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By O. D. Sherby, J. E. Dorn

SEVERAL years ago Zener and Hollomon1 suggested that the flow stress of metals might be related to the temperature and strain rate in accord with the functional equation: s=s(eeh/rt) [1] at the same state. The Zener-Hollomon relation also contains the significant tacit implication that the energy for activation, AH, is substantially independent of the state of the material. The utility of this method for correlating creep data with tensile data was illustrated in a preliminary reportL on the effect of alloying additions on the secondary creep rates of binary a solid solutions in aluminum as shown for Al-Mg alloys in Fig. 1. Not only do the secondary creep and ultimate tensile properties for each alloy correlate well on this plot but in addition the activation energy, AH = 17,900 R cal per mol. is identical for the various compositions. Similar types of curves correlating the secondary creep rates at 422°K (300°F) with ultimate tensile data were also obtained for a series of dilute a solid solutions of copper, germanium, zinc, and silver in aluminum. In all cases the activation energy for creep, AH, was found to be equal to about 17,900 R cal per mol independent of the type of alloying element or its concentration. The coincidence of the activation energies for these alloys is probably due to the fact that the activation energies for creep are rather insensitive to small composition changes. Alloying additions, as shown in Fig. 1, however, increased the stress necessary to obtain equivalent values of ee?H/RT. Thus the stress level in curves of the type represented by Fig. 1 gives the relative creep strengths of the various alloys. Inasmuch as these correlations between creep and tensile data were obtained for creep tests at 422°K, it appeared advisable to ascertain the range of secondary creep rates and temperatures over which correlations between creep and tensile data could be made on the basis of the Zener-Hollomon relationship. If, for example, the activation energy changes with different ranges of creep temperatures, the utility of the proposed analysis would be severely weakened. But if AH is constant not only for all dilute alloys, but also over wide ranges of temperature and secondary creep rates, confidence will be developed not only in the broad utility of the Zener- Table I. Chemical Analysis':' and Grain Size of Alloys Mean Grain Residual Impurities. Wt Pct Diam- Alloying Atomic-eter, Element Pct Si Fe Cu Mg Mn mm Aluminum 99.987 0.003 0.003 0.006 0.001 0.25 Magnesium 1.617 0.003 0.004 0.006 0.26 Copper 0.101 0.003 0.003 0.0006 0.001 0.29 Zinc 1.616 0.003 0.005 0.007 0.001 '0.26 * The authors express their appreciation to the Aluminum Company of America for the preparation and chemical analyses of these alloys. Hollomon relationship, but also in its theoretical justification. The following investigation was instituted in order to ascertain the range of validity of the Zener-Hollomon relationship when it is applied to creep and tension data. Materials, Equipment, Technique In view of rather extensive correlatable data now available on the plastic properties of a series of binary a solid solutions of magnesium, copper, germanium, zinc, and silver in aluminum, these alloys were again selected for the present investigation. Previous reports have already covered the tensile properties of these alloys at subatmospheric temperatures," and at elevated temperature," as well as their fatigue properties at atmospheric temperatures, nd their creep properties at 422°K.' Resistivity measurementsa as well as precision lattice constant determinations? evealed that these alloys are a solid solutions. After homogenization. 0.100 in. thick sheets were rolled to 0.070 in. in thickness and recrystallized to about the same grain size. Since the details of these treatments were reported previously," they will not be repeated here. In order to appropriately reduce the scope of creep tests in this investigation only the typical alloys shown in Table I were investigated. All creep specimens were machined such that their tensile axes were in the rolling direction of the 0.070 in. sheet stock. The gage section was 2 in. long and 0.500 in. wide with a reduced section of 3.50 in. Creep strains were measured by means of rack and pinion type extensometers with a sensitivity of 0.005 in. per division. Readings were estimated to 1/10 of

Jan 1, 1953

THOSE NOT MARKED ARE MEMBERS; MARKED THUS t ARE ASSOCIATES. HEAVY-FACED TYPE SIGNIFIES HONORARY MEMBERSHIP. JUNIOR MEMBERS ARE MARKED II. THE FIGURES AT THE END OF THE ADDRESS INDICATE THE YEAR OF ELECTION. AARONS, J. BOYD, Genl. Mgr., Chaffers G. M. Co., Boulder City, West. Australia. '05 ABADIE, EMILE R., Min. Engr Box 291, Porterville, Tulare Co., Cal. '76 ABBOTT, CLARENCE E., Genl. Supt., Iron Mines Div., 1405 Minnesota Ave., Bessemer, Ala. '04 ABBOTT, J. W., Min. Engr., "St. Omer," 123 N. Grand Ave., Los Angeles, Cal. '94 ABBOTT, Louis BENJAMIN, Chief Engr., Consolidation Coal Co., Elkhorn Div., Jenkins, Ky. '15 ABBOTT, ROBERT R., Met. Engr., Peerless Motor Car Co., Cleveland, Ohio. '12 ABE, ASAKA Yamagano G. M., Satsuma-Gori, Satsuma, Japan. '14 || ABRAHAMS, A. I., Student 1391 Madison Ave., New York, N. Y. '14 tACKER, E. O'C., Met Bethlehem Steel Co., Bethlehem, Pa. '86 ACKER, Louis K., JR., Min. Engr 565 Highland Place, Bellevue, Pa. '08

Jan 1, 1917

New York Meets first Wednesday after first Tuesday of each month. Chairman. PERCY E. BARBOUR, Vice-Chairman. A. D. BEERS, Secretary, 55 Wall St., New York, N. Y. C. A. BOHN,.Treasurer. JOHN V. N. DORR, LEWIS W. FRANCIS. Boston Meets first Monday of each winter month. W.. E. C. EUSTIS. Chairman. R. L. AGASSIZ. Vice-Chairman. E. E. BUGBEE, Secretary-Treasurer, Mass. Inst. of Technology, Cambridge, Mass. ALBERT SAUVEUR, H. L. SMYTH. Columbia Holds four sessions during year. Annual meeting n September or October. W. H. LINNEY, Chairman. OSCAR LACHMUND, Vice-Chairman. LYNDON K. ARMSTRONG, Secretary-Treasurer, P. O. Drawer 2154, Spokane, Wash. STANLY A. EASTON. S. SHEDD. Puget Sound Meets second Saturday of each month SIMON H. ASH, Chairman. I. F. LAUCKS, Vice-Chairman. CHARLES SIMENSTAD, Secretary-Treasurer, 425 Lyon Bldg., Seattle, Wash. GLENVILLE A. COLLINS, JOHN N. POTT

Jan 5, 1917

[Arizona BRENT N. RICHARD, Chairman ROBERT W. HUGHES, Vice-Chairman ROBERT E. S. HEINEMAN, Secretary-Treasurer Arizona Bureau of Mines, University of Arizona, Tucson, Ariz. THOMAS G. CHAPMAN A. MENDELSOHN WILLIAM KOERNER A. C. REIFSNIDRR C. R_ . KUZELL WILLIAM M. SABEN ERNEST WITTENAU Black Hills NATHANIEL HERZ, Chairman C. E. DAWSON, First Vice-Chairman BANCROFT GORE, Second Vice-Chairman C. E. SCHMIDT, Secretary-Treasurer Homestake Mining Co., Lead, S. D. R. S. BLITZ NATHANIEL HERZ C. E. DAWSON A. I. JOHNSON L. B. EAMES F. C. LINCOLN BANCROFT GORE C. E. SCHMIDT]

Jan 1, 1940

Executive.. CHARLES F. RAND, Chairman. JAMES F. KEMP, JOSEPH W. RICHARDS. ALBERT R. LEDOUX, BENJAMIN B. THAYER. Membership. BENJAMIN B. THAYER, Chairman. WALTER R. INGALLS, JOHN H. JANEWAY, Jr., JOHN D. IRVING, HERMAN A. PROSSER. Finance. EDWARD L, YOUNG, Chairman. KARL EILERS, JAMES GAYLEY. Library. JAMES F. KEMP, Chairman. JOHN HAYS HAMMOND,3 E. GYBBON SPILSBURY,2 ALES. C. HUMPHREYS 4 BRADLEY STOUGHTON.

Jan 7, 1913

By Pol Duwez

IN the course of an investigation of the V-CO system, two intermediate phases were found. One of these phases corresponds approximately to the stoichiometric composition VCo and is isomorphous with the sigma phase in the Fe-Cr system.' The second phase has the composition V3Co; its crystal structure is described in the present note. The alloys were prepared by mixing the two metals in the powder form, pressing a small disk weighing about 5 g at 80,000 psi, and arc melting this disk on a water-cooled copper plate in an atmosphere of pure helium. The details of this technique have been described.' The vanadium powder was obtained from Westinghouse Electric Corp., Bloomfield, N. J. This powder is probably of very high purity, since when it is properly sintered or melted in the above-mentioned arc furnace, ductile specimens are obtained. The cobalt powder, from Charles Hardy, Inc., New York, contained 0.5 pct Ni, 0.1 pct Cr, and traces of Si and Fe. After melting, the V,Co samples were sealed in evacuated quartz tubes and homogenized for ten days at 800°C. Powder diffraction patterns were obtained with a 14.32 cm diam camera, using Ka copper radiation. The patterns were readily indexed on the basis of a primitive cubic lattice with a parameter equal to 4.675A. The density, determined by the immersion method, was 6.71 g per cu cm; hence the number of molecules per unit cell is approximately 1.95; i.e., 2. At this point, the possibility that the structure might be that of beta tungstena became apparent. The beta tungsten structure is described as follows: Space group 03,, — Pm3n 2 Co in (a) : 000; ?4lhYZ (hhl) reflection present only if 1 = 2n. Assuming this structure to be the correct one, intensities were computed by means of the usual eauation: 1 + cos220 I oc p F sin 0 cos 6 where F is the structure factor, 0 the Bragg angle, and p the multiplicity factor. The observed and calculated values of sin 0 and the intensities are given in Table I. The agreement between the observed and the calculated sin 0 is good and there are no flagrant discrepancies between the calculated intensities and those estimated visually. The (hhl) reflections for which 1 is odd are not observed, as required by the space group. In addition, the (410), (430), and (531) reflections are missing as expected, because of the special (a) and (c) positions in0%. However, six reflections—(llo), (220), (310), (411), (422), and (510)—which have very weak computed intensities were not observed. For these reflections, the structure factor is proportional to the difference between the scattering factors of the two atoms in the structure. Since the scattering factors of vanadium and cobalt are not very different, these reflections are weak. However, by using Ka chromium radiation, whose wavelength is just above the absorption edge of vanadium, the effective scattering factor of vanadium may be decreased by one or two units; consequently the difference between the cobalt and vanadium scattering factors is increased. It was, indeed, found that in a powder pattern taken with chromium Ka radiation, the three reflections (110), (220), and (310) were actually present. The three other reflections (411), (422), and (510), with spacings smaller than half the wavelength of chromium Ka, were obviously not obtainable with chromium radiation. All the experimental results appear to confirm the beta tungsten structure for V,Co. In this structure, each cobalt atom is surrounded by twelve vanadium atoms at 2.61A; each vanadium atom is surrounded by two vanadium atoms at 2.34A, four cobalt atoms at 2.61 A, and eight vanadium atoms at 2.86A. Acknowledgment This work was done at the Jet Propulsion Laboratory, California Institute of Technology, under contract number W-04-200-ORD-455 with the Army Ordnance Department, Washington, D. C. The author wishes to thank this agency for the permission to publish the results of this investigation. References 'P. Duwez and S. R. Baen: X-Ray Study of the Sigma Phase in Various Alloy Systems. Symposium on the Nature, Occurrence, and Effect of Sigma Phase. ASTM Special Tech. Pub. No. 110, pp. 48-54. Philadelphia, 1951. 2 C. H. Schramm, P. Gordon, and A. R. Kaufmann: The Alloy Systems Uranium-Tungsten, Uranium-Tantalum, and Tungsten-Tantalum. Trans. AIME (1950) 188, pp. 195-204; Journal of Metals (January 1950). 3 M. C. Neuburger: The Crystal Structure and Lattice Constants of Alpha and Beta Tungsten. Ztsch. fiir Krist. (1933) 85, pp. 232-237.

Jan 1, 1952

By J. M. Stuart, G. D. Bengough, A. R. Lee

Corrosion tests should be designed so as to facilitate as far as possible the interpretation of results, consequently factors which may affect the rate of corrosion should be controlled as far as practicable, and very full data should be given regarding the conditions of the test. Among the most important factors affecting the rate of corrosion is often the rate of supply of oxygen to the metal surface. It is essential therefore to understand the mechanism by which oxygen is transferred from the liquid surface to the surface of the metal. The work of Adeney and his coworkers has thrown much light on this mechanism. They have shown1 that the aeration of deaerated water and salt solutions proceeds much more rapidly than can be accounted for by mere diffusion, and have suggested that downward "streaming" takes place from the surface of the water, due mainly to an increase of density brought about by evaporation. The evaporation reduces the temperature of the surface layer, and also increases the concentration in the case of salt solutions. The effect of evaporation in facilitating the transfer of oxygen to a metal and increasing the corrosion of the metal was shown in some experiments due to Friend.2 He tested the corrosion of mild steel plates immersed in water in glass jars, a steady stream of air being drawn over the surface of the water in the jars. The air passing through half the number of jars was saturated with moisture, that passing through the others was dried with calcium chloride. He found that "in every case the water exposed to dry air was approximately twice as corrosive as that exposed to air saturated with water vapor." Conditions for Quantitative Corrosion Tests These results show that we must either control or prevent evaporation at the liquid surface, if we wish to avoid effects on the rate of cor-

Jan 1, 1929

By A. R. Lee, G. D. Bengough, J. M. Stuart

Corrosion tests should be designed so as to facilitate as far as possible the interpretation of results, consequently factors which may affect the rate of corrosion should be controlled as far as practicable, and very full data should be given regarding the conditions of the test. Among the most important factors affecting the rate of corrosion is often the rate of supply of oxygen to the metal surface. It is essential therefore to understand the mechanism by which oxygen is transferred from the liquid surface to the surface of the metal. The work of Adeney and his coworkers has thrown much light on this mechanism. They have shown1 that the aeration of deaerated water and salt solutions proceeds much more rapidly than can be accounted for by mere diffusion, and have suggested that downward "streaming" takes place from the surface of the water, due mainly to an increase of density brought about by evaporation. The evaporation reduces the temperature of the surface layer, and also increases the concentration in the case of salt solutions. The effect of evaporation in facilitating the transfer of oxygen to a metal and increasing the corrosion of the metal was shown in some experiments due to Friend.2 He tested the corrosion of mild steel plates immersed in water in glass jars, a steady stream of air being drawn over the surface of the water in the jars. The air passing through half the number of jars was saturated with moisture, that passing through the others was dried with calcium chloride. He found that "in every case the water exposed to dry air was approximately twice as corrosive as that exposed to air saturated with water vapor." Conditions for Quantitative Corrosion Tests These results show that we must either control or prevent evaporation at the liquid surface, if we wish to avoid effects on the rate of cor-

Jan 1, 1929

By R. C. Ku, A. J. McEvily, T. L. Johnston

The microplastic response of a series ofas-quenched Fe-Ni-C martensites has been measured at 77°K. At strains less than JO'3 the flow stress is governed primarily by the transformation-induced dislocation structure of the martensite. Only at strains in excess of 10-3 is the influence of carbon manifested in the flow stress. At these macroscopic strains, typically 10-2, the solid-solution hardening is proportional to (wt pct C)1/3, and, in an alloy containing 0.39 wt pct C, amounts to 50 pct of the flow stress. THE technological significance of high-strength ferrous martensite has stimulated many investigations of its structure and properties. Although our knowledge of the characteristics of martensite has increased immensely, especially with the advent of high-resolution techniques, an understanding of the basic strengthening mechanism still remains elusive. The purpose of the present paper is to consider certain aspects of micro-plastic behavior of Fe-Ni-C martensite which we feel can help to resolve this important problem. Such alloys are particularly suitable for experimental investigation because their compositions can be adjusted to reduce the M, to a temperature low enough essentially to eliminate the diffusion of carbon in the freshly formed martensite.1 The mechanical properties in this condition are of interest inasmuch as they reflect a state that is free of the important but complicating influence of precipitation processes. In this virgin martensite the carbon is distributed as it was inherited from the parent austenite; i.e., it is present interstitially, and gives rise to tetragonality through strain-induced ordering.' In order to determine the source of strength of such alloys, Winchell and Cohen1 investigated the low-temperature macroscopic stress-strain behavior of a series of virgin martensites of increasing carbon content but of common M, temperature (-35°C). They found that the flow stress increased rapidly with carbon content up to 0.4 wt pct; beyond this point the flow stress increased at a much slower rate. It was concluded that martensite is inherently strong. To account quantitatively for the strength of virgin or as- quenched martensite in terms of the role of carbon, Winchell and cohen3 suggested that the carbon atoms, trapped in their original positions by the diffusionless martensite transformation, interfere with dislocation motion according to a model akin to that of Mott and Nabarro. 4 In this treatment, individual carbon atoms are considered to constitute centers of elastic strain and thereby generate an average stress resisting the motion of dislocations throughout the lattice. The additional stress necessary to move dislocations, over and above that necessary for motion in a carbon-free martensite, is given by where L is an effective length of dislocation capable of motion. L was assumed to be limited to the spacing between the twins that are an essential structural element of Fe-Ni-C martensites. They assumtd the spacing to be invariant and of the order of 100A. However, recent work5 has shown that L is variable and can be in excess of 1000Å, so that the assignment of an appropriate value of L is not straightforward. In contrast to the above conclusion that there is an intrinsically high resistance to plastic flow, it has been suggested by Polakowski6 that freshly quenched martensite is in fact "soft" in the sense that dislocations are initially free to move upon application of stress. The high indentation hardness and macroscopic yield stress of ferrous martensites are then a consequence of rapid strain hardening that depends upon carbon in solution. Consistent with this point of view are the results of Beau lieu and Dubé who measured the rate of recovery of internal friction as a function of aging (tempering) temperature in a freshly quenched steel containing 0.90 wt pct C, 0.37 wt pct Mn, 0.1 wt pct Cr, and 0.07 wt pct Ni. The kinetics were clearly consistent with the idea that many dislocations are unpinned in the as-quenched state and that during aging they become progressively pinned by carbon at a rate controlled by carbon diffusion in the body-centered martensite lattice. In order to provide a basis upon which to distinguish between the "hard" and "soft" interpretations indicated above, we have made studies of the initial stages of plastic deformation in Fe-Ni-C martensites similar to those'used by Winchell and Cohen. It will be shown that the results support the contention that dislocation segments in as-quenched material are indeed

Jan 1, 1967

By J. B. Cohen, S. L. Sass

The nucleation process for y', Ni3Ti, is shou'n to change from heterogeneous to uniform as the undercooling within the phase boundary increases. As unifornz nucleation beconres copious, (100) alignment is observed in the early stages of aging; howecer. whether or not the alignment is due to spinodal decomposition could not be determined. The presence oi a large-scale reversible segregation of titanium and not the intermediate precipitate y' may be the cause of the initial strengthening in this alloy system and the discrete regions detected magnetically by Ben-Israel and Fine. Evidence is presented for the role of dislocations in the formation at long aging tines oJ the equilibrium precipitate . ThE nickel-rich portion of the Ni-Ti phase diagram consists of a terminal fcc solid solution of titanium in nickel called y.' For temperatures below 1290°C if the solubility limit is exceeded and the temperature is high enough, the excess titanium will combine with nickel to form q, Ni3Ti, a four-layer hcp ordered structure with stacking sequence ABAC."~ Since a change in structure is involved, formation of q is slow and a metastable precipitate referred to as y' forms. This metastable precipitate is an ordered cubic phase in the unconstrained state having a structure similar to Cu3Au (LIZ) with the composition Ni,Ti."'5 From X-ray studies,8, 7 the following sequence is indicated for the precipitation reaction at low temperatures: 1) The appearance of satellites around low-index diffraction spots and splitting of high-index spots, indicating the formation of a slightly tetragonal phase in an imperfectly periodic arrangement. The tetragonal phase is y' or the depleted matrix, depending on the volume fractions of matrix and precipitate (and hence, the alloy composition); tetragonality apparently arises from coherency strains. 2) The appearance of diffraction spots from the equilibrium second phase, q. Ben-Israel and Fine'" used magnetic methods to measure the changes in matrix composition during aging, and to estimate the precipitate composition in a Ni-10.1 at. pct Ti alloy. They observed that the alloy, solution-treated at 1270°C and quenched, contained heterogeneities with discrete compositions which gradually vanished upon aging. It was suggested that y' may initially form as a defect structure with several possible compositions deficient in titanium as compared to Ni3Ti; the composition Ni3Ti develops with prolonged aging. The initial composition was Ni6Ti which would require a very large deviation in stoichiometry for y'. It was noted that at 700°C the precipitation reaction was 80 pct complete after 2 hr and that the volume fraction of second phase was 0.2 after 1 hr. Mihalisin and Decker' suggested that the equilibrium precipitate, besides being nucleated at grain boundaries, could also form at stacking faults. ~errick" examined the formation of in Ni-Cr-Ti, and suggested that a collapsed vacancy cluster within y' acted as a nucleus for intragranular q at high temperatures, 820" and 900°C. After long aging times at lower temperatures, 650" and 750°C, diffraction patterns taken from regions containing ribbons of stacking faults showed spots associated with q. Aging greatly enhances the mechanical properties of these alloys, even at high temperatures, and the metastable precipitate y' is thought to be responsible.' At 600°C the hardness of a Ni-10.1 at. pct Ti alloy increases rapidly during the first 20 hr of aging and continues to increase slowly thereafter.'" At 700°C the hardness reaches a maximum at 1 to 2 hr and then decreases.l1 In this paper the kinetics of formation of y' and the mechanism of transformation to in a Ni-Ti alloy are described. Evidence is presented that suggests that large-scale regions of titanium segregation are present initially and these may have an important influence on the initial strengthening of the alloy: these regions may be the heterogeneities detected by Ben-Israel and Fine. I) EXPERIMENTAL TECHNIQUES The Ni-10.3 at. pct Ti-0.6 at. pct A1 alloy was prepared by vacuum melting. Its chemical analysis is given in Table I. A 0.007-in.-thick strip was sandwiched between foils of the alloy and placed in an open Vycor tube with titanium chips (to get oxygen) and solution-treated for ; hr at 1150°C in a Globar Furnace under a flowing argon atmosphere. Following a quench into an ice-brine mixture at -5" to -2"C, a sample to be aged at temperatures up to and including 700°C was sealed in an evacuated Vycor capsule before being put into a fused salt bath. Aging above 700°C was carried out on bare samples in a salt bath. When removed from this bath and quenched into an ice-water mixture, the sample was normally coated with a thin layer of oxide easily removed with emery

Jan 1, 1970

By J. M. Markowitz

The movement of hydrogen in two-phase Zircaloy-2 under the influence of a thermal gradient was studied in specimens of cylindrical geometry. A gross displacement of hydrogen toward the cooler regions of the specimen was observed with consequent copious precipitation of 6-ztrconium (ZrH) there. The kinetics of the diffusion are analyzed and discussed. X HE temperature-gradient redistribution of hydrogen in a-Zircaloy-2 has been treated both theoretically and experimentally Hydrogen moves toward the cold side of the temperature gradient until a steady state has been established; tendency for further hydrogen movement because of temperature differences is nullified by the tendency to move in the reverse direction because of the concentration gradient. The steady state condition is described by the equation in which iV is the concentration of hydrogen at a point in the specimen corresponding to absolute temperature T, R is the gas constant,k is a constant of integration, and Q is a parameter called the heat of transport, characteristic Of the particular system. The value of Q has been determined for hydrogen in Zircaloy-2 by several investigators, using Eq. [11. There is considerable variation in the results, the cause of which has not been resolved; reported values lie in the range 3 to 6 kcal per mole. The physical situation for two-phase thermal migration is much more complex. The -phase boundary for the solubility of hydrogen in Zircaloy-2 ranges from a concentration of 25 ppm at 200°C to a maximum of about 600 ppm at 550°C.4a Thus, if the concentration of hydrogen in Zircaloy-2 is sufficiently great (>600 ppm), the specimen will be entirely two-phase, consisting of a matrix of a-Zircaloy-2 surrounding particles of zirconium hydride. At time zero, with a temperature gradient imposed, the relative amounts of hydride and a-phase in each infinite-simally thin isothermal section of the specimen can be determined from the phase diagram by the lever rule. Moreover, the concentration of hydrogen in the matrix phase varies from point to point, following the a solubility line. Over most of this temperature range (<450°C) 6 phase, Fig. 3, has a constant concentration.5 The diffusion rate toward the cold side should be governed by 1) the slope of the a solubility line and 2) the temperature gradient, The extra complication of two-phase thermal diffusion lies in the fact that migration of hydrogen would leave the a-phase concentration gradient unaffected, since it is fixed at any temperature only by the solubility; gross concentration changes would reflect only the relative amounts of matrix and hydride, which could vary continuously at every point. Migration of hydrogen out of a region would lead to dissolution of hydride, and

Jan 1, 1962

By R. D. Daniels, T. G. Oakwood

A study was made of the effects of small quantities of hydrogen on the mechanical properties of colum-bium. Tensile specimens, hydrogenated to concentrations of 20 to 200 ppm, were tested at temperatures of 300°, 191°, and 77°K. Although hydrogen was found to have little effect on the strength of columbium, the ductility of Cb-H alloys was found to be quite sensitive to both hydrogen concentration and temperature. At 300°K, an abrupt loss in ductility occurred at a critical hydrogen concentration, although some ductility was observed beyond the tolerance limit. A similar result was found at a lower hydrogen concentration at 191°K. At 77°K, however, a more gradual loss in ductility with increasing hydrogen concentration was observed. Hydrogenated columbium was thus observed to undergo a ductile-brittle-ductile transition. Metallographic examination of fractured specimens revealed extensive porosity at both 77° and300°K which was a distinct function of hydrogen content. At 191°K, although some secondary cracking was noted, the amount of observed porosity was minimal. These observations are interpreted in terms of hydrogen solubility and mobility as a function of temperature and in the role of hydrogen in promoting growth of microcracks. lHE effect of hydrogen on the mechanical properties of the refractory metals is not, at present, completely understood. A number of studies have shown these materials to be susceptible to hydrogen embrittlement. Roberts and Rogers1 have found that vanadium can be embrittled by hydrogen. It was further demonstrated that fracture undergoes a ductile-brittle-ductile transition as the temperature is lowered from 150° to -196°C; i.e., there is a ductility minimum observed at a certain temperature. The ductility is increased by either raising or lowering the temperature from this point. A more complete study by Eustice and Carlson2 on vanadium containing 10 to 800 ppm placed the ductility minimum at about -100°C with variations reportedly due to hydrogen content and strain rate. Ductility minima have also been found at certain temperatures for tantalum containing 7 ppm H3 and 140 ppm H.4 At hydrogen concentrations above 270 ppm, however, the ductility return at low temperatures was considerably reduced.4 In the case of columbium, some disagreement exists in the literature. Eustice and Carlson,5 Wilcox et al.,6 and Imgram et al.4 failed to find a ductility minimum although a composition-dependent ductile-brittle transition was observed. Hydrogen concentrations in these investigations were 20 ppm,5 1 to 30 ppm,6 and 200 to 390 ppm.4 However, Wood and Daniels7 observed a rather pronounced ductility minimum at hydrogen contents ranging from 19 to 252 ppm. Those theories of hydrogen embrittlement involving the precipitation of diatomic hydrogen which have been applies to ferrous metals8-12 do not seem to be applicable to the case of columbium and other exothermic occluders. Such theories propose that extensive crack formation and propagation occurs by the precipitation and expansion of diatomic hydrogen at internal voids and microcracks. However, photomicrographs of hydrogenated columbium do not show any evidence of damage introduced by the sorption and precipitation of diatomic hydrogen; rather, at high hydrogen concentrations, a hydrogen-rich second phase is precipitated.13&apos;14 In addition, a number of these theories require the development of high hydrogen pressures at voids in the structure.8&apos;10&apos;12 This does not appear to be feasible in the concentration ranges discussed in the aforementioned paragraphs. The possible interaction of atomic hydrogen with microcracks resulting from dislocation pile-ups15,16 remains in doubt since pile-ups have not been observed in bcc metals17 including columbium.18 Wood and Daniels7 have put forth the possibility that a hydride precipitation could be responsible for crack nucleation in columbium. Work by Longson19 has shown that hydrogen embrittlement of columbium parallels the bulk solubility limit; i.e., as the solubility increases, for instance with temperature, the amount of hydrogen necessary to cause embrittlement also increases. Although a hydride precipitation appears attractive as a means of nucleating microcracks in columbium, what require more intensive study are the low-temperature anomalies which have been observed, i.e., the ductile-brittle-d&apos;ictile transition characteristics. Also, the hydrogen concentrations where embrittlement occurs are often below the bulk solubility limits determined by Albrecht et al.13,14 and Walter and Chandler.20 This work is an attempt to determine more definitively the effects of concentration and temperature on the mechanical properties of dilute Cb-H alloys. EXPERIMENTAL PROCEDURE Ultrahigh-purity columbium rods, obtained from the Wah Chang Corp., were cold-reduced by rotary swaging. A chemical analysis is given in Table I. The material was cut into cylindrical blanks 1.50 ±0.005 in. long. Individual specimens were either given a stress relief anneal at 750°C or recrystal-lized at 1200°C. Resulting microstructures were either a "bamboo" structure characteristic of a wrought material or a recrystallized structure with a grain diameter of approximately 100 n. All heat treatments were carried out in a vacuum of 10-5 Torr or less.

Jan 1, 1969

By S. E. Haszko

SEVERAL new XGa2 intermetallic compounds, Table 1, where X is a rare earth, having the AlB, structure were prepared as part of a continuing study of the magnetic and structural properties of rare-earth alloys.&apos; In this note, the crystallographic results of these compounds are presented. Chart, Eq. 121 for the data in Fig. 1 can be adequately represented by The corresponding standard free-energy change is AF; = -4.576 T log K = -20,900 + 10.20T [5I At low nitrogen concentrations the ratio of mole fraction to weight percentage is a constant so that the mole fraction X of nitrogen is given by X = 0.0392 [%NJ. At low values of X, the activity and the concearation approach each other, hence K, = 0.0392 K,, where K, is expressed in terms of the mole fraction of nitrogen. Hence Eqs. [4]. and [5] become

Jan 1, 1962

By Herbert Hoover

THERE is one problem of the new administration that has received the attention and thought of the organized engineers of America for many years past. This is the problem of the reorganization of the Federal Government. The, inadequacy, the wastefulness, and the inefficiency of our federal organization was evident, enough under pre-war conditions. These inadequacies, these inefficiencies, these wastes were exhibited to the country during the war at the cost of millions. Congress has placed the problem in the hands of a very able Congressional Joint Committee, but if this Joint Committee succeeds in securing the imminently necessary results it will only be by full insistent support to it by public opinion. Many attempts have been made at reorganization before but all, of them have gone to the same crematory-the interminable differences in opinion among the executive and legislative officials over details.

Jan 1, 1921

By W. I. Duvall, D. E. Stephenson. Discussion by R. G. K. Morrison

R.G.K. Morrison (Chairman, Dept. of Mining Engineering and Applied Geophysics, McGill University, Montreal, Que. Canada) - The authors have introduced a subject, the intensive study of which has awaited scientific developments. These are now such as to justify a thorough review of our thinking on the causes and control of rockbursts. The formulae developed in the paper, the comparison between rockbursts and earthquakes in figure 1 and the energy data relating to explosives serve as an effective foundation. In the paper this writer is quoted as suggesting that energy of the order of 10 x 10 11 ft. lb. may have been released in some of the heaviest rockbursts in the Kolar Gold Field. He now hastens to add that such an estimate has no scientific validity. It arises only from a casual comparison of surface and underground effects of the medium heavy bursts, referred to in the paper and estimated by Jones at 3.0 x 1010 ft.lbs., with those of obviously greater magnitude. In any case, we have the estimate by Jones above, that by a team of seismologists 1 on the Witwatersrand of 10 x 1010 ft.lbs., that by Coates of 3.8 x 10" ft.lbs., also referred to in the paper, that by Blan-chard2 for the catastrophic rockburst at Springhill, N.S., of only 7.4 X 107 ft. lbs., and finally the range covered by Cook, referred to in the paper. It is probable also that data for the heavy rockburst at Merkers3 in the WERRA potash area of Germany are available as it was recorded on seismographs from Moscow to Spain. It is the writer&apos;s impression that some standardization is present in the estimates above for 10 x 10 10, 3.8 x 1010 and 7.4 x 107 ft.lbs., respectively. The latter, for Springhill, represents a relatively low order of magnitude. It is obvious that any energy estimate must be related to the local geometry of openings at the time of the event. It is also obvious that any explanation of the causes of rockburst must be capable of providing a wide range of energy. However, we must remember that the energy release is an effect indicating magnitude. The cause lies with the mechanism initiating the primary failure, generating the seismic activity, to which much of the damage is probably due.

Jan 1, 1967

By Hans Conrad, W. D. Robertson

FORMAL theories of yielding and flow have been developed to describe thermally activated plastic flow in metal crystals.&apos;-" hey are all based on Becker&apos;s&apos; original idea that thermal fluctuations aid the applied stress in overcoming internal barriers to flow and lead to the following relation. where j is the strain rate; C is a constant which includes a frequency factor, the entropy, the number of flow units, and the amount of strain associated with each successful fluctuation; E(T) is the activation energy associated with flow, and is a decreasing function of the applied stress, 7; k is Boltzmann&apos;s constant; and T is the temperature in OK. The various theories differ mainly in the model chosen and in the nature of the relationship between the applied stress and the activation energy. Beckerl and Orowan&apos; suggest a relationship of the form E a(Ti — t)2, where .ri represents the stress required for flow without the aid of thermal fluctuations; Kauzmann,3 Cottrel1,5 and Seeger6,7 suggest E a(t — t) ; Fisher8 suggests E while Cottrell and Bilby4 suggest a more complex relationship between E and 7. Additional data are needed to test these various theories., esweciallv- in view of Dorn&apos;s9 ork. which indicates that the activation energy for creep is independent of the stress and strain. The present paper presents the stress-strain data derived from incremental loading of magnesium single crystals in tension and direct shear, in the temperature range of 78" to 364°K. Incremental loading was employed in order that the creep component of the strain could be determined. Stress-strain curves of aluminum10-13 and copper" single crvstals. derived from incremental loading tests, have been found to be in agreement with those obtained by the more conventional constant strain rate or loading rate tests. Two types of tests were conducted in the present investigation: 1) tests in which the temperature was maintained constant throughout the entire

Jan 1, 1958

The following is a, partial list of members and guests who called at Institute headquarters during the period Aug. 10, 1917, to Sept. 10, 1917. L. P. Barrett, Ann Arbor, Mich. Milo W. Krejci, Great Falls, Mont. H. J. Brown, Ridley Park, Pa. Chas. N. La Porte, Peoria, Ill. George M. Cheney, Guayaquil, Ecuador. Askin Nicholas, Bismuth, Australia. W. Lorrain Cook, Chicago, Ill. C. Edwin Nighman, Butte, Mont. John J. Croston, Atlanta, Ga. W. L. Remick, Norfolk, Va. A. F. Duggleby, Santiago de Cuba. T. C. Roberts, Jerome, Ariz. Geo. A. Easley, La Paz, Bolivia. Burr A. Robinson, New Haven, Conn. Burr J. French, Magdalena, Jal., Mex. J. L. Schueler, Peoria, Ill. A. D. R. Galloway, Komfrodua, W. Af. Walter L. Steele, Van Horn, Tex. P. R. Hines, Milwaukee, Wis. F. J. S. Sur, Denver, Colo. T. H. Jenks, Wickenburg, Ariz. C. A. Thomas, Dawson, Y. T., Canada. Paul S. King, Wilmington, Del. E. E. White, Ann Arbor, Mich. Harry Wolf, Golden, Colo. L. W. Bahney has left the Sheffield Scientific School, Yale, to become metallurgical engineer with the Scovill Manufacturing Co., Waterbury, Conn. H. B. Barling, formerly chief engineer of Breitung & Co., of New York, has been appointed manager of the mining department.

Jan 10, 1917

By ED. E. Furman, R. H. Atkinson

HITHERTO the practical creep testing of precious metals has received little or no attention. The only previous creep tests of precious metals have been made with wires under conditions such as to yield much more rapid rates of creep than in engineering tests.&apos;, &apos; Up to the present time the value of creep bars of adequate size, in the absence of real need for engineering data, has deterred investigators. However, the increasing use of platinum at high temperatures has demonstrated the need for reliable creep data for the guidance of engineers, especially those engaged in designing certain specialized chemical plant equipment. In order to supply this need, creep tests were conducted at 1382°F (750°C) on 0.290 in. diam specimens of platinum, 90 pct Pt, 10 pct Rh and palladium. The platinum was high purity, nominally 99.95 pct Pt. The 90 pct Pt, 10 pct Rh was of the same high quality as is used for making gauzes for the catalytic oxidation of ammonia. The palladium was also of high purity; two batches of palladium bars were tested, one deoxidized with calcium boride and the other with aluminum. Spectrographic examination of the palladium confirmed its good quality; the only significant impurities apart from the residual deoxidizers were traces of silicon and lead. Procedure The creep bars, which were furnished by Baker and Co. to our specification, were 6 ¾ in. in overall length with a 4½ in. (4 in. gage length) reduced section 0.290 in. in diam and had the ends threaded (?-NC16). It may be of interest that the bars were valued at up to $600 each. The specimens were supplied in a 50 pct cold-worked condition to facilitate attachment of the creep extensometer, which was of the push rod type. Because of the softness of the platinum and palladium, the extensometer rings were secured to the test section by means of circular knife edges instead of the usual pointed set screws. The extensometer rods extended through the bottom of the furnace and readings were taken with a 0.0001 in. "Last Word" dial gage fastened to the rods for the duration of the test. The bars were directly loaded by hanging weights from the lower specimen grip. All tests were conducted at 1382°F ± 2°F, and an effort was made to maintain the temperature gradient over the test section within 2°F. The ends of the furnace tube were packed with asbestos wool, which allowed a very slow circulation of air through the tube. Annealing was accomplished in the creep furnace before the load was applied. The platinum and palladium specimens were annealed at the test tem- perature for about 17 and 24 hr respectively; in the case of the rhodioplatinum it was found expedient to anneal for 1 hr at 1922°F (1050°C). Pilot samples cut from the same stock as the bars were used to check annealing procedures. Pertinent measurements of grain size and hardness were recorded. Results and Discussion The creep data obtained are given in Table I and the creep curves are plotted in Figs. 1, 2, and 3. Two platinum specimens, tested under a stress of 250 psi, had almost identical creep rates at 2000 hr, namely 0.000008 and 0.000009 pct per hr. A third platinum specimen, stressed at 400 psi, had a creep rate at 2000 hr of 0.000026 pct per hr; the reason for a rather sharp decrease in creep rate during the period from 1200 to 1600 hr is unknown. As it was thought that 90 pct Pt, 10 pct Rh would have a lower creep rate than platinum, the first sample was tested at 400 psi; however, the creep rate was approximately 50 pct greater. Microex-amination revealed that differences in grain size might be responsible for the unexpected result, as annealing at 1382°F developed an average grain diameter of 0.0021 in. in the rhodioplatinum specimen compared with 0.004 in. in the platinum bar. Annealing the alloy for 1 hr at 1922°F (1050°C) increased the average grain diameter to 0.0032 in. and materially improved the creep resistance, making it much better than platinum. A second specimen annealed at 1922°F (1050°C) and tested under a stress of 550 psi had a creep rate of 0.000022 pct per hr at 2000 hr, which was still substantially lower than that shown by the specimen annealed at 1382°F (750°C) and stressed at only 400 psi. In contrast to the creep behavior of the platinum and rhodioplatinum specimens, the palladium bars, whether deoxidized with calcium boride or aluminum, were characterized by high first stages of creep. However, after about 1200 hr of test, the creep

Jan 1, 1952

Safety Factor Characteristic Curves. Their Application to Mine Hoisting Ropes. (Paper by W. A. Boyer, Transactions AIME, 199, 989; Mining Engineering, October 1954. Discussion by B. E. Grant.) ............................................................................................................................. 1101 The Use of Wooden Rock Bolts in the Day Mines. (Paper by Rollin Farmin and Carville E. Sparks, Transactions AIME, 196, 922; Mining Engineering, September 1953. Discussion by Edward Thomas.) ................................................................................................................................. 1101 An Analysis of Mine Opening Failure by Means of Models. (Paper by Bernard York and John J. Reed, Transactions AIME, 196, 705; Mining Engineering, July 1953. Discussion by J. P. Zannaras.) ... 1102 B — Minerals Beneficiation Flotation and the Gibbs Adsorption Equation. (Paper by P. L. de Bruyn, J. Th. Overbeek, and R. Schuhmann, Jr., Transactions AIME, 199, 519; Mining Engineering, May 1954. Discussions by W. E. Ewers and Masayoshi Wada.)........................................................................................... 1103 Manganese Upgrading at Three Kids Mine, Nevada. (Paper by S. J. McCarroll, Transactions AIME, 199, 289; Mining Engineering, March 1954. Discussion by J. Bruce Clemmer, J. B. Rosenbaum, and C. H. Schack.)............................................................................................................. 1105 A Physical Explanation of the Empirical Laws of Comminution. (Paper by D. R. Walker and M. C. Shaw, Transactions AIME, 199, 313; Mining Engineering, March 1954. Discussions by Dimitri Kececioglu, George B. Clark, and Fred C. Bond.) ......................................................... 1106 F — Coal Underground Electrocarbonization of Coal and Related Hydrocarbons. (Paper by T. C. Cheasley, J. D. Forrester, and Erich Sarapuu, Transactions AIME, 199, 908; Mining Engineering, September 1954. Discussions by John G. Tripp and James L. Elder.)....................................................... 1108 Longwall Mining and Mechanization, with Special Reference to Nova Scotia. (Paper by Frank Doxey, Transactions AIME, 199, 701; Mining Engineering, July 1954. Discussion by Louis A. Turnbull.) ........................................................................................................................................ 1109 Cleaning Various Coals in a Drum-Type Dense-Medium Pilot Plant. (Paper by M. R. Geer, W. A. Olds, and H. F. Yancey, Transactions AIME, 196, 696; Mining Engineering, July 1953. Discussion by John Griff en.)................................................................................................................................. 1110 Frontiers in Heat Extraction from the Combustion Gases of Coal. (Paper by Elmer R. Kaiser, Transactions AIME, 199, 304; Mining Engineering, March 1954. Discussion by G. A. Vissac.) ............ 1112 Exploration of the Oaxaca Coal Fields in Southern Mexico. (Paper by Luis Toron and Salvador Cortes-Obregon, Transactions AIME, 199, 505; Mining Engineering, May 1954. Discussion by John D. Price.).................................................................................................................. 1113 H — Industrial Minerals Alkali Reactivity of Natural Aggregates in Western United States. (Paper by William Y. Holland and Roger H. Cook, Transactions AIME, 196, 991; Mining Engineering, October 1953. Discussions by Dexter H. Reynolds and W. L. Merritt.) ......................................................... 1114 Characteristics of Titaniferous Concentrates. (Paper by L. E. Lynd, H. Sigurdson, C. H. North, and W. W. Anderson, Transactions AIME, 199, 818; Mining Engineering, August 1954. Discussion by D. R. Grantham.)........................................................................................................................ 1116

Jan 1, 1955

The first meeting of the Naval Consulting Board was held at the office of the Secretary of the Navy, Washington, D. C., on Oct. 6, 1915. The Board organized by electing Thomas A. Edison, Chairman, Peter Cooper Hewitt, First Vice-Chairman, William L. Saunders, Second Vice-Chairman, and Thomas. Robins, Secretary. All of these officers are members of the American Institute of Mining Engineers. The other members of the Board are given below, and those who are members of the Institute are marked with an asterisk: *W. R. WHITNEY MATTHEW B. SELLERS. L. H. BAEKELAND. HUDSON MAXIM. FRANK JULIAN SPRAGUE. HOWARD T. COFFIN. BENJAMIN C. LAMME. ANDREW J. RIKER. R. S. WOODWARD. HENRY A. WISE WOOD ARTHUR GORDON WEBSTER. ELMER A. SPERRY. A. M. HUNT. *BENJAMIN B. THAYER. ALFRED CRAVEN. *J. W. RICHARDS. *SPENCER MILLER. *LAWRENCE ADDICKS. WILLIAM LE Roy EMMETT.

Jan 12, 1915