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By Robert S. Williams

NO new ferrous alloys have been produced in the last five or six years that are as outstanding contributions to civilization as were the high-speed steels of the early part of the century or the stainless steels announced at the close of the World War. There have been, however, many developments of major importance having to do either with modifications of existing alloys or with new methods of treatment of older iron or steel alloys. Only a limited number of these new developments can be discussed and their selection does not necessarily imply that these are the most important but merely that they are of general interest rather than perhaps of greater importance in highly specialized fields.

Jan 1, 1939

By H. W. Gillett

Unlike most previous Howe lecturers, I had not the good fortune to be associated with Henry Marion Howe, nor to be directly one of his students. Yet, through his writings, he has been my teacher, as he has of all American metallurgists. Instructive as his writings are—I use the present tense because Howe thought so keenly and reasoned so surely, seeing clearly, as if by intuition, what was hazy to lesser minds, that his writings are still vital—it is not those books and papers, nor even the minds he trained in his classes, that were his most outstanding service. It was the spirit of Howe in his approach to the problems of metallurgy, his broad-mindedness and fairness, his recognition of the need for theories and hypotheses to explain metallurgical phenomena, his willingness to use them as servants, as well as his questioning attitude—his refusal to accept them as masters—that comprise his greatest service. This most thoroughly warrants the honor the Institute pays each year to his memory. These traits I so respect and honor in any man that I glory in this opportunity to do reverence to him in whom they were so notably united. Howe's Discussion of a Creep Problem I have often wished that Howe were still with us to turn his keen insight upon the problems of the use of metals at high temperatures, a field much studied but still very hazy. Indeed, 53 years ago, in a paper1 before this Institute, Howe stated a problem closely allied to some that still perplex metallurgists and engineers dealing with the high-temperature field. Howe was intrigued by a report2 from another old master, Robert Henry Thurston, on the behavior of annealed vs. cold-drawn iron wire, and in order to broaden the foundation for metallurgical generalization, Howe made experiments of his own on copper and silver. In these tests by Thurston and by Howe, the wires were rapidly loaded to determine the

Jan 1, 1939

By Albert E. Wiggin, Frederick Laist

Page I. Introduction............................470 II. The Sources and Amount of Slime................470 II. The Composition of the Slime..................471 IV. The Experimental Development of the .Anaconda Slime Plant.. 471 1. The Great Falls Slime Plant and Experimental Work......471 2. The Experimental Work Done at Anaconda..........473 (a) SlimeThickening Devices.............. 474 (b) SlimeConcentrators................. 475 (c) Dewatering the Slime Plant Concentrate......... (d) The Use of Chemicals to Accelerate the Settlement of Slime........................ 478 (e) The Effect of Temperature upon the Settlement of Slime 478 V. A Description of the Anaconda Slime Plant........... 479 1. A Diagrammatic Flow Sheet of Plant............. 480 2. The Slime-Thickening Division................ 480 3. The Concentrating Division.................. 481 4. The Concentrate-Dewatering Division............. 483 5. General Data........................ 484 I. IntRoduction The new slime-concentrating plant at the Washoe Reduction Works, Anaconda, was put into operation during March, 1914. This plant, which has a capacity of 26,000,000 gal. of slime pulp carrying 2,500 tons of solid matter per day, consists of Dorr thickeners and Anaconda multiple-deck slime concentrators. This plant is the culmination of a great deal of experimental work extending over a considerable period of time, which , work will be described briefly in the following pages. II. The Sources and Amount of Slime Up to the beginning of this year, the ore from the Anaconda company's mines in Butte, Mont., has been concentrated both at the Great Falls

Jan 1, 1915

By H. S. Munroe

The dressing-works of the St. Joseph Lead Company were destroyed by fire, February 26th, 1883. Within about four months, or on July 5th, 1883, the new mill, with a capacity of 500 tons per day, was built and in active operation. The capacity of the new mill has since been increased to 800 tons per day. The old mill was built in 1867, by Mr. C. B. Parsons, the present superintendent. It was a curious rambling old structure, which had grown with the demands of the business; a few jigs having been added in one place, a table or two in another and wings and sheds added to the main buildings, from time to time, as it was found necessary to increase the efficiency or the capacity of the mill. The old mill was, moreover, a most interesting place to the student, a perfect "museum of ore-dressing." Nearly every form of dressing apparatus known to the art had, at one time or another, found a place under its roof, jigs of many kinds, concave, convex, side-bump and stationary tables, tyes, buddles, dolly-tubs, etc., etc. The method of dressing followed in the main the lines of English practice, but with many modifications, both in the machinery and the methods of working, due to the inventive genius of Mr. Parsons. Different forms of crushing apparatus were tried, and the best method of handling the ore and the different products of

Jan 1, 1889

Edward Keller, Baltimore, Md. (communicatioin to the Secretary*):—It is pleasing to note the increasing amount of work on metallurgical problems that is being carried on by exact scientific methods, and the results of such labor issued by the laboratories of our universities. Without doubt, Mr. Bolles's paper will be welcomed by all progressive practitioners. Many of the results which Mr. Bolles presents to as are new; and I take exceptioil to a few minor points only. The first of his concluding remarks is as follows: "Mattes are not homogeneous, but are composed of distinct mineral entitier, and may be likened to igneous rocks, in which the mineral constituents fall out upon the lowering of the temperature and ensuing solidification." He quotes an introductory remark to a paper1 of mine, as follows: "The true chemical character of copper-mattes does not yet seem to have been definitely determined, i.e, it is still more or less of an open question whether they are true chemical compounds, or mixtures, such as igneous rocks." This quotation, taken alone, would convey the impression that Mr. Bolles's conclusion is entirely new. Had he quoted also another paragraph from my paper in question, it would be clear that he was, to a certain extent at least, anticipated. I take the liberty, therefore, to state the substance of my own work. In the paper referred to, I showed the existence of the phenomenon of liquation in mattes, and, continuing, said: " A more direct method to test whether a matte is a compound sulphide or a mixture of individual sulphides was attempted by applying hydraulic separation. A clean piece of matte was selected containing practically no magnetic oxide and of the following composition: Cu, 37.96; S, 24.45; Fe, 33.63; Zn, 1.25; Pb, 1.02 ; Sb, 0.26 ; As, 0.065 ; insoluble, 1.15 per cent. ; Ag, 26.7 ; Au, 0.04 oz. per ton. For such a test it is essential to select a chemically uniform piece, other-

Jan 1, 1905

LIST OF THE MEETINGS OF THE INSTITUTE AND THEIR LOCALITIES FROM ITS ORGANIZATION Transactions Number Place Date Vol Page 1 Wilkes-Barre, Pa May, ?71 1 3 2 Bethlehem, Pa August, ?71 1 10 3 Troy, N Y November, ?71 1 13 4 Philadelphia, Pa February, ?72 1 17 5 New York, N Y May, ?72 1 20 6 Pittsburg, Pa October, ?72 1 25 7 Boston, Mass February, ?73 1 28 8 Philadelphia, Pa May, ?73 2 3 9 Easton, Pa October, ?73 2 7 10 New York, N Y February, ?74 211 11 St Louis, Mo May, ?74 3 3 12 Hazleton, Pa October, ?74 3 8 13 New Haven, Conn February, ?75 3 15 14 Dover, N J May, ?75 4 3 15 Cleveland, 0 October, ?75 4 9 16 Washington, D C February, ?76 4 18 17 Philadelphia, Pat June, ?76, 5 3 18 Philadelphia, Pa October, ?76 5 9 19 New York, N Y February, ?77 5 27 20 Wilkes-Barre, Pa May, ?77 6 3 21 Amenia, N Y October, ?77 6 10 22 Philadelphia, Pa. May, ?78 6 18 23 Chattanooga, Tenn May ?78 7 3 24 Lake George, N.Y. Oct. ?78 7 25 Baltimore, Md. Feb. ?79 7 26 Pittsburgh Pa, May ?79 8 27 Montreal, Canada Sept, ?79 8 28 New York, N.Y. Feb, ?80 9 29 Lake Superior, Mich Aug, ?80

Jan 1, 1923

Jan 1, 1966

By F. R. Koeberlin

ABOUT thirty miles south of the port of Coquimbo, Chile, nestling in one of the western outliers of the main Andes range, lies the little mining town of Andacollo, a place whose history and traditions make up one of the most romantic pages in the life story of this southern republic. The beginning of Andacollo is shrouded in the penumbra of the pre-Columbian era, but its first mining activity probably dates from about the years 1440 to 1460. It was in the middle of the fifteenth century that the Inca Tupac-Yupanqui, grandfather of Atahualpa, conquered this part of Chile. His domain extended even as far south as the present site of Santiago, and perhaps farther, but was maintained with increasing difficulty against the fiercely independent and indomitable tribes of Araucanian Indians of the South.

Jan 1, 1938

LIST OF THE MEETINGS OF THE INSTITUTE AND THEIR LOCALITIES FROM ITS ORGANIZATION Transactions Number Place Date Vol Page 1 Wilkes-Barre, Pa May, ?71 1 3 2 Bethlehem, Pa August, ?71 1 10 3 Troy, N Y November, ?71 1 13 4 Philadelphia, Pa February, ?72 1 17 5 New York, N Y May, ?72 1 20 6 Pittsburg, Pa October, ?72 1 25 7 Boston, Mass February, ?73 1 28 8 Philadelphia, Pa May, ?73 2 3 9 Easton, Pa October, ?73 2 7 10 New York, N Y February, ?74 211 11 St Louis, Mo May, ?74 3 3 12 Hazleton, Pa October, ?74 3 8 13 New Haven, Conn February, ?75 3 15 14 Dover, N J May, ?75 4 3 15 Cleveland, 0 October, ?75 4 9 16 Washington, D C February, ?76 4 18 17 Philadelphia, Pat June, ?76, 5 3 18 Philadelphia, Pa October, ?76 5 9 19 New York, N Y February, ?77 5 27 20 Wilkes-Barre, Pa May, ?77 6 3 21 Amenia, N Y October, ?77 6 10 22 Philadelphia, Pa. May, ?78 6 18 23 Chattanooga, Tenn May ?78 7 3 24 Lake George, N.Y. Oct. ?78 7 25 Baltimore, Md. Feb. ?79 7 26 Pittsburgh Pa, May ?79 8 27 Montreal, Canada Sept, ?79 8 28 New York, N.Y. Feb, ?80 9 29 Lake Superior, Mich Aug, ?80 9 30 Philadelphia, Pa. Feb, 81 9 31 Staunton, Va May, 81 10

Jan 1, 1923

LIST OF THE MEETINGS OF THE INSTITUTE AND THEIR LOCALITIES FROM ITS ORGANIZATION Transactions Number Place Date Vol Page 1 Wilkes-Barre, Pa May, ?71 1 3 2 Bethlehem, Pa August, ?71 1 10 3 Troy, N Y November, ?71 1 13 4 Philadelphia, Pa February, ?72 1 17 5 New York, N Y May, ?72 1 20 6 Pittsburg, Pa October, ?72 1 25 7 Boston, Mass February, ?73 1 28 8 Philadelphia, Pa May, ?73 2 3 9 Easton, Pa October, ?73 2 7 10 New York, N Y February, ?74 211 11 St Louis, Mo May, ?74 3 3 12 Hazleton, Pa October, ?74 3 8 13 New Haven, Conn February, ?75 3 15 14 Dover, N J May, ?75 4 3 15 Cleveland, 0 October, ?75 4 9 16 Washington, D C February, ?76 4 18 17 Philadelphia, Pat June, ?76, 5 3 18 Philadelphia, Pa October, ?76 5 9 19 New York, N Y February, ?77 5 27 20 Wilkes-Barre, Pa May, ?77 6 3 21 Amenia, N Y October, ?77 6 10 22 Philadelphia, Pa. May, ?78 6 18 23 Chattanooga, Tenn May ?78 7 3 24 Lake George, N.Y. Oct. ?78 7 25 Baltimore, Md. Feb. ?79 7 26 Pittsburgh Pa, May ?79 8 27 Montreal, Canada Sept, ?79 8 28 New York, N.Y. Feb, ?80 9 29 Lake Superior, Mich Aug, ?80 9 30 Philadelphia, Pa. Feb, 81 9

Jan 1, 1923

Thomas H. Beddall, so we are informed by Major J. B. Carlock, has been promoted and is now Adjutant of the 1st Battalion, 1st Gas Regi¬ ment. He was awarded, last summer, the Croix de Guerre. R. A. Bull. See letter in Proceedings of Milwaukee Meeting. Captain Stanley C. Bullock's record since entering the service is given as follows in a letter recently received from Mrs. Bullock: Resigned position of mine manager in Chile in November, 1915, to return to England to obtain commission in Royal Engineers. Joined Officers' Training Corps, Dec. 20, 1915. Commission gazetted, Jan. 27, 1916, 2d Lieut., R. E. Landed in France, Feb. 6, 1916. Posted to 179th Tunnelling Co., R. E. Took part in following battles: Somme, 1916; Ypres;1917; Arras, 1917; Somme, March and July, 1917; Messines, 1917. Gazetted: Acting Captain, July 11, 1916; Temp.-Lieutenant, Oct. 26, 1916; Captain, Sept. 29, 1918. Awarded Military Cross, Jan. 1, 1918, for conspicuous bravery and devotion to duty under a heavy enemy gas bombardment, when, by his example and perseverance in spite of every difficulty and obstacle, mining work was successfully completed which was vital for the success of the operations. The Cross was presented to Capt. Bullock by the King, on Sept. 25, 1918. First Lieut. J. J. Cadot, in a letter sent to Mr. H. `V. Hardinge from France, says he has been at the "Front." He also mentions that the Boche "is a good sprinter."

Jan 12, 1918

By L. L. Wyman

THE exact nature of the changes that take place in the iron-nickel alloys, giving rise to the interesting and useful expansion alloys in the Invar range, has yet to be fully understood. Similarly, the ternary iron-nickel-cobalt alloys, which also possess such commercially useful expansion characteristics, 1,2 are concerned with transformations that appear to be identical with those found in the parent iron-nickel alloys. The investigations on iron-nickel alloys in the range 26 to 29 per cent Ni have been reported by several authors" wherein it is shown that there are factors other than temperature, such as stress and grain size, which play an important part in determining the temperature at which the low-temperature transformation takes place. It will be shown in this paper that the ternary iron-nickel-cobalt alloys having nickel contents comparable to the alloys mentioned above behave in a parallel manner. The alloys in the range of 26 to 31 per cent Ni and 16 to 21 per cent Co have a coefficient of expansion of about 4.0 X 10-1 per degree Centi-grade, and the alloys in this range of composition find considerable application in making glass-to-metal seals, because these expansion properties so well match commercial glasses. The behavior of these alloys is not a simple matter, for it has been observed in alloys of 28.5 per cent Ni and 18.5 Co that severe working can cause the appearance of a second phase having a needlelike structure similar to the martensite structure in carbon steels. Fig. 1 shows the change brought about in an alloy of this composition when a strip of this material was cut with tin shears. This second phase has been identified as the body-centered cubic alpha phase, and it is the purpose of this paper to describe the results of some of the preliminary investigations in the study of the changes involved in these alloys.

Jan 1, 1939

Aamot, Olav Crone, (Member '29) Met , Det Norske Aktieselskab for Elektrokemisk, Industry, Inc , Oslo, Norway Aase, Glenn D , (Junior Member '40) Met Engr , Western Research Dyv , American Smelt & Refin Co , Selby, Calif Abadye, Henry G., (Member '43) Petr Engr , Sr Prod Engr , Long Beach Oil Development Co, 255 So Santa Clara Ave, Long Beach, Calif Abbott, Clarence E , (Member '04) Civil Engr , 'P , Tennessee Coal, Iron & R R Co , 1542 Brown Marx Bldg Birmingham, Ala Abbott, Fred E , Jr , (Member '44) Petr Engr , c/o Arabian American Oil Co , A P 0 816, c/o Postmaster, New York, N Y Abbott, John H , (Member '46) Resident Mgr , Hickman, Williams & Co, 230 No Michigan Ave, Chicago 1, Ill Abbott, R W R., (Member '47) Asst Power Supt, Cananea Consolidated Copper Co , Cananea, Son , Mexico Abbott, Robert H? Jr., (Junior Member '47) Petr Engr, Producing Dept, The Texas Cc, P 0 Box 951, Houma, La Abel, Raymond L., (Member '28) Chem Engr, Prof of Chem Engrg, Univ of Pittsburgh, Pitts¬burgh Pa Abel, Walter D , (Member '32) Min Engr, Div of Corporations, 403 State Bldg , Los Angeles 12, Cal if

Jan 1, 1952

By J. C. Uy, T. E. Davidson, A. P. Lee

The effects of hydrostatic pressures to 26 kbars on the micro structure of poly crystalline Cd, Zn, Bi, Sn, Zr, Mg, Cu, and Fe were examined. Pressure-induced microscopic plastic flow in the form of boundary migration, slip, multiple slip, or twinning has been observed either singly or in combination in cadmium, zinc, bismuth, and tin. No deformation was observed in zirconium, magnesium, copper, and iron. The occurrence of such deformation, in terms of its intensity and initiation pressure, relates directly to the degree of anisotropy in the linear compressibility. Pressure cycling does not significantly affect the residual tensile properties of a zinc alloy which exhibits pressure-induced deformation similar to that of Pure zinc. CLASSICAL elastic theory predicts that a superim-posed hydrostatic pressure will not induce shear stresses in an ideal material. Thus, in the case of homogeneous and isotropic materials plastic flow will not occur as a result of pressure exposure, regardless of the magnitude of the pressure, unless some form of phase transformation or permanent density change takes place. However, real materials, such as metals, often vary considerably from the condition of homogeneity and isotropy. For this reason, Vu and johannin' examined and observed hydrostatic pressure-induced microscopic deformation in polycrystalline cadmium and, zinc, but not in aluminum, to pressures of 9 kbars and indicated that its occurrence is related to anisotropy in the linear compressibility. In addition, Davidson and omaan' have reported pressure-induced deformation in polycrystalline bismuth below the 1-11 transformation pressure. It becomes apparent then that under certain conditions hydrostatic pressure can induce localized internal shear stresses in some metals of sufficient magnitude to cause plastic flow. In this work, eight pure single-phase metals of different lattice structures and degrees of elastic anisotropy were examined after pressure exposures of up to 26 kbars in order to establish the conditions under which such deformation occurs and the type of deformation as a function of pressure. The effects of pressure cycling on the mechanical proper-

Jan 1, 1965

Aase, Glenn D., (J'40) Jr. Met.. American Smelt. k Refin. Co., Selby, Calif. Abadie, Henry G., (J'43) Petr. Engr., Avenal, Calif. Abbott, Clarence E., (M'04) Civil Engr., V.P.. Tennessee Coal, Iron & R.R. Co., 1542 Brown Marx Bldg., Birmingham, Ala. Abel, Raymond L., (M'28) Chem. Engr., C.O., Pitts¬burgh Chem. Warfare Procurement Dist., American Bank Bldg., Pittsburgh. Pa. Abel, Walter D.. (M'32) Min. Engr., Supvr. Engr., R.F.C.Lee Angeles, Calif. Abele, Louis T., (M'31) Route No. 1, Adameville, Tenn. Abell, Leo M., (M'31) Mill Supt. & Met., Emperor Gold Min. Co. Ltd., Vatukoula, Fiji Is. Abernathy, G. E., (M'38) Geol., Kansas State Geol. Survey, Pittsburg, Kans. Abernathy, Jack H,, (M'40) Asst. Cenl. Supt. of Prod., Sunray Oil Co., 11th Floor, Philtower Bldg.. Tulsa 3. Okla. Abernethy, D. Carl, (M'44) Min. Engr. Rm. 3217, N. Int. Bldg., Washington, D. C.

Jan 1, 1944

By SIDNEY ROLLE

ACURSORY glance through the literature on the subject reveals that the ablest minds in the land are devoting themselves to the great question of labor, of which employment is one of the fundamentals. Volumes have been written and the end is not in sight. Employment management is today about in the position that efficiency was 15 years ago. During the early days of the war, and perhaps for a year or so before, labor was plentiful. As the war progressed and Europe drew on us for munitions, employers began to compete with one another for', all, classes of labor. Labor was difficult to obtain, wages rose, the labor turnover increased, and employers began to install employment departments, welfare plans, and all sorts of schemes, but the labor efficiency dropped. As the war progressed, greater and greater production was demanded. New factors were introduced each day. The government, labor unions, industrial councils, all tended, it seemed, to make the situation almost intolerable. Wages rose to fantastic heights, the cost of living rose higher and higher, and the efficiency dropped still further.

Jan 1, 1921

By J. H. McCormick

THIS plant, near Marysville, Mont., was planned to treat the ore from the Piegan and Gloster mines, the latter being one of the early and famous producers of the Marysville district. When the mill was closed in 1888, treatment consisted of stamp milling, followed by pans and settlers for pan amalgamation. The extraction was evidently poor; because, a few years later, thousands of tons of tailings were re-treated by the ranchers in the valley below the mill, by the then new cyanide process, and gave a handsome profit. In 1914, the present owners, after laboratory tests and an experimental mill run, decided upon the following treatment: crushing to 40 mesh in cyanide solution, concentration, amalgamation, classification, and cyanidation of sands by leaching, and of slime by agitation and decantation in charges. The ore averaged about $7 per ton, gold and silver, the ratio of weight being 1 oz. gold to 7.56 oz. silver. The ratio of gold and silver in tailings was 1 oz. Au to 36.6 oz. Ag; the quartz vas sharp and, sandy, however finely ground, and rather difficult to slime. The mechanical 'equipment was a No. 5 Symons gyratory crusher; three 10-ft. Lane slow-speed Chilean mills; one Wilfley roughing and one finishing table; one submerged-type Akins classifier; five 26 by 10-ft. fir leaching tanks; one 24 by 7-ft. Dorr thickener; four 14 by 16-ft. Dorr agitators; four 6-compartment double-row zinc-boxes having compartments 18 in. wide, 18 in. deep, and 34 in. long; Johnson zinc lathe; acid and vacuum filter tanks for treating precipitate; roasting furnace; and Case tilting No. 275 crucible furnace for melting precipitate. The mill is driven by electric power supplied by the Montana Power Co. at the following rates, per kw.-hr.: 200 to 300 hp.,.0.68 c.; 300 to 500 lip., 0.61 c.; 500 to 750 hp., 0.55 c.; plus $1 per month per installed motor horsepower.

Jan 8, 1918

By H. O. Hofman

(Canal Zone Meeting, November, 19]0.) THE sudden decease, April 1, 1910, in Chicago, of Dr. Franklin R. Carpenter was a shock to his- many friends. He died in his sixty-second year, of heart paralysis. To most fellow-members of the Institute who have followed the progress of the. last twenty-five years in the mining and treatment of non-ferrous ores, the work of Dr. Carpenter in that line is familiar ; but very few, even of those who knew him well in the later years, are acquainted with his earlier struggles to satisfy an inborn hunger for knowledge. The story of his life resembles that of the pioneer who opens up new country; overcoming hardships with indomitable courage, meeting doubts and difficulties with an alert and open mind, and exercising in the face of reverses an unconquerable perseverance. It seems appropriate to place on record in the Transactions a brief outline of the life and work of this eminent engineer. During the past 15 years of his life Dr. Carpenter was much interested in genealogy. In the pursuit of this study as an avocation, he traced his own ancestry to the time when ?Hugh," called "le Charpentier" on account of the dexterity with which he had swung his battle-axe as a crusader, settled in Sussex on lands received from William the Conqueror. The Carpenters came to this country with William Penn. A prominent member of the family was Joshua Carpenter, the founder of Christ Church, Philadelphia. Dr. Carpenter's branch of -the family moved from Pennsylvania into that part of Virginia which is now West Virginia, where his grandfather settled in Harrison county, while the grand-uncle went further west, and built the first iron-furnace at Hanging Rock, Lawrence county, Ohio. In fact, since early times, the Carpenters appear to have been iron-masters. Franklin R.. Carpenter was born, Nov. 5, 1848, in Parkers-

Aug 1, 1910

By A. J. Stosick, J. R. Hoffman, E. Rudy, St. Windisch

The binary alloy system Mo-C zoas investigated by means of X-ray, metallog/aphic, thermoanalytical, and melting-point techniques on chemically analyzed specimens. The system, Fig. 39, is characterized by three congruently melting, intermediate phases, Mo2C, n MoCi-x, and aMoC1-,, of which only Mo,C is stable at temperatures below 1650°C. Substoichio-metrzc (~32.5 at. pct C) dimolybdenum carbide undergoes a homogeneous sublattice order-disorder transformation at temperatures of approximately 1400°C, whereas hyperstoichiorrletric compositions undergo a discontinuous Phase change. The order-disorder transitions in the Me, C phases are discussed in terms of the structural changes involved in the transformation processes and the absence of long-range sublattice coherency in stoichiometric or hyperstoiclziomet-ric compositions attributed to the impossibility of obtaining long-range order in a linear chain of alternating carbon atoms and vacancies. From the experimental phase relutionships and the known thermody-namic data for Mo2 C, limits for the free energies of formation for the high-temperature phases r) MoC1-, and aMoC1-, are deriued and found to be in good agreement with data previously obtained from phase equilibria in ternary metal-carbon systems. IN the course of studies of the high-temperature phase relationships in ternary systems of refractory transition metals with carbon,' a number of inconsistencies found in previous work necessitated a reex-amination of some of the related metal-carbon binaries. A reassessment of the binary system data also seemed

Jan 1, 1968

By S. K. Asunmaa, W. D. English, N. A. Tiner, W. A. Cannon

This paper discusses the reaction of metal surfaces with fluorine. Fluorination reactions result in the formation of metal fluoride films which are "passive" toward further reaction of the metal with fluorine. These films are very adherent, and do not easily detach from the substrate metal by mechanical flexing or thermal shock. Exposure of passive films to a humid atmosphere produces hydrated metal fluorides which cause secondary fluorination reactions upon reexpo-sure of the metal surface to fluorine. The surface films formed range from 10 to 30A in thickness and they pow at the expense of surface oxide films. The apparent film formation is completed rapidly in 15 to 30 min on stainless steel and nickel surfaces. On copper and on Monel surfaces, the film at first grows rapidly, then increases slowly over an extended period of time. Passive films are formed at all fluorine pressures in the range from 0.1 to 1.4 atm at room temperature. ALL metals react when exposed to fluorine. These reactions generally produce surface films which consist of metal fluorides. The rate of reaction is largely determined by the extent to which these films are protective. Although there is an extensive literature concerning reactions of oxygen with metals, there are very few investigations reported concerning fluorine-metal reactions. Brown, Crabtree, and ~uncan' investigated the kinetics of the reaction of gaseous fluorine with copper metal which had been freshly reduced in hydrogen. The reaction rate was independent of pressure over the range from 6 to 60 torr. A logarithmic rate law was obeyed in the temperature range from 25" to 300" ~. There was some deviation at higher temperatures which could have been the onset of a parabolic law. The calculated film thicknesses ranged from about two molecular layers, 10A, for 5 hr exposure at room temperature to thirty-five molecular layers for 5 hr exposure at 200" . The authors concluded that no single mechanism could explain all the observations. O7Donnell and spatkowski2 studied the reaction of fluorine with copper at 450°C at pressures from lo to 133 torr. The reaction was found to be pressure -dependent and followed a logarithmic rate law. It was not entirely diffusion-controlled, and fluorine was thought to be the migrating species in the reaction. Miscellaneous metal-fluorine reactions were investigated by Haendler et ~1.~ Reaction products were identified but no rate data were determined. Air Prod- ucts and Chemicals, Inc., have conducted an investigation of reactions between fluorine and various metal powders at room temperature and 85° C. Fluoride film thickness as a function of time of exposure was reported on the assumption that the reaction takes place between fluorine and metal to form the normal metal fluoride. Surface areas of the powders were only estimated so the relative film thicknesses may not be exact. The data showed reaction rates which were generally logarithmic in character, the rate of film growth virtually ceasing after a few hours exposure time for some alloy powders. The effect of moisture on fluoride films was also investigated by measuring additional reaction with fluorine after exposure of passivated powders to atmosperic moisture. The fluorination of iron was studied by 0'~onnell~ at temperatures from 225" to 525" ~ and at pressures ranging from 20 to 200 torr. In all ranges, the reaction followed a logarithmic rate law and was dependent on the square root of the gas pressure. The author concluded that fluorine gas passes through pores in the film. As the film grows, the blocking of pores leads to a rapid decrease in reaction rate; hence a logarithmic rate law is observed. Jarry, Fischer, and Gunther' investigated the mechanism of the reaction of fluorine with nickel at about 600" to 700°C. On the basis of the metallographic examination of fluoride scales growing on the nickel and from separate radioautographic data, it was claimed that fluorine is the migrating species in the reaction. This is in sharp contrast to the growth of oxide films on nickel where it has been shown that nickel ions migrate through the scale to the gas-solid interface to react with oxygen. Few investigations have been reported of the reaction of fluorine with metal oxides. Such investigations should be of great significance for a better understanding of passivation in view of the ubiquitous oxide films on technical alloys. Haendler et al.3 studied the reaction of fluorine with oxides of copper, tin, titanium, zirconium, and vanadium. Copper (I) oxide reacted as follows in the temperature range 150" to 300"~: temperature above 300" ~ was required for the CuO to react to form additional copper fluoride. Ritter and smith7 also investigated the reaction of fluorine with copper (11) oxide. An oxide powder comprised of spherical particles with a fairly high surface area was reacted with fluorine, starting at room temperature and increasing to 100° C over a period of 3 or 4 hr. The initial reaction was slow until the fluoride film thickness reached about to or 15R at which time the reaction rate accelerated, then decreased again. Most of the kinetic data was obtained during this final phase of reaction. The authors conclude that the film grows slowly at first until the stresses developed in the distorted lattice are sufficient to rupture the initial

Jan 1, 1969