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By R. G. Charles, E. A. Gulbransen, S. Barnartt

KINETICS of the reaction of zirconium with pure oxygen at elevated temperatures have been studied by several workers for periods of time up to 6 hr.1-1 In two cases,3-4 . the experimental values of oxygen uptake, w, as a function of time, t, were best fitted to the parabolic rate law w2 = kPt + constant. In others,3,4 the cubic rate law w3 = kot + constant, showed better agreement. The most recent data of Gulbransen and Andrew4 indicate that the choice between the parabolic and cubic laws for empirical representation of the data will often be arbitrary. This is particularly true if the first few minutes of the reaction with a clean zirconium surface is attributed to a different oxidation mechanism, for deviations from either rate law were found primarily during the initial period. Thus, the kinetics of this reaction have been too uncertain to permit safe extrapolation to oxidation periods of practical interest (many hundreds of hours). The data to be described are of interest, for they indicate that the cubic rate law applies over long oxidation times. The reaction of zirconium with oxygen at 1 atm pressure was followed at 350" and 450°C for 500 and 200 hr, respectively. Abraded test specimens of pure zirconium sheet' 3.0 X 2.0 X 0.012 cm in size were oxidized by the procedure previously described,3 which included periodic cooling to room temperature for weighing. The surfaces were polished to a 4/0 finish using polishing paper wet with kerosene, then wiped with petroleum ether and washed in redistilled acetone. Fig. 1 shows plots of log ? vs log t. Each curve represents the average of duplicate measurements, and deviations from the average were generally less than 3 pet. The cubic rate law (slope = 1/3) is closely followed. The rate constants, 5.2, x 10 -6 and 2.4, X 10- (mg cm-2)3 per hr at 350" and 450 oC, respectively, are plotted as log k, vs 1/T in Fig. 2, together with cubic constants calculated from the data of Gulbransen and Andrew4 for abraded specimens from the same lot of zirconium. Their data refer to runs of 6-hr duration at a pressure of 0.1 atm 0 and under conditions of uninterrupted heating. In spite of these differences, the latter data yield a straight line which appears to apply equally well to the new extended time data. The energy of activation for the oxidation process, calculated from the slope of this line, i.s 38 keal per mole. This may be compared with the value of 47 keal per mole found by Belle and Mallett3 at higher temperatures. It may be concluded tentatively that extrapolation of short-term oxidation data for zirconium to obtain the long-term behavior is best done through the cubic equation ?3 = kpt + constant. References ' E. A. Gulbransen and K. F. Andrew: AIME Trans., 1949, vol. 185, p. A.515; JouRNal OF Metals, August 1949. 'D.p. Cubicciotti Journal Amer Chemical August1949.Soc., 1950, Vol. 72, P. 3 V. Belle and M. W. Mallett: Joulnal Electro chemical Soc., 1954, ' E. A. Gulbransen 339.and K. F. Andrew: Oxidation of Zirconium Between 400" Gulbransenand 800'C.and AIME Trarzs.. 1957, vol. 209, p. 394; JOUR-Nal of Metals, April 1957. IS Barnartt, B G. Charles, and E. A. Gulbransen: Oxidation of 50 weight pet uranium-zirconium alloy, Journul Electrochemical SOC., 1957, vol. 104, p. 218.

Jan 1, 1959

Jan 1, 1961

Jan 1, 1923

Jan 1, 1898

NORTH AMERICA Number Members Alaska 31 Canada 302 Mexico 175 Newfoundland 3 United States Alabama 52 Arizona 131 Arkansas 9 California 723 Colorado 184 Connecticut 98 Delaware 19 District of Columbia 133 Florida 16 Georgia 6 Idaho 61 Illinois 241 Indiana 57 Iowa 7 Kansas 32 Kentucky 33

Jan 1, 1932

NORTH AMERICA Number Members Alaska 32 Canada 300 Mexico 165 Newfoundland 3 United States Alabama 43 Arizona 121 Arkansas 9 California 674 Colorado 184 Connecticut 94 Delaware 19 District of Columbia 120 Florida 17 Georgia 5 Idaho 66 Illinois 211 Indiana 56 Iowa 8 Kansas 32 Kentucky 31

Jan 1, 1934

Jan 1, 1923

The following is an incomplete list of members and guests who called at Institute headquarters during the period Oct. 10, 1918 to Nov. 10, 1918. J. Carson Adkerson, Virginia. George H. Parsons, Hayden, Ariz. Andrew B. Armstrong, Connecticut. W. E. Pomeroy, New York. Courtenay DeKalb, San Francisco. Ezra C. Rider, Bisbee, Ariz. Clifford G. Dennis, San Francisco. H. W. Seaman, Chicago, Ill. Rudolph Emmel, Boston, Mass. William Allen Smith, Northampton. Emil Gathmann, Baltimore Md. R. K. Stockwell, Salt Lake City, Utah. Ernest S. Geary, Denver, Colo. W. G. Swart, Duluth, Minn. W. E. Hopper, Washington, D. C. Kirby Thomas, New York. W. Spencer Hutchinson, Boston, Mass. - Warren D. Thompson, Harvard Club. E. W. Kohl, Jr., Philadelphia, Pa. H. Vincent Wallace, Los Angeles, Cal. E. C. Nighman, Butte, Mont. Paul T. Benson, formerly with the Tacoma smelter, has resigned his position there to accept one with the Great Metals Mining and Milling Co. at Nespelem, Wash. Prof. Edward E. Bugbee, of the Mining Department of the Massachusetts Institute of Technology, has been granted a leave of absence to accept the position of Assistant Director of Education for the S.A.T.C. of five southern states with headquarters at Raleigh, N. C.

Jan 12, 1918

Jan 1, 1909

ALABAMA Anniston.-Carrington, F. G. Auburn.-Brown, R. L. Bessemer.-Abbott, C. E. Dobbs, G. G. Ferguson, V. Salmon, H. S. Schaber, C. F. Birmingham.-Aldrich, T. H. Aldrich, T. H., Jr. Allen, A. W, Ball, E. M. Bonnyman, J. Bowron, J. Bush, M. W. Crawford G. G. Crockard, F. H. Ellis, E. E. Fairbairn, C. T. Gallacher, J. Geisiner, H. S.

Jan 1, 1917

By Philip B. Bucky

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Jan 1, 1942

By Fred W. Gordon

It is my purpose to call attention to the close approximate correctness of certain coefficients and formulas concerning the flow of gases, and their applicability to the practical construction of flues and

Jan 1, 1886

By R. A. Swalin, A. H. Geisler

THIS study represents an investigation of the effect of annealing temperature on the texture of drawn molybdenum, iron, and an iron alloy containing 14 pct Al. The effect of temperature on annealing textures has not been widely investigated in the past. One of the obstacles in making such a study using usual X-ray diffraction techniques results from the

Jan 1, 1957

ALABAMA Alabama City.-Eddy, L. Altoona.-Cain, J. America.-Foreman, J. T. Anniston.-Foster, R. N. Ashland.-Sturdevant, J. C. Bessemer.-Ball, E. M. Calhoun, F. W. Maschmeyer, W. L. McKenzle, W. C., Jr. Birmingham.-Abbott, C. E. Aldrich, T. H. Aldrich, T. H, Jr. Ashton, J J.

Jan 1, 1923

Jan 1, 1892

R. L. Fleischer (Department of Metallurgy, Massachusetts Institute of Technology)— The authors have presented valuable observations of oehavior of aluminum at intermediate and high temperatures. I should like to consider their interpretation of the appearance of cross slip plane traces in sample B-3 as partly due to "bending of the crystal due to grip constraint." Because bending moments might be set

Jan 1, 1960

By P. D. Merica, H. Scott, R. G. Waltenberg

The remarkable phenomena exhibited by the aluminum alloy known as duralumin were discovered during the years 1903—1911 by A. Wilm1,2 and have been described by him and by others. 3, 4,5.6 The unusual feature of this alloy is the fact, as was shown by Wilm, that it can be hardened quite appreciably by quenching from tempera-

Jan 1, 1921

By Chester S. Conrad

SEVERAL years ago Pittsburgh Consolidation Coal Co. intensified efforts to combat the hazard of mine fires. The program consisted of three parts in the order of likely accomplishment: 1) Purchase and installation of newer and more practical fire fighting equipment. 2) Establishment of trained fire fighting teams at every mine plant. 3) A drive to remove the causes of mine fires. Experimentation with alternating current on section equipment is a major development in this part of the program. Use of alternating current to power mining equipment had been recognized as being most practical from the standpoint of safety. A means to re- place the d-c traction motor is all that has delayed complete section mechanization with a-c power.

Jan 1, 1958

By Charles H. Morgan

Jan 1, 1905

Jan 1, 1920