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By J. J. Gilman, T. A. Read

FOLLOWING the deformation 01 zinc monocrys-tals, sharply bent basal planes are observed near several types of inhomogeneities. Three of these in-homogeneities have characteristics which are quite regular so that they can be studied and analyzed. These are compressive kink bands, "deformation bands," and the inhomogeneities near end restraints. The present paper describes experiments in which "deformation bands" were artificially produced, and bend plane phenomena are discussed in terms of dislocation theory. Also, two new bend plane phenomena are described. The importance of bend plane phenomena in the deformation of crystals is not widely recognized. Many phenomena may be explained in a manner similar to the discussion in this paper. Jillson1 has pointed out that the "punching effect" in zinc is a bend plane phenomenon and is not caused by prismatic slip.' Bowles3 has suggested that they may be involved in diffusionless phase changes. Cahn4 has discussed the role of bend plane formation in the polygonization of zinc. Experimental Work Tensile Kink Bands: Because of the geometrical similarity between "deformation bands" and "kink bands" (compare Fig. 1 of this paper with Fig. 1 of the paper by Hess and Barrett"), the band shown in Fig. 1 of this paper will be called a "tensile kink band," and that shown by Hess and Barrett will be called a "compressive kink band." It is felt that the term "deformation band" should be reserved for banded structures in polycrystalline materials such as iron." Tensile kink bands seem to form spontaneously in aluminum crystals deformed by tensile loading.7-10 In zinc and cadmium crystals they do not form in good, carefully loaded specimens.'." However, tensile kink bands can be produced artificially in zinc crystals. The present authors did this by scratching one of the flat surfaces of triangular crystals transversely with a sharp needle. Natural tensile kink bands caused by inhomogeneities sometimes appeared in deformed crystals which were identical in appearance with the artificially produced ones. Zinc monocrystals were grown by the Bridgman method in graphite molds. Chemically pure zinc (99.999+ pct Zn) was used and the molds were sealed inside evacuated pyrex tubes during growth. The crystal cross sections were equilateral triangles with a typical base of 0.210 in. The artificial kink band shown in Fig. 1 is typical of tensile kink bands in zinc. The band lies between two bend planes which run from upper right to lower left and is inclined oppositely to the slip bands which are sharply bent at the two bend planes. The general form of the artificial tensile kink bands was independent of the scratch depth (1 to 5 mils deep) and also independent of which side was scratched. These variables did cause variations, however. Deep scratches produced more localized kink bands than light scratches. Also, if the angle between the slip plane traces and a transverse scratch varied appreciably among the three sides, then localization of the resulting kink bands also varied. Furthermore, if the slip direction lay nearly parallel to the scratched side, the band was more developed near the scratched side than at the opposite edge. Scratches produced tensile kink bands for crystal orientations from xo = 15" to x, = 75". Fig. 2 shows a scratched crystal after deformation. One triangular side lies in the plane of the photograph. The right hand tensile kink band was produced by a transverse scratch on the upper right side. The next two kink bands were the result of scratches on the front surface. The kink band at the left was caused by a scratch on the lower back side. All four bands have the same general form. A longitudinal scratch was also made on the crystal shown in Fig. 2 to determine the effect of a scratch on the critical shear stress. The critical shear stress of the scratched region was 33.9 g per sq mm compared to 24.4 g per sq mm for the un-scratched region above it. Fig. 3 shows Laue patterns of the crystal shown in Fig. 2. Fig. 3a shows the pattern of the undeformed crystal. The orientation was x, = 21°, A, = 31". After deformation, Fig. 3b was made of the homogeneously deformed portion of the crystal. The spots are compact but split into two halves. This region was elongated 45 pct and its orientation was x = 14", X = 20"; the sine law predicts x = 14", A = 20.5". Fig. 3c was taken near the center of the middle tensile kink band of Fig. 2. The pattern shows a range of orientations and polygonization in this region. The spread in orientation was due to the fact that the basal planes were curved (see Fig. 1) rather than flat as in the ideal case. Some may also have been the result of elastic distortions and "local curvatures." The orientation range was x = 23" to 32", A = 30" to 42". It is apparent from Fig. 3 that the material inside and outside the kink band rotated in opposite directions with respect to the tension axis during deformation. The orientation calculated from the ideal configuration of Fig. 9,

Jan 1, 1954

By N. K. Chen, R. Maddin, K. T. Aust

Lattice rotations occurring on the tension and compression sides during the bending of molybdenum single crystals at room temperature were followed in detail. Observations were also made concerning crystallite rotations and slip traces. &apos;The results indicated the participation of (110) as slip planes and the<111>as slip directions. Crystallite fragmentation during bending was also noted. EVERAL investigations have been conducted on pure bending of face-centered cubic metals.&apos;-" Structural changes as a result of "bend-gliding," and the importance of bending and constraints during conditions of axial stressing, have been noted.&apos;," It was evident that the mechanism by which the bending deformation occurs is more complex than the case of simple shear. Studies of the bending of body-centered cubic metals from the aspect of the crystallographic mechanism appear to be lacking. Molybdenum single crystals therefore were subjected to deformation by bending in order to determine the reaction of the body-centered cubic lattice to bending stresses. It might be expected for the bending of single crystals that lattice rotation as represented by the axis of compression would proceed toward the pole of the active slip plane and that rotation of the tensile stress axis should indicate the slip direction.&apos; It was believed therefore that a study of the tension and compression sides of bent molybdenum single crystals should give data concerning the operative slip system. Specific problems which are pertinent to the overall picture of plastic deformation were also investigated, e.g., whether the constraints offered by pure bending give rise to the deformation band, and also the nature of the asterism occurring on the tension and compression sides during the stages of deformation. Experimental Procedure Eight single crystal specimens were grown from sintered molybdenum rods 143 in. diameter using the method described previously.6 The purity of this material was reported as 99.9 pct as described elsewhere.&apos; The specimens were % to 1/10 in. in diameter x 7 in. long, with single crystals approximately 1 to 2 in. in length occupying the entire center sections of each specimen. The specimens were elec-trolytically polished using an electrolyte of 300 cc methyl alcohol, 60 cc H2SO4, 130 cc HCl, and a current density of 4 amp per sq in. Each specimen was then loaded in a bending apparatus similar to that used by Yen and Hibbard,&apos; as shown in Fig. 1. The load was applied by means of a spring and screw arrangement through four ball-bearing surfaces set 1.5 in. apart. Either the inner two bearings or the outer two (A, B, Fig. 1) were attached to a movable steel plate (D) through which the load was transmitted. Since the apparatus was mounted on a track of the X-ray apparatus, the tension or compression side of the specimen could

Jan 1, 1954

By D. L. Douglas

The ß decomposition of Zr-U-O alloys was studied during an interrupted quench from the a + ß region. Decomposition was more rapid than in binary Zr-U alloys of the same uranium content or qf equivalent ß composition. The rapid transformation has been ascribed to the presence of the primary a phase which provided nucleation sites and which permitted preferential partitioning of oxygen to the a phase and of uranium to the COMMERCLAL heat treatments are designed to produce certain strength and toughness character- istics by controlling the microstructure of an alloy. A desired distribution of microconstituents is achieved in practice by treating an alloy under the correct time-temperature conditions. A knowledge of the phase equilibria in any alloy system is essential in outlining heat treatments, but in addi-

Jan 1, 1961

By Jack L. Taylor

As expected from similar crystal structures and favorable atomic size factors, titanium, vanadium, and molybdenum are completely soluble in one another above the transformation temperature of titanium. The fl phase parameters of the continuous solid solution are shown graphically. Limiting compositions for retained fl phase have been determined. VANADIUM and molybdenum both have body-centered-cubic structures at all temperatures and, from the atomic diameter comparison factor, 3.9 pct, would be expected to form a complete series of solid solutions. The existence of complete solubility has been confirmed by work&apos; at the Jet Propulsion Laboratory. Furthermore, vanadium and molybdenum have favorable atomic size factors to form complete binary solid solutions with the B phase, high temperature form of titanium, which also has body-centered-cubic structure. Pietro-kowsky and Duwez&apos; and Hansen et al." have established the existence of the complete series of solutions in these binary systems. It would be logical, therefore, to expect that p-titanium, vanadium, and molybdenum would be completely soluble in one

Jan 1, 1957

By H. R. Ogden, A. G. Imgram, D. N. Williams

The effects of composition on the mechanical properties and aging characteristics of several alloys in the Ti-V-Cr system, with and without aluminum modifications, were evaluated. Increasing the chromium, vandium, or aluminum content increased the strength of quenched structures with chromium being the most effective strengthener. Appreciable aging response was obtained with low chromium alloys, but high chromium alloys age softened rather than. hardened. High vanadium contents had a similar effect. Aluminum additions shifted the aging behavior toward that observed in lower chromium alloys, enabling high chromium alloys to be age hardened. DURING the course of titanium alloy development many a and a-ß alloys have been evolved to commercial status. However, only one all-ß alloy has achieved this same stature. This is the Ti-13V-11Cr-3Al alloy. It is characterized by a very sluggish ß-phase decomposition reaction such that very slow cooling rates can retain the 0 phase at room temperature. In addition, very high strength levels can be obtained by long-time aging treatments. Combinations of cold or warm working followed by aging produce even further improvements in strength. This paper describes the results of a research program in which the effects of composition on the mechanical properties and aging characteristics of several alloys in the Ti-V-Cr system, with and without aluminum modifications, were evaluated. EXPERIMENTAL PROCEDURES Electrolytically refined, high-purity titanium was used as the alloy base for these studies. Iodide chromium, electrolytically refined vanadium granules, and high-purity aluminum sheet were used as alloying additions. The compositions of interest were melted as 250-g ingots in a direct current arc melting furnace under a flowing atmosphere of argon. The ingots were hot forged to 3/4-in.-diam bars, vacuum annealed for 6 hr at 1800°F to reduce residual hydrogen content, and then hot swaged to 1/4-in.-diam rods. Fabrication history, and interstitial analyses after fabrication are given in Table I. All specimens to be heat treated were sealed in Vycor capsules under a partial pressure of argon. Samples used to define the ß transus were quenched from temperatures ranging from 1350° to 1100°F after holding at temperature for 15 min. Samples for aging studies were quenched from above the ß transus temperature and then aged for up to 64 hr at 750°F and for 100 hr at 850°, 900°, and 950°F. The effects of straining prior to aging were also investigated. The results of these studies were used to select the heat treatments for the tensile specimen blanks. Heat treatments of the tensile specimens are described in Table 11. Alloys were aged after solution heat treatment or after solution heat treatment and cold swaging to 50 pct reduction in area. Standard 0.125-in.-diam tensile specimens were machined from the heat-treated blanks. All tensile tests were performed in a Baldwin-Southwark uni-

Jan 1, 1963

By Niels Hansen

Dispersion-strengthened sintered aluminum products are normally manufactured from surface-oxidized aluminum powder, SAP,&apos; or from atomized aluminum powder.&apos; The powder-blending technique consisting in mechanical mixing of the constituents has been used in the manufacture of numerous dispersion-strengthening alloys, but has never been successfully applied to aluminum alloys. This technique may, however, be applicable if it is possible to produce an unagglomerated mixture of the constituents in the form of fine powders, and the present study was initiated to test this assumption in the aluminum/aluminum oxide system.3 Table I lists the two grades of aluminum powder and the aluminum oxide powder used in the manufacture of the alloys. MD 105 A is an aluminum powder with an average grain size less than 5 IJ., which is isolated from the MD 105 powder by centrifugal separation in cyclohexanol. The aluminum powders and the aluminum oxide were blended in a high-speed blender and then subjected to cold compaction and hot compaction at 550" to 600°C. Subsequently the compacts were hot-extruded with an extrusion ratio of 15 to 1. The alloys were evaluated by tensile testing at room temperature and at 400°C, microscopic examination, and heat treatment at 500°C followed by tensile testing at room temperature. For the purpose of comparison, a commercial SAP quality supplied by Swiss Aluminium Ltd. was tested in the same manner. The tensile data at room temperature and at 400°C are plotted in Figs. 1, 2, and 3 as a function of the weight percent of oxide. The oxide content

Jan 1, 1964

By J. H. O’Dette

BLISTER formation on wrought aluminum products has been a matter of concern to aluminum fabricators for many years. The fact that blisters make their appearance during the final stages of fabrication means that much time and effort have been expended before it is evident that the material must be scrapped. This and the loss of production are ample reasons for embarking on a research program to find out more about blistering and possible methods of control. Many excellent papers on this subject have appeared in the technical literature in the last few years. In one of the more recent papers, Kostronl gives a fairly complete review of the problem of gas in aluminum and blistering in general. From the work of the various investigators, a general mechanism for the formation of blisters has evolved and may be summarized briefly as follows: Hydrogen gas is usually present in the cast ingot, in the atomic or ionic state, in excess of the solid solubility. At room temperature the gas atoms are relatively immobile, but at elevated temperatures they become mobile and diffuse to free surfaces where they associate to form molecules. If these free surfaces are discontinuities within the ingot then the associated gas molecules collect and build up considerable pressure until equilibrium is reached with the dissolved gas around the discontinuity. Since the solubility of the gas is proportional to the square root of the partial pressure it is evident that large pressures may be built up at the discontinuities. When the metal is rolled to sheet the pressure of the gas in these, discontinuities is sufficient to deform the surface of the sheet and form a blister, particularly when the strength of the material is reduced during the annealing. Although the mechanism of the formation of blisters was fairly well known, the actual impor- tance of the individual roles played by the gas and the discontinuities was not so well established that positive methods for control of blistering were at hand. It was the object of the investigation to learn more about the nature of the discontinuities giving rise to blistering and to develop methods of control. The investigation was carried out in three stages as follows: a) A study of the more commonly used methods of removing hydrogen from aluminum, such as fluxing and holding, and their effects on blistering. b) Location of the discontinuities giving rise to blistering. c) A study, by indirect methods, of the movement of gas in the metal and its effect on blistering, and the development of methods of blister control during fabrication. Removing Gas and Reducing Blistering by Fluxing or Holding-—The work of removing gas and reducing blistering by fluxing or holding was carried out on metal of Alcan 2s (1100) composition with an artificially high gas content. The high gas content was obtained by introducing water into the melt prior to casting; the water reacted with the aluminum forming A12O3 and hydrogen. The procedure was to raise the gas content by introducing water into an aluminum melt and using half the melt to cast one ingot immediately. The remaining metal was treated again with water to make up for the reduction in gas content during holding, while the first ingot was being cast, and then given a fluxing or holding treatment and cast into an ingot. Samples for gas determination were cast from the molten metal before and after the gassing operation; before, after, and during fluxing, and while casting. Samples were also cut from sections of the ingots. Gas determinations were made on these samples using the well known vacuum fusion technique. All ingots were hot rolled at 500°C to 0.250-in. slab which, in turn, was cold rolled to 0.040 in. sheet. The sheet was coiled and annealed for 2 hr at 500 °C and then cut into 5-in. squares which were inspected for

Jan 1, 1958

By R. G. Gifkins

Mean boundary migration depended linearly upon creep extension under various conditions. Prolonged annealing or air-casting increased the proportion of immobile boundaries at a given stage of tests. Grain growth during annealing followed a power law. The linking of migration and sliding in creep and models for migration are examined; activation energies are calculated from these models. Segregation of oxygen to boundaries appears to be a controlling factor. THE idea that boundary migration and boundary sliding during creep are linked has often been suggested,&apos;-5 especially when evidence has been obtained for an alternation between the two processes. In simple bicrystals sliding can occur without any migration6 but in more complex bicrystals7 it is observed. McLean&apos; and Couling and Roberts 5 made measurements of both sliding and migration; McLean concluded that there was no linking of the two processes whereas Couling and Roberts supported the idea. McLean&apos; also developed a model for migration during creep and annealing. The present work was initiated as part of a study of the recrystallization of lead during creep9 but has been extended to examine some aspects of the mechanism of migration. MATERIALS AND METHODS Specially refined high-purity lead* was used; the total of impurities, excluding oxygen, was 0.0008 wt pct. Oxygen was removed as far as possible by melting in vacuo, treating at 550" to 600°C with hydrogen and then casting at 450°C under a vacuum of 10-2 mm Hg; the oxygen was then believed to be 0.00005 wt pct. Specimens were made from extruded strip and then annealed at the required temperature in an air oven, controlled to 5 lac. They were then polished in a mixture of acetic acid and hydrogen peroxide. At this stage some specimens were etched to give grain contrast and their grain sizes determined by the intercept method. Migration of boundaries during creep was measured on the surface of polished (not etched) specimens, directly loaded at room temperature (22°C) or 50°C (52"C) to initial stresses of 300 to 700 1b per sq in. Twenty six vacuum-cast hydrogen-reduced specimens were used and, in addition, two specimens were from material air cast after hydrogen reduction ("partial" air cast) and two from air-cast material not treated with hydrogen ("full" air cast). Duplicates were made in the majority of tests. At intervals through the creep tests, specimens were unloaded and the migration measured, normal to the direction of migration at the point of measurement, for each boundary along standard traverses. Usually between 110 to 180 boundaries were measured at each of some twelve stages of the tests. Migration was measured on the projected image (X100) using prism illumination. Fig. 1 illustrates the method of measurement and shows the kind of variation of migration found from boundary to boundary and along particular boundaries. Fig. 2 gives an example of more extensive migration. The mean value of distance migrated was generally reproducible to *10 pct but occasional points gave a scatter of *20 pct. The correctibn applied by McLean8 to allow for the contribution sliding makes to the apparent distance of migration could not be used, for the sliding at most boundaries was too small to measure with the equipment available. There were two reasons for supposing the correction unnecessary in the present work;

Jan 1, 1960

By E. S. Machlin, Morris Cohen

The martensite reaction in single crystals and polycrystals of 70 pct Fe-30 pct Ni alloys is shown to be autocatalytic in nature, producing bursts of transformation during cooling. The temperature of the first burst of transformation, called Mb, occurs below M, in these alloys. Experiments were devised to test the athermal embryo and strain embryo theories of martensite nucleation. The results indicate that internal strains, either within the virgin austenite or around existing martensitic plates, control the nucleation process in these alloys. Furthermore, the growth of martensitic plates is not limited by the attainment of an elastic balance with the austenitic matrix, but by the occurrence of plastic deformation at the martensite boundaries which interferes with the propagation mechanism. IN an investigation of the martensitic habit in single crystals of a 69 pct Fe-31 pct Ni alloy,&apos; it was observed that about 25 pct of the austenite transformed during subatmospheric cooling within the time-interval of an audible click. This event proved quite spectacular: The shock wave sent out from the specimen freely suspended on a thread in the refrigerating liquid was occasionally sufficiently intense to shatter the Dewar container and to separate the toluene column in the immersed thermometer. The Present investigation was undertaken to determine- the kinetics and mechanism of this "burst" type of martensitic reaction. The analyses of the alloys studied are given in Table I. The composition of the single crystal specimens is designated by alloy A, while the polycrystal-line specimens were made of alloys B and C as noted in the text. The single crystals were prepared in a vacuum furnace, using a modified Bridgman technique. Most of these crystals were homogenized by holding for 24 hr at about 1300°C just after solidification. However, it may be emphasized here that the degree of homogenization was not a controlling factor in the subsequent experiments, inasmuch as specimens having different degrees of homogenization yielded the same results. All of the single crystals were fully austenitic as slowly cooled to room temperature. An illustration of the burst phenomenon is given in Fig. 1, which shows oscillograms of electrical resistivity and temperature vs. time during the continuous quenching of 1/16 in. wire specimens (alloy B) in a dry ice and acetone bath at —77°C. There are at least two observable bursts in this case, as indicated by the sharp decreases of resistance accompanying the sudden formation of substantial quantities of martensite. The thermal arrest during the quench probably corresponds to the larger burst. Usually the bursts are followed by more or less progressive transformation during continuous cooling. It will also be noted that the resistance continues to decrease after the specimen has reached the bath temperature. This isothermal change denotes the formation of martensite at constant temperature, and will be the subject of another paper. Examination of fiducial scratches on the surface of a transformed single crystal has shown2 that the scratches in adjoining nonparallel martensitic plates are usually bent in opposite directions, as though one plate forms in such a way as to relieve the matrix stresses set up by the adjacent plate. This, together with some of the results described in ref. 1, Table I. Compositions of Alloys Studied, in Percent Alloy Ni C N Mn Si P S Cr A 31±0.3 0.048 0.027 0.003 0.56 0.007 0.002 B 29.5±0.2 0.036 0.02 0.19 0.09 0.008 0.006 C 19.99 0.52 0.37 0.47 0.010 0.015 0.04 led to the tentative concept that a cooperative action exists which provides the impetus for much of the transformation that appears during the burst. The following series of experiments were performed in order to test this idea. Cooperative Nature of the Burst Two adjacent disks, Va in. thick x % in. diam, were cut from a single austenite crystal of alloy A using a jeweler&apos;s saw. One of the disks was then cut into 15 parts. Then 12 of the latter pieces and the second disk were austenitized (stress relieved) at 600°C for 30 min and water quenched to room temperature. The temperatures at which the first burst of transformation appeared were determined for

Jan 1, 1952

By E. M. Baroody

MUCH information on intermetallic diffusion has been obtained in experiments in which two volumes, initially at different uniform concentrations, are maintained in contact at an interface which is plane, or nearly so. Concentration-distance curves are obtained after suitable times, and analyzed on the basis of a one-dimensional form of Fick&apos;s law In early work the linear equation to which Eq. 1 reduces when D is independent of concentration was used. However, when the initial concentrations c, and c, are appreciably different this simplification is often unjustified, and the suggestion by Matanol in 1933 of a way of avoiding it was welcomed. Matano&apos;s paper was based on work done as early as 1882 by Boltzmann.2,3 In 1938 Rhines and Meh14 reported an extensive investigation of systems in which the diffusion coefficient depends strongly on concentration, and included a detailed description of the Matano-Boltz-mann method. To a large degree, this description represents the formal method as it is understood and applied today, most later discussions having emphasized thermodynamic and mechanistic aspects of diffusion. Exceptions are the comments of R. V. Churchill, contained in a paper by Ham, Parke and Herzig,5 and the papers by Hall8 and by Kirkaldy.7 More discussion appears necessary since some aspects of the problem remain obscure. Better computational procedures are also needed. The common method, involving graphical determination of slopes and areas, is inconvenient and makes the estimation of errors difficult. Background of the Matano-Boltzmann Method Eq. 1 is to be considered along with initial and boundary conditions. Take the origin of x at the

Jan 1, 1958

By M. Cohen, C. Wagner, J. E. Reynolds

If the total volume of a diffusion couple changes during the diffusion, the measurement of distance becomes ambiguous. Use of distance parameters as suggested by Hartley and Crank is discussed. For small concentration differences, the standard form of Fick&apos;s second law is retained with conventional length units and the in- terdiffusion coefficient D. It is shown how D can be calculated from experiments involving large concentration differences and analyzed in terms of distance parameters. &apos;The merits of incremental diffusion couples involving small concentration differences are emphasized. THE conventional form of Fick&apos;s second law for one-dimensional diffusion of component B in a binary solution of A and B is where c, is the concentration of component B; x, the distance; t, the time; and D, the interdiffusion coefficient which may depend on ca. Hartley and Crank&apos; have pointed out that Eq. 1 applies only if the total volume of the diffusion couple does not change during the diffusion process; otherwise, the definition of x becomes ambiguous. No change in total volume takes place if the specific volume of the solution is a linear function of the weight fraction Wb, or if the molar volume is a linear function of the mol fraction N. In some alloys, however, these relationships do not hold, and then it is necessary to introduce a modified measure of distance, 4 in order to retain the general form of Eq. 1. The application of Hartley and Crank&apos;s suggestions to diffusion in alloys has been discussed by Wagner.&apos; Relation Between Measure of Distance and Units of Concentration The definition of [ depends on the choice of units for the concentration c,, as follows: 1—If the concentration ca is measured as the weight fraction W, (or weight percent), [ = 5, has to be defined so that equal increments of contain equal increments of mass m of the solution, e.g., dm = pSdx = Sdw [2] where p is the local density of the solution, and S is the cross-sectional area in sq cm which is taken to be constant in this problem of one-dimensional diffusion." * da Silva and Mehla have demonstrated the constancy of the cross-sectional area in the usual type of diffusion couple. However, experiments involving diffusion into thin wires4, 5 may exhibit changes in cross-sectional area, and therefore are excluded from the present treatment. Thus and the unit of is gram per sq cm instead of cm. 2—If the concentration c, is the mol fraction N, must be defined so that equal increments of contain equal numbers of mols of solution, e.g., dn= (S/V)dx= Sd [41 where V is the local molar volume of the solution. Thus dt, = dx/V [51 and the unit of is mols per sq cm. 3—If, as may be advisable in the case of interstitial solutions, the concentration C is measured in terms of the molar ratio of components B and A (c,, = Y, = nH/nA, where n and nl are numbers of mols of B and A), = Y has to be defined so that equal increments of contain equal numbers of mols of A, e.g., dnA= (NAS/V)dx = Sdf [6]

Jan 1, 1954

By D. Turnbull, J. C. Fisher

ACCORDING to the "reaction-path" modell,2 of martensite nucleation, the shear angle of the embryonic martensite plate must be treated as a variable, and included in any calculation of nucleus critical size. Also, as can be deduced from this model, the interfacial free energy between austenite and martensite does not reach its final value until the shear is completed. It is zero for zero shear angle. However, in order to account for the kinetics of the martensite transformation, some sort of interfacial energy barrier appears to be necessary even with the reaction-path model, for otherwise the volume and the energy of formation of the critical size nucleus both collapse to zero.3 Cohen independently suggested that surface energy could be incorporated into the reaction-path model, with the overall free energy of a martensite embryo being a function of its volume and shear angle.&apos; It is possible to estimate the energy associated with the formation of a critical-size martensite nucleus starting with the reaction-path model and including a surface free-energy barrier. As the dependence of interfacial free energy upon shear angle is unknown, a simple type of dependence will be assumed, with the belief that the true dependence would not lead to appreciably different results. Consider the work required to form a lenticular martensite plate with radius r, thickness t, and shear angle 8. There are three contributions; one being the interfacial free energy, one being the free energy change in the martensite plate, and one being the free energy increase in the surrounding austenite. The interfacial free energy u is assumed to depend upon the shear angle 0 according to the relationship s=s0(?/?0)n [1] where 8, is the equilibrium shear angle and n is an exponent that may lie in the range 0 n 2. The work required to form the interfaces of a martensite plate then is W. = 2pr² s0(?/?0)n [2] The free energy change per unit volume of martensite is composed of two parts, one the ordinary volume free energy ?f1. which is negative, and the other the elastic strain energy G?m²/2, where G is the shear modulus and 7, the shear strain relative to the martensite structure. This expression for the strain energy is valid only when the shear strain ym, is sufficiently small that the martensite is within its linear elastic range. There is no doubt that ym, lies beyond the linear elastic range for embryos that are considerably subcritical. However, for critical nuclei it will be shown that ym, is 1.5 pct or less, within the linear elastic range of martensite. For embryos of nearly critical size, then, the strain energy of the martensite is correctly given by G?m²/2. The shear strain in the martensite is ym, = 8, — 8, and the work required to form the strained martensite is Wm --= (pr²t/2) [?fv + G(?O - ?)²/2] [3] The free energy change in the austenite is entirely that due to elastic distortion. The elastic strain is not uniformly distributed in the austenite, being large near the martensite plate and small elsewhere. Approximately, however, the energy corresponds to a uniform shear strain ya= (?t/2)/r [4] throughout the volume 4pr³/3 surrounding the plate. The work required to strain the surrounding austenite then is Wa = (4pr³/3) (G?a²/2) = (G?²/6) prt² [51 For simplicity, the same shear modulus G is assumed for each structure. The total free energy for forming a plate then is W = W3 + Wm + Wa. = 2pr² s0 (?/p?0)n + (pr²t/2) [?fr+G(?0-?)²/2] + (G?²6) prt2 [6] This expression is correct for nuclei and for embryos of nearly critical size, where, as will be shown, the strain energy in the martensite is correctly given by the expression G (? — ?)². Having W as a function of r, t, and 8, as in Eq. 6, there is a saddle-point where W has a stationary value, W subsequently decreasing indefinitely as the nucleus volume increases along the reaction path. The stationary value of W is the energy of the critical nucleus. The critical nucleus has radius, thickness, and shear angle such that ?W/?r - awlat: = ?W/?p? = 0. Performing these differentiations and calculating the critical nucleus energy, W* = [8192p(G?/6)²;s/27 ?fv4] [7] where a= (?/?0)3n+1[l +G(8"-8)&apos;/2af.]&apos; [7a] and where 8 is to be determined from the equation (1 + 3n/4) + G8(6O - (9)/[Af. +G(6>o-6>)72] = 0 [8] For ?f, near —200 cal per mol or —10" ergs per cc, and 8, near 1/6, as for iron-base alloys, Eq. 8 gives ?0 - ? ~ - (4 + 3n) ?f1./4G0O [9] as the difference between the equilibrium shear angle and the actual shear angle for a critical nu-

Jan 1, 1954

By M. J. Pool

The partial molar heats of solution in liquid tin of cadmium, silver, tellurium, and zinc have been measured at 655°. 700°, and 750°K by liquid-metal solution calorimetry. Silver, cadmium, and zinc are endothermic at these temperatures while tellurium is exothermic. Only the heat of solution of silver depends on composition while all four elements show a temperature-de pendent heat of solution. The heat of solution of tellurium is constant up to 0.6 g-at. pct, becomes increasingly more exothermic, and reaches a limiting value at 1 g-at. pct Te. The limiting value has been used to calculate the heat of formation of SnTe at 750°K. The heat effects associated with the dissolution of the compounds Ag2 Te, CdTe, and ZnTe in liquid tin were measured at 750°K. These values are cotnOined with the measured hat effects at 750°Kfor silver, cadmium, tellurium, and zinc to detertrline the heats of formation of the telluride compounds. Cadmium lelluride exhibits a heat of dissolution which has a compositional dependence. THERE is a considerable amount of interest in the compounds of tellurium because of their electronic properties. Both cadmium and zinc tellurides are thermoelectric materials and considerable work has been done on their electronic properties but a limited amount of data is available on their ther-modynamic properties. This work was undertaken to elucidate the heat of formation data on cadmium and zinc telluride. Since both cadmium and zinc are in Group II it seemed to be of interest to compare the values obtained for them with the heat of formation of a Group I telluride. Silver telluride was selected for this comparison. In the course of the work it was also possible to determine the heat of formation of tin telluride and therefore to make a comparison of some of the Group I, 11, and lV tellurides with the metallic elements silver, cadmium, and tin being in the same period. There is also a great deal of interest in the energetic changes which occur upon addition of solute elements to a common solvent. This investigation provided an opportunity to study the partial molar heats of solution of silver, cadmium, tellurium, and zinc in liquid tin. The partial molar heats of solution are of theoretical interest because solute-solute interactions are a minimum in dilute solutions and application of solution models is simpli- fied. In order to complete the analysis of solute-solute and solute-solvent interactions the temperature dependence of the partial molar heats of solution was also measured. MATERIALS AND EXPERIMENTAL PROCEDURE All materials were of the highest purity available. The silver, zinc, cadmium, and tellurium were obtained from American Smelting and Refining Co. and were reported to be 99.999 pct pure. The silver telluride, zinc telluride, and cadmium telluride were obtained from Atomergic Chemetals Co., a division of Gallard-Schlesinger Chemical Manufacturing Corp., and were electronic-grade material of 99.999 pct purity. Tin used for the solvent bath and for calibration was obtained from the Vulcan Manufacturing Co. and was reported as being 99.99 pct pure. The liquid-tin solution calorimeter used in this work is similar in principle to the differential twin-type calorimeter described by K1eppa.l Two of three identical calorimeter wells are used together during any set of experiments, one well being active and the other being passive. The wells are positioned 120 deg apart in an aluminum calorimeter block. Each well contains a multijunction thermopile and a Pyrex test tube to hold the liquid metal bath. Forty-eight of the thermopile junctions are distributed over the surface of each calorimeter well adjacent to the test tube and serve to integrate the heat effects occurring. The other forty-eight are next to the aluminum calorimeter block. The thermopiles for the three wells are connected differentially so that any change in temperature at the outer junctions (which will be the same for both wells because of the high conductivity of the aluminum block) will oppose for the two wells and result in no shift of the zero. The electrical output represents the true temperature difference between the two reaction vessels. A reaction occurring in the active well gives a comparison with another body of very similar thermal properties. In this way, any spurious heat effects due to slight temperature drifts within the entire calorimeter block are eliminated. The output of the differential thermopile goes to a dc amplifier with multiple ranges of from * 10 pv to 1 30 mv. The output of the amplifier is then fed into a Leeds and Northrup strip-chart recorder. The adiabatic temperature change is then calculated using the technique of Howlett, Leach, Ticknor, and ever.&apos; The aluminum calorimeter block is contained in a cylindrical furnace with main and control heaters

Jan 1, 1965

By G. Pomey

Heat-resisting chromium steels and alloys treated at 825° or 9.50°C (1527° or 1742°F) in a carburizing atmosphere exhibit an extensive carbide precipitation. This carbide precipitation may be succeeded by the FeCr a phase or by a carbide with a higher carbon content. Point analyses carried out with an electron mi-croanalyzer make it possible to study the depletion of chromium in the matrix after precipitation has occurred and to determine the chemical composition of carbides. In particular the content in the carbides of Fe, Ni, and W, elements which substitute Cr, can be accurately determined. HEAT-resisting chromium steels and alloys employed in the construction of gas carburizing and carbonitriding furnaces are subjected to a succession of oxidizing atmospheres during heating and cooling and to carburizing atmosphere during isothermal stage. Such a sequence of thermal cycling causes embrittlement and corrosion in the furnace materials. A quantitative study of the structural changes induced in the furnace materials has not received much attention in the past. However, utilization of the electron probe microanalyzer and other modern techniques has permitted a point analysis of the various phases formed and to follow their relative evolution. This paper gives results as regards the nature and composition of the carbide precipitation and the distribution of chromium in the matrix during only the carburizing periods. The structural changes subsequently produced during oxidizing periods will be presented eventually. METHODS AND MATERIALS Metallographic, X-ray diffraction and Castaing electron-probe microanalysis1 techniques have been employed to study carbide precipitation and evolution and the changes in the composition of the matrix in heat-resisting steels and alloys.

Jan 1, 1961

By J. W. Clark, C. T. Sims

Wrought chromium-base alloys containing yttrium, cubic monocarbides of the Ti(Zr)C type, and similay alloys containing manganese and rhenium have been melted and fabricated. Strength has been studied by hot hardness and elevated-temperature tensile and rupture measurements, low-temperature ductility by tensile testing, and surface stability by oxidation testing. In additiod, studies have been conducted of the carbide stability, and of aging behavior. The carbide dispersion generates effective elevated-temperature strength, which is further enhanced hv strain-induced precipitation. The dispersion exhibits classical dissolution and aging response. The ductile-to-brittle transition temperature of these alloys is above room temperature. The alloys reported show fairly good oxidation resistance, but nitrogen contamination can cause fortnation of a hard Cr2N layer under the oxide scale. Manganese does not appear to be a promising alloying element in chromium. In the years 1945 to 1950, the metal chromium was considered as a possible base for alloy systems due to its considerably higher melting point than superalloys, its low density, its high thermal conductivity, and its apparent capacity for strengthening. However, this interest in chromium was short-lived. It was found difficult to melt and cast, to be exceptionally sensitive to the effect of minor imperfections, to have a lack of ductility at both room and elevated temperatures, and to be subject to a deleterious effect of alloying elements upon the ductile-to-brittle transition temperature.&apos; Since then, chromium, as a practical alloy base, has remained virtually unstudied. Further, purposeful ignoring of chromium has been promoted by statements that its bcc structure would not allow it to be strengthened to useful values, when compared to the "austenitic" alloys.2 Recently, a new look has been taken at chromium-base alloy systems. Study of the literature will show that chromium, providing some of its disadvantages could be eliminated or minimized, actually has a rather attractive potential as an alloy-system base. Analysis of rather scattered data suggests that chromium is quite capable of being strengthened to high levels. Also, significant strengthening of its two sister elements in Group VI-A, molybdenum and tungsten, has been demonstrated in a number of commercial and exploratory alloys. Chromium should be similar. Since chromium does not readily form a volatile oxide like tungsten or molybdenum, it offers a much higher probability of giving birth to alloy systems with useful oxidation resistance. Concerns about possible high elemental vapor pressure have been mitigated by recent data.3 In addition, the physical properties exhibited by chromium are attractive for application as a high-temperature structural material. For instance, its thermal conductivity varies from 49 to 36 Btu-ft/hr-sq ft-°F over its range of usefulness (which is two to four times higher than most superalloys), its density is about 7.2 g per cc (20 pct less than most nickel-base alloys), its coefficient of thermal expansion varies from 4 to 8 x 10-6 per OF, and it has a relatively high modulus of elasticity, approximately 42 x 10&apos; psi.4 Alloying studies on a chromium base in the past have usually encompassed rather sweeping solid-solution alloy additions for strengthening. This is not consistent with contemporary alloying practice in Group VI-A. For instance, molybdenum, also in Group VI-A, is primarily alloyed for strength improvement by use of heat-treatable carbide dispersions.5 Chromium and molybdenum are similar in their chemical activity and other properties. Thus, strengthening of chromium by carbide dispersions was studied. Chromium-base alloys are plagued with room-temperature brittleness, although high-purity unal-loyed chromium can be made ductile.4,8 Use of yttrium as a scavenger has done much to improve ductility and resistance to nitrogen embrittlement in chromium systems,7 so it was utilized in this program. It has also recently been found8 that small rhenium additions (1 to 5 pct) create improvement in the ductility of Type 218 tungsten wire. This is apparently related to the remarkable effect of rhenium additions near its terminal solid solubility in all Group VI-A metals.9&apos;10 Investigation to establish if dilute concentrations of rhenium would also be effective in chromium appeared to be logical for this program. Since rhenium is too expensive to be practical in alloys for application as structural components, ductility improvements through solid-solution alloying were also sought by substitution of manganese for rhenium; manganese, like rhenium, exists in Group VII of the periodic system. The optimum amount of carbide dispersion for chromium-base alloys was obtained by analogy with molybdenum. Strengthening in molybdenum is achieved by use of Ti-Zr carbide dispersions. A

Jan 1, 1964

By W. Crafts, J. L. Lamont

Electrolytic extraction of carbides from quenched and tempered steel and their examination under the electron microscope were found to be helpful in understanding the mechanism of secondary hardening in alloy steels1 and the same technique has been applied to isothermally transformed steels. A preliminary survey of the utility of the method has indicated that it has promising possibilities for investigating the characteristics of pearlite and bainite. The examination of a few carbon and chromium steels has suggested that pearlite is formed with carbides of two varieties representing the lamellar and nonlamellar forms and that bainite appears to form with a structure analogous to, but significantly different from, martensite. Procedure The method used for examining the carbides was similar to that described previously.1 The chromium steels used in the investigation were made from an Armco iron base in an induction furnace and were not treated with grain-refining deoxidizers. The composition of the steels is given in Table 1. Three-inch square ingots were forged and rolled to 1/8-in. thick sheet for use in the isothermal studies. After rolling, the sheets were sandblasted to remove the rolling scale. Specimens approximately 3/4-in. wide and l1/2-in. long were prepared from the 1/8-in. sheet. They were heated in a salt "bath at 2100°F (1150°C) for 1/2 hour, transferred to other salt baths at 1300°F (704°C), 1000°F (538°C), 800°F (426°C), or 600°F (315°C), held for various periods up to 100 hr and finally quenched in water. After quenching, the specimens were cut in half, one half being submitted to microscopic examination and the other half being used for the electrolytic extraction. The isothermally transformed specimens were submitted to examination under the light microscope to determine the degree of transformation and type of structure and were photographed at 2000 X. Carbide residues were obtained by electrolyzing in 10 pet hydrochloric acid and collecting the residue in glycerine to minimize attack by the acid. As pointed out in the earlier paper, the carbides are attacked to some degree during electrolysis. This attack is relatively minor on the coarser carbides but may be quite severe on the fine bainitic carbides. The residues were washed free of the glycerine with water and alcohol. The alcohol was removed by repeated washings of amyl acetate, and the amyl acetate suspensions were transferred to stoppered vials. Debye-Sherrer X ray diffraction patterns of the residues were prepared using a chromium target. A selection based on the microstructure and X ray data was then made of samples considered most illustrative of the progress of transformation. Electrolytically extracted residues from these samples were submitted to examination by W. D. Forgeng and A. C. Jenkins on the electron microscope at the Research Laboratories of The Linde Air Products Co. and electron micrographs were made at X 5000 and enlarged to 25,000 X. The micrographs obtained with both the light and the electron microscopes are mounted side by side in the accompanying figures. Although no effort was made to establish the T-T-T diagram for the chromium steels, the times for holding in the salt bath were adjusted with the intention of making the samples represent different stages in the transformation at temperatures of 600, 800, 1000, and 1300°F. The degrees of transformation and results of X ray examination are shown in Tables 2—4. The carbide designations refer to orthorhombic or trigonal carbide types and are not meant to imply that the compositions are exactly as indicated. X ray Diffraction Data The occurrence of Fe3C and Cr7C3 in these steels was found to be consistent with published data on comparable chromium steels. Steels A and B with relatively low ratios of carbon to chromium contained Cr7C3 in the pearlitic structures and FeuC in the

Jan 1, 1950

By J. L. Lamon, W. Crafts

Study with the electron microscope of the carbides in vanadium-chromium-molybdenum steels after tempering up to 1000 hr at 600 teelsto 1400°F confirmed that alloy carbides are formed at the secondary hardening temperature by decomposition of the plate-like iron carbides. It was also demonstrated that vanadium carbide persists as much smaller particles than do chromium- or molybdenum-bearing carbides. Conditions conducive to the formation of fine vanadium carbides are indicated to be favorable for high temperature strength. IN order to determine the effects of long exposure at high temperatures on vanadium-bearing steels, a survey has been made of their hardness and carbide structure. The behavior of carbides in the tempering of martensite was studied by X ray diffraction and electron microscope examination of electrolytically extracted residues in greater detail than in an earlier investigation.&apos; A group of steels with about 0.25 pct carbon and containing chromium up to 5 pct, molybdenum up to 1 pct, and vanadium up to 1 pct was either quenched or annealed and then tempered for peri- ods of up to 1000 hr at 600° to 1400°F. Their hardness after tempering agreed with the Hollomon and Jaffe2 relation of equivalency of time and temperature, and with the degree of secondary hardening predicted from composition. Further, the appearance of the carbides indicated that the time and temperature equivalency relation was also applicable to the degree of carbide development. The mechanism of the tempering of martensite was demonstrated more clearly than in the earlier study. It was confirmed that carbides develop from martensite as poorly defined plates of the Fe2C type carbide followed by thickening of the plates with a transition to Fe,C. Finally the plate structure deteriorates into a lacy mass from which alloy carbides emerge as chunky particles that grow slowly with further increase of tempering temperature. Vanadium carbide derived from tempered martensite was found in characteristically small particles that tended to grow very slowly. The addition of chromium or molybdenum to a steel with predominant vanadium carbide tended to introduce carbides of a chromium- or molybdenum-bearing type having a somewhat larger particle size. The Cr,C, type carbide particles were larger than those of the V,C, type and somewhat smaller than the carbides in steel containing both Cr,C and M,C. Similar observations were made of the carbides in the pear lite of annealed steels. It appeared that high temperature properties would be benefited by the retention of the fine carbide particles that result from a balance of composition and heat-treatment designed to produce a maximum amount of vanadium carbide. Procedure: The steels used in the investigation were made with a base of Armco iron in a high-frequency furnace at the Union Carbide and Carbon Research Labs., Inc. The steels were deoxidized

Jan 1, 1951

By J. L. Lamon, W. Crafts

P. Coheur and L. Habraken—We read this paper with great interest and are glad to congratulate the authors for their valuable work, supplying an important contribution to the mechanism of tempering on the carbides in vanadium steels. We are in a good position to appreciate this work since we have been studying, for more than a year, Cr-Mo steels of a composition similar, but less highly alloyed (namely 0.1 pct C, 3 pct Cr, 1 pct Mo). Our results are quite in concordance with the authors&apos;, however, we wish to point out that it is very interesting to use equally the electron microscope in order to observe the variations of microstructure in steels. We have studied simultaneouslv the evolution of the carbides in situ with the electron microscope, and, after extraction, again with the electron microscope, and then with X-rays. The first results which we have obtained have been communicated at the Congress of Delft (July 1949) and at the "Journbes de la Metallurgie" in Paris (October 1949). These may be summarized as follows: After tempering with varying either the tempering temperatures or the tempering times, the carbides show two evolutions. The first one is connected to the carbides existing in the steels, principally in the boundaries of the grains. For some groups of steels these carbides may coalesce and for other groups they may

Jan 1, 1951

By L. C. Brown, J. S. Kirkaldy

Measurements have been made of carbon diffuswn in the five ternary austenites Fe-C-Si, Fe-C-Ni, Fe-C-Co, Fe-C-Mn, and Fe-C-Cr in which the carbon (component 1) diffuses through interstitial sites and the ternary addition (component 2) diffuses substitutionally. Values of the diffusion-coefficient ratio, D12/D11 were determined for each system with finite couples using the transient equilibrium method. The effect of temperature and of concentrations of both the carbon and substitutional component upon D12/D was examined and was found to agree with the theoretical predictions. It is concluded that within an experimental uncertainty of 10 to 15 pct, it is possible to calculate the ratio D12/D11 from purely thermody-namic data. Difficulties of measuring the other off-diagonal coefficient, 4,, are discussed. Any quantitative attack on the fundamentals of the hardenability problem in steel must begin with the multicomponent diffusion formalism and with the accumulation of data pertaining thereto. In a recent paper Kirkaldy and purdy 1 employed the formalism derived from irreversible thermodynamics to treat the problem of diffusion in ternary austenites. In the latter solutions, carbon diffuses through interstitial sites and the substitutional component diffuses through the lattice. Examples were given of diffusion in the systems Fe-Mn-C and Fe-Si-C. In the present paper, we present new results on and discuss their agreement with the thermody-namic theory. Since the theory has been slightly modified from the original presentation of Kirkaldy and Purdy, their results on Fe-Si-C and Fe-Mn-C have been recalculated and are presented here for completeness. The flux of the interstitial component with respect to a fixed lattice framework can be written as a linear expansion in the independent concentration gradients, where X1 and X2 are the independent thermody-namic forces in the lattice fixed frame of reference. These forces can be obtained from the general statement for forces in a volume fixed frame2 if the partial molar volume of carbon atoms is set equal to zero and that of the substitutional component 2 is set equal to unity, viz where the are the chemical potentials and the N&apos;s are mole fractions. Introducing into [3] and [4] the function If, as suggested by statistical arguments, the off-diagonal interaction L12 is sufficiently small, [6] reduces to i.e., the coefficient ratio becomes purely thermo-dynamic. The activity of components 1 and 2 in a dilute ternary system (standard state at infinite dilution) may be represented by the expansion3

Jan 1, 1964

By G. W. P. Rengstorff, R. B. Fischer

A study was made of the effect of impurities on the bend ductility of cast molybdenum. High purity molybdenum was repared by re-melting under high vacuum. The ductility of "transverse-grain" specimens indicated that intergranular brittleness decreased with an increase in purity of the metal. THE production of as-cast molybdenum with high ductility at room temperature would make working of the metal easier and increase the usefulness of the as-cast metal. Furthermore, a .knowledge of the factors that influence the ductility of as-cast molybdenum might be applied to the problem of making fusion weldments having satisfactory room-temperature ductility. Individual grains of commercial as-cast molybdenum are slightly ductile at room temperature. However, the presence of carbides at the grain boundaries may cause the metal to fracture in a brittle manner. This behavior has been discussed.&apos; The amount and distribution of the impurities in as-cast molybdenum would be expected, from previous research on the metal, to have considerable influence on its ductility. Some effects of oxygen and carbon on the mechanical behavior of the metal were discussed by Parke and Ham,2 Woodside,3 and Zappfe. Landgraf, and Worden.4 Parke and Ham2 found that, if a sufficient number of molybdenum oxide particles were present at the grain boundaries, the intergranular cohesion was reduced to the extent that arc-melted molybdenum would rupture intergranularly during hot forging. They also found that if the oxygen content was less than 0.003 pct, the cast molybdenum was hot forgeable. It is suspected, however, that forgeable molybdenum may contain a small amount of oxide that could reduce the ductility of the as-cast metal at room temperature. Also, there is the possibility of the unfavorable distribution of other impurities having a detrimental effect on the ductility of cast molybdenum. The results of a study of the influence of purity on the room-temperature ductility of cast molybdenum are presented here. Vacuum Arc-Melting to Produce High Purity Mo One way of determining the effect of impurities on the ductility of molybdenum is to prepare and test metal as free of all impurities as possible. Accordingly, the present investigation was undertaken with this in view. Arc melting in high vacuum (less than 0.1 micron of mercury) was chosen as the method for reducing the impurities below the concentrations occurring in commercial molybdenum. Commercial arc melting of molybdenum is carried out at about 50 microns pressure. During the arc melting, carbon and oxygen in the metal react to form carbon monoxide. By virtue of the vacuum process, the partial pressure of carbon monoxide is maintained at such a low value that the reaction greatly lowers oxygen and carbon contents. An excess of at least 0.03 pct C is used in commercial arc melting to insure that the oxygen content will be below 0.003 pct. The excess carbon remaining after the deoxidation step forms carbides on freezing. Some of the carbides precipitate at the grain boundaries and, as will be shown, have an unfavorable effect on the room-temperature ductility. In the present work, only the small amount of carbon (0.003 pct) contained in the commercial powder-metallurgy molybdenum used for melting stock was present. Partial removal of oxygen from the melt probably occurred as the result of the volatilization of molybdenum oxides, or by distillation of oxygen at the high melting tem-

Jan 1, 1953