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By P. D. Zemany, G. W. Sear, B. W. Roberts

Vanadium metal is embrittled by hydrogen at a temperature as low as 250°C when held in the presence of manganese metal and water vapor in a rough vacuum. It is established that the property changes are caused by the catalytic decomposition of water vapor at the vanadium surface and the diffusion into and solution in the vanadium of the resultant hydrogen. It is found that manganese is a necessary component of the catalyst. The manganese is transported in the vapor phase by an unknown molecule. A deuterium tracer experiment demonstates the role of water vapor in the embrittle-ment process. VANADIUM metal foils were observed to become embrittled' at a temperature of about 300 °C when held in the presence of manganese metal and a small amount of moist air, This paper describes the investigation to find the embrittling agent and an understanding of the relatively low temperature reactions that are involved. Experimental The vanadium metal foil used was prepared by cold-rolling and pack-rolling 32 mil sheet" in a series of steps down to 1 mil foil. The original observation was confirmed by sealing vanadium foils of 3 x 10 sq cm into individual Pyrex tubes with manganese powder† and a con- trol tube containing only the vanadium foil. These tubes were evacuated to 10 -5 mm Hg without baking and sealed. After heat treatment for 200 hr at 300°C, the control foil showed no change in duetility, whereas the foil contained in the manganese— containing tube was embrittled. The visual appearance of each was unchanged. A series of Pyrex sample tubes, about 2.5 cm diam and 25 cm long, were prepared, each containing a 3 x 10 sq cm piece of foil and 5 g manganese powder at the lower end of the tube. By reducing the time of anneal and the temperature of these samples, it was found that embrittlement could be created at 250°C in a time as short as 1 hr. Since the vanadium metal used here has been drastically cold-worked by rolling, it is assumed that it contains a maximum number of dislocations. To check the possible necessity of dislocations in this low temperature reaction, a vanadium foil sample was annealed in Vycor for 2 hr at 800°C to re crystallize and reduce the dislocation concentration. Metallographic examination showed grains which were not visible before annealing. The embrittlement procedure was carried out at 300°C and 3 hr. Upon checking the foil no embrittlement was observed. Further experiments demonstrated that about 6 hr at 300°C are required to create embrittlement in the foil. This delay in the onset of embrittlement in the vanadium foil suggests but does not prove that dislocation channels play a role in the embrittlement phenomena. If manganese metal is necessary for this low temperature embrittlement, do other elements in the transition metals group yield the same result? To check this qualitatively, a group of elements of similar atomic radii were obtained and sealed as before into Pyrex tubes with a sheet of vanadium foil. These tubes were annealed at 250°C for 6 hr and included (with radii)-2 A1 (1.4A), As (1.25A), Be (1.2A), Co (1.25A), Cr (1.45A), Cu (1.25A), Fe (1.25A), Ga (1.2A), Ge (1.25L%), Mn (1.3A), Ni (1.25A), Si (1.2A), Ti (1.45A), Zn (1.3A), air, H,O, 10 cm Hg of dry hydrogen, and MnO, powder. Upon testing the above sample foils for brittleness, only the manganese-containing tube yielded a brittle foil. Manganese Transport—To eliminate contact of manganese metal powder and vanadium foil, sample tubes were prepared with fritted glass barriers. The embrittlement reaction was still found to occur. Thus, the mode of transfer of manganese is certainly vapor transport. A vanadium foil was embrittled by this mechanism in an evacuated Pyrex tube for 8 hr at 300°C. By means of X-ray fluorescence analysis,' the amount of manganese added to the surface was established at 5 ±2 x 10 -6 g per sq cm. Since the average rate of manganese deposition is known, an effective average pressure of an assumed carrier compound can be computed. ___ P = M/T v2p mkT

Jan 1, 1959

By L. W. Berger, R. I. Jaffee, D. N. Williams

The effects of hydrogen on the properties of binary Ti-A1 alloys containing 2.5, 5, and 7 pct aluminum and ternary alloys of the same compositions with added interstitial elements oxygen, nihrogen, and carbon were studied. Aluminum increases the apparent hydrogen solubility of the a-phase, resulting in a marked increase in resistance to impact embrittlement. In the Ti-5Al and Ti-7Al alloys, for example, the addition of 180 and 305 ppm hydrogen, respectively, did not cause embrittlement, while unalloyed titanium was embrittled by as little as 75 ppm. The role of aluminum in increasing hydrogen solubility of the a-phase probably accounts for the excellent hydrogen tolerance of a-ß alloys containing considerable amounts of aluminum. There is some evidence that aluminum retards the rate of hydride precipitation. If so, these alloys may be susceptible to slow-strain embrittlement. UNALLOYED a-titanium is extremely sensitive to small amounts of added hydrogen in that there is a marked decrease in notch properties. For example, as little as 100 ppm hydrogen is sufficient to lower the room-temperature notch-impact strength from over 100 to less than 20 in.-lb.' This loss of impact Strength has been associated with the Presence of hydride phase in the microstructure. Hydrogen in the amounts encountered in commercial practice

Jan 1, 1959

By L. W. Berger, and R. I. Jaffee, D. N. Williams

The effects of hydrogen on the properties of binary Ti-A1 alloys containing 2.5, 5, and 7 pct aluminum and ternary alloys of the same compositions with added interstitial elements oxygen, nihrogen, and carbon were stzdied. Aluminum increases the apparent hydrogen solubility of the a-phase, resulting in a marked increase in resistance to impact embrittlement. In the Ti-5Al and Ti-7Al alloys, for example, the addition of 180 and 305 ppm hydrogen, respectively, did not cause embrittlement, while unalloyed titanium was embrittled by as little as 75 ppm. The role of aluminum in increasing hydrogen solubility of the a-phase probably accounts for the excellent hydrogen tolerance of a-ß alloys containing considerable amounts of aluminum. There is some evidence that aluminum retards the rate of hydride precipitation. If so, these alloys may be susceptible to slow-strain embrittlement. UNALLOYED a-titanium is extremely sensitive to small amounts of added hydrogen in that there is a marked decrease in notch properties. For example, as little as 100 ppm hydrogen is sufficient to lower the room-temperature notch-impact strength from over 100 to less than 20 in.-lb.' This loss of impact Strength has been associated with the Presence of hydride phase in the microstructure. Hydrogen in the amounts encountered in commercial practice

Jan 1, 1959

By W. M. Albrecht, M. W. Mallett

The solubilities of hydrogen in titanium and several of its alloys were determined at 600 to 1000°C and pressures of 0.05 to 10µ of mercury. Solubility increases with increasing beta phase in the alloys. Factors found to affect degassing rates are specimen size and presence of thick surficial oxide. Removal of hydrogen by heating in vacuum and in flowing inert atmospheres was studied. Practical curves predicting minimum degassing times are presented. THE presence of hydrogen in titanium and titanium alloys has detrimental effects on the mechanical properties of the metal.'"," The hydrogen content of commercial titanium is sometimes of the order of 200 ppm by weight' and varies with alloy composition. As a consequence, titanium and some titanium alloys as normally processed are sometimes not ductile unless treated to lower the hydrogen content. The best known hydrogen-removal treatment is heating the material in a vacuum. The rate of removal (degassing) at a give temperature determines the duration of the treatment required to attain a satisfactory low hydrogen level.

Jan 1, 1959

By R. N. Zitter

PRESENT work was done in connection with a program for obtaining a low energy gap semiconductor suitable for photodetection. The inter-metallic compound InSb, which is now being in-

Jan 1, 1959

By C. F. Frey, P. J. Ahern, J. F. Wallace

THE high affinity of molten titanium for oxygen and nitrogen has resulted in considerable difficulty in developing a satisfactory melting procedure. It has been found necessary to perform melting operations either in a vacuum or inert atmos-phere, and failure to obtain a satisfactory crucible material has necessitated the use of special melting techniques. These techniques have included cold-mold arc-melting utilizing both consumable and nonconsumable electrodes, skull-melting, drip-melting, and levitation melting.' It has been recognized generally that the melting of both titanium sponge and titanium scrap would be expedited by the use of induction-melting procedures but the lack of a crucible capable of containing molten titanium without objectionable contamination thus far has prevented the use of induction-melting procedures. An extensive investigation: which included the common refractory materials was not successful in developing a satisfactory crucible for induction-melting. Some success in induction-melting has been attained with the use of a graphite crucible material, but in all instances sufficient carbon contamination was encountered to cause an appreciable reduction in the optimum mechanical properties of the titanium or titanium alloys. These investigations"" report an increase in the carbon content from approximately 0.3 to 1.0 pct. A serious reduction in the tensile and forming properties has been observed as a result of this carbon contamination. The development of a satisfactory induction-melting procedure for titanium without undue contamination undoubtedly would have considerable economic significance. Such a process would be particularly useful in melting the large quantities of low-cost scrap now available that can only be reprocessed at considerable expense and difficulty by the more elaborate techniques referred to previously. In addition, the process could provide a satisfactory method of melting and alloying of bri-quetted sponge for forging ingots.

Jan 1, 1959

By C. G. Dunn, P. K. Koh

Microstructure, magnetic torque, and texture data before and after grain growth were obtained on two 3.25 pet Si-Fe specimens having initially the same cold-rolled textures and the same primary recrystallization textures. The latter textures consisted of four components, two only of which were strong; the strong components were near (120) [001] and (320) [001]. The textures of the two specimens obtained by grain growth were different. In one specimen the two weak components were converted into strong components by a secondary recrystallization process; in the other specimen the primary recrystallization texture was retained by a normal grain-growth process. The difference in behavior of the two specimens was interpreted in terms of a difference in the relative grain sizes between weak and strong components; i.e., in terms of a geometrical factor that would alter the early growth rates of grains belonging to the two weak components of the texture. Specifically the growth rate was considered as the product of two terms: a driving force and a boundary mobility. The texture changes observed are considered to favor the oriented-nucleation growth-selectivity theory more than the oriented-growth theory. WHEN primary recrystallization and grain-growth textures form as a result of annealing deformed metals or alloys, the fundamental processes involved are nucleation and growth. Knowledge, therefore, about nuclei and the factors influencing their growth is required not only for the understanding of texture development but also for its control. In the oriented-growth theory of texture formation1, 2, 3 the problem of nuclei is generally disposed of by the assumption that nuclei are available in all orientations; the theory then has to explain the final texture from the initial texture and the way boundary mobility depends on orientation. In the oriented nucleation theory of texture formation"' nuclei are considered to be present only in certain orientations but the importance of growth selectivity is still recognized. For example, the mobility of boundaries of approximately the same orientation and of the coherent type in twins is believed to be low while that of high-angle boundaries, in general, is high. Because of this the theory may be described as an oriented-nucleation growth-selectivity theory. The main feature of the oriented-nucleation theory, however, is the importance given to nuclei; i.e., how they form in specific orientations and how they grow. In the present investigation two cold-rolled single crystals were used to study the effects of growth after primary recrystallization. The cold-rolled textures and the primary recrystallization textures were determined from portions of these specimens and reported earlier.",' The two cold-rolled crystals were in the (111) [112] stable end orientation, the recrystallization textures were nearly identical and consisted of two strong components, designated M and M', which were near (120) [00l] and (320) [00l], respectively, and also some specific weak components near (111) [110] and (111) [110]. It is well recognized that a single strong component in the primary recrystallization texture may be needed for secondary recrystallization3, 5, 8 but unfortunately when this is the case the amount of material left in deviating orientation may be too small either for growth or for positive identification. The present samples proved to be almost ideal for the study of minor components and their influence on texture changes produced by growth after primary recrystallization. The results obtained are interpreted in terms of present knowledge of grain-growth processes. Experimental Procedure Two lots of silicon-iron alloy of essentially the same composition, namely, 3.25 pet Si, 0.004 C, 0.009 P, 0.010 S, 0.035 Mn, 0.070 Ni, 0.090 Cu, 0.009 Sn, with traces of A1 and Cr and the balance Fe, were converted into single crystals 0.025 in. thick and 1.25 in. wide. The orientations were predetermined by the method of reorienting a seed crystal as described elsewhere.3 pecimen 1 from one lot had the (335) [556] orientation while specimen 2 from the second lot had the (111) [112] orientation.* Both crystals were cold rolled to a reduction in thickness of 70 pet while widening approximately 20 pet. Samples of each were selected for determining 1) the cold-rolled texture, 2) the time required at

Jan 1, 1959

By B. J. Reid, J. N. Greenwood

It has been shown1 that cavities are formed in the grain-boundaries of copper and 70:30 brass (as well as in magnesium) by the application of tensile stresses at elevated temperatures. For a given rate of strain, cavities are formed in brass at a lower temperature than in copper, and they are larger; it was thought that this earlier onset of cavitation in the alloy might be caused by the distortion produced in the metal lattice by the alloying element. If the cavitation is caused by the vacancy-migration mechanism, ' the distortion of the lattice would reduce the energy required for vacancy formation, and thus provide vacancies more readily to assist in the cavitation process. It was decided to study a range of alloys to find out whether increasing amounts of an alloying element would cause any progressive increase in, or modification of, the cavitation in copper. Nickel was chosen for this purpose, since it is soluble in copper throughout the whole range of alloys. A further advantage was its low vapor pressure, which enabled the preparation of the alloys in vacuum and the consequent reduction of their hydrogen content. It has been suggested that cavities may be nucleated by the migration of hydrogen atoms to the less regular atomic spacing at the boundary, and their combination to form molecules. The latter being too large to diffuse back into the lattice, form stable cavities into which vacancies could condense. PREPARATION OF ALLOYS All alloys, ranging from pure OFHC copper to 43.7 at. pct of nickel (carbonyl), were prepared in a vacuum furnace employing high-frequency induction heating. When a charge was melted, vigorous gas evolution occurred initially, after which the pressure was reduced to 10-4 mm Hg, using an oil-diffusion pump. After remaining molten for a further 1/2 to 1 hr to aid degassing, the melt was allowed to solidify in the crucible. In this way contamination by gases evolved from the surface of a separate mold was avoided. The list of alloys prepared is shown in Table I. The percentage of hydrogen present in the OFHC copper was reduced from 0.0054 at. pct to 0.0012 at. pct, as measured by a vacuum-fusion method. The alloys were cold-rolled to 0.03-in.-thick strip, and were homogenized in vacuum for 1 hr at 900°C after every 30 pct reduction. At a thickness of 0.05 in., the strip was held at 450°C for 24 hr under high vacuum (10-5 mm Hg) in an attempt to reduce the hydrogen content still further. Tensile specimens were prepared with a gage length of 1 in., and were finally annealed for 2 hr at 800°C to give an average grain diameter of 0.1 mm. TENSILE DEFORMATION The specimens were deformed in a tensile straining machine operated by a synchronous motor at a constant rate, equivalent to 1.7 pct per hr on a 1-in. gage length. The specimen and grips were contained in a vacuum jacket. A pressure of 10-2 mm Hg was maintained, which was sufficient to prevent surface tarnishing of a specimen held at 650°C for 24 hr. Tests were made between 20. and 650°C and the temperature was controlled to within ±3° over the gage length. The load was measured by the deflection of a cantilever spring. a) Mechanical Properties-The ductility curves shown in Fig. 1 fall into two groups. Figs. 1(a) and (b) for copper and the 5 pct nickel alloy, respectively, show a continuous fall in ductility with a steep fall between 200° and 400°C. Figs. l(c) to (f) show the same sudden loss of ductility between 200° and 400°C. With higher temperatures, however, there is a recovery in ductility values to a maxi-

Jan 1, 1959

By E. H. Greener, M. E. Fine

The internal friction (1/Q) of cobalt Fig. 1 (measured by an electrostatic dynamic method1) near 250°C begins to increase rapidly on heating and continues to increase until 560°C, the highest tem- perature measured. In the plot of log of 1/Q against 1/T, above 250°C the data nearly fit two straight lines intersecting at 400°C, approximately the temperature of the hexagonal-cubic transformation. The higher temperature branch corresponds to an effective activation energy of 6500 cal per mole, the lower temperature branch 11,000 cal per mole. Young's modulus Fig. 2 increases approximately

Jan 1, 1959

By L. S. Castleman, L. L. Seigle

THE formation and growth of intermetallic phase layers is of considerable practical importance to metallurgists interested in diffusion bonding and cementation processes and has been the subject of extensive qualitative investigation. In contrast, it is somewhat surprising that so little quantitative data have been amassed. The need for additional fundamental work was pointed out by Mehl in 1936,' and persists to a large extent to the present day. The early studies have been reviewed by Rhines,2 and his conclusions have been summarized by Lustman and Mehl3 substantially as follows: 1) All phases that are stable at the temperature at which diffusion occurs will appear in the interdiffusion of two metals; however, in some cases, certain of the phases may be too thin to be observed and identified easily. 2) The isothermal growth of intermetallic phases generally obeys a simple parabolic equation of the form X2 = Kt, where x is the thickness of the alloy layer, K the temperature dependent reaction rate constant, and t the time. 3) The rate of thickening varies with temperature according to the Arrhenius equation k = Ae -Q/RT , where k is the parabolic rate constant, A, a temperature independent constant, Q the heat of activation for the process, R the gas constant, and T the absolute temperature. Subsequently, Lustman and Mehl made a quantitative study of the laws of growth in intermediate layers in a number of binary systems, in which one of the components was either zinc or cadmium, and the other component was one of the following: nickel, copper, silver, cobalt, gold, iron, or Monel metal; the interdiffusion times used were for the most part less than 24 hr. It was found that the simple parabolic law was not obeyed in general, but that a generalized parabolic law of the form xn = kt was valid, where n was a temperature dependent constant; also,

Jan 1, 1959

By J. H. Wernick, J. E. Kunzler

HIGHLY pure metals are needed for low-temperature electron transport studies in progress. Recent improvements in purification techniques, such as zone refining, have made it possible to obtain metals with improved purity. For some metals, the improvement has been to the extent that ordinary analytical techniques are inadequate and special methods are needed.1 For other metals purification is more difficult, so that simple but rapid analytical methods are desirable as an aid in evaluating the effectiveness of purification procedures. Furthermore, it is desirable to be able to determine the impurity level of the sample or ingot with the minimum of physical disturbance of the material. In order to aid in the preparation of purer metals, techniques involving the measurement of electrical resistance at liquid-helium temperatures have been devised for studying impurity distributions in zone-refined ingots and other bulk samples without destroying the ingot or its geometry. The method yields information on the variations in purity along the length of the ingot or sample and provides a measure of the overall purity of the material. Compared with ordinary analytical methods, the resistivity method is rapid, sensitive, and does not require significant physical disturbance of samples with reasonable shapes. It has the disadvantage that resistance measurements are not specific, i.e., they do not identify the impurity. However, this disadvantage is offset by the advantage of being able to establish a measure of the overall purity so far as electrically active" impurities are concerned. METHOD AND ITS BASIS The method is based on the well-known fact that the resistivity, at Liquid helium temperatures, of a reasonably pure metal containing no regions with additional phases decreases with increasing chemical purity or a decrease in the number of physical defects. It is convenient to separate the total resistivity into three parts: where is the resistivity due to the scattering of the conduction electrons by the lattice vibrations or phonons, p is the contribution due to physical defects, and originates from the effect of chemical impurities in the metal. Insofar as Matthiessen's rule is obeyed,2 pphys and pchem are independent of temperature. Except possiblyin the very purest metals, ptherm is negligible at liquid helium temperatures and For zone-refined metals, which normally are well annealed and consist of large grains, at the chemical purity levels thus far attained the available data indicate that pphys is negligibly small or at least constant throughout the ingot. Assuming that the effect of physical defects is negligible for isotropic metals, This assumption appears consistent with most of

Jan 1, 1959

By M. T. Simnad, R. F. Mehl, L. Yang

Techniques for studying marker movement in K-Rb interdiffusion have been worked out. The results indicate that Rb diffuses faster than K and that the ring mechanism of diffusion cannot be the dominant one operating in this case or probably in cases involving other alkali metals, despite their low ion core repulsive energies. SEVERAL theoretical attempts have been made in the past decade to elucidate the mechanism of diffusion in body-centered-cubic metals. No general agreement, however, has been reached by different authors. Zener,1 and later LeClaire,2 on the basis of a correlation between the entropy of activation for self-diffusion and the temperature dependence of the elastic constants, predicted that a ring mechanism should operate in the diffusion of body-cen-tered-cubic metals. Paneth3 calculated the activation energies of various ring, vacancy, and interstitial mechanisms for the self-diffusion in alkali metals and concluded that the most likely one was based on the linear motion of "crowdions," which is in fact a different form of interstitial diffusion. Fumi,1 however, showed that the experimental values of the activation energies for self-diffusion in the alkali metals could be better accounted for if the diffusion process in these metals was assumed to follow a vacancy mechanism. The same conclusion was reached by Kojima5 for the self-diffusion in lithium. Experimental evidences published during the past few years seem to exclude the ring mechanism as the predominating one in the diffusion of body-centered-cubic metals. For instance, maker movement has been observed in ß-brass, first in this laboratory" and later by Resnick and Baluffi.5 Shewmon and Bechtoldh also found marker movement in the body-centered-cubic system Ti-Mo and showed that the argument which led Zener and LeClair to favor a ring mechanism was not incompatible with a vacancy mechanism. In spite of this, it seemed to the authors that further experimental tests should be made by studying the Kirkendall effect in body-centered-cubic systems that characteristically have small ion core repulsion, such as the alkali-metal systems. Since the ion core repulsion term constitutes the main part of the activation energy needed for the rotation of a ring, such a test should be the most critical of all. The system K-Rb was chosen for experimental study because these metals form a continuous series of solid solutions. Experimental Investigation Owing to the extremely active nature of these two metals, a brass dry box (18 x 11 x 10 in.) was built for making the diffusion couple. It had a big lucite window on top, two side ports through which neo-prene-rubber gloves were inserted, and another side port covered with an optically flat-glass window for microscopic examination of the sample. Inside the box there were a circulating fan driven with a rotating horse-shoe magnet located outside the box, a heater used to generate potassium vapor for getter-ing the box, and a cold trap for keeping the inside of the box cool. Chemically pure grade K and Rb were triple distilled before they were transferred in vacuum into cylindrical steel molds kept in pyrex-glass ampules, Fig. 1. The latter together with the tools needed for making the diffusion couple were put into the dry box. After the box was flushed with purified argon and gettered with potassium vapor, generated from a heated steel crucible inside the box, the glass ampules were broken and the mound on the top of the alkali-metal ingot was cut off with a razor blade to yield a flat surface. To make the diffusion couple, one K ingot and one Rb ingot were pushed out of the molds together with their steel supports by screwing a metal plunger into the bottom of each mold. They were then laid on a brass cradle inside the assembling carriage (shown separately in Fig. 2) with the flat faces opposite to each

Jan 1, 1959

By I. S. Servi, N. F. Graves

THE etch-pit technique has long been used to reveal low-angle boundaries and, in general, the distribution of dislocations in high-purity metals. Often this technique is amenable to quantitative computations,' but generally is affected by some degree of uncertainty because etch pits can be nucleated not only by dislocations, but also by inclusions and surface imperfections. In the case of high-purity zinc, Gilman' reported that etch pits were produced only after adding 0.1 atomic per cent of cadmium to the crystals and aging at a proper temperature. In the course of a study of low-angle boundary behavior in zinc crystals, etch pits were produced in 99.999 pct zinc without resorting to intentional contamination, by etching in a 50:50 HNO3H2O solution. The technique consists of etching until the heat of reaction brings the solution to a boil, and in displacing the etchant rapidly with a stream of cold water, thus avoiding staining. The undesirable features of this technique are the heating effect and the removal of a considerable amount of material. A high polish is obtained if staining is controlled properly; therefore, the etch pits appear very clearly and with excellent contrast when observed under dark field illumination. This is especially helpful for cursory examinations at low magnifications. Several observations were made on zinc crystals of square cross section, having one face parallel to the basal plane and one edge parallel to a slip direction, Fig. l(a). When such a crystal was bent about 2" over a glass die and annealed at 390°C, a sharp boundary was formed only in the inner portion of the crystal. Near the two prismatic faces, perpendicular to the basal plane, the boundary was always branched into many lower-angle boundaries, Fig. 1(b). Attempts to move the main boundary by applying a shear stress to the specimen invariably resulted in curving the boundary, the branched ends remaining pinned in their original location, Fig. 1 (c). The prismatic face, when etched as indicated in the foregoing, revealed the existence of numerous (sometimes up to 30) fine boundaries, nearly parallel to each other. Pre-existing lineage boundaries, generally parallel to the direction of growth, were barriers to the formation of polygonization boundaries and interrupted the continuity of the substructure, Fig. 2. Twin

Jan 1, 1959

By C. S. Smith

It is the policy of The Metallurgical Society to provide, in the TRANSACTIONS OF THE METALLURGICAL SOCIETY OF AIME, a prompt and accurate medium for publication of reports of significant new research in both the scientific and engineering aspects of metallurgy. Papers submitted to the Society are judged by competent reviewers according to established criteria for technical merit, accuracy, originality, and presentation. STAFF: Editor, Dr. Gerhard Derge; Editorial Assistant, M. A. Redmyrski; Staff Coordinator, James J. Burke. THE METALLURGICAL SOCIETY: W. R. Hibbard, Jr., President; J. C. Kinnear, Jr., Post-President; John Chipman, Vice President; T. D. Jones, Treasurer; R. W. Shearman, Secretory. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: A. W. Thornton, Chairman- Dennis Carney John Chipman J. C. Fulton J. H. Hollomon H. H. Kellogg, A. E. Lee, R. Moddin, J. D. sullivan, and D.' Swan. Review and selection of manuscripts is under the supervision of the following Publications Committees: Extractive Metallurgy Division: T. B. King, Chairman; S. J. Dickenson, R. P. Hermsdorf, R. Schuhmann, Jr., and P. T. Stroup. lnstitute of Metals DM lion: Robert Maddin, Chairman. F. Lincoln Vogel, Jr.. Vice chairman. W. A. Backofen R. W. Boliuffi J. H. Bechtold' M. B. Bever R: S. Busk C 6. Goetzel poul Gordon C. D. Grobom, Jr., Robert F. Hehe-mann R. I. Joffee F. i. Joumot Jr. lrvin R. Kromer, A. J. Leno. Horold Morgolfn, C. J. McHargue, Russell A. Meussner, J. B. Newkirk, H. W. Paxton, G. E. Pellissier, I. S. Servi, Alon U. Seybolt, A. J. Shaler, and Jack Washburn. Iron and Steel Division: J. C. Fulton, Chairman. T. B. King, F. C. Laogenberg, W. O. Philbrook, and T. 0. Winkler. Publishod bimonthl by the American Institute of Mining Metollurgicol and Petroleum Engineers Inc., 29 West 39th Street, New York 16, N. Y. Telephone: PEonylvanie 6-9220. Subscription $20 par yew for non-AIME members in United States and North, South and Control Americo $25 foreign; $5 for AIME members. Single copies, $4.00, single copios foreign $5,00. The AIME is 1958 by the Amarican mode or opinion axpressed in it* publications ... Copyright by the Amarican lnstitute of Mining, MataIlurgicol, and Petrolum Engineers, Inc,. . . Reg. istered cable address AIME New Yark ... Indexed in Engineering Inderx, Industrial Arts ...Index and Chemicol Number5. Absrtracis . . . Second class postage paid at New York,Indor. N. Y., Industrialond Ann Arbor, Mich.

Jan 1, 1959

By D. Turnbull, H. N. Treaftis

Precipitation of tin from Pb-Sn alloys (lead-rich) occurs by the nucleation and growth of hemispherical cells which consist of tin lomelloe interspersed in the depleted solid solution. Nucleation and growth of these cells and the tin interlamellar spacing at various compositions and temperatures have been investigated. The interlamellar spacing increases approximately as the reciprocal of the logarithm of the supersaturation ratio. For constant initial tin concentration the concentration of cell nuclei increases with decreasing temperature to a limiting temperature-independent value. The kinetic results support the view that the cell growth rote is governed by the diffusion of tin along the cell boundary. In the main, the results confirm the authors' earlier deductions, drawn from resistometric and calorimetric data, about the precipitation mechonism. IT has been shown1, 2 that tin (ß) precipitates from lead-rich (a) PbSn solutions by the nucleation and growth of cells (cellular or discontinuous precipitation). These cells consist of tin lamellae, with a spacing 1, interspersed in a depleted a solution. Reorientation of a also accompanies cell growth. The kinetics of cellular precipitation of tin from lead have been measured by resistometric2, 3 and ca1orimetric1, 3 techniques. The time-transformation isotherms (t equals time; x, volume fraction of specimen transformed) of the initial rapid precipitation, which drains about 60 pet of the tin from solution, have been described by a kinetic law having the form x = 1 —exp (—bt n) [I] where n usually has the value 3.0. It was shown" that this law and the other kinetic facts can be explained satisfactorily if it is assumed that the cells grow at a constant rate and that all the cells nucleate in a time negligible in comparison with the period of cell growth before impingement. Thus, for hemispherical cells b = (2/3)pNG3 [21 where G is the rate of cell growth in cm per sec, and N is the number of cell nuclei per unit volume. The rapid rate of cell growth at low temperatures can be accounted for"' if it is assumed that the dissolved tin drains to the lamellae edges by diffusion along the sweeping cell boundary rather than by diffusion through the a crystal (volume diffusion). For cell growth governed by cell boundary diffusion it was shown, approximately G=2(X° - X° / X° ) DBA / l2 where A equals the thickness of the cell boundary; D R, the coefficient of diffusion of tin atoms within the boundary; and X° and X, are the atom fractions of tin in the supersaturated and saturated solutions, respectively. Zener8 had already shown that, where

Jan 1, 1959

By G. W. Preckshot, J. W. Gorman

MOLTEN metals offer an excellent medium for the study of molecular diffusion and interphase transfer. In the absence of intermetallic compound formation, solutions of molten metals are solutions of elements. Therefore, complicating factors such as molecular structure, dissociation, association, polarization, and so on, are generally absent. Further, metals remain in the liquid state over a wide range of temperature. Thus, the effect of temperature on transport processes can be studied in more detail. Although some data are available for the diffusion of metals in the molten state at high temperatures,"""".'!' the most useful and accurate data are those for the diffusion of various elements in mercury at room temperature. The effective radius of diffusion for the various elements in mercury may be calculated from the Stokes-Einstein relation.'-These calculated radii are compared with the atomic and ionic radii calculated from X-ray data on crystals." The effective radii of diffusion of the alkali and alkali-earth metals correspond to those of the neutral atom; those of cadmium, silver, lead, zinc, thallium, bismuth, and tin correspond to ionic radii; and those of copper and gold indicate larger radii due to association with mercury or more likely, faulty diffusion data. Independent evidence"' supports the notion that alkali metals are uncharged in amalgams. The concept of metals moving free of their conductance electrons in the liquid state has been discussed by Eyring, et al,'" in connection with studies on the viscosity of pure molten metals. Considering the approximate nature of the tabulated atomic and ionic radii and the variance in the diffusion measurements, the application of the Stokes-Einstein equation to the diffusion of metals in mercury gives gratifying results. It is noted that a number of these metals have article radii eaual to or less than those of the solvent mercury.".'*,"' Soba1,'" sing the inaccurate Roberts-Austin20 data, indicated that the effective radius of diffusion might well be a function of temperature. Additionally in studies of mass transfer between phases, many conflicting opinions have been expressed concerning the assumption of equilibrium at the interface." ,","," The results of the present work on the diffusion of solid copper in molten lead throws light on the tempera- ture variation of the diffusion radius as well as the extent of the interfacial resistance. The theoretical background and experimental procedure are presented here in detail. Results on other systems will be presented in subsequent papers. Nomenclature The following nomenclature is used in the paper: A—cross-sectional area of diffusion column, sq cm C, C,—concentration of solution and saturated solution respectively, g per cc D,D'—-diffusivity, sq cm per sec e—Naperian base h—ratio, k/D k—mass-transfer coefficient, cm per sec L—diffusion column length, cm n—series index q—flux, g per sq cm-sec r—radius, cm or A R—-gas constant t—time, sec T—temperature, K V—volume, cc w—weight of copper-lead alloy on copper cylinder WT—-total copper transferred to lead diffusion, column, g Z—distance from top of diffusion column, cm 2'—distance from copper-lead interface, cm (2' = L-2) u,,—roots of diffusion equation Mathematical Apparatus The model shown in Fig. 1 applies to the diffusion of solid copper into molten lead. Here Fick's first law may be written where all terms are defined in the nomenclature. It is assumed that the volume of the lead column is constant. This is justified since experimental densities compared favorably with calculated densities based on perfect interstitial mixing. Thus there is no counter diffusion of lead. It is clear that 2 in Equation [I] should be measured relative to the interface which moves relative to the diffusion cell but not to the liquid phase. Hence, the frame of reference is the plane of the copper-lead interface. The diffusivity calculated at constant volume, D", is that defined by Hartly and Crank" and is designated herein as D. No Interfacial Resistance—The two situations of the presence and absence of interfacial resistance will be treated. The simplest is the latter which re-

Jan 1, 1959

By W. D. Forgeng, B. F. Decker

IT has been known for almost a century' that silicon and nitrogen combine when heated to a high temperature. Three nitrides have been reported, SiN, Si3N,, and Si,N, containing 33.3, 40.0 and 42.9 pct nitrogen by weight, respectively. The existence of SisN, is well established but that of Si,N, and SiN is doubtful. The first systematic study of the reaction between silicon and nitrogen was made in 1910 by Weiss and Engelhart" who determined the rate at which silicon absorbed nitrogen at temperatures from 1250°C to

Jan 1, 1959

By B. N. Das, J. B. Darby, P. A. Beck, Y. Shimomura

A POWDER pattern for the (Cr, Mo, Co)R-phase annealed at 1200°C was reported in 1951.1 Through the courtesy of Prof. D. P. Shoemaker of Massachusetts Institute of Technology the authors became aware of inconsistencies of this pattern with that to be expected from the structure of the R-phase, as determined by Komura, Shoemaker, and Shoemaker.' In addition, Professor Shoemaker also noted that the powder pattern reported8 for the (Cr, Mo, Co)D-phase, annealed at 1300°C, agreed fairly well with that to be expected from the newly determined structure of the R-phase. In view of these findings, the previously reported powder patterns of the R-phase and of the D-phase were compared carefully. It was found that most lines in the two patterns (22 lines) were to a fair degree of accuracy related to each other by a single conversion ratio for the corresponding d spacings. The value of the conversion ratio was found to be 1.0058, so that the d spacings of the D-phase pattern previously reported were larger than the correspond- ing d spacings for the reported R-phase pattern by approximately that factor. The intensity relationships between corresponding lines in the two patterns were similar, as judged visually. The following exceptions were noted: Lines Nos. 2, 3, 19, 20, 21, 22, 23, 24 and 25 of the D-phase pattern,:' all designated weak or very weak, were missing in the apparently somewhat fainter R-phase pattern used.' Lines 1, 2, 3, 5, 15 and 34 (all weak or very weak), reported for the R-phase, were missing in the D-phase pattern, Table I. In view of these observations it seemed probable that the two patterns differed from each other mainly by a slight change in lattice parameters (with c/a remaining approximately constant), and that the pattern previously reported for the R-phase contained some weak extraneous lines, most likely to be attributed to impurities. In order to check the foregoing assumption, two specimens of an alloy containing 43 pct by weight of cobalt, 41 pct molybdenum, and 16 pct chromium, which was within the composition range of stability of both the D-phase at 1300°C and of the R-phase at 1200°C, were homogenized at 1200 and 1300°C, respectively, and quenched. X-ray diffraction patterns of the powders of these two specimens, obtained with CrK radiation, were compared carefully with each other and with the D-phase pattern previously

Jan 1, 1959

By M. Cohen

THERE seems to be a natural urge for the human mind to wonder about the beginning of things. When an explosion occurs, we immediately inquire "what set it off?" If a person contracts a disease, we are likely to ask "how did it happen?" On a much loftier plane, when we reflect about the universe, there is the inevitable question "what, or rather Who, started it all?" In principle, these varied queries have at least one attribute in common: they are attempts, whether earnest or casual, to search out the origin of events in nature. Accordingly, they involve not only scientific, but philosophical and even re1igious matters of deep concern. It is evident that, in a broad sense, the phenomenon of nucleation is enmeshed in this enticing concept of "the beginning", but we must extract the scientific component of the problem for our present purposes. Nucleation, as in the case of phase transformations, is best regarded from the standpoint of kinetics. There are then two main steps, which may come in either order: (a) Experimentally, one attempts to measure the frequency with which transformation centers spring into existence; and (b) theoretically, one seeks a model that will account for this observed birth-rate. Temperature, composition, strain, and prior history are some of the important variables that must be considered both experimentally and theoretically when dealing with nucleation in the solid state. Such interaction of theory and observation is an integral part of science in general, but it is particularly significant in the nucleation problem because the very beginning of a phenomenon invariably occurs on too localized a scale in both space and time to be detected with available techniques. Thus, there is little hope of making direct measurements on the nucleus during its birth or to ascertain the exact nature of the process; one can only infer the details of nucleation from the model whose predicted behavior seems to harmonize best with the measured rate of nucleation and its dependence on known parameters. In the field of solid-state nucleation, both theory and experiment call for much ingenuity, but somehow the conceptual schemes have spawned faster than they can be tested by observation. This is not to say that there are many basically new ideas in modern nucleation theory; rather, as we shall see, it is because the required fine-scale measurements are of immense technical difficulty. Quite likely, some of the nucleation models existent today have survived only because of the latitude permitted by meager data. There is great need to bring theory and experiment into better balance in this important area of physical metallurgy. Although one can

Jan 1, 1959

By U. F. Kocks

SINGLE slip and a single parallel array of edge dislocations have been obtained in silicon single crystals by homogeneously bending them in a four-point dead-loading device at 1000°C around the [211] axis with [253.] as the tensile axis which encloses an angle of 40° with the glide plane. Other orientations or lower temperatures proved unsuitable. The homogeneity of the bending was checked by the method shown in Fig. 1. The chemically polished specimen was exposed to parallel light from a microscope-stage lamp. The sharpness of the focus of the reflected light is an approximate measure of the circularity of the sample. This method permitted the determination of the actual radius of bent specimens within 10 pct accuracy. The etching solution developed to show up dislocations consisted of the following volume parts: 2 HF, 1 HNO,, 2 CH,COOH, 1 a solution of 5 wt pct of CuNO, in water (Rosi'). The acetic-acid content was adjusted to produce fine well-defined etch-pits in about 2 min at room temperature. The effectiveness of the etch did not depend on the crystal-lographic orientation of the face etched. The number of etch pits produced after a given deformation was checked in the usual way against the Cahn formula' and showed good agreement. As it is to be expected from the orientation of the primary system there are slip steps on the top and bottom faces but not on the side faces (perpendicular to the bending axis), whereas etch pits appear on the side faces but not on the top and bottom faces. This is different only for occasional dislocations of a secondary glide system. All the micrographs included have been taken in places where the most of secondary glide could be seen. From this it is evident that in the homegeneously deformed region the number of secondary dislocations was less than 1 in 1000 of the primary type. Dislocation Distribution—A series of tests with varying amounts of deformation is shown in Figs. 2(a-c). An observation that can readily be made from these pictures is that the linear density of dislocations within slip lines is relatively constant and independent of the amount of deformation. "Slip line" in this context is understood to mean a line that is a straight connection of individual etch pits. The heavily pitted bands which can be seen in each of these three pictures may be resolved fairly definitely, at higher magnifications, into many "slip lines" the distance between them being of the order of 0.5p The distance between dislocations in slip lines is of the order of 2p and it is also fairly constant in going from the neutral zone outward. The higher over-all dislocation density in the outer regions of any sample and the higher total number in a more heavily deformed sample, are effected by a larger number of "slip lines." The relative constancy of the dislocation distance within an individual slip line is surprising. The absence of pile-ups" may imply, if there is no rear- rangement on unloading," that there are no substantial obstacles to slip in this case. It seems that the equilibrium distribution of the dislocations in each active slip plane under the higher external stress on

Jan 1, 1959