electronic conductivity may become noticeable at lower oxygen activities. The Tho,(Yz03) electrolyte is found to be an ionic conductor at the oxygen pressure as low as that for the Mn + MnO equilibrium, but exhibits partial electronic conductivity at oxygen pressures higher than 10"1 atm (1500°C). fi. better control of oxidation and deoxidation reactions in steelmaking may be facilitated if the oxygen activity in the steel is known during various stages of the process. In the present work oxygen activities have been measured in liquid iron, manganese, and iron alloys with galvanic cells using ZrOz(CaO) and s solid electrolytes with the object of establishing the range of oxygen pressure in which these materials can be used as electrolytes at steelmaking temperatures. Calcia-stabilized zirconia and Tho2-Y203 solid solutions are oxygen ion conductors. Such electrolytes were first used by Kiukkola and Wagner1 and Peters and ~ann&apos; in galvanic cells for the determination of thermodynamicquantities of oxide systems in the temperature range 700" to 1200°C. At these moderate temperatures calcia-stabilized zirconia has been found to exhibit predominantly ionic conductivity at oxygen pressures as low as those for the Cr + Crz03 equilibrium,394 but at lower oxygen pressures elec- tronic contribution to conductivity becomes significants4 The Th02-Y203 solid solutions are ionic conductors at oxygen pressures lower than those applicable to zirconia base electrolytes.5&apos;6 At high oxygen pressures Thoz base electrolytes exhibit significant p-type semiconduction. At the time the present experiments were carried out several papers1&apos;-* were published on the electrochemical determination of oxygen activities in liquid iron using the ZrOz(CaO) electrolyte. The results of different authors do not agree well. For instance, according to Fischer and ~ckermann" stabilized zirconia can be used to measure oxygen contents in liquid iron larger than 0.02 wt pct, but according to Baker and west1&apos; ZrOz(CaO) cannot be used for the determination of oxygen content in liquid iron because of high electronic contribution to the conductivity. Fig. 1 is a schematic diagram of the apparatus used. About 500 g of liquid metal is contained in a crucible into which a stabilized zirconia or Th02(Y203) tube is immersed. A platinum contact wire is pressed (with a spring mechanism) against the inside bottom wall of the electrolyte tube. The tube is flushed continuously with a stream of air, CO-CO, (or Hz-C02) (at 0.96 atm and at a rate of about 300 cu cm per min), via an alumina tube inserted inside the electrolyte tube. This alumina tube also contains the Pt-Pt/10 pct Rh thermocouple. A capillary alumina tube shielding the other contact wire is immersed in the melt. The molybdenum contact wires were used mostly; in some cases platinum wire was employed. Molybdenum has the advantage that it dissolves more slowly in the melt than platinum. The whole cell was contained in the alumina reaction tube of a resistance furnace with molybdenum winding. The reaction tube was closed gas tight at both ends and flushed continuously with argon. Because of the poor thermal shock resistance of the electrolyte tubes the cell had to be assembled in the cold furnace. The electrolyte tube and alumina sheath

Jan 1, 1968