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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 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 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 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

By H. L. Armstrong

SOLID-STATE diffusion is an important technique in certain aspects of metallurgy, and especially the metallurgy of semi-conductors and semi-conductor devices. If the diffusion is carried out under constant conditions for a time, t, the concentration, C, of the diffusant at a depth, x, below the surface from which the diffusion is carried out is given by an expression of the form. C = Cof(x,Dt) [I] Co being a constant, and D the diffusion constant of the diffusant in the material and at the temperature

Jan 1, 1959

By W. Rostoker, A. S. Yamamoto, K. Anderko

ALTHOUGH the corrosion resistance of magnesium and its alloys is closely related to iron content, there has been no direct measurement of the solid solubility of iron in magnesium. Bulian and Fahrenhors;1 and Mitchel]2 agree that pure iron or a limited terminal solid solution crystallizes from the Mg-rich liquid. For this reason a magnetic-moment method was selected to estimate that portion of the total iron content which is not in solid solution. Since iron in solid solution in magnesium cannot contribute to ferromagnetism, the difference between chemical and magnetic-iron analyses should yield the solid solubility. By experimentation it was found that the melting of pure sublimed magnesium (99.995 wt pet purity) in Armco-iron crucibles at about 800°C is a convenient way to introduce small amounts of iron. Melts retained 5, 10 and 20 min at 800°C analyzed 0.003,, 0.005,, and 0.018 & 0.001 weight pet Fe, respectively, after being stirred, heated to 850°C, and cast into graphite molds. The as-cast alloys were pickled in acid (dilute HC1 + HNO3), annealed at 600°C for 3 days, scalped on a lathe to remove the pitted surface, pickled again, extruded at about 100°C to 3-mm wire, reannealed 41/2 days at 500°C, and water-quenched. The specimens were again scalped, pickled, and used both for chemical and for magnetic analysis. Most of the precautions described were intended to prevent iron pickup by contact with tools or superficial iron enrichment by volatilization of magnesium during heat-treatment. It is believed that the specimens ultimately used for test were homogeneous and characteristic of phase equilibria at 500°C. Magnetic Analyses A susceptibility apparatus of the Curie type was used for magnetic analyses. Field strengths of up to 10,400 oersteds could be generated. By this method, an analytical balance measures the force of attraction which a calibrated magnetic field exerts on a suspended specimen. The force equation is as follows f/m = M dh/dy where f/m = force per unit mass of sample M = magnetic moment per unit mass dH/dy = magnetic field gradient The dH/dy characteristic of the instrument is determined by the use of a standard palladium sample, and the calibration is made independently for all values of H. Since a large finite field is required to saturate an assembly of ferromagnets, it is necessary to measure the apparent magnetic moment for increasing steps of H until a saturation value is obtained. The percentage of iron in the sample as free ferromagnetic iron may then be computed simply C= 100 (M1/M1) where C = percent content of undissolved iron in sample M1 = saturation magnetic moment of sample per unit mass M1 = saturation magnetic moment of iron per unit mass taken as 217 emu-cm per gm There is no serious difficulty in applying this method except for the unusual magnetic behavior of very fine particles of ferromagnetic substances. It has been found and is the basis for a widely accepted theory that with sufficient subdivision, the magnetic fields required to saturate and the coercive force after saturation rise to exceedingly high values. Recent work on precipitates of Fe and Co from copper solid solutions8 showed that about 5000 oersteds were necessary to approach saturation. The magnetic moments as a function of field strength measured in the present investigation are listed in Table I. Only the 0.018 wt pet Fe alloy yielded a magnetization curve with a fairly well-defined saturation plateau at 3.76x10 -2 emu-cm/ gm. This corresponds to 0.017 & 0.001 wt pet Fe in the alloy. This indicates that the solid solubility must be of the order of 0.001 wt pet Fe. The magnetic-moment data of the other two alloys are badly scattered, indicating that the amount of ferromagnetic iron in these samples is so low that the magnetic forces acting on them cannot be measured accurately by the analytical balance used. Nevertheless, the fact that even the 0.003, wt pet Fe alloy shows ferromagnetism indicates that the solid solubility must be below that value. Acknowledgment This work was sponsored by the Pitman-Dunn Laboratory of Frankford Arsenal, Philadelphia, Pa. The support and permission to publish are gratefully acknowledged. References W. Bulian and E. Fahrenhorst: Zeic. Metallkunde, 1942, vol. 34, pp. 116-170. 2 D. W. Mitchell: AIME Transactions, 1948, vol. 175, pp. 570-578. 3 G. Bate, D. Schofield, and W. Sucksmith: Philosophical Magnsine, 1955, vol. 46, pp. 621-631.

Jan 1, 1959

By G. C. Fryburg, H. M. Murphy

ThE rates of oxidation of metals are usually obtained by heating the metal specimens in furnaces. Such a procedure is satisfactory for most metals. However, there are several metals that oxidize according to the reaction.

Jan 1, 1959

By E. A. Gulbransen, K. F. Andrew

The vacuum-microbalance method was used to study the oxidation behavior of Zircaloy-2 and -3A over the temperature range of 300 to 850°C and at 0.1 atm pressure. The results fit in well with the authors' earlier studies on zirconium. Tin was found to increase the rate of oxidation and also the temperature at which the metal burns. Both the cubic-rate law and the parabolic-rate law gave imperfect fits to the rate data. Since the parabolic-rate law has been derived from accepted physical principles, this rate law was used to interpret the rate data. A heat of activation of 28,600 cal per mole was calculated. The transition phenomenon previously observed in hot-water and steam-corrosion processes was studied systematically for oxygen atmospheres. Observations on the rate of oxidation, color and properties of the oxide films show that the transition phenomenon was associated with a failure in the adherence of the oxide to the alloy. ZIRCALOY-2 and -3A have found important uses in the field of reactor metals due to their low neutron adsorption, good strength and good resistance to corrosion. One feature of the corrosion reaction in steam or hot water is the sharp transition in the rate of corrosion to a higher value after a certain amount of reaction has occurred. This paper presents a study of the reaction of Zircaloy-2 and -3A with oxygen including a study of the transition phenomenon which has been found to occur also in oxygen atmospheres. A comparison will be made between the oxidation behavior of these alloys and the pure metal. It was hoped that a study of the details of the oxygen reaction would lead to a better understanding of the reactions occurring in hot-water and steam atmospheres. Literature Kinetics-—The reaction of Zircaloy-2 and -3A with hot-water and steam atmospheres has been studied by Thomas.' Goldman and Thomas,' Thomas and Forscher," and Thomas and Kass.' Empirical equations for the kinetics of the reaction have been given by Thomas and Forscher." The change from the initial slow rate of reaction to the final rapid rate of reaction has been termed transition with the post-transition corrosion kinetics following a simple linear equation in time. The corrosion behavior in high-temperature steam was similar in many features to the corrosion in high-temperature water. Goldman and Thomas' and Pray and Peoples' have shown that the addition of tin, while increasing the rate of corrosion, counteracts the deleterious effect of nitrogen. The beneficial effect of iron, nickel and chromium was to improve the adhesion of the oxide to the metal as well as to counteract the deleterious effect of nitrogen. Mallet and Albrecht" have studied the oxidation of two zirconium-tin alloys. The cubic-rate law was found to fit the oxidation data for the 1.5 pct tin alloy while the parabolic-rate law was found to fit the data for the 2.5 pct alloy. Kendall' in a recent paper has studied the oxidation of Zircaloy-2 containing 1.5 pct tin in air atmospheres. Transition Phenomenon—In steam atmospheres Thomas' has observed fora 1.8 pct tin alloy containing small amounts of iron, nickel and chromium that transition to a more rapid rate of corrosion at 400°C

Jan 1, 1959

By R. I. Jaffee, E. S. Bartlett, D. N. Williams

The oxidation resistance and fabricability of molybdenum powder-metallurgy alloys containing up to 20 wt pct nickel in the form of a fine dispersion were studied. The effects of dispersion distribution and of amount and type (pure nickel or nickel compounds) of additive were considered. A definite improvement in oxidation resistance was observed, but the amount of improvement fell far short of requirements for an oxidation-resistant alloy. Fabricability by hot-rolling was limited. INVESTIGATIONS at Ohio State university1 and Battelle Memorial institute2 have indicated that the attainment of a truly oxidation-resistant molybdenum-base alloy for high-temperature service, with the coincident retention of high-temperature strength and toughness, will be a difficult, if not impossible, feat. Among the most promising alloy systems studied was the molybdenum-nickel system shown in Fig. 1. Alloys in this system show good oxidation resistance at temperatures well above the normal melting point of molybdenum trioxide because of the regenerative formation of protective nickel-molyb-date (NiMoO4) on the surface of the alloy during exposure at high temperatures. Unfortunately, the required alloy content to obtain oxidation resistant molybdenum-nickel alloys far exceeds the limits of the narrow terminal solid-solution boundary, and closely approaches the peri-tectic composition involving the brittle intermetal-lic compound, MoNi. Because of the peritectic reaction, fusion alloys are characteristically brittle, since the MoNi phase, being the last to form, tends to occur as a continuous grain-boundary network around each molybdenum grain. An added problem with this system is that the protective nickel-molybdate layer formed at high temperatures is unstable, undergoing one or more allotropic modifications upon cooling. The volume changes associated with this modification during cooling are such as to cause violent expulsion of the protective molybdate coating from the surface of the piece. This is, of course, quite detrimental in material exposed to cyclic temperature during service. The research reported here resulted from an attempt to overcome the aforementioned problems associated with the molybdenum-nickel alloys primarily by controlling the amount, size, and location of the MoNi phase. By using powder-metallurgy techniques of alloy preparation and sintering the blended molybdenum-nickel powder mixtures at a temperature below the peritectic reaction temperature, molybdenum-nickel alloys with a randomly dispersed MoNi phase were produced. MATERIALS The molybdenum powder used in the preparation of alloys for this study was commercial hydrogen reduced, minus 325-mesh (Tyler) material. Master alloys, by which nickel was added, consisted of elemental carbonyl nickel powder (12 average particle size), an alloy of 50 wt pct Ni-50 wt pct Cr, and compounds of MoNi, Ni,Si, and Ni2B. The nickel-chromium powder was prepared by filing a vacuum-arc-melted ingot, separating impurities magnetically, and screening to minus 200-mesh. The MoNi powder was prepared by pulverizing a hydrogen-sintered powder-metallurgy compact to minus 325-mesh material. Further sizing of this powder for study of effects of dispersion distribution was accomplished by air classification of the minus 325-mesh powder. The Ni2Si and Ni2B powders were prepared by crushing vacuum-sintered powder-metallurgy compacts to minus 200-mesh material. EXPERIMENTAL PROCEDURE Specimen Preparation—The general procedure followed in the preparation of alloys for testing is described as follows: 1) Blending. Either hand-blending of the powders in a ceramic mortar and pestle for X 1/2 or mechanical blending was used. Hand-blending seemed preferable for optimum homogeneity. 2) Compacting. Most of the blended powders were pressed to green compacts at pressures of 15 tons per sq in. in a single-action die, although some were pressed at 80 tons per sq in. A 1 X 11/4 X 1/4-in. green compact was the standard size for oxidation test material, and 7 X 1/2 X 1/4-in. compacts were used for fabricability test specimens. 3) Sintering. All green compacts were sinteredat

Jan 1, 1959

By G. M. Gordon, J. W. Spretnak, R. Speiser

AT present, considerable research is being directed toward the development of high-temperature, oxidation-resistant columbium alloys. Columbium. along with molybdenum and tungsten, exhibits good high-temperature strength. Unlike molybdenum and tungsten. however. columbium does not form a volatig oxide below 1375°c.l Although the outermost oxide formed on pure columbium, Cb2O3 is stable in air at elevated temperatures, it is not of a protective nature. It is porous and voluminous, and

Jan 1, 1959

By P. R. Swann, J. G. Parr

Quenched structures were studied in alloys containing up to 12.5 pct cobalt. The subsequent decomposition of a 10 pct cobalt retained-ß phase alloy was investigated using metallographic and X-ray diffraction methods. Hardness measurements also were made during the decomposition process. Precipitation of Ti2Co is by nucleation and growth; and an activation energy of 50,000 cal per mole was determined. The values of the coefficient ß suggest that the precipitate is pearlitic at temperatures between 450 and 475°C, and spheroidal between 500 and 525°C. THIS paper describes part of a series of invesligations into phase transformations in binary alloys of titanium with transition elements. The general approach is similar to that taken in work on titanium-iron and titanium-nickel alloys.' Previous investigators'' have established the titanium-rich end of the titanium-cobalt phase diagram, reproduced in Fig. 1. Orrell and Fontana' showed that alloys containing more than about 6 pct" cobalt quenched from the ß range, produced 100 pcl retained-p phase. The isothermal decomposition of alloys containing between 0.8 pct Co and 15.5 pct CO was investigated by the same workers in the temperature range 650 to 1000°C. They reported that these alloys transformed into a or Ti,Co depending on the cobalt content, but no quantitative data were given. In the work to be described a series of alloys containing 0.8 pct Co to 12.5 pct Co was examined in the quenched condition. The 10 pct Co alloy (the lowest cobalt content to retain 100 pct ß on quenching) was selected for further work on the tempering kinetics of the ß decomposition. Experimental Procedure Since our own melting equipment was not installed at the outset of this work, the Physical Metallurgy Division of the Department of Mines and Technical Surveys (Ottawa, Canada) prepared the alloys. These were made of Japanese sponge, (which when melted had a value of 103 DPH, using a 1-kg load), and electrolytically prepared cobalt. The al- loys, made up to contain 0.8, 1.6, 3.3, 5.8, 8.3, 10.0 and 12.5 pct Co, were homogenized by swaging into rods at 900°C. Filings were taken from the rods, and any iron chips from the file were separated magnetically. Size fractions of both plus and minus 200 mesh (about 75p) were shown by their constitution, after annealing just below the eutectoid temperature, to contain the same cobalt content. Consequently, it was permissible to use the —200-mesh fraction, knowing it to be representative of the rod composition. Quenching in argon was carried out in a newly designed furnace, whose features include (1) an Inconel furnace tube, (2) a positive pressure of argon maintained at all times in the furnace—even when a sample is removed or inserted. The furnace is shown in Fig. 2 and is described in the Appendix. The tempering processes were carried out on powder samples sealed in evacuated quartz capsules. Since the highest tempering temperature was 525OC, no protection against reaction with the quartz was necessary. (Tests were made on filings of iodide titanium and showed no hardness increase after equivalent heat-treatments.) A thermocouple was attached to the capsule, which was heated to the

Jan 1, 1959

By J. J. Becker

Changes in magnetic properties with particle size are used to study the precipitation process in a Cu-Co alloy. In particular, the effect of a field during aging in producing anisotropy is shown to occur entirely during the growth of the particles, after precipitation is complete. HEAT-treatment in a magnetic field is done commercially to improve the magnetic properties of a number of materials. These can be divided into solid-solution alloys and precipitation alloys. The Permalloys are representative of the first type, and magnetic annealing greatly increases their maximum permeability. On the other hand, in precipitation alloys such Alnico 5 the important result is an increase in maximum energy product. The effect of the field in all cases is to bring about an additional magnetic anisotropy, uniaxial in nature, which makes the hysteresis loop more upright when measured in the direction in which the field was applied. The structural origin of the anisotropy brought about by magnetic annealing is not well understood. In the solid solution alloys, one possible explanation is based on ordering.' Another possibility is the orientation of like-atom pairs.' The precipitation systems known to respond to magnetic heat treatment are Alnico 2, in which the effect was first discovered," Alnico 5, cobalt ferrite (oxide),' and Cu-Co alloys.3 n these materials, the field affects the precipitation process itself in some way. Although there has been much work on Alnico 5. its nature is still incompletely understood. According to Geisler,' the precipitation reaction is of the

Jan 1, 1959