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By F. Weinberg

INTEREST is currently being directed toward grain boundary morphologies in zinc in terms of grain boundary facetingl and grain boundary energies.' Some years ago the present author attempted to measure grain boundary energies in 99.999 pct purity Zn as a function of boundary angle, using the standard procedure of measuring equilibrium angles of the boundary traces at triple points. This followed an investigation he carried out on preferential melting of |H (112) Fig. 1—Electron transmission micrograph of a stacking fault, grain boundary intersection in copper. GRAIN BOUNDARY STACKING FAULT Fig. 2—Schematic representation of the intersection of Fig. 1, indicating inclination angles 0 and trace angles $. specimens were prepared by the Bollman technique in an electrolyte of 70 pct methanol, 30 pct HNO3 main-tained at -30°C. The interfacial free energy of the high angle grain boundary and of the stacking fault is assumed to be thermodynamically equivalent to the corresponding in-terfacial tensions. In terms of the true dihedral angles & between the intersecting interfaces, the equilibrium of interfacial tensions in the direction parallel to the stacking fault yields: ysF = -ygb(cos F1+ cos ±cosF2) Here, ysF is the stacking fault free energy and ygb is the grain boundary free energy, assumed equal on both sides of the intersection. Forces acting normal to the grain boundary, of the form ??gb/?F,l are assumed negligible as the grain boundary remains straight for a considerable distance on either side of the intersection. The micrograph of Fig. 1 may actually consist of several closely spaced stacking faults on the same slip plane. The actual point of intersection between the grain boundary and the first stacking fault, and the equilibrium configuration of the intersection, should not be affected by the presence of the other faults, as

Jan 1, 1970

By C. T. Young, J. L. Lytton

In recent investigations,1,2 the strength and thermal stability of dislocation substructures prepared by 5 to 25 pct room temperature tensile straining and recovery annealing at 120°, 160°, and 200°C have been studied in randomly oriented polycrystalline high purity aluminum. The techniques of transmission electron microscopy revealed that a major source of the strength and stability of dislocation substructures was the formation, during room temperature straining, of well-defined cells bounded by dislocation tangles which rearranged into nearly perfect dislocation networks during recovery, forming the boundaries of subgrains. The strength of such substructures increases with decreasing cell or subgrain size,2"6 and the formation of fine subgrain structures can provide thermally metastable strength at low temperatures and can favorably alter the course of primary creep at elevated temperatures.7'8 For maximum benefit, however, sub-grain growth should be reduced or eliminated. It was, therefore, decided to investigate the use of heterogeneous precipitation on dislocation networks as a means of imparting increased strength and thermal stability to subgrain structures through effective pinning. C.T. YOUNG, STUDENT MEMBER AIME, and J. L. LYTTON, Member

Jan 1, 1970

By Gernot Kostorz

In a recent paper, Raffo and itcheell1 compared solid solution hardening of various bcc alloy single crystals at room temperature and concluded that the expression for localized elastic interaction between dislocations and solute atoms2 that gives the critical resolved shear stress (CRSS) 7,: to = Z . µE3/2 C1/2 where c = concentration, e = misfit parameter, (µ = shear modulus, Z = numerical constant Fig. 1—The slope dT0/dc1/2 for niobium alloy single crystals deformed at 570°K plotted against the misfit parameter € = In' I + 1616 I. from Ref. 6, •estimated from Ref. 7. Table I. Plateau Hardening and Alloy Parameters for Niobium Alloys dT0/dc1/2, kg/mm2 Solute Ref. 6 Tantalum 3.7 ± 0.3 1.9 0.73 + 0.06 9 0.0 ± 0.5 15 Vanadium 16.1 ±1.4 - 0.69 i 0.01 9 -7.4 ± 0.5 16 Tungsten 12.5 ? 1.5 20.9 0.92 i 0.05 10 -5.0 t 0.4 17 Rhenium - 25.9 1.24 11.12 -8.5 ± 0.4 I5 Molybdenum - 14.6 1.04 13,14 -4.6 s†±?˜µ?fF?? 0.5 17 Hafnium - 13.9 0.37 12 4.8 ± 0.5 17 Table 11. Solid Solution Hardening and Alloy Parameters for Tantalum Alloys i)' dTo/dc1/2 kg/mm2, dTp/dc1/2 kg/mm2, Ref. 22 1006 Solute ˜570°K Ref. 7 See Text Ref. 25 Rhenium 44.3 32.5 0.65 -8.5 Tungsten 32.1 24.3 0.34 -4.6 Molybdenum 29.3 19.1 -0.19 -5.9 Niobium 5.8 5.5 -0.43 0.I

Jan 1, 1970

By Richard A. Queeney, Lance G. Peterson

ESTIMATES of the stacking fault free energy of copper reported in the literature show an extensive divergence of results. Based on measurements of dislocation node radii, Thornton et al.7 find the lower limit of stacking fault energy to be 60 ergs per sq cm: Jossang and coworkers4 estimate the same value should be less than 40 ergs per sq cm. Assuming stacking fault free energy to be twice the coherent twin boundary free energy, Valenzuela8 reports 72 ergs per cm, while Inman and Khan2 cite a value of 24 ergs per sq cm. which can no doubt be accounted for by almost complete absence of interstitials in solution. However, the minute concentration was sufficient to permit observable recovery of dislocation damping. Assuming a dislocation density of 1010 CM -2 and an average loop length of 0.5 , a concentration of interstitials as low as 0.01 at. ppm is sufficient to reduce dislocation damping by more than a factor of ten. The concentration of interstitial solute atoms in Ferrovac E-0.15 pct Ti was thus estimated at 0.01 at. ppm < (C + N) < 2 at. ppm. The absence at elevated temperature of strengthening due to interstitials, Fig. 1, was therefore anticipated in the titanium alloy. The temperature dependence of the flow stress below 300°K was unaffected by addition of either titanium&apos; or zirconium.&apos; Observed, however, was an initial difference in the absolute value of the flow stress below 320oK, Fig. 1. Grain size may account for the difference; the grain diameter of Ferrovac E was 30 to 45 µ and that of Ferrovac E-0.15 pct Ti 65 to 90 µ. Although second phase particles in the form of titanium carbides and nitrides precipitated in the Ferrovac E-0.15 pct Ti alloy, the spacing was too large to produce any strengthening effect. The mechanical properties measured, therefore, were inherent to the bcc lattice. 1W. C. Leslie and R. J. Sober: Trans. ASm, 1967, vol. 60, pp. 99-111. 2 H. Conrad: Journal of Metals, 1964, vol. 16, pp. 582-88. 3 A. S. Keh and W. C. Leslie: Materials Science Research. H. H. Stadelmaier and W.W.Austin, eds., vol. 1.pp. 208.50, Plenum Press, New York, 1963. 4A. S. Keh, Y. Nakada, and W. C. Leslie: Dislocation Dymmics, Rosenfield, Hahn, Bement, Jr., and Jaffe, eds., pp. 381-406, McCraw-Hill Book Co., New York, 1968. &apos;W. J. Bratina, J. T. McCrath, and H. E. Rosinger: Can. Met. Quart., in press. 6 W. J. Bratina, J. T. McGrath, and D. Mills: Suppl. Trans. Japan Inst. Metals. 1968, vol. 9, pp. 436-43. &apos;H. E. Rosinger and C. B. Craig: Can. Met. Quart., In press. %. Mills. J. T. McGrath. and W. J. Bratina: ScriptaMet,, 1968, vol. 2, pp. 311-13. The purpose of this note is to present the results of a direct measurement of the stacking fault free energy in copper. The present method avoids both the question of interaction forces of nodal dislocations and the assumption that the coherent twin boundary free energy is one-half that of a stacking fault. Fig. 1 shows a transmission electron micrograph of a stacking fault intersecting a high angle grain boundary in copper: Fig. 2 is a schematic representation of the intersecting interfaces. To produce the specimen, pure copper was rolled to 0.002 in. thickness and annealed for several hours at 875°C. These foils were strained in tension to l04 µ in. per in., and rean-nealed to 8 min. Recrystallization and/or grain growth were not observed during the second anneal, indicating that intersections such as Fig. 1 are equilibrium configurations. Many such stacking faults were observed, but few were noted as intersecting grain boundaries in well-illuminated areas. The intersection of Fig. 1 was well away from the specimen edge. Since similar defects have not been observed in fully recrystal-lized and annealed copper, it is felt that this defect is due to the tensile straining. Electron transmission

Jan 1, 1970

By G. R. St. Pierre, A. Ghosh

In the Si-C-0 system at temperatures of interest in process metallurgy there are four stable condensed phases—silicon, carbon, silica, and silicon carbide (Sic). Silicon melts at 1683oK1 and shows negligible solubility for carbon and oxygen at 1700°K. However, silicon dissolves approximately 1.5 at. pct C at 2500oK.2 Carbon in the form of graphite remains pure and dissolves negligible amount of silicon.&apos; Silica (crysto-balite) melts at 2001°K&apos; and is essentially a stoichio-metric compound. Silicon carbide is a solid and shows negligible deviation from stoichiometry up to approximately 2800oK.2 Besides the condensed phases there is a gas phase

Jan 1, 1970

By S. G. Proctor, D. L. Baaso, W. V. Conner

A double crucible system was developed for I-g scale plutonium reductions. The equipment consists of an inner MgO crucible, an outer MgO crucible, and a stainless steel pressure vessel. The reduction charge is PIaced in the inner crucible and the annulus between the inner and outer crucibles is filled with a mixture of calcium and iodine. The exothermic reaction between the calcium and iodine in the annulus supplies the heat required for complete reaction of the reduction charge ana&apos; good metal coalescence. Metal yields of 80 to 85 ,pct were obtained from I-g scale reductions and yields as high as 97.5 pct were obtained from 0.5-g scale reductions. The system was used to reduce charges containing as little as 0.1 g of Pu resulting in metal yields up to 90 Pct. THIN metal foils of highly enriched plutonium isotopes are used as targets for cross section and other measurements. The isotopes are separated in the calutrons at Oak Ridge and are very expensive to prepare. Often, only 1 or 2 g of material are available thereby emphasizing the need for a method of preparing these small quantities of metal. Procedures for 1-g scale plutonium reductions have been described, but these procedures require elaborate or expensive equipment. For example, the procedure described by Anselin et al.1 requires an inert atmosphere glovebox and induction heating equipment. The procedure described by Baker2 also uses induction heating equipment to obtain the recommended heating rates and liner temperatures. Baker&apos;s procedure also requires high purity PuF4 with very little PuO2 present. The procedure described in this paper resulted from a search for a simple and inexpensive method for making 1-g scale plutonium reductions. EXPERIMENTAL Equipment. The equipment required for the double crucible system consists of a pressure vessel, two MgO crucibles, a MgO crucible lid, and a resistance-heated, vertical crucible furnace. The crucibles were slip cast from high purity MgO and were supplied by the Coors Porcelain Co. and the Norton Co. The pressure vessel and lid were fabricated from 316 stainless steel. Materials. The PuF4 used for this study was obtained from the P1utoniu:m Metal Production Department at Rocky Flats. The PuF4 was prepared in a con- tinuous hydrofluorinator by reacting Pu02 with HF at 650°C. The isotopic composition of the plutonium was approximately 93 pct 239PU, 6 pct 240PU, and 0.5 pct 241PU. Some of this PuF, contained less than 1 pct Pu02 (Batch No. 6 and 7), while other batches contained up to 15 pct Pu02 (Batch No. 3). The chemical analyses of all the PuF4 used for this study is given in Table I. The calcium was 99 pct pure, AEC grade, and only that fraction which would pass through a 20 mesh screen was used. The I2 was USP grade re-sublimed I2 which was ground before being used. Procedure. Various charge compositions and methods for loading the double crucible system were tested. The optimum conditions for 1-g scale reductions are described below. The double crucible system was loaded as shown in Fig. 1. The outer crucible was placed in the pressure vessel and the annulus between them was filled with MgO sand. The inner crucible was placed in the outer crucible, supported by a layer of MgO sand in the bottom of the outer crucible. A mixture of 5.2 g of Ca and 25 g of I2 was placed in the annulas between the two crucibles. The upper portion of the annulas was filled with MgO sand. Next, a layer of a mixture of calcium and I, equal to 20 wt pct of the calcium and I2 used in the main charge was placed in the bottom of the inner crucible. The PuF, to be reduced was mixed with a 30 pct excess of calcium and 1 mole of I2 per mole of Pu and this mixture was placed in the inner crucible. The charge was topped with a layer of a mixture of calcium and I2 equal to 20 wt pct of the calcium and I2 used in the main charge. The pressure vessel was sealed with a flat copper gasket and was purged by alternately evacuating and filling with argon. The purge valve was closed and the vessel was placed in a vertical crucible furnace which was preheated to 950°C. The furnace was turned off after 20 min of heating and the vessel allowed to cool. Experience has shown that. this amount of heating is sufficient to assure complete reaction of the charge. RESULTS AND DISCUSSION The double crucible system has been used to produce plutonium metal on a 0.1- to 1-g scale. Reduction

Jan 1, 1970

By H. C. Gatos, J. T. A. Pollock

It is well known that the superconducting critical current densities of many alloy superconductors may be increased by cold working and in some cases further enhanced by a short heat treatment. This latter enhancement has been attributed to the redistribution of dislocations into cell-like networks&apos; and to the precipitation of second phase particles,2&apos;3 which act as flux pinning centers. In a manner analogous to dislocation pinning in precipitation hardening alloys,4 it is expected that here also a critical distribution of the pinning centers should result in maximum pinning effect. Concentration inhomogeneities exist in most or all commercial alloys yet there have been only a few attempts made to determine their effect on critical current capacity in the absence of cold working. Sutton and Baker,5 and Kramer and Rhodes6 have found that the complex precipitation processes occurring during the aging of Ti-Nb alloys can result in critical current density enhancement. Livingston7-10 has clearly shown, for lead and indium based alloys, that the distribution of precipitated second phase particles is of critical importance in determining magnetization characteristics. However, these &apos;(soft" alloys age at room temperature and the time involved in specimen preparation prevents metallographic examination in the state in which the superconducting measurements are made. Thus results with such alloys are expected to be biased towards larger precipitates and interpar-ticle spacing. The present study of Ta-Zr alloys was undertaken to examine the influence of second phase precipitation, as controlled by heat treatment, on the critical current capacity of well annealed polycrystalline material. A study of the published phase diagram11 indicated that annealing supersaturated samples containing up to 9 at. pct Zr at suitable temperatures would result in the precipitation of a zirconium-rich second phase. It was MATERIALS AND PROCEDURE The alloys were prepared from spectrochemically pure tantalum and zirconium. Analysis was carried out by the supplier. Major impurities in the tantalum were: 12 pprn of 02, 17 pprn of N2, 19 pprn of C, and less than 10 ppm each of Mo, Nb, Al, Cr, Ni, Si, Ti. The crystal bar zirconium was pure except for the following concentrations: 15 pprn of 02, 17 ppm of C, 23 ppm of Fe, 11 ppm of Cu, and less than 10 pprn each of Al, Ca, N2, Ti, and Sn. Samples were prepared in the form of 8 to 10 g but-tons by arc melting using a nonconsumable electrode on a water-cooled copper hearth in a high purity ar-gon atmosphere. Each button was inverted and re-melted three times to ensure an even distribution of the component elements. The samples were then homogenized at temperatures close to their melting points for 3 days in a vacuum furnace maintained at 5 x 10-7 mm Hg. After this treatment the buttons were cold rolled to sheets approximately 0.020 in. thick from which specimens were cut, 0.040 in, wide and 1 in. long suitable for critical current density (J,) and critical temperature (T,) measurements. These strips were then recrystallized and further grain growth was allowed by an additional vacuum heat treatment at 1800°C for 60 hr. Some second phase precipitation occurred during cooling of the furnace and a solution treatment was necessary to produce single phase supersaturated samples. This treatment was successfully carried out by sealing the samples together with some zirconium chips in quartz tubes under a vacuum of 5 x 10-7 mm Hg, heating at 1000°C for 5 hr and then quenching into water or liquid nitrogen. The samples were then heat treated at either 350" or 550°C and quenched into water or liquid nitrogen. All samples which were heat treated at 350°C were quenched in both cases by cracking the capsules in liquid nitrogen. The samples treated at 550°C were quenched by dropping the capsules into water. Analysis for oxygen in randomly selected samples indicated that the oxygen content was in the range of 175 to 225 ppm. Values of Tc were determined by employing a self-inductance technique. Jc measurements were made at 4.2oK by increasing the direct current through the wire in a perpendicularly applied field until a voltage of 1 pv was detected with a null meter. The risk of resistive heating at the soldered joints during these latter measurements was reduced by first plating the ends of the wires with indium and then soldering to the copper current leads using tin. Metallographic examinations were performed after mechanical polishing of the same samples and etching in a 4H20:3HN03 (conc):lHF(conc) solution.

Jan 1, 1970

By Peter R. Morris, Alan J. Heckler

THREE angles are required to specify the orientation of a crystallite with respect to a physical reference frame. The distribution of crystallite orientations in a polycrystal is thus a function of three angular variables. The most widely used experimental techniques for studying orientation in polycrystals lead directly to the pole figure representation, i.e., the distribution of the poles of certain crystallographic planes in terms of two angular variables. In recent years1-5 methods have been developed which permit determination of the (three-angle) crystallite orientation distribution from several (two-angle) pole figure distributions. In this work Roe&apos;s method has been applied to the study of orientation in hcp materials. The method is illustrated for commercial purity titanium sheet (Ti-70) which was cold rolled (65 pct reduction), annealed at 1450°F for 3 min, and air cooled. The grain shape was observed to be equiaxed after this treatment. EFFECTS OF PHYSICAL, CRYSTALLOGRAPHIC SYMMETRY In Roe&apos;s method the crystallite orientation distribution, w(?,?,F), is expanded in a series of generalized spherical harmonics 11(?,?,F) = E E E W^Zirmtye-tote-in* [l] 1=o ,,,=-I ,,=-I where { = cos 8. The set of Euler angles employed here is illustrated in Fig. 1. The axis for each rotation is denoted by a double arrowhead. The positive sense of each rotation is that of a right-handed screw advancing in the direction of the double arrowhead. The X, Y, and Z directions correspond to the rolling direction, cross direction, and normal direction, respectively. In the initial orientation (10.O), (12.O), and (00 . 1) planes are perpendicular to the X, Y, and Z directions, respectively. The IC/ rotation about the Z axis is carried out first by rotating X into X&apos;, Y into Y&apos;, and leaving 2 unchanged, i.e., Z&apos; = Z. The 8 rotation about the Y&apos; axis is carried out second by rotating X&apos; into X", 2&apos; into Z", and leaving Y&apos; unchanged, i.e., Y" = Y&apos;. The I$ rotation about the Z" axis is carried out last by rotating X" into X"&apos;, Y into Y"&apos;, and leaving 2" unchanged, i.e., 2"&apos; = 2". Any specified orientation of the X&apos;", Y&apos;", and Z&apos;" crystal-fixed axis system relative to the X. Y, and Z physical axes (rolling direction, transverse direction, and sheet normal direction, respectively) can be obtained by appropriate IC/, 8, and (F rotations. The Zl,, of Eq. [l] are the Jacobi polynomials, augmented by the square root of the weight function. The Zl,, are symmetric in m,n, i.e., Zl,,= Zlnm. For orthotropic physical symmetry and hexagonal crystallographic symmetry, the coefficients, W!,,, of the series are all real, W!mn = Wzfi, = Wlm~ = Wlfi~, 1 and m are even and n is restricted to 6k, where k = ...,-2,-1, 0, 1, 2, .-.. The determination of the Wlmn from pole figure data has been previously described.&apos;~~ The Zl,, may be written in multiple angle form

Jan 1, 1970

By Meguru Nagamori

DURING the smelting of the sulfide ores of copper, nickel, and certain other metals, a matte phase is formed. For a better understanding of the physico-chemical properties of mattes, binary systems such as Cu-S, Ni-S, Fe-S, and so forth, should be studied, especially in the vicinity of liquid compounds such as Cu2S, Ni3S2, FeS, and so forth. These compounds are relatively stable in the solid state although they can exhibit appreciable deviations from stoichiometry. With small deviations from stoichiometry there are large changes in the activity of both sulfur and metal this is a characteristic of both solid and liquid sul-fides near the stoichiometric compositions. In the vicinityof molten Cu2S,1 for instance, the activity of sulfur increases about 100 times for a 0.012 increase in the mole fraction of sulfur and, correspondingly, the activity of copper decreases greatly. In this sens the minor deviations from stoichiometry should be carefully taken into account in studies of such metal-sulfur melts. Metal-sulfur melts may be considered to have properties intermediate between metallic solutions and molten salts, i.e., neither entirely metallic nor entirely ionic. The radius of the ion sZ- is 1.84 as compared with 1.04? for a single bond covalent s.2 It is therefore inferred that when the sulfur is more ionic its partial molar volume is larger, although metal-metal, metal-sulfur, and sulfur-sulfur interactions may bring about further complexities. Thus, it is to be expected that the molar volumes, which are derived from density-composition relations, will help in resolving the structure of the melts. In this study the maximum bubble pressure method with bubbling gases of H2, H2S, and Ar, .was employed to measure the density. EXPERIMENTAL Materials. Silver of 99.95 pct purity was melted in an alumina crucible and hydrogen gas was then bubbled through the liquid for the deoxidation. In preparation of Cu2S, electrolytic copper powder (>99.9 pct Cu) was mixed with precipitated sulfur and heated to 1200°C in an alumina crucible under a hydrogen atmosphere. Mixtures having the approximate compositions FeS and Ni3S2 were prepared by heating reagent grade electrolytic iron or reduced nickel powder with precipitated sulfur under a hydrogen atmosphere. The H2S gas was of 98.5 pct purity, the impurities being mostly CO2 and CS2 which hardly contaminate the melts. Apparatus. The crucible system is shown schematically in Fig. 1. To minimize the variation of melt composition during a density measurement, the apparatus was designed in such a way that either Ar, H2, H2S, or mixtures of these gases could be used as the bubbling gas. When the melt had a high partial pressure of sulfur, H2S gas was used. When the partial pressure of sulfur was so low that oxygen might dissolve in the melt, the use of H2 was preferred. In intermediate cases, argon or mixtures of H2-H2S were used. Density of Dibutylphtalate. Dibutylphtalate was used as the manometer fluid. Relative to distilled water, the density of the dibutylphtalate, pdib g per cc, was measured and found to be: pdib (25°C) = 1.046 i 0.002. With the use of the temperature coefficient reported by Kemppinen and Gokcen,3 the following value was

Jan 1, 1970

By B. C. Allen

Surface free energy and surface self-diffusion of solid molybdenum were studied in the temperature range 1600" to 2400°C using pressure-sintered bi-crystals. Comparison of groove angles formed in various surfaces perpendicular to the grain boundary indicate a maximum of 1 pct variation in surface free energy with crystallographic mientation. This anisotropy tends to decrease with increasing temperature. The surface diffusion of the bicrystals is equivalent to that of sheet with a mild (100) Preferred orientation. Anomalously low values found for bi-crystals with surface orientations of (OOl), (012), and (011) are rationalized in terms of anisotropy in surface free energy. THE effect of crystallographic orientation on surface free energy1,&apos; and surface self-diffusion3,4 has been primarily studied in fcc metals. The object of this work was to study the effect of orientation on surface diffusion and surface free energy of bcc molybdenum using pressure-sintered bicrystals. EXPERIMENTAL WORK Materials and Crystal Preparation. Arc-melted molybdenum rod was obtained commercially and electron beam zone refined at 50 cm per hr at 10- 5 torr to form single crystals about 8 cm long and 0.65 cm diam. Three crystals were prepared with axial orientations about 1 deg from [001.], [011], and. [111]. To reduce the carbon content, the crystals were annealed 2 hr in 1.4 atm flowing wet hydrogen at 2050°C. Then the oxygen content was reduced by annealing for 2 hr in -30°C dewpoint hydrogen at 2020°C. The resulting impurity analysis is given in Table I. Bicrystal Preparation. The single crystal rods were cut into transverse slices with a thin silicon carbide abrasive wheel to produce specimens about 0.6 cm long. They were mounted in epoxy and surrounded by stainless steel washers. Cutting in half was done longitudinally at various angles to known crystallographic planes containing the cylinder axis according to Fig. 1. To reduce surface deformation resulting from the cutoff wheel and thus reduce parasitic grain boundary formation on subsequent annealing, about 0.003 cm was manually ground off each cut surface with 600 grit paper. Care was taken to keep the surface flat. After removal from the mounts, one half was generally ro-tated 180 deg with respect to the other to give a po- tential symmetrical tilt grain boundary between the two halves. In the other cases when low misorienta-tion angles were desired, the crystals were not rotated. On the basis of symmetry, sufficient bicrystals were prepared to cover the entire range of misorientations for symmetrical tilt boundaries. The misorientations, +, ranged from 0 to 45, 0 to 90, and 0 to 60 deg for [001], [011], and [111] bicrystals, respectively. One [Ill] twist bicrystal was prepared from 2 single crystal discs rotated 17 deg relative to each other. Each specimen consisted of two pieces which were placed in a cylindrical tantalum can. Sharp edges were rounded and the fit was made as snug as possible to reduce subsequent deformation during bonding. The assembly and crystals generally were vicuum outgassed at 900" or 1700°C and then electron beam welded in the can at l x 10-4 torr. After being leak checked, the samples were placed in an autoclave and hydrostatically gas-pressure bonded5 in four batches under helium at 10,000 to 18,000 psi at 1650°C for 3 hr. Satisfactory bonds were obtained in many cases, and most of the crystals bonded after two exposures. The results did not appear to be affected by the various pressures used, preannealing conditions, crystal orientation, or time-pressure-temperature route taken to the final bonding condition. After bonding, the tantalum cans were selectively removed in cold concentrated HF. Measurements indicated overall deformation was under 1 pct. The bicrystals were metallographically ground and polished flat and perpendicular to the axis. Examination showed the boundaries were straight and almost free of parasitic grains caused by extraneous local deformation. Annealing. In preparation for thermal grooving, the bicrystals were cleaned and annealed by outgassing at 10-5 torr at 1900°C and heating at 2300°C under 1 atm 99.996 Ar for 0.5 hr. The crystals were held in a closed 4-deck box made of molybdenum sheet, and were heated in a Ta-1OW resistance furnace. The ar-

Jan 1, 1970

By F. A. Crossley

The additions: o, Sn, Zr, Cb, Mo, and V were studied for their effects on the a/a + Ti3A1 boundary of Ti-A1 base ternary alloys. These additions were chosen because of their importance to commercial titanium alloy practice—oxygen as the major impurity (in terms of influence on mechanical properties) and the others as major alloying additions. The composition and temperature ranges of investigation varied according to the system as shown in Table I. The principal means of investigation was light-microscopy. The basis of the ternary studies was the recently determined titanium-rich end of the Ti-A1 system.&apos; MATERIALS, METHODS, AND PROCEDURES Ingots were prepared in 15 g size for all alloys except those of the Ti-Al-Mo and Ti-A1-V systems which were prepared in 20 g size. These alloys were prepared from high-purity, electrolytically refined titanium obtained from the Bureau of Mines, Boulder City Metallurgical Laboratory, Boulder City, Col., and Chicago Development Corp., Riverdale, Md., for the 15 g and 20 g ingots, respectively. The alloying additions were obtained from commercial sources, and were at least of 99.9 pct purity, except the V-15 wt pct A1 master alloy for vanadium additions. This alloy was of 98.2 pct purity; the major impurities were 0.37 wt pct Fe and 0.38 wt pct Si. The ingots were prepared by multiple melting in a nonconsum-able-electrode arc furnace. The ingots were covered with Markal coating "CR-T22" (Markal Co., Chicago) to protect them from scaling. Markal coating is applied as a slurry of solids in a volatile carrier liquid. The coated article is air dried. Upon heating to the hot working temperature the coating fuses to form a glassy, protective film. The ingots were heated to 1000°C and rolled to 0.16 in. thickness, reheating after each pass. The glassy film was removed by sand blasting. Ten mils were removed from all surfaces by grinding and/or pickling (3 pct HF, 30 pct HN03, balance water). Grinding was always followed by pickling to remove traces of the grindmg medium. Hydrogen removal was accomplished by vacuum annealing at 1000°C for 2 hr to a final pressure of about 0.02 µ Hg. This was followed by annealing in evacuated Vycor bulbs (800°C, 2 hr, ice brine quenched (IBQ)) in order to maximize ductility. The materials were then lightly pickled and cold rolled to 0.12 in. thickness or cracking, whichever occurred first. After rolling, 1/2 by 1/4 in. specimens were cut for the equilibration anneals given in Table 11 and carried out as previously described.1 Final polishing of the specimens for metallographic examination was done by electrolytic means. Specimens were first examined without etching under bright field and polarized light illumination, for this is the only means of detecting the "two-phase" phenomenon.1,2 The term "two-phase syndrome" refers to Ti-A1 al-loys which appear on the bases of their chemical, phys-ical, and mechanical properties, to be two-phase, but are actually single phase and inhomogeneous in composition. Since processing and heat treatment of the alloys of the first group were completed before the two-phase syndrome was discovered, a number of the specimens were found to exhibit this phenomenon—80 pct of those of the Ti-Al-Zr system, 5 pct of those of the Ti-Al-Sn system, 30 pct of those of the Ti-Al-Zr system. The affected specimens were homogenized by heating above the ß transus temperature and quenching. The heat treatment and working schedules to accomplish this are given in Table 111. After rolling, specimens were pickled (3 pctHF, 30 pct HNO3 in water) to remove 1 to 2 mils from the

Jan 1, 1970

By William D. Klopp, Joseph R. Stephens

Chromium alloys were coated with silicon, alumi-nuw, and boron by pack cementation. None of these simple coatings provided adequate nitridation/oxida-tion protection for a Cr -0.17pct Y alloy substrate as shown by a substantial Increase in the ductile -brittle transition temperature after air exposure for 100 hr at 2100°F. Iron-modified silicide coatings afforded good protection, holding the transition temperature of air-exposed specimens to 350° F compared to 200° F for uncoated unexposed specimens and 800°F for un-coated exposed specimens. Additional attractive cant-binations of modi-tying elements included Fe-mo, Fe-Mo-W, Fe-,Mo-W-Ti, and V-Mo-W-Ti. THE desirability of increased operating tempera-tures as a mcans of improving the performance of ad-vanced air breathing engines has resulted in emphasis on the development of materials with high operating temperature capabilities. Chromium, because of its relatively low density (7.19 g per cu cm), high melt-ing point (3410°F), and adequate strength upon alloy-ing, is a candidate material for turbine buckets and stator vanes of advanced air breathing engines. How-even, chromium is not without severe limitations, the major one being susceptibility to nitrogen embrittle-ment upon exposure to air at high temperatures.1,2 For example, a 25-hr air exposure of a Cr-5 pct W* * All compositions in wt pct. alloy at 2100°F produces a 600°F increase in the duc-tile-brittle transition temperature.&apos; Although dilute alloying with such elements as yttrium, lanthanum, arid thorium3,4 or strong nitride formers5 has been shown capable of reducing nitrogen embrittlement, it is apparent that some additional form of surface protection, such as coatings or claddings, will be required for long time service in air breathing engines. Studies of aluiminide6 and silicide7 coatings and of nickel-base claddingsl on chromium alloys to date have suggested that these protection systems are inadequate. Of the aluminidc systems Studied,6 a simple aluminum and an Fe-Al coating on a Cr-5 pct W-0.1 pct Y alloy showed the lowest air exposure weight gains. However, the air exposures raised the ductile-brittle transition temperature of the coated specimens to above 1600°F from an initial level in unexposed specimens of about 500°F. A second in-vestigation for protection of Cr-5 pct W-0.1 pct Y employed gas pressure bonded alloy foils as protective claddings.1 An aluminized Ni-20 pct Cr-20 pct W alloy plus an unalloyed tungsten barrier layer gave the best performance with air exposure lives based on appearance and weight gains of over 600 hr at 2100°F. However, the bend ductile-brittle transition tempera-ture was increased to at least 1000°F after 100 hr at

Jan 1, 1970

By S. Feuerstein

THE influence of environment on the mechanical properties of metals has been extensively studied and documented.&apos; Most investigations have dealt with an interaction between a particular environment and a specific metal surface and the concomitant change in bulk mechanical behavior. Typical contributing media are oxide and metal film:;, electrolytes, and other surface-active agents. In the last category fall controlled gaseous environs (i.e., pressure or vacuum). Most vacuum exposure experiments prior to 1963 were conducted at pressures s>10-6 torr and elevated temperatures, or in such a manner as to prolong the exposure (e.g., by stress-rupture, creep, and fatigue). Little attention has been given to vacuum environment effects on the mechanical behavior of metals subjected to simple uniaxial deformation at room temperature. Test times and temperatures were assumed too ineffective as far as bulk changes were concerned. Further, the contribution of surface effects to the bulk mechanical behavior of metals was considered minimal. Under vacuums of the order of 1.0- 8torr and higher, molecular densities and, consequently, the rate of monolayer formation are such that exposures from seconds to days would be required for complete gas coverage. Thus, atomically clean surfaces created under ultra-high vacuum could conceivably maintain their cleanliness for time intervals orders of magnitude greater than at higher pressures. The influence of this unusual type of environmental surface phenomenon on the short-term bulk mechanical behavior of aluminum was first observed by Krame and Podlaseck in 1963.&apos; kin equivalent effect was reported for magnesium by Williams and Nelson.3 It was concluded from these studies2,3 that vacuum and, consequently, the monolayer formation rate of the oxide, were responsible for the described changes in flow behavior. The presence of an oxide layer impedes dis- I) EXPERIMENTAL DATA: MOLYBDENUM The tensile behavior of molybdenum was investigated by the author4-6 at ambient temperature over a range of pressures from 760 to 10-10 torr. These studies revealed that the flow behavior of the bulk specimens (0.200 in. diam by 2 in. gage length) was independent of pressure on sintered (0.062 mm grain size) and arc-cast polycrystals (0.012 to 0.149 mm grain sizes) and single crystals. Since the specimens were relatively large in size, it was assumed that any flow behavior effect would be surface-limited because of the short-term deformation procedure. Strain-rate-change experiments performed to determine the activation volumes for individual specimens at 760 to 10- 10 torr further indicated that the surface flow contribution was either minimal or zero, contrary to the findings of Shen el a1.7 on aluminum. Although the flow behaviors did not change, specimen ductility did change. For the sintered material at a strain rate of 4.2 x 10-4, specimen ductility was -9 pct higher at l0- 10 torr than at atmospheric pressure (dry nitrogen). A more comprehensive investigations on this same material revealed a distinct pressure dependence, Fig. 1. Intermediate and atmospheric pressure tests were obtained by backfilling the system from l0- 10 torr with extra dry, prepurified nitrogen. Other environments (air and purified argon) were also utilized for the 760 torr experiments; the results were essentially the same as those for dry nitrogen atmospheres. Departure from the fracture strain values obtained at 760 torr takes place in the vicinity of l0-6 torr, as indicated by the scatter band; a noticeable ductility increase is apparent at l0-8 and 10-10 torr.

Jan 1, 1970

By J. D. Hunt, R. J. McDonald

It is proposed that extensive fluid motion occurs between the dendrites of a Partially solid casting and it is suggested the A segregates in steel castings are a direct result of this motion. The fluid flow arises because of density differences between liquid ahead of the dendrites and the interdendritic liquid. Experiments are described on a model system investigating this fluid motion. The importance of interdendritic fluid flow is discussed with reference to longitudinal segregation. SERIOUS macro segregation is often found in large killed steel ingots. Among the most common segregates are those known as A and V, Fig. 1. The A segregates are arranged over the surface of cones, the wide parts being at the base of the ingot. The A segregates are pencil like in shape and extend from the columnar into the equiaxed region. The V segregates are distributed over inverted cones but have a less well defined shape. They occur at the center of the ingot. Because of the commercial importance of macro inhomogenities these segregates have attracted wide-scale attention. The segregates contain alloying elements and impurities which depress the freezing temperature and are thus the last liquid to freeze. A number of explanations have been proposed to explain their presence. It has been suggested1&apos;&apos; that the segregates are the result of the equiaxed zone growing towards the columnar region together with the interaction of convection within the bulk liquid. It has also been proposed that the segregates are the result of nucleation and rapid growth ahead of the dendritic front.3 Neither of these explanations is completely satisfactory because A segregates are pencil shaped and are not found as continuous cones. In this paper an alternative mechanism is proposed, and experiments are described on a model system to determine whether the mechanism occurs in practice. It is thought that A and V segregates are not peculiar to steels but should occur in many other large castings. Fluid motion within the bulk liquid region of a casting has been extensively discussed. Little attention has been paid to fluid motion within the partially solid regions. The work415 that has been done has been mainly concerned with the fluid motion which results from the volume contraction on freezing. The volume contraction is used to explain various types of macro segregation. The present authors suggest that in many cases the fluid flow resulting from volume contraction will be small compared with that due to other causes. When the columnar region is growing, the liquid still remaining between the dendrites has a much lower temperature near the ingot walls than at the dendrite tips. The composition of the liquid in contact with solid will vary with temperature. The density of the liquid will thus vary both because of changes in temperature and composition. The layers of different density liquid will give rise to a slow but steady liquid flow through the interdendritic regions. If there is no density change with composition, the temperature gradient within the dendritic region should give rise to a downward flow between the dendrites, shown schematically in Fig. 2. When the liquid density changes appreciably with alloy concentration this motion could either be en-

Jan 1, 1970

By K. R. Garr, D. Kramer, A. G. Pard

EXPOSURE of steels to a fast-neutron flux results in helium generation by (n,a) reactions. The elements Fe, Ni, Cr, and N are major participants in the (n,a) reaction and helium concentrations of up to 5 x 10"5 atom fraction could accrue in fuel clads after a year of service in proposed fast reactors.&apos; Such concentrations of helium can severely reduce the ductility of alloys at temperatures of reactor service. The phenomenon of helium embrittlement has been studied in austenitic alloys which were irradiated with particles as a rapid means of producing significant helium concentrations.2-5 The pres-ent work is a continuation of those studies and is concerned with helium effects in a ferritic stainless steel. I) EXPERIMENT Small sheet tensile samples with a gage length of 0.50 in. and a cross-section of 0.009 by 0.040 in. in the gage length were punched from cold-rolled type 405 stainless steel. The composition of the steel used in this work is given in Table I. Prior to helium injection, the samples were annealed 24 hr at 760°C which caused complete recrys-tallization with a resulting grain size of 40 u. This treatment rendered the alloy completely ferritic and carbide particles, 0.5 to 2 uin size, were present at a density of 1 x 1011 cm-3, Fig. 1. These carbide particles were probably a mixture of the M7C3 and M4C types.6 Helium was injected into the samples by irradiation with a particles from a cyclotron, which produced uniform concentrations through the center two-thirds of the sample thickness. Details of this procedure were previously described.&apos; The average helium concentration, as measured on a gas-source mass spec- 11) RESULTS A) Tensile Tests. The results of the tensile tests are given in Table I1 where the values shown are averages of two samples. There was no significant effect of helium on either the yield strength or tensile strength at 550" or 650°C but an increase in both is apparent at 750°C. Samples with helium showed a 20 pct loss in total elongation at 650°C which increased to a 55 pct loss at 750°C. The uniform elongation is not affected by helium at 550" or 650°C but shows an increase at 750°C.

Jan 1, 1970

By R. E. Maringer, B. A. Wilcox, A. H. Clauer, J. H. Sovik

Internal friction measurements from 25° to 1100°C have been made on specimens machined from TD nickel bar. The use of miniature torsional pendulum specimens alloived damping measurements to be made on specimens whose axes were parallel to the original bar axis, at 45 deg to the bar axis, and at 90 deg to the bar axis. There was a marked difference in damping with varying specimen orientation, and this was related to the pronounced micro structural anisotropy of this material. Varying the microstructure by cold working plus re crystallization annealing also greatly affected the damping behavior. Recrystallization essentially removed the broad peak found at 400° to 650°C in as-received TD nickel, and in addition greatly lowered the background damping. DlSPERSION hardened metals such as SAP-type alloys (Al + AI2O3) and TD nickel (Ni + 2 pet ThO2) have been developed primarily to improve high temperature strength properties. There have been numerous damping studies on SAP-type alloys,1"9 and one of these6 showed that the damping capacity was greater than that of 99.5 pet pure Al from 25° to 600°C. Several preliminary observations on TD nickel10 and an experimental Ni-ThO2 alloy11 indicated that here, too, the damping capacity was quite high. A high damping capacity in TD nickel, combined with its relatively good high temperature creep strength, could provide an additional benefit for some high temperature structural applications. This work was undertaken to study the internal friction behavior of TD nickel bar over the temperature range 25° to 1100°C. In Ni-ThO2 and Ni-Cr-ThOz alloys, other properties such as steady-state creep rate,12 creep rupture life,12&apos;13 modulus of elasticity,14 and ultimate tensile strength,14 are sensitive to orientation with respect to the primary working direction. Thus, in order to examine anisotropy effects in damping, studies were made on specimens machined with their axes parallel, at 45 deg, and transverse to the original bar axis. MATERIAL DESCRIPTION AND EXPERIMENTAL PROCEDURES The material used in this investigation was from the same £ in. diam TD nickel bar that has been studied previously.13&apos;15 The structure typical of the as-received TD nickel is shown in Fig. 1, and additional details of the structure can be found in Refs. 13 and 15. Elongated grains are parallel to the bar axis and are about 10 to 15 u long and about 1 u in diam. This structure is very stable, since no recrys-tallization or grain growth occurred after annealing for 3 hr at 1300°C.13 The total ThO2 content was 2.3 vol pct and the particles ranged in diameter from 100 to 1000. The average particle diameter was 370Å and the mean planar center-to-center particle spacing was 2340Å. To examine the influence of grain and subgrain structure on damping, a section of TD nickel bar was swaged and drawn at room temperature from 1/2 in. diam bar to 0.040 in. diam wire (99.3 pct re-duction in area). The structure in Fig. 2 resulted after the wire was annealed for 3 hr at 1250°C. The recrystallized grains were much larger than the grains in as-received bar, but still showed considerable elongation in the direction of working. A high

Jan 1, 1970

By J. D. Livingston, H. E. Cline

The lamellar-dendritic transition in Sn-Pb alloys near the eutectic composition has been studied at high growth rates. Lamellar structures were found over a substantial range of tin-rich compositions, and this range extended to increasingly tin-rich concentrations as growth rate increased. These results are discussed in terms of stability and competitive-growth arguments. Various experimental and structural limitations to the rate of directional solidification are discussed. The rate of heat removal at the heat sink is the major experimental limitation. ReCENT interet1,2 in the use of fine composite structures produced by directional solidification of eutectic alloys makes it important to determine the range of composition and growth conditions that yield such microstructures. Because increasing growth velocities produce increasingly finer microstructures, it is particularly significant to determine the factors limiting the rate of solidification. Mollard and Flemings3 have shown that composite structures, free of primary dendrites, can be obtained in Sn-Pb alloys of off-eutectic composition. The composition range of composite structures was found to increase with increasing values of G/V, where G is the temperature gradient and V is the growth velocity. These results are in good quantitative agreement with an analysis of the stability of a planar eutectic interface.4 This analysis specifically predicts that over a small range of compositions stable lamellar structures will be obtained even for G/V = 0, hence, even at very high growth rates. The lamellar-dendritic transition in Sn-Pb alloys has also been analyzed with a model based on competitive growth between dendrites and the composite structure.576 This treatment, based on earlier work on organic eutetics,7 predicts that the composition range yielding composite structures in Sn-Pb will increase rapidly at high growth rates. An increase in the composition range of composite structures at high growth rates was recently observed in Cu-Pb alloys near the monotectic composition.8 In view of these results, and the predictions of the stability and competitivegrowth analyses, it was decided to study the lamellar-dendritic transition in Sn-Pb alloys at high growth rates. EXPERIMENTAL Using 99.999 pct pure materials, a series of Sn-Pb alloys were prepared containing 16.8 at. pct to 27.6 at. pct lead. (Eutectic composition is 26.1 at. pct Pb.) Ingots were extruded to 0.175 in. rod, and some rod was drawn to 0.070-in. wire. Directional solidification was accomplished in two different ways, Fig. 1. For growth rates up to 2 x 10-1 cm per sec, a 0.175 in. diam sample was placed in a graphite crucible 5 in. long with 0.250 in. OD and 0.035 in. walls. Samples were melted under flowing argon in a vertical, platinum-wound furnace, and solidified by driving the crucible downwards through a \ in. hole in a water-cooled copper toroid, Fig. l(a). An insulated chromel-alumel thermocouple was imbedded in the center of a representative sample, and moved with the sample during solidification. The local temperature is plotted against the distance travelled by the sample in Fig. 2. As the growth rate increased, the solid-liquid interface moved closer to the water-cooled toroid and the temperature gradient increased. At growth rates above 10-1&apos; cm per sec, heat was not removed fast enough and the sample moved into the toroid in the liquid state. The curve for V = 2 x 10-1 cm per sec shows a plateau caused by incomplete removal of latent heat from the interface, a problem which will be discussed later. To improve the heat removal, the toroid was cooled by nitrogen gas precooled in liquid nitrogen. This allowed successful solidification at rates up to 2 x 10-1cm per sec. Higher solidification rates required still more effective heat removal. Samples 0.070 in. in diam were placed in graphite tubes 0.125 in. in diam with 0.020 in. walls. Instead of cooling by sliding contact with a cooled toroid, these thinner samples were sprayed or directly immersed into water, Fig. l(b). After solidification, samples were stored in liquid nitrogen until they could be examined metallographic-ally. The surface was prepared with a diamond-knife microtome, followed by a light etch. The presence or absence of tin dendrites, Fig. 3, or lead dendrites, Fig. 4, was noted by optical microscopy, usually of a transverse section near the center of the sample. Replicas of the surface were prepared and examined in an electron microscope to resolve the fine lamellar structures, Fig. 5. The structures observed at various compositions and growth rates are summarized in Fig. 6. Composite structures were observed at increasingly cin-rich compositions as growth rate increased. This transition from dendritic to composite structure with increasing growth rate was also demonstrated by solidifying half a sample at a slow rate and then suddenly increasing the growth rate by lifting the furnace and quenching the sample with a water spray. A longitudinal section of this sample, Fig. 7, shows that the tin dendrites, which extended ahead of the slow-moving composite interface, were bypassed by the composite when the growth rate was increased. The range of composite structures at high growth rates was limited by the appearance of primary lead dendrites on the tin-rich side of the eutectic composition. Observation of representative longitudinal

Jan 1, 1970

By M. H. Yoo

Possible interactions of the perfect dislocations of six slip systems or the c dislocation with the (10i2f (ioii), {ioIi}(ioiZ), {1122}(1123), and {1121}(ii26) type twins in hcp metals have been analyzed from the crystallographic and the energetic points of view. Twenty-six distinct types of possible interactions were identified, and those selected based on crystallographic constraints were examined for their energetic feasibilities by use of the anisotropic energy factors. No long-range elastic interaction exists for a dislocation when its Burgers vector is parallel to the twin interface. Under a suitable applied stress, a screw dislocation can cross slip at the twin interface. For basal mixed dislocations in cadmium and zinc, the interaction with {1012} twins is found to be attractive, indicating that incorporation of these dislocations into the twins is energetically feasible and that twin growth will result. On the other hand, the interaction between both basal and Prism mixed dislocations and the {1012} and (1121) twins is found to be repulsive in Mg, Co, Re, Zr, Ti, Hf, and Be. This indicates that under an applied stress a local stress concentration will develop due to a dislocation pileup at the interface, which may result in a site for either the nucleation of other twins or the formation of a crack, depending on the cleavage strength. WHEN a metal undergoes plastic deformation, a certain configuration of slip dislocations will result in a state of dislocation pileup against an obstacle. The stress concentration thus developed may enhance the process of twin nucleation and also twin growth. Furthermore, once formed and dispersed in the crystal, twins can act as effective barriers against slip dislocations. The degree of such mutual influence or interrelation between slip and twinning is generally known to be pronounced in the case of hcp, metals. It is also known that deformation by twinning occurs more commonly in hexagonal metals than in cubic metals. In fact, under suitable stress states, all hexagonal metals exhibit {1012) <1011> type twinning.&apos; In addition to this common type, deformation by (1151) <1126> type twinning occurs in zirconium, titanium, and rhenium, which show remarkable ductility.&apos; The importance of twinning during general deformation to the ductility of hcp polycrystals has been briefly discussed in recent review works.2&apos;3 The purpose of this paper is to analyze the interaction between slip dislocations and twins in the hcp structure and to discuss the nucleation and growth processes of twinning and the role of twinning in the <"°" noil) o, 1/3[112O] (OOO2) 1/3[1123] Fig. l—-Slip systems in hcp structure. ductility of hexagonal metals. The problem will be discussed from the geometric and the energetic points of view in a manner similar to that of the previous work on zinc.4 Since hcp crystals deform by several slip and twin systems, numerous interactions result as possibilities. The Burgers vectors of six slip systems and the c dislocation shown in Fig. 1 and the four twin systems listed in Table I are considered here. A complete tabulation of the possible interactions is followed by discussion of those that are more likely to occur on the basis of crystallographic constraints and energetic considerations. 1) CRYSTALLOGRAPHY OF TWINNING The crystallographic elements, K1, K2, n1, and n2, for the four compound twin systems are now well established.= A unit cell with the base vectors n1, and n2 is shown in Fig. 2 for each twin system. The unit cell before twinning is shown in solid line, and the corresponding unit cell after twinning is shown in dashed line. Also shown in Fig. 2 are the following crystallographic parameters: S is the plane of shear, d the interspacing of the twin habit planes K1,Ø Iis the acute angle between n1, and n 2, e is a numerical factor, and q is the number of K, lattice planes intersected by 17&apos;. These parameters can be expressed in terms of the axial ratio, y = c/a, as listed in Table 11. The macroscopic shear strain of twinning, s, and the magnitude of a "unit twin dis-l~cation,"4 bt, are also expressed in terms of y and given in Table 11. In Table 11, K1 and q1 are given in both Miller-Bravais and Miller indices. In double lattice structures, shuffling of atoms in addition to a homogeneous shear of the lattice is generally required if the original crystal structure is to be restored after twinning. The extent of current understanding on this problem of atom shuffling is per- Table I. Four Twin Systems in Hcp Structure

Jan 1, 1970

By H. E. Cline, E. F. Koch, J. L. Walter

It has been postulated and, in a few instances shown, that some kind of dislocation structure will be present at semicoherent interfaces to accommodate small lattice mismatches. In the present study of the NiAl-Cr eutectic, regular arrays of interface dislocations are observed at the boundary between the chromium-rich rods and the NiAl-rich matrix. The networks were examined by transmission electron microscopy and selected area diffraction. The rods and the matrix have a crystallographic relationship in which all directions and planes of the two phases are parallel. The dislocation networks are cmposed of a<100> dislocations lying on the intersections of the cylinders with (100) planes. Dislocations forming hexagonal rather than square arrays are also observed at certain areas of the network. The morphology of the network is consistent with the interpretation of mismatch being accommodated by interface dislocations in the cylindrical geometry. The measured spacing between dislocations was used to calculate an apparent lattice mismatch between the phases (˜0.35 PCt)interface network energy (-140 ergs per sq cm), and network strengthening (-10,000 psi). It has been proposed by Frank and Van der Merwe1 that dislocations should be present at the boundary between two semicoherent crystallographically related phases. The role of the interface dislocations would be to reduce the internal stresses, caused by the mismatch in atomic spacing across the interface. Such dislocations have been observed at the interface between expitaxially grown films and Substrates.2-4 Interfacial dislocations have also been observed at precipitate-matrix interfaces.&apos;-&apos; Directionally solidified eutectics have been shown to have semicoherent phases1&apos; and would, therefore, be expected to have interfacial dislocations as found by Weatherly at a lamellar fault in A1-A12Cu.11 The NiAl-Cr eutectic appeared to be a promising system to examine because both phases are cubic, the lattice mismatch is small, and the phases are crys-tallographically related. Furthermore, the eutectic is easily thinned for transmission microscopy. Indeed, interfacial dislocations were observed and this report describes the nature of the dislocation networks in the boundary between the NiAl-rich ma-trix-phase and the fine chromium-rich rods.21 I) EXPERIMENTAL PROCEDURE Ingots, 3/4 in. in diam and 6 in. long were made by melting in vacuum and casting under argon using 99.9 pct pure material. The composition, in at. pct, was 33 pct Ni, 33 pct Al, and 34 pct Cr. The ingots were then placed in A1203 crucibles on a water-cooled base, melted by means of induction, and withdrawn from the hot zone at the rate of 1 in per hr under argon.* * T his material was first directionally solidified in this laboratory by E. R. Stover Slices were taken perpendicular to the growth direction of the directionally solidified ingot for metallography and for transmission electron microscopy. The electron transmission samples were thinned mechanically, then thinned electrolytically in A-2 electrolyte* *A-2 electrolyte: 62 ml perchloric acid, 700 ml ethanol, 100 ml butylcellosolve, 137 ml distilled H20. until a hole appeared in the foil. 11) EXPERIMENTAL RESULTS A) Optical Microscopy. The microstructure, viewed on a plane perpendicular to the growth direction, is shown in Fig. 1. The structure consists of cells or colonies of parallel chromium-rich rods in the NiAl matrix. The cells occur when there are impurities present12 or, in a ternary eutectic, if the composition is slightly off the eutectic composition. The axis of the chromium-rich rods is parallel to the growth direction except near the cell boundaries. Here the rods may assume angles to the growth direction; however, examination shows that the crystallographic relationship between the rod and the matrix remains the same. Fig. 1 includes cell boundaries where the rods formed at a large angle to the growth direction. The variation of rod position across the cells made it possible to Fig. 1-Structure on plane perpendicular to growth direction. Rods near cell walls are at large angle to growth direction. Magnification 315 times.

Jan 1, 1970

By William M. Boorstein, Robert D. Pehlke

The rates of solution (of hydrogen in liquid pure iron and in several liquid binary iron alloys were meas-ured using a constant volume technique. The rates of absorption and desorption were found to be equal un-der all experimental conditions. increasing concen-trations of S, Si, or Te decrease the rate of hydrogen uptake but additions of Al, B, Cr, Cu, or Ni have no measurable effect up to concentrations normally en-countered in steelmaking practice. No relation ship was found between the effect of an alloying element on the equilibrium solubility of hydrogen in liquid iron and its effect on the solution rate constant. Mathe-rnatical analysis of the data indicates that under the present experimental conditions the rate of reaction of hydrogen with liquid iron is controlled by transport of gas solute atoms in the metal phase. Comparison of the present resuts with data on nitrogen taken un der similar conditions establishes that the hydrody-nurnic conditions which exist near the surface of a metal bath are best approximated mathematically by a surface renewal model for the case of rapid in-ductive stirring and by a boundary layer model for more quiescent melts. HYDROGEN has long been recognized as being a detrimental constituent in steel. If dissolved in the molten metal in excess of its solid solubility, hydro-gen can be evolved during solidification and cause bleeding or porosity in ingots and castings. In the solid metal, lesser amounts play a definite role in causing other defects such as hairline cracks, blisters, and embrittlement. For significant refinements to be made in metallurgical procedures designed to control or eliminate hydrogen from liquid iron or steel dur-ing processing, available equilibrium solubility data must be supplemented with reliable fundamental in-formation pertaining to the kinetic factors involved in the transfer of hydrogen to or from the metal. The scarcity of such information in the literature prompted the present investigation. PREVIOUS RESEARCH Whereas much of the existing data on the solution kinetics of gases such as nitrogen were obtained during the course of thermodynamic investigations, the solu-tion rate of hydrogen has been found too rapid to be accurately determined by conventional solubility meas-urement techniques. Consequently, little work on hy-drogen solution kinetics has been reported in the lit-erature. Carney, Chipman, and crant1 attempted to study the rate of solution and evolution of hydrogen from liquid iron by employing a newly devised sampling method. Although no significant quantitative data could be obtained, it was observed that the rate of solution was approximately equal to the rate of evolution of hy-drogen from the melt. Karnaukov and Morozov2 stud-ied the rate of absorption and Knuppel and Oeters3 the rate of desorption of hydrogen from molten iron by measuring pressure changes with time in a constant volume system. Karnaukov and Morozov determined the hydrogen pressures over their inductively stirred melts with the aid of a McLeod gage and therefore, were forced to work at pressures not in excess of 40 mm of Hg. Their experimental data conformed to a mathematical correlation based on diffusion control: and the rate coefficients calculated on this basis were shown to be independent of the initial absorption pres-sure. These authors reported the solution rate of hy-drogen to be eight-to-ten times higher than they had found for nitrogen in a previous study. They also re-ported that under identical conditions, hydrogen dis-solves somewhat more slowly in iron-columbium alloys than in pure iron. Knuppel and Oeters found that the desorption of hydrogen from pure iron at 1600°C was controlled in all cases investigated by diffusion in the metal bath as long as bubble formation was sup-pressed. This was substantiated by Levin, Kurochkin, and umrikhin4 who studied the kinetics of hydrogen evolution from liquid (technical) iron while applying a vacuum. Salter5 measured the rate of hydrogen ab-sorbed by iron buttons, arc-melted by direct current, as a function of hydrogen partial pressure in a hy-drogen-argon atmosphere. A carrier gas technique was used for analysis of the hydrogen absorbed. The initial rate of absorption was found to increase di-rectly with the square root of the partial pressure of hydrogen. EXPERIMENTAL METHOD Because of the rapid uptake and evolution of hydro-gen by iron-base melts, a constant volume technique was devised in order to obtain meaningful kinetic data over the entire course of the solution process. Apparatus. A schematic view of the experimental apparatus is given in Fig. 1. The hydrogen-liquid iron reaction system consisted of a gas storage bulb con-nected to a meltcontaining reaction chamber through a normally-closed solenoid valve. The gas storage bulb, an inverted 250 ml round-bottomed Pyrex flask was joined to the inlet port of the solenoid valve by a glass-to-metal seal. A more detailed illustration of the reaction chamber is shown in Fig. 2. The design of the Vycor reaction bulb was essentially that de-scribed by Weinstein and Elliott6 with the exception of a shorter, larger diameter gas inlet for this kinetic study. In position, the reaction bulb was closely by an eight-turn coil of water-cooled copper tubing which, when energized by a 400-kc oscillator, provided the inductive heating source. The walls of the bulb were maintained relatively cool by circulating cold water along their outer surface, thus preventing

Jan 1, 1970