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By J. Leja, N. Sheikh

The stability of lead ethyl xanthate precipitate in aqueous environment of different pH (4.5 to 10.5) and at temperatures 25°C-60°C was investigated. Dissolution leads to a wide variation of pH, xanthate, and lead ions concentration in solution and to a deposition of solid products of reactions. X-ray diffraction patterns of these solids enabled identification of Pb(OH)3, PbCO3, and PbS as constituents of the remaining undecomposed Pb(EtX)1, together with some unidentified compounds (which give rise to intensive peaks with d values of 2.82A and 1.71A, and numerous peaks of lesser intensity).

Jan 1, 1974

By P. W. Bakarian, John C. McDonald

Three magnesium alloys were processed in various ways to exhibit a wide variation in the ratios of yield strength and tensile strength in the rolling direction compared to the cross-rolling direction. Basal-plane pole figures were prepared from several specimens. A fair correlation was observed between the property ratios and the ratio of percent of poles oriented in the cross-direction quadrants compared to the percent oriented in the rolling-direction quadrants of the pole figures. THE modes by which magnesium crystals deform are such as to lead to marked preferred orientations in all forms of wrought products. The effect of the active modes at room temperature, coupled with these orientations, is often to produce a lower compressive yield stress compared to the tensile yield stress. The phenomenon is due to easy twinning in compression, and has been well-related to the preferred orientations as described by basal-plane pole figures of the hcp magnesium single crystal. The literature contains some information on the variation with test direction of the tensile properties of sheet, but no quantitative relationship to the observed pole figures has been established. These effects have been reviewed in the few com- prehensive treatises in English which have been written on magnesium technology and metallurgy.1°3 Roberts presents several pole figures, but no tensile-property data in the plane of the sheet. Raynor has no pole figures, but quotes Frommer's4 results. The information in Beck's compendium more or less parallels the results of Jones and powell.5 In both a Mg + 1.5 Mn alloy and a Mg + 4.6 A1 alloy, cold rolling was found not to change the general situation of higher properties in the cross-rolling direction,* than in the rolling direction. Thomas'6 X-ray studies of Jones and Powell's specimens did not permit correlation of properties and preferred orientation. Ansel and Betterton7 report tensile and compressive properties on three other alloys as a function of degree of cold rolling, plus a recrystallizing anneal. As rolled, there was a change in anisotropy with degree of reduction, but all alloys were reasonably isotropic in tension when annealed. X-ray diffraction photograms illustrated the kinds of orientations present, but were not correlated with the properties. Bakarian8 has described a method of determining quantitatively a preferred orientation, and illustrated the method by applying it to pure magnesium and two of its alloys. This method was used in the present work as a basis for correlating the strength properties with the texture.

Jan 1, 1965

By Arnulf Muan, Klaus Schwerdtfeger, L. S. Darken

The equilibrium ratios CO/CO, of. a gas pharse coexislitrg with selected oxide phase assemblages of the system "FeO"-MnO-SiO2 and metallic iron have been determined at 1150°C. The data obtained are combined wilh the thermodynamic data on fayalite (Fe2SiOi) and "FeO"-MnO solid solutions to derive the actiuity-coiHpQsiUon relations for the various oxide components of the olivine (Fe2SiO4-,lIn2Si04) and pyroxenoid (standard free energies of formation of ferrosilile (FeSiO,), tephroite , and rhodonite from their oxides have been evaluated. In the Appendicc~s by Darken and Schivcerdtjeger the ideal solution law for solid deri oed. THE quaternary system Fe-Mn-Si-0 is of interest in many important phases of iron- and steelmaking. For instance, reduction in the blast furnace of ores containing Fe-Mn silicates, deoxidation of liquid steel with Mn-Si alloys, formation and subsequent alterations of oxide inclusions in steels, and the oxidation of manganese- and silicon-containing steels during processing are all governed largely by the thermodynamic relations existing in the system Fe-Mn-Si-O. Although the equilibria between liquid iron and Fe-Mn silicates have been studied in detail previously,' experimental data are lacking for equilibria among the solid phases. The present paper provides such data for a selected temperature, 1150°C. I) PREVIOUS WORK The general feature of subsolidus phase relations in the system iron oxide-manganese oxide-silica under strongly reducing conditions is known.' Fig. 1 represents an isothermal section at 1150°C. The phases present, in addition to silica, are three solid-solution series, viz.. the oxide solid-solution series "Fe0"-MnO (manganowiistite), the orthosilicate solid-solution series Fe2SiO4-Mn2SiO4 (olivine), and the metasilicate solid-solution series FeSi03-MnSi03 (pyroxenoid). The "FeO"-MnO solid solution is continuous between the two end members wustite and manganositeV3 as is the orthosilicate series between the two end members Fe2SiO4 and Mn2 SiO4. 4 The metasilicate solid solution, on the other hand, extends only part way from the MnSi0.l end member toward FeSiO because the latter end member is unstable relative to the phase assemblage fayalite + silica. The letters a through m in Fig. 1 identify end members of the individual solid phases dealt with [for instance, c designates fayalite (FeZSiO4) in equilibrium with wustite, e designates fayalite in equilibrium with silica, and so forth]. In addition to the phase relations there are some thermodynamic data available for the end members of the silicate solid solutions and for the "FeO" -MnO solid solution. The free energy of formation of fayalite (Fe2Si04) from its oxide components has been studied by several investigators. Unfortunately, the data obtained show considerable discrepancies. According to recent tabulations by Kelley, the change in standard free energy Affn for the reaction

Jan 1, 1967

By H. T. Sumsion, A. U. Seybolt

The results of an investigation of vanadium-rich V-O solid solutions are presented, indicating the structure and lattice parameters of two solutions, a and ß, and their approximate temperature-composition existence. The a solution is the terminal body-centered cubic one, and contains up to 3.2 atomic pct 0. The ß solution has an ordered body-centered tetragonal structure, is formed at 1270°C, and exists from about 15 to 22 atomic pct 0. From the evidence available, the various phase boundaries have no appreciable temperature dependence. Evidence has been found for a polymorphic transformation in pure vanadium at 1550°C. IN an earlier investigation' dealing with the preparation of pure vanadium by calcium reduction of the oxide, it was found that small amounts of oxygen drastically reduced the ductility of the metal. Because this effect was so marked, it was decided to make a study of the solubility of oxygen in solid vanadium. This report deals principally with this solubility and the nature of the phase relationships in the vanadium-rich region, particularly at temperatures below 1300 °C. However, during the investigation enough data on the V-0 system were obtained to make it appear worthwhile to present a tentative phase diagram up to the composition VO. The only significant prior work found on this system are the contributions of Klemm and Grimm,' and Mathewson et al.3 Klemm and Grimm prepared a wide range of V-O compositions by powder techniques including the compositions VO.l, VO.2, VO.3 and VO4 (9.1, 16.8, 23, and 28.6 atomic pct 0, respectively). The first three compositions were found to consist of a body-centered tetragonal solid solution, while the last also showed lines of VO (NaCl structure). They found that the parameter c, increased and the parameter a, decreased with increasing concentration of oxygen. For their composition VO.27, or about 16.8 atomic pct O, they cite the values a, = 2.948A, c, = 3.53A, and c/a = 1.2. Klemm and Grimm made no attempt to determine the solid solubility limit nor to construct a phase diagram. They did, however, give some data on the homogeneity range of VO, and they proposed a structure for the body-centered tetragonal solid solution; these points will be taken up later. Materials and Preparation of Samples The vanadium used in this investigation was prepared in the laboratory by the method previously mentioned.' A typical analysis is as follows: Fe, 0.007 pct; Si, 0.02; Ca, 0.06; C, 0.224; O2, 0.044; N,, 0.0017; H2, 0.003; and V, 99.34 ±0.3 (assay). The vanadium assay is probably low by about the error given. The impurities total about 0.36 which, if subtracted from 100, gives a purity of about 99.6. At the time material was being prepared for this work no suitable technique was available for melting vanadium without appreciable contamination. The procedure adopted therefore was to cut the calcium-reduced regulii into slices which were then rolled to strip about 0.025 in. thick for oxygen diffusion. Pieces of rolled vanadium of approximately 0.025xY4xl in. and weighing about 0.3 g were suspended in a vertical fused-silica tube which was part of an ordinary gas absorption apparatus. The silica tube was heated by an electric resistance-tube furnace which could be raised around the silica tube or lowered away from it as desired. This apparatus had no novel features which require detailed description. Other than the silica tube and furnace, it consisted of a glass system evacuated by a liquid nitrogen trapped mercury diffusion pump, a mercury-operated gas burette, a McLeod and a Pirani gage, and a mercury manometer. It was also equipped with suitably located stopcocks for isolating various parts of the system; the vacuum ordinarily attained was between 10" and 10-6 mm of mercury. Oxygen generated by decomposing MnO2 was passed through anhydrous magnesium perchlo-rate before introducing it into the gas burette and thence to the absorption chamber.

Jan 1, 1954

By A. B. Stickney

UPWARDS of 200,000 engineers in this country are sufficiently interested in engineering as a profession to have joined a society, but not over 10% of them belong to any one society. There is a widely-felt need of an over-all organization of all the societies to act as spokesman for all engineers on matters of common concern. On a local basis, over 100,000 engineers in 35 metropolitan areas have organized themselves into local councils, and are doing an effective job of intersocietal co-operation within their sphere of activity. In the last few years much has been said and written about a similar organization on a national scale. Everybody wants iteverybody is talking about it-it's in the air-it's coming-it's inevitable. Although it is no longer necessary to talk about why or whether there should be such an organization, there is no such unanimity about what it should be like. This paper outlines a proposed organization by answering four questions-who, how, what, and who will pay for it.

Jan 1, 1946

By J. Armanet

THREE MINING colleges are maintained in France; the École Nationale Supérieure des Mines, of Paris; École Nationale Supérieure des Mines, of Saint Etienne; and the École Supérieure de la Metallurgie et des Mines at Nancy. Besides graduates of these schools, a few graduates of the École Centrale des Arts et MIanufactures and of the École Polytechnique are employed as ]nine managers or engineers; however, most of the latter have taken a graduate course at one of the mining schools.

Jan 1, 1939

By Rollin A. Pallanch

THE Midvale mill of the United States Smelting Refining and Mining Company is situated on a flat site whose elevation is 50 ft above that of the Jordan River. Tailings are impounded in the area between the river and the flat upon which the mill and railroad switchyard are located. The water supply is pumped from the Galena canal which leads from the river at a point some ten miles to the south. The mill has a present capacity of approximately 1700 tons daily. It started out originally in 1926 as a 750 ton three-unit plant. The tonnage was gradually increased to 1200 tons by 1934, and in late 1935 a fourth unit was added. The accompanying flowsheet shows the principal equipment and how it is utilized. The ore is principally sulphide with varying degrees of oxidation, with individual lots ranging widely in both precious and base metal content. In each of the four individual units of the mill there will often be mixtures of as

Jan 1, 1948

By A. E. Austin, J. R. Doig

Ti-Cr alloys age harden after B-quenching by formation of an W-phase. The structure and orientation of this transition phase have been determined. The hardness ap-pears to be caused by strain in the B-matrix produced by concurrent enrichment of alloy content in the W-phase. EARLY studies of age hardening in B-stabilized titanium alloys revealed the formation of a transition phase named o' This phase was detected by X-ray diffraction in binary alloys of Ti-Fe, Ti-Cr,

Jan 1, 1958

By Frank Milliken

IN September 1937, the Ohio Copper Co. inaugurated the treatment of its copper-bearing mill tailings at Lark, Utah. These tailings had been accumulated during the regular operation of the Ohio Copper mine and mill over the period 1007 to 1019. Gravity concentration had been employed except for a comparatively short period in 1919, when flotation was used. The ore milled during that period assayed about I per cent Cu. The chief copper mineral, chalcocite, was dissemi-nated in a shattered quartzite, mainly along fracture or cleavage planes. The quartzite gangue was extremely hard and grinding to liberation resulted in excessive sliming of the "sooty" chalcocite, with consequent high tailings losses. Recovery on the seven million tons treated was prob-ably less than 6o per cent of the total copper content. As early as 1918, attempts had been made to sample the dump. In 1928, a com-plete sampling program was undertaken. The sampling consisted of seventy-four 5-in. post auger holes drilled to the full depth of the dump at regular intervals of 250 ft. Each 10-ft. portion thereof com-prised a sample for analysis. Each sample was screened, rolled, divided into three parts, dried and assayed. The reject was retained for testing purposes. From the depth of the auger holes a contour map of the dump was plotted, Fig. 1, which gives percentages of tonnage and copper content.

Jan 1, 1940

By H. M. Howe, W. E. C. Eustis

The processes which form the subject of this paper have been experimented on in the laboratory of W. E. C. Eustis, but have not passed beyond the experimental stage. The first is the invention of Mr. J. L. Thomson, of Capelton, Quebec, Canada, the others have been invented by the writers. Thomson's PRocess foR the Extraction oF Nickel. This consists essentially in first rendering the nickel magnetic, and then separating it from the materials with which it is mechanically vol. X.—20

Jan 1, 1882

Jan 1, 1901

By S. H. Ash

IN no part of the world other than a small area in Pennsylvania is anthracite mining an industry of major magnitude. As the deposits of anthracite in the United States are limited virtually to Pennsylvania, the difficulties of this industry have been commonly considered a state rather than a national problem. However, there is also national interest in the conservation and wise utilization of all the country's fuel resources and in the control of interstate waterways. The anthracite industry is confronted with a serious problem of water accumulation in many of the mines, a problem that must be solved in the near future if progressively higher mining costs are to be avoided. It cannot be solved by the operating companies without state or Federal aid, or both, owing to the magnitude of the work required, the diversity of interests of the coal and surface ownerships, the hazard to the whole mining community, and interests affected outside the mining region. 'The costs of abating the ever-increasing surface seepage to mine workings and of handling this seepage once it has occurred are beyond the eco¬nomic resources of the operating managements.

Jan 1, 1941

By Goro Shimaoka, Kichizo Niwa

IN the past, the crystalline states of graphite in cast iron have been studied by many investigators. Recently several authors 1-4 have published interesting information on the crystal texture of the individual graphite grain, especially spherulites in nodular cast iron. In regard to the crystal structure of graphite, Lipson and Stokes0 howed by powder X-ray analysis that most of the crystals contain about 14 pct rhombohedra1 structure (ß-form) which differs from the hexagonal structure (a-form) in the sequence of layer stacking. Hoerni6 onfirmed the existence of the ß-form in a single crystal with electron diffraction by Kossel-Moellenstedt's method. Furthermore, Hoerni and Weigle7 found extra reflections in electron diffraction patterns, which are given by a unit cell twice as large as the usual one in the basal plane. Recently, Lukeshs observed graphite twinning and satellite reflections in his X-ray work and considered them as evidence for the existence of an orthorhombic superstructure. Owen and Street" and Matuyama" studied the structures of graphite crystals in several types of cast iron, using the X-ray powder method, and they showed that the graphite crystal contains a certain amount of the ß-form, an amount which varies with the sources of the cast iron used. The present study was made in order to secure structural information on graphitization in cast iron. Electron diffraction studies on the structure of single graphite flakes segregated from molten carbon or silicon-rich iron at 1200" to 1500°C are reported. Experimental Honkeiko pig iron (4.05 pct C, 1.59 pct Si, and 0.65 pct Mn) was used as the solvent of carbon or silicon. The pig iron was melted in an open furnace and a small quantity of metallic silicon was added to the melt at 1300°C. The melt was heated to 150O°C, and then retort black carbon or metallic silicon was added little by little. The components added to the bath contained approximately 5.0 pct C and 2.0 pct Si in the carbon-rich material, and 3.8 pct C and 5.4 pct Si in the silicon-rich iron. These two types were held at 1500°C and then cooled without graphitizing by cutting the heat sup-

Jan 1, 1958

By B. D. Cullity

GOLD and beryllium form an intermediate phase composed of the two metals in equal atomic proportions and having the formula AuBe. According to Winkler,1 this phase probably exists in two modifications: beta, stable below about 600°C, and alpha, stable between 600°C and the melting point, about 740°C. Only the low- temperature beta form will be considered in this paper. EXPERIMENTAL PROCEDURE The gold used had a fineness of 999.75 to 999.85, balance mainly silver, and the beryllium purity was better than 99.8 pct. AuBe was prepared by melting the constituents in a beryllia crucible in an evacuated induction furnace. After melting and thorough mixing, the alloy was allowed to solidify in the crucible. No difficulty was encountered in obtaining a homogeneous ingot. Both chemical analysis and microscopic examination of the ingot showed that the alloy was essentially one phase, containing 50 at. pct gold. The alloy was quite brittle and powder samples could easily be pre- pared by grinding in an agate mortar. The X-ray diffraction patterns were made with CuK-alpha radiation in a Debye-Scherrer powder camera 57.3 mm in diameter. The film was placed unsymmetrically in the camera in order to afford a basis for am-shrinkage corrections. A sample homogenized at 5o0°C gave the same diffraction pattern as a sample taken from the as-melted ingot. GENERAL RESULTS The diffraction pattern of AuBe was readily indexed on the basis of a simple cubic lattice with ao = 4.659 ± 0.001kX. If the unit cell is assumed to contain four AuBe "molecules," the calculated X-ray density is 13.46 grams per cc as compared with the measured density of 13.55 gm per cc. The only missing reflections in the dsraction pattern are (100) and (220) (see Table I). Since these missing reflections are not those characteristic of body or face centering, the lattice of AuBe must be simple cubic. To locate the positions of the atoms within the unit cell, two possibilities had to be considered: I. The structure was disordered and there were eight positions to be filled by an "average" gold-beryllium atom. That the structure was disordered seemed unlikely since the lattice parameter did not vary with composition in alloys containing some- what more and somewhat less than 50 at. pct gold, indicating a fixed composition for AuBe.

Jan 1, 1947

By C. J. Rosa, W. C. Hagel

An attempt is made to determine the diffusion coefficients of oxygen ions in hypostoichiometric zirconium oxide. A phenomenological theory is developed for three-phase, unidirectional volume diffusion of a gaseous species from a planar source. Knowledge about oxygen diffusion in a and ß zirconium and experimentally measured rates of movements of interfaces permit the evaluation of oxygen ion diffusivi-ties in ZrO2-x. The results conform to the relationship: sq cm per sec, for the temperature range of 875" to 1050° C. DIFFUSION coefficients of oxygen ions in stoichio-metric oxides have been studied by many investigators. The obtained results not only supplement the knowledge about the lattice-defect structures of oxides and conduction mechanisms but also provide information of technological importance. Rate processes such as oxide sintering, high-temperature creep deformation, and oxidation of metals and their alloys are directly dependent on diffusion phenomena. Unfortunately, diffusion coefficients obtained from studies on stoichio-metric oxides cannot be treated without restraints when applied to oxidation kinetics, if precise evaluations of oxidation rates are desired. Oxides formed on metals are usually nonstoichiometric and exhibit nonuniform distribution of either cation or anion vacancies across their thicknesses. Debuigne and Lehr1 extended Danckwerts'2 mathematical analyses and furnished a semitheoretical treatment for evaluating oxygen diffusion coefficients in zirconium oxide in terms of weight gain measurements during oxidation of zirconium in the temperature range 400° to 850°C. Their calculations are based on theoretical partitioning3 of the total amount of oxygen between a zirconium and its oxide phase. An inherent discrepancy appears to continue throughout their calculations. The amount of oxygen confined to the oxide phase should be corrected by multiplying the calculated oxide thickness by the inverse of Pilling-Bedworth ratio, if expansion of zirconium dioxide is taken into account. The purpose of the present investigation is to provide a new semitheoretical treatment for evaluating diffusion coefficients of moving species in hypostoichiometric oxide. The analyses are relevant to unidirectional volume diffusion. Although the presented method is quite general, its applicability will be discussed in terms of kinetic measurements from oxidation of zirconium at temperatures above the a/ß transition, for reasons stated in the later part of this paper. EXPERIMENTAL Pure, 99.93 wt pct, zirconium samples of approximately 2 by 1 by 0.35 cm were exposed to oxygen for various times at four temperature levels: 875°, 950°, 1000°, and 1050°C. High-purity, better than 99.9 vol pct oxygen was passed through a cold trap and columns containing anhydrous CaSO4 to remove residual water vapor. Before exposing to oxygen at a pressure of 500 Torr, specimens were subjected to wet abrasion on 200- through 600-grit Sic papers and polished with 1—p diamond dust. Prior to oxidizing, all zirconium samples were vacuum-annealed at 10-6 mm Hg for about 15 min at the test temperature. The temperature variation across the uniform heat zone was ±2°C from the preset value. Final polishing, for phase thicknesses measurements, was performed by using 8- and 1-p diamond dust and followed by vibrator polishing with 0.05-µ ? Al2O3 solution. Measurements of phase thicknesses were made by projection on a metallographic viewing screen. Conventional powder X-ray analyses for the oxide were employed. RESULTS Fig. 1 is an example of the cross section of oxidized zirconium. Designations of phases given below this figure are the same as those used in the three-phase diffusion system represented by Fig. 5 in the following section. Zirconium oxidized for longer exposure times showed two types of oxides: white oxide at the surface and an underlaying layer of gray oxide. X-ray powder patterns of these oxides at room tern-

Jan 1, 1969

F A. THOMSON, president of the Montana School of Mines, gave an interesting talk on mining schools of the past, present and his ideas of the future before a recent meeting of the Montana Section of the A. I. M. E. He covered the history .of the various mining schools and com- pared the three main types of schools; those attached to or forming part of an endowed college or university such, for example, as' the Columbia School of Mines, the Mining Department of the Massachusetts Institute of Technology and the Mining Department of Stanford University. These resemble in a general way the second class, those attached to the state universities and colleges. The schools of this general type have had varied success.

Jan 1, 1928

By W. A. Forbes

OUR present-day geological surveys show that 36 of our States are underlain with bituminous coal, covering a total area of 496,709 square miles. The North American continent possesses 69 per cent of the world's coal reserves, with the United States alone having an estimated 55 per cent. The American coal reserves, in tons, are calculated to he about 3,500,000,000,000 tons, of which we have exhausted about 1 to 1 1/2 per cent. If this coal were mined at the rate of the 1918 production-a record output of 579;000,000 tons-it would not be depleted for 4,000 years. The more easily accessible and high-grade coals would obviously be consumed much before this; some estimates are 100 years. The natural progress of the nation's industries up to 1910 encouraged on every hand the development of new mines, especially where cheap and easy access to coal measures was coupled with short hauls to the consumer. Over-development resulted, which is perhaps today one of the fundamental causes for the many difficulties faced by the coal industry, which is highly competitive; about 70 per cent of the production cost is labor. Salient statistics for 1930, recently issued by the U. S. Bureau of Mines, follow:

Jan 1, 1932

By L. Thomassen, N. Spooner, J. M. Thomas

NI-CR and some Ni-Cr-Fc alloys, when used as electrical resistance heating elements in reducing atmospheres, at times suffer rapid breakdowns due to so-called "green rot." These reducing atmospheres are most frequently used in bright annealing and heat-treating furnaces which are kept for long periods of time at 1500' to 1800°F. The green rot is a preferential oxidation of the chromium in the alloy to such an extent that the remaining metal frequently becomes ferromagnetic. The Curie point (magnetic transition point) at room temperature for a pure Ni-Cr alloy is known to be at about 7 pct Cr.¹ This represents a severe loss in chromium for one popular grade of resistance alloy, which is nominally 80 pct Ni-20 pct Cr. The formation of oxides along the grain boundaries makes the ribbon brittle and gives the fracture a green, earthy appearance—hence the name. The authors have studied this phenomenon, simulating the industrial conditions by heating resistance ribbons in various reducing atmospheres, such as moist hydrogen or the atmosphere specified in the ASTM test.² This atmosphere contains 16 pct H2, 10 pct CO, 4 pct C02, 1 pct CH1, 1.5 to 2.5 pct H2O, balance N2. Little success was had in producing severe corrosion with the commercial 80 pct Ni-20 pct Cr alloys. It had been noticed, however, that 90 pct Ni-10 pct Cr alloy wires deteriorated very rapidly when placed in the bottom of narrow thermocouple protection tubes. The bottoms of the tubes with the wires were heated in air. This took place both in porcelain tubes and in Inconel* tubes either with the cold end open or loosely stoppered with asbestos. On examination the wires showed microstructures which would be classified as green-rot corrosion. Subsequent investigations with various alloy wires confirmed the observation that corrosion occurred in some wires, including 80 pct Ni-20 pct Cr alloys, much more rapidly in such tubes than had occurred previously in test atmospheres mentioned above. When 90 pct Ni-10 pct Cr alloys are oxidized with an abundant air supply, the oxide coat consists of both nickel and chromium oxides. In this case thermodynamic equilibrium between the oxides is not established. However, when oxidized 90 pct Ni-10 pct Cr alloy specimens were heated to 1500" to 1800°F inside small diameter tubes, the oxide coat transformed to a bright metallic outer layer of nickel or nickel-rich alloy, beneath which appeared a green oxide, followed by intergranularly attacked metal. The obvious explanation is that in the narrow tubes, thermodynamic equilibrium is being established according to the equation NiO + Cr (in alloy) ? Ni + Cr2O3 This reaction is favored due to the fact that the oxygen pressure over nickel oxide is more than 10"' times the oxygen pressure over the green chromium oxide. The initial oxygen in the tubes is depleted very rapidly by oxidation of the wire and of the tube, if it is metallic. A confirmation of the occurrence of the reaction, reduction of NiO by the chromium in the alloy, was obtained by putting oxidized nickel foil into an evacuated quartz tube along with a piece of bright 90 pct Ni-10 pct Cr alloy ribbon, and heating the tube at 1820°F for a number of hours. The nickel oxide on the foil was completely reduced to pure nickel, leaving a bright foil. The 90 pct Ni-10 pct Cr alloy became strongly magnetic and showed the typical green-rot structure. Weights of the samples before and after testing showed the weight loss of the foil to approximately equal the weight gain of the ribbon. Evidently the bottom of long, narrow protection tubes, stoppered or not, may under certain conditions act just as the sealed quartz tubes in respect to being a confined space in which oxygen is not freely replenished. This condition of oxygen depletion can be prevented by introducing a small amount of air into the bottom of the tube. Many conditions becloud the green-rot phenomenon, such as carburization, sulphidization, and the presence of other corrosive agents. However, these experiments have shown that the basic reaction is a case of internal oxidation which can occur simply by adjusting the oxygen pressure to a low enough level so that the atmosphere will leave the nickel intact and oxidize the chromium. The action of the other agents in commercial atmospheres can then be taken up as individual cases. From these and numerous other tests completed to date or still in progress, it is believed that a more critical evaluation of electrical resistance alloys for their resistance to green-rot corrosion can be made. A much better understanding of the mechanism for this type of corrosion should also result. A more complete report on these experiments will be published later. In the May 1953 issue: TP 35213 Discussion: Solubility of Carbon and Oxygen in Molybdenum by W. E. Few and G. K. Manning, discussion by N. A. Gokcen: p. 747, first column, the fifth, sixth, and seventh lines should be the first, second, and third lines, followed by the present first, second, third, fourth, eighth, ninth, and tenth lines.

Jan 1, 1954

By J. A. Rowland, C. W. Funk

THIS investigation is a part of the United States Bureau of Mines work in conserving the Nation's resources. The isothermal sections presented were developed as a guide to a comprehensive investigation of the properties and fabricating characteristics of copper-base alloys containing manganese and tin. These alloys are being investigated as possible replacements for the commercial bronzes containing substantial quantities of tin. Development of the isothermal sections has, therefore, been limited to the area between 0 to 20 pct Mn and 0 to 25 pct Sn. Since Heusler1 reported the ferromagnetic properties of the Cu-Mn-Sn alloys in 1903, the system has been the subject of several investigations. These studies were largely concerned with correlation of magnetic properties and crystal structure.2-6 Vero,' however, established the solidus surface of the system, between 20 pct Mn and 40 pct Sn, by thermal and microscopic methods. The a, ß, and y solid solutions were also observed by Vero and reported to extend into the interior of the ternary system. For the present study, the annotated diagram of the Cu-Sn system prepared by Raynor' and the Cu-Mn diagram by Dean and coworkers9 were used as the binary borders of the ternary system. Procedure The metals used in this investigation were electrolytic manganese, washed cathode copper, and three-star tin. The manganese, produced at the Boulder City pilot plant of the Bureau of Mines, had a purity of 99.9 pct; the copper contained less than 0.004 pct Bi and 0.001 pct S; the tin contained 0.070 pct Pb, 0.070 pct Sb, 0.050 pct Fe, and 0.065 pct Si. Heats of 1 lb were melted in alundum crucibles with a 3-kw induction furnace. The heats were chill-cast in iron or copper molds to form 6-in. ingots 3/4 in. in diameter. Molds were washed with graphite or zirconia, depending on the manganese content, and preheated to 150°C. The maximum impurity content of any alloy was 0.03 pct Fe, 0.02 pct Si, and 0.02 pct Al; in most cases, they contained less than half this quantity of any of these impurities. Composition of the alloys and their treatment prior to homogenizing are shown in Fig. 1. Designations adjacent to each composition refer to the heat numbers. With a few exceptions, ingots containing 20 pct Sn or less were hot-swaged. These ingots were swaged, after a 24-hr preheat at 650°C, to obtain a total reduction of 70 pct in cross section. Intermittent reheating was necessary, and reductions were limited to either 0.025 or 0.050 in. in diameter per pass. Selection of a 200-hr homogenizing treatment was based on extensive experiments which indicated that virtual equilibrium was reached after 150 hr. Structures were retained by quenching in water. Grain sizes in the specimens homogenized at 350" and 450°C were generally small. These homogenizing treatments were preceded by a 50-hr anneal at 650°C to facilitate phase identification by increasing the grain size in these specimens. The specimens were furnace-cooled from this temperature to the homogenizing temperature, and the heat treatment was continued for the standard 200-hr period. The homogenized samples were bisected to provide an internal section for metallographic examination. Optimum definition of the microstructure was obtained by successive polishing and etching. Quarter-strength ASTM copper reagent No. 13 gave the most satisfactory results.10 Filings from interior sections of the samples were used for diffraction studies. These filings were annealed in evacuated glass tubes at homogenizing temperatures for periods exceeding 50 hr and quenched in water. During this treatment the manganese content was reduced by significant amounts, probably by vaporization. This change in composition was considered in applying the diffraction data, which were used only as a means of identifying phases where the data were consistent with the metallographic evidence. Phase Identification The a solid solution is readily distinguished by the copper-colored, twinned, polyhedral grains, as shown in Fig. 2, and a face-centered cubic X-ray pattern. Tukon indentations, using a 25-g load, indicate a Knoop hardness of 155 for a quenched from 650°C. Using white light developed by a Wratten 78 A filter, the ß grains in etched specimens have a dark brown tint in contrast to the lighter copper-colored grains of the a phase. Knoop hardness values of 284 were obtained for the ß structure in specimens quenched from 650°C. The ß structure was also distinguished from the a phase by its body-centered cubic lattice. The acicular structure appearing in Fig. 3 was evident in several alloys of higher tin content after quenching from either 750' or 650°C. Since a trans-

Jan 1, 1954

(The following -list, contains the navies of those members of the Institute of whose connection with military service we have only recently become acquainted; it also includes the names of a few who have recently been promoted or transferred. A com-plete list was published in the Year Book, issued as a supplement of the Bulletin for March, 1918.) ADDICKS, LAWRENCE, Naval Consulting Board. ALINE, P. A., Camp Lewis. BARCUS, WALTER .J. E., Captain, Ordnance Department. BAUSH, JOHN R., Private, 1st Army Headquarters Regiment, Co. M. BENNETT, A. F., Lieutenant. BILLINGSLEY, PAUL, Engineer Officer, Aviation Section, Signal Officers' Reserve Corps. BOOTH, L. E., Ordnance Department. BROWN, JAMES F., 2d, 1st Lieutenant, Ordnance Reserve Corps, A. E. F.

Jan 4, 1918