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Report of the Secretary TO THE BOARD OF DIRECTORS AND THE MEMBERS OF THE AMERICAN INSTI¬TUTE OF MINING AND METALLURGICAL ENGINEERS GENTLEMEN As will be shown by the special reports of the Finance, Membership, Library, Papers and Publications, Increase of Membership, and other standing Committees, together with that of the Treasurer, the year 1927 was one in which the Institute made very satisfactory progress in a number of directions. In total numbers the membership is no larger but in revenue from dues there has been a marked increase. This has been due to the promotion to full membership of Junior Associates of earlier years, to the larger proportion that come in originally as members rather than juniors, and to the keener interest in the work of the Institute reflected in prompter payment of dues. The latter is important, since experience shows that of those who fall behind a large number must ultimately be dropped for non-payment. Conditions in the mining in¬dustries have been healthy though not booming. It has been much easier for members to find employment and meet their financial obligations but there has not been that flow of young men into mining, and hence in part into the Institute, that characterized certain earlier years. Rather the tendency toward centralization and larger industrial units has re¬stricted the number, though not the scope, of opportunities for technical men in the mineral industries. The Institute is constantly receiving resignations from members crowded out of mining into other lines of activity. On the other hand, those who remain in mining and metal¬lurgy have a greatly increased necessity for information and contacts with technology. A few years ago many superintendents and most foremen were non-technical men. Today the reverse rule obtains and shift bosses and men who occupy even lower positions in industrial units are called upon to know and to apply such an amount of technical knowl¬edge that graduate engineers are the rule rather than the exception. The curious situation has obtained that with a much smaller enrollment of students in the schools of mining and metallurgy there has been at times an actual shortage of young engineers for beginners' jobs. The young men retort that the conditions of employment and pay offered in mining are not equal to those in other lines and, while it is undoubtedly true that the young engineer beginning in mining is able to start under conditions markedly better as to pay, living, and responsibility than did the men who are now leaders, they are required to know much more and have usually spent more in time and money to qualify for their jobs. The whole matter is one which warrants much more attention than has been given to it. For the Institute it is important since the young men

Jan 1, 1923

By D. J. Mack, R. E. Reiswig

Six examples of the peritectoid transformation were selected from the literature and studied by the method of isothermal transformation. The kinetics and mechanisms of five of the examples are presented as TTT diagrams and photomicrographs. The exist-enc- of a peritectoid in the sixth case is doubtful. ALTHOUGH the peritectoid transformation per se has been known for many years, no precise published data exist concerning the kinetics or mechanisms involved in transformations of this type, except for the brief treatment by Rhines, et al. 1,10 Bearing in mind the fact that investigations of recent years are uncovering more and more peritectoids and suspected peritectoids, a thorough study of the well-established peritectoids appeared to be in order. It was for this reason that a study of the kinetics and morphological mechanisms of six binary peritectoids was undertaken. The six peritectoids selected from the literature for study were those reported at 7.02 wt pct Al-Ag, 26.0 wt pct Sb-Cu, 30.5 wt pct Sb-Cu, 32.3 wt pct Sn-Cu, 8.35 wt pct Si-Cu, and 21.2 wt pct Al-Cu. These selections were based on availability and purity of components, ease of preparation and heat-treatment, and estimated reliability of the available equilibrium diagrams in the regions of interest. EXPERIMENTAL PROCEDURE The alloys used in this investigation were induction melted in electrode-grade graphite and chill-cast in cast-iron split molds. In all cases, the alloys were so brittle that they could easily be broken into samples weighing 1 or 2 g. Chemical analyses showed that the alloys used were close to the respective peritectoid compositions reported in the literature and that the impurity levels were low in all cases. Metallographic examination showed uniform distributions of phases in all samples, indicating uniformity of composition in the samples studied. Isothermal transformation studies were carried out in fused-salt media, using the familiar inter-rupted-quench method. Uniformity of temperature in the salt baths was maintained by continuous stirring with a stainless-steel agitator. On the basis of actual observations of the temperature fluctuations, the estimated temperature control was + 10C for the Ag-Al and Cu-Sb alloys and ±30C for the Cu-Sn, Cu-Si, and Cu-Al alloys. The accuracy of all temperature measurements was estimated to be ±1°C. It was found necessary to mount metallographic specimens of the Ag-Al alloy in cold-curing methyl methacrylate, since the temperatures encountered in mounting in bakelite or lucite caused an appreciable degree of transformation to the ß phase. For the other alloys, wood-flour-filled bakelite mounts were used to avoid extraneous X-ray diffraction lines during the later examination of the metallographic specimens on a Norelco Geiger-counter d if f r ac tomete r. In the X-ray diffraction procedure, agreement between the published diffraction patterns and those obtained in this study was good. This was particularly important for phase identification, since the literature contained little in the way of micrograph description in some cases. Etching of the silver-aluminum alloy for metallographic examination was done by swabbing with either of the following reagents: 1) 10 g CrO3, 1 g (NH4), SO2, 0.5 g NH4NO3, 100 ml H2O, or 2) 10 ml NH4OH, 1 ml 20 pct KOH, 4 ml 3 pct H2O2, 5 ml H2O. The other alloys were etched with the usual bichromate etchant: 2 g K2Cr2O7, 1.5 g NaC1, 8 ml conc. H2SO4, 100 ml H20 (swabbed vigorously). EXPERIMENTAL RESULTS A) The Ag-Al peritectoid at 7.02 wt pct Al— The phase equilibrium involved in this peritectoid is shown in Fig. I.2 The phase boundaries in the vicinity of the peritectoid were most comprehensively established by Hume-Rothery, et al,3 who placed the equilibrium temperature at 448 °C and the equilibrium compositions of the a ß' and y phases at 6.11, 7.02, and 7.24 wt pct Al, respective The alloy used in this study analyzed4 6.95 wt pct A making it slightly hypoperitectoid according to the accepted equilibrium diagram. The rate of the transformation a+ y — ß' varies rapidly with degree of undercooling below the equilibrium temperature, passing through a maximum in the vicinity of 350°C. Thus the TTT dia-

Jan 1, 1960

By AIME AIME

A PERIOD of business depression and falling prices always raises questions as to the possible responsibility of the monetary or banking system. This is natural enough, for it is agreed that the supply of money or credit is a very important factor in modern business and in prices. However, it is far from being the only important factor. One of the chief merits of the gold standard is that under its workings the supply of currency and credit is regulated automatically to the masimun extent, in- stead of by the control of any arbitrary authority. The supply of new gold comes from the mines, and mining is free. It is distributed among the countries by the currents of trade and the play of economic forces, with the general result that the distribution tends to be in accordance with the economic development of the countries and their ability to use it or command it. Inasmuch as the accumulated stock of monetary gold is very large in comparison with the annual additions, the total avail- able supply changes but little from year to year, and it may be assumed that price-changes that are properly chargeable to gold will take place gradually rather than suddenly.

Jan 1, 1930

By George D. Dub

Owens Lake is at present a source of important nonmetallic minerals, sodium carbonate (soda ash, Na2CO3); sodium sesquicarbonate (trona, Na2CO3.NaHCO3.-2H2O) and borax, (Na2B4O7.10H2O). Owens Lake is a closed basin in the southern part of Inyo County, California, at the southern end of Owens Valley, east of the Sierra Nevada Mountains and west of the Coso and Inyo Mountains. Broadly considered, it is in the Great Basin area, but at no time was it a part of Lake Lahontan. Closed Basins Closed basins are phenomena of arid or semiarid regions where outflow is considerably less than inflow and where accordingly soluble salts concentrate in residual liquid. When inflowing waters originate in areas where the rocks are predominantly marine sediments, the residual basin liquid is primarily a chloride, brine; if the rocks are largely igneous, the residual brine tends to be alkaline containing carbonates, and sometimes borates as well. Since normally, both types of rocks occur in regions contiguous to closed basins, residual liquids do not often fit into the two broad divisions mentioned. No two residual brines are exactly alike, just as no two ore deposits are exactly alike. Even out of the same closed basin, it is possible to get widely different analyses of liquids since underground and surface flows, as well as local evaporation rates and other conditions might have a marked influence on residual-liquid compositions. At Searles Lake, The American Potash and Chemical Corporation is building a plant to process a lower-level brine which is considerably higher in sodium carbonate and borax, and lower in potassium chloride, than that company has processed for many years. F. W. Clarke1 has classified waters of closed basins as follows: I. Chloride type; largely sodium chloride (NaC1) and of oceanic type, such as Great Salt Lake. Related is -the Dead Sea, a bittern residue of magnesium, potassium and sodium chlorides. a. Sulphate type; largely sodium sulphate (Na2SO4) with considerable sodium chloride such as Sevier Lake, Utah; Laramie Lakes, Wyoming; Dale Lake, California. 3. Carbonate type; high in carbonates and fairly high in sulphates, such as Moses Lake, Eastern Washington; and the Nebraska Potash Lakes. 4. Carbonate—chloride type; lower in carbonates than type 3 and about equally rich in sulphates, such as Pyramid Lake, Nevada. 5. Sulphate—Carbonate type; quite high in sulphates and carbonates, such as Pelican Lake, Oregon. 6. Triple type; considerable quantities of carbonates, sulphates and chlorides

Jan 1, 1948

By George D. Dub

Owens Lake is at present a source of important nonmetallic minerals, sodium carbonate (soda ash, Na2CO3); sodium sesquicarbonate (trona, Na2CO3.NaHCO3.-2H2O) and borax, (Na2B4O7.10H2O). Owens Lake is a closed basin in the southern part of Inyo County, California, at the southern end of Owens Valley, east of the Sierra Nevada Mountains and west of the Coso and Inyo Mountains. Broadly considered, it is in the Great Basin area, but at no time was it a part of Lake Lahontan. Closed Basins Closed basins are phenomena of arid or semiarid regions where outflow is considerably less than inflow and where accordingly soluble salts concentrate in residual liquid. When inflowing waters originate in areas where the rocks are predominantly marine sediments, the residual basin liquid is primarily a chloride, brine; if the rocks are largely igneous, the residual brine tends to be alkaline containing carbonates, and sometimes borates as well. Since normally, both types of rocks occur in regions contiguous to closed basins, residual liquids do not often fit into the two broad divisions mentioned. No two residual brines are exactly alike, just as no two ore deposits are exactly alike. Even out of the same closed basin, it is possible to get widely different analyses of liquids since underground and surface flows, as well as local evaporation rates and other conditions might have a marked influence on residual-liquid compositions. At Searles Lake, The American Potash and Chemical Corporation is building a plant to process a lower-level brine which is considerably higher in sodium carbonate and borax, and lower in potassium chloride, than that company has processed for many years. F. W. Clarke1 has classified waters of closed basins as follows: I. Chloride type; largely sodium chloride (NaC1) and of oceanic type, such as Great Salt Lake. Related is -the Dead Sea, a bittern residue of magnesium, potassium and sodium chlorides. a. Sulphate type; largely sodium sulphate (Na2SO4) with considerable sodium chloride such as Sevier Lake, Utah; Laramie Lakes, Wyoming; Dale Lake, California. 3. Carbonate type; high in carbonates and fairly high in sulphates, such as Moses Lake, Eastern Washington; and the Nebraska Potash Lakes. 4. Carbonate—chloride type; lower in carbonates than type 3 and about equally rich in sulphates, such as Pyramid Lake, Nevada. 5. Sulphate—Carbonate type; quite high in sulphates and carbonates, such as Pelican Lake, Oregon. 6. Triple type; considerable quantities of carbonates, sulphates and chlorides

Jan 1, 1948

By J. M. Boutwell

I. Introduction. THE object of this paper is to present a concise statement on the genesis of the copper- and lead-deposits of the Bingham Mining District, Utah. It is essentially a condensation of a chapter in a detailed report on this district, together with so much on geologic features, and on the character and occurrence of the ores as bears on the problems of ore-deposition. The studies upon which the paper is based were undertaken in 1900 under the direction of S. F. Emmons, Geologist-in-Charge of the Section of Metalliferous Deposits, U. S. Geological Survey; and a little additional data was secured in subsequent years. The evidence then obtained as to the genesis of the replacement copper-ores has led, to conclusions which differ somewhat from explanations hitherto current. Accordingly, it seems desirable briefly to present the facts together with the resulting conclusions in a separate paper.

Nov 1, 1905

By James Douglas

THOUGH liberality is not supposed to be a prominent trait of the Scottish character, Canada owes to a Scotchman, Sir Wm. Macdonald, more than to any other of its people, not only wise ideas, but pecuniary help towards extending education: and another Scotchman, in New York, has sumptuously housed under one roof three branches of the engineering fraternity, of which we are one. Having thus created us members of the same family-for the metaphorical meaning of house and kinship is identical-Mr. Carnegie expresses more emphatically than even he could in words, that, by affording facilities for closest intercourse, he in¬vites the mechanical, electrical and mining engineers to par¬ticipate in the freest interchange of idea and experience, and to correlate and combine the results of their studies and activi¬ties; and, being members of the same household, to banish re¬serve and secrecy. And now we, the members of the - American Institute of Mining Engineers, meet as though we were at home in a neighboring country. For whether we meet in Canada, in England, or elsewhere, the Institute is always received as though no political or geographical divisions separated its members from those of congenial associations in the land of its host. In truth, the title which we have assumed claims for the sphere of our activities the whole American continent, regardless of such trifling details as boundary-lines. The fact that we meet to communicate each other's experience, to discuss our difficulties, and to seek each other's aid in solving the intricate problems that so often present themselves in the course of our profes¬sional life, is an acknowledgment of our individual helpless¬ness; and therefore an argument for united effort. But no effort can be of any value if there is an underlying suspicion

Jan 9, 1907

By W. A. Backofen, N. E. Paton

DEFORMATION twinning contributes to the plasticity of titanium and has been reported on {10i2}, {1121},{11221}, {1123}, and {1124} planes.' Twinning on {1011} has also been reported in commercially pure titanium as a result of quenching from 1000', but no reports of such twins occurring as a result of deformation alone are known to the authors. In this study single crystals grown from iodide titanium were compressed parallel to the c axis over the temperature range 25 to 800°C. From it has come evidence that (10il) deformation twins are the most common type between 400" and 800°C. Crystals about 6 mm high with a rectangular cross section measuring about 3 by 4 mm were used in the tests. Chemical analyses showed them to contain 220 to 250 ppm 0 arid 10 to 15 ppm N. The long axes of the crystals were made parallel to the c axis while the sides were parallel to (i100) and (1120), as shown in Fig. 1. The crystals were compressed between polished alumina platens with no lubrication, in a vacuum of 2 x lom5 torr. Between 25' and 300°C the predominant twinning mode was (11221, which is to be expected for this stress state. There was an abrupt change at 400°C, however, and from that temperature up to 800°C twinning took place almost entirely on (10i1 ). Twin planes were determined by the two-surface rnethd. Measurement of the crystal orientation within several (10i1) twins by means of polarized-light4 and transmission electron microscopy showed that the lattice reorientations were the same as those previously reported for the (10i l ) twinning in magnesium.' This reorientation is consistent with The calculated (10il ) twinning shear for titanium is 0.10, while that measured from surface offsets on a (1150) face, which is parallel to the shear direction, was about 0.15. Slip within the twins, or in the matrix adjacent to the twins, probably accounts for the larger measurement. Slip in both locations was judged to have occurred from observations on foils in the electron microscope.

Jan 1, 1970

All the TECHNICAL PUBLICATIONS and CONTRIBUTIONS published in 1933 are available at Institute headquarters, unless otherwise noted. They are also on file in many public, university and technical libraries and, when so indicated in the list, may be found in the TRANSACTIONS. Copies of the TECHNICAL PUBLICATIONS have been mailed to those members of the Institute who are registered in the different classes: A-Metal Mining; B-Milling and Concentration; C-Iron and Steel Division; D-Nonferrous Metallurgy;. E-Insti¬ tute of Metals Division; F-Coal Division; G-Petroleum Division; H-Nonmetallic Minerals; I-Mining Geology; J-Mineral Industry Education Division; K-Mining Administration; L-Geophysical Prospecting. Other members may obtain copies by writing to the Secretary. Copies of CONTRIBUTIONS may also be obtained from the Secretary's office. Additional copies are sold at the rate of 1 cent per page; minimum charge, 25 cents. Nonmembers may purchase the papers at the prices mentioned. METAL MINING TECH- NICAL PUBLI- TITLE AUTHOR MEETING TRANS. CATION VOLUME No. AND PAGE* 499-A.47 Red Ore Mines of the Woodward T. C. DeSollar New York, Iron Company at Bessemer, Feb., 1933 Alabama (11) CONTRI¬ BUTION No. 1-A The Owyhee Tunnels (16) P. R. Hines New York, Feb., 1933 2-A Sinking and Equipment of the No. D. D. Homer New York, 2 Shaft at Minas de Mata- R. H. Cromwell Feb., 1933 hambre (25) 3-A Subsidence Resulting from the Charles W. Allen New York, Athens System of Mining at Feb., 1933 Negaunee, Michigan (8) 4-A Effect of Approximately Vertical P. B. Bucky New York, Cracks on the Behavior of Hori- Feb., 1933 zontally. Lying Roof Strata (16) 21-A Selection of a Mining System (11) R. K. Warner New York, Feb., 1933

Jan 1, 1933

By S. S. Lau

The authors of the previous comment stated that Dorn and Rajnak33 and others34-40 concluded that "agreement with this function [(t'/tp) -f(Un/2Un) = T/Tc} may be used as a criterion for that (the Peierls) mechanism of deformation". In contrast, however, Dorn and Rajnak33 and others34-40 never made such a statement. In order to clarify the issues involved it is appropriate to recapitulate the conditions that must be satisfied in order to suggest that some deformation process might obey the Peierls mechanism: 1) Within permissible variations due to changes in the slope of the Peierls hill the T*/Tp - T/Tc relationship must be obeyed. Although some mechanisms, e.g.. solute atom stress field, recombination of dissociated partials in bcc metals, intersection of dissociated dislocations, and so forth, give about the same t* - T relationship, other mechanisms, such as cross slip, disruption of attractive junctions, climb, motion of jogged screw dislocations, and so forth, give distinctly different t*-T relationships. On this basis some distinction can be made of the various mechanisms. 2) An important feature of the Peierls mechanism concerns its physical origin based on the nucleation of pairs of kinks. The value of T* at 0°K increases with the density of dislocation (i.e. , cold work) for the intersection mechanism and it increases with the square root of the atomic fraction of solute atoms in the solute atom interaction mechanism. In contrast the value of t* at 0°k, for the Peierls mechanism which depends only on the line energy and the shape of the Peierls hills. is independent of cold working and the square root of the solute atom concentration. These differences have been employed by various investigators for elimination of a few other possible mechanisms. On the other hand it is not possible to eliminate all mechanisms, e.g., the recombination of dissociated dislocations in bcc metals, and so forth, on this basis alone. 3) Further discrimination between possible mechanisms is based on the activation volume. For the in-

Jan 1, 1968

By Leonard R. Weisberg

The general properties of diffusion in GaAs are reviewed. A total of .fourteen atoms have been studied to date, and activation energies for eleven reported are (in ev): Ga (5.6), As (lo), Zn (2.49), Cd (2.43), Sn (2.5). Mn (2.75). S (4.0). Se (4.2). Ag (0.33), Cu (0.52). and Li (1.0). The dijfusion of the first eight atoms, as measured by Goldstein using radiotracer techniques, established the principle of sub lattice diffusion for both host and impurity atoms, since atoms substituting for gallium have lower activation energies than those substituting for arsenic. The diffusion constant of interstitial copper has been determined for the first time by Hall and Racette using heavily doped p-type samples in which interstitial copper predominates. The anomalous behavior of zinc, which has an abrupt diffusion front and a strong dependence on zinc concentration, has recently been quantitatively explained in terms of an interstitial-substi-tutional equilibrium-diffusion mechanism. Lithium and silver diffuse mainly interstitially, while the diffusion of phosphorus is complicated by the continual formation ofGap. Junction-migration measurements indicate diiferent results than radiotracer techniques, and this is one problem that still remains, together with discrepancies in cadmium-diffusion results, and an unexplained dependence of impurity diffusion on arsenic pressure. BESIDES the usual insights into the behavior of atoms in solids, studies of diffusion in semiconductors have additional importance for device applications. In fact, the amount of diffusion studies performed on a semiconductor might serve as a simple barometer of its technological importance. Thus, the information accumulated for GaAs is not yet quite comparable to that for germanium or silicon, but considerable knowledge is available. The diffusion of at least fourteen atoms has been investigated for GaAs, and the diffusion constants have been determined for eleven of these. Interesting results were found for GaAs that elucidated problems not previously solved for germanium or silicon. For example, the interstitial-diffusion constant for the very fast diffusant, copper, was first measured in GaAs. Also, solutions for interstitial-substitu-tional equilibrium diffusion in extrinsic material were provided first for GaAs, although they are ap- plicable to germanium, silicon, and other semiconductors. Studies in GaAs firmly established the concept of sublattice diffusion, which should have application in many different compound systems. The purpose of this paper is to review briefly the general state of knowledge concerning diffusion in GaAs. First some general aspects of diffusion will be covered, and next attention will be given to the results mentioned above. Diffusion in GaAs has been measured both by radiotracer and junction-penetration techniques, and some discussion will be given of differences in the two sets of results. The comprehensive work of oldsteinl-' has served as the primary reference for the diffusion of well-behaved substitutional atoms in GaAs. Since a review has recently been presented of many of these reults, details of the diffusion data will not be repeated. Neither will any discussion be given of the experimental techniques of diffusion measurements, except to note here, in passing, the simplicity and effectiveness of the precision lapping device employed by Goldstein.' I) EXPERIMENTAL RESULTS AND DISCUSSION A) Summary of Experimental Results. Diffusion constants D = Do exp(E/kT) have been determined for eleven atoms in GaAs: a,' AS,' n,'" Cd,'" n,' n,8 s, e,' Ag,O CU," and i." These results are summarized in Table I. In addition, diffusion was investigated for phosphorus,4'12 germanium,I3 and ilicon,' but Do and E were not determined. Radiotracer techniques were used for most of the studies except for lithium, where a combination of chemical and electrical techniques was employed, and germanium and silicon, where junction-migration techniques were applied. The diffusion of zinc, manganese, sulfur, and tin was also measured using junction migration.13'14 Goldstein demon-

Jan 1, 1964

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 Charles R. Keyes

PAGE. I Introduction,........674 11. Occurrence............ 676 III. Geology of Death Valley BoRate-Region,....677 1. Surface.Relief ......677 2. Geologic Formations,....680 3. Geotectonics,..684 IV. FURnace Canyon Deposits..686 1. General Features..686 2. Geologic Structure..688 3. Ores.....690 4. Typical Section ...691 V. Lost Valley Deposits...693 VI. Mojave Desert Deposits..693 1. Distribution....693 2. Geologic Structure ........694 3. Ores............ 696 VII. Santa Clara Valley Deposits .699 1. Distribution....699 2. Geologic Structure..700 3. Ores.....700 VIII. Ventura County Deposits..701 IX. Geologic Occurrence of Borax .701 1. Original Sources...701 2. Solfataric Borax...702 3. Lacustrine Borax...703 4. Marsh Borax....703 5. Terranal Borax...704 X. Chemistry of Natural Borates.... 705 1. General Considerations.....705 2. Composition of Saline Waters...706 3. Solubility of Components....707 4. Time-Element in Water.Concentrations . 707 5. Effect of Temperature.....708 6. Effect of Pressure......709 XI. Occurrence of Other Commercial Salines,.... 709 I. Introduction. A complete transforrnation has taken place in the borax industry during the year 1908. A most remarkable factor in

Jan 1, 1910

Member ship L P MATHEWSON, Chairman GEORGE D BARRON LOUIS D HUNTOON JOHN A CHURCH, JR H N SPICER Alternates LEWIS W FRANCIS WILBER JUDSON F T RUBIDGE Increase of Membership JOHN A CHURCH, JR, Chairman Other members to be appointed

Jan 1, 1923

PRESIDENTS DAVID THOMAS 1871 R W RAYMOND 1872-1874 A L HOLLEY1875 ABRAM S HEWITT 1876 T STERRY HUNT 1877 ECKLEY B COXE 1878 - 1879 WILLIAM P SHINN 1880 WILLIAM METCALF 1881 RICHARD P ROTHWELL 1882 RICHARD W HUNT 1883

Jan 1, 1917

PRESIDENTS DAVID THOMAS 1871 R W RAYMOND 1872-1874 A L HOLLEY1875 ABRAM S HEWITT 1876 T STERRY HUNT 1877 ECKLEY B COXE 1878 - 1879 WILLIAM P SHINN 1880 WILLIAM METCALF 1881 RICHARD P ROTHWELL 1882 RICHARD W HUNT 1883

Jan 1, 1917

PRESIDENTS DAVID THOMAS 1871 R W RAYMOND 1872-1874 A L HOLLEY1875 ABRAM S HEWITT 1876 T STERRY HUNT 1877 ECKLEY B COXE 1878 - 1879 WILLIAM P SHINN 1880 WILLIAM METCALF 1881 RICHARD P ROTHWELL 1882 RICHARD W HUNT 1883

Jan 1, 1917

By P. R. Gage, R. W. Bartlett

At high temperatues and reduced oxygen pressuves, molybdenum silicicles oxidize to form SiO(g) vathev than a passivating SiO2 film. This is a sevious problem for low-pressure applications of sili-cide-coated rejvactory tnetals. As oxiclalion pvoceeds, the higher oxidntion potential of silicon initially suppresses oxidation of molybdenum and silicon is depleted near the surface. Eventually, silicon depletion causes secondary passivation (SiO2) mid an active to passiue transition in oxidntion behavior at moderately low pressures. At very low pressures, silicon depletion continues until steady-state oxidation of both silicon and rnolyhdenum can proceed at rates propovtional to their initial stoicliiorrzetvies. Ohsel-vations of 'oxidatiou-rate belzcriliov at temperatures from 1101° to 1700°C and oxygen pressures from 10-7 to 1 at in were made using thermogravimetn'c, X-ray diffraction, and elect?*on-rtric?ro/,vobe techniqrres. The experimental results are in good agreement with calculated lirnits for the various types of behavior that were based on tlievtnochernicnl atzd dffusion rate data for the Mo-Si system. A protective oxide film normally forms during the oxidation of elemental silicon. However, at elevated temperatures and reduced pressures this film is not present and oxidation is rapid. wagnerl has shown that this behavior occurs because SiO(g) is more stable than SiO2. The behavior of the silicides at high temperatures is similar but more complicated. Molybdenum and several silicide compounds are involved and the chemical activity of silicon, or the equivalent silicon vapor pressure, can vary considerably in these phases. Also, diffusion in the silicides resulting from reactions in which a higher silicide is reduced to a lower silicide, or molybdenum containing dissolved silicon, must be considered. EXPERIMENTAL AND ANALYTICAL METHODS Isothermal oxidation experiments were conducted using hot-pressed MoSi2 and Mo5Si3 wafers. Each experiment was conducted at a fixed oxygen pressure by controlling the flow of oxygen in and out of the furnace chamber. Most of the experiments were conducted in a molybdenum-wound tube furnace. Special construction features, including use of a high-purity dense A12O3 refractory tube, permitted operation in high vacuum to 1500°C. Higher temperatures could be obtained at higher working pressures and with a sacrifice of tube lifetime. Temperature was measured with three Pt 6 pct Rh/Pt 30 pct Rh thermocouples and controlled with a proportional controller. Weight changes were monitored with a quartz spring balance. The few experiments, at higher temperatures and low pressures, were conducted in a cold wall vacuum chamber using induction heating with direct susceptance of the sample. Because of the variable levitation effect of the induction coil on the sample, weight changes could not be monitored continuously in these experiments. All samples representing both experimental methods were weighed before and after oxidiation and examined with a microscope and analyzed by X-ray diffraction. The analytical treatment assumes equilibrium at interfaces and uses existing thermodynamic data. For convenience, equilibria are expressed as chemical potentials or as vapor pressures of the gases involved. The resulting differences in equilibrium vapor pressure between adjacent interfaces and between the surface and external atmosphere drive diffusion processes in the solid and gas boundary film, respectively. These diffusion processes govern the rate of oxidation. A bibliography of the sources of thermochemical data for the reactions pertinent to the Mo-Si-O system is given in Table I. Reactions are listed with the sources of free-energy data referenced. Since all of these reactions involve one or more gas species, usually oxygen, a plot of the product-gas chemical potential, -RT In Pg, vs absolute temperature for each reaction is given in Fig. 1. These curves can be used to determine equilibrium vapor pressures or to compare the stability of different compounds in the various gases: O2, Si, SiO, and Moo3,. The data of Table I and Fig. 1 were used to determine the analytical results presented in this paper. EXPERIMENTAL RESULTS The weight changes for three MoSi, samples oxidized at 1500°C are plotted against time in Fig. 2. The treatments were identical except for the indicated variance of oxygen pressure and each curve represents one of three characteristic types of behavior that were observed. The upper curve is an example of passive oxidation, which is defined as

Jan 1, 1965

PRESIDENTS DAVID THOMAS 1871 R W RAYMOND 1872-1874 A L HOLLEY1875 ABRAM S HEWITT 1876 T STERRY HUNT 1877 ECKLEY B COXE 1878 - 1879 WILLIAM P SHINN 1880 WILLIAM METCALF 1881 RICHARD P ROTHWELL 1882 RICHARD W HUNT 1883

Jan 1, 1917

Ferrous and Nonferrous Physical Metallurgy Established as a Division April 26, 1918 T A Read, Chairman O T Marzke, Past Chairman J H Jackson, Senior Vice-Chairman David Swan, Vice-Chairman D C Johnston, Secretary-Treasurer AIME, 29 West 39th Street New York 18, New York

Jan 1, 1960