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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 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' 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'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' and to the precipitation of second phase particles,2'3 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 '(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'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'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', Y into Y', and leaving 2 unchanged, i.e., Z' = Z. The 8 rotation about the Y' axis is carried out second by rotating X' into X", 2' into Z", and leaving Y' unchanged, i.e., Y" = Y'. The I$ rotation about the Z" axis is carried out last by rotating X" into X"', Y into Y"', and leaving 2" unchanged, i.e., 2"' = 2". Any specified orientation of the X'", Y'", and Z'" 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.'~~ 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,' 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.' 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.' 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.' 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.' 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 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.' 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.' 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 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' 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 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

By Cuppam Dasarathy

The incidence of liquid inzmiscibility in binar)) indium alloys has been theoretically analyzed on the basis of the Hildebrand-Alott equation. Bedictions of miscibility or otherwise Imve in general been found to agree with those phase diagrams that are already publislzed in the literature. Out of a total of 27 systems, where either the complete phase diagrams are published or liquid immiscible behavior is reported, the Predictions agree with the experimental data in 25 systems, the exceptions being the Te-In and Ni-In systems. According to the equation, liquid immiscibility is also indicated in the binary alloys of indium with K, Rb, Cs, Na, Sr, Ba, Ti, Zr, V. Nb(Cb), Ta, W, U, Re, Ru, Rh, Os, and Ir. RECENT investigations by the author have shown that indium when alloyed with iron, chromium, and cobalt shows liquid immiscible behavior.1"3 The Fe-In phase diagram shows a wide range of compositions where the liquids are immiscible.4,5 No intermediate phases are present in this system. No precise information is available about the extent of liquid immiscibility in the Co-In system. However, it is certain that there is a range of compositions where the liquids are immiscible and that there are two or three intermediate phases,376 in the system. Liquid immiscibility is also strongly indicated in the Cr-In system and no evidence was obtained in the brief investigation to indicate the presence of intermediate Cr-In phases.2 The present paper deals with a theoretical analysis of binary alloys of indium with certain elements of the periodic table and indicates the systems where liquid immiscibility may be expected. The incidence of liquid immiscibility in binary systems has been theoretically examined by many workers and many excellent papers are available on the subject. In this paper, the alloy systems are examined on the basis of the more recent ideas proposed by Mott.7,8 It has been claimed8 that the Mott parameter predicts the incidence of miscibility or otherwise with reasonable accuracy and consistency. BACKGROUND TO MOTT&apos;S APPROACH Hildebrand applied his immiscibility rule for non-polar liquids to various alloy systems.9 The basis of this rule is that the equation for the excess free energy of formation of a liquid solution is rather similar to the theoretical expression for the energy of mixing of a regular solution. He postulated that when the heat of mixing is sufficiently high, separation into liquid phases will occur and the condition for complete CUPPAM DASARATHY is at the Research Centre, British Steel Corporation, (South Wales Group), Port Talbot, Glamorgan, Great Britain. Manuscript submitted March 12, 1969. IMD miscibility was shown as where VA and VB were the atomic volumes of the components A and B, and ?EV the energy of vaporization of the component. The term (?EVA/VA)1/2 was regarded as a measure of the binding energy of the component A and was called the L&apos;solubility parameter" 8A. On this basis immiscibility occurs when 1/2(VA+VB)(bA-bBf > 2RT [2] Apparently, however, there were several inconsistencies in that according to Eq. [2] several systems known to be miscible in the liquid state were predicted as immiscible. MOTT&apos;S ANALYSIS ~ott&apos;" regards that the reason for the inconsistencies arising out of Hildebrand&apos;s equation was largely due to the electrochemical attraction between the two elements, not being considered. Hence, Eqs. [I] and [2] were modified by taking into account the electro-negativities of the two elements XA and XB, and Mott arrived at an equation for immiscibility, i(VA + VB)(6A - aB)2 - 23,Q60n(XA - XBf > 2RT [3j which can be written as i **&£*&* >&apos;*°™- &apos;• HI T being the melting point of the more refractory component of the system. In Eq. [4], the numerator was called the Hildebrand term, the denominator, the electronegativity term, and their ratio, the Mott number. Mott observed that if the Mott number of a given binary system was greater than the maximum number of Pauling bonds which the two metals could form, then liquid immiscibility could be expected. The maximum number of bonds formed by a given metal was considered to be directly related to the number of bonding electrons available, i.e., to its maximum valency. Since the valencies of the elements considered vary from 1 to 6, Mott assumed that if the ratio of the Hildebrand term to the electronegativity term was >6, then immiscibility could be expected. On the contrary, if the ratio is <1, the metals should be miscible. Further, the alloying behavior is not only influenced by the valencies of the two elements but also by the relative atomic sizes that influence the types of packing and hence the coordination number. Mott considers that on average the maximum number of near neighbors of unlike atoms is 6. Thus, on both valency and size factor considerations, Mott concludes that the maximum number of bonds&apos; possible in any system was 6, this being the upper limit of the Mott number for miscibility. In considering the alloying behavior of systems with Mott numbers between 1 and 6, Mott plotted the num-

Jan 1, 1970

By Niels Hansen

The substructure formed by drawing at room temperature in aluminum (99.5 and 99.998 pct purity) and in recrystallized aluminum aluminum-oxide products containing from 0.2 to 4.7 wt pct of aluminum -oxide was examined by transmission electron microscopy, and the flow stress of the drawn materials was measured by tensile testing at room temperature. A sub-grain structure was present after a reduction in area by drawing of 10 to 20 pct, and the subgrain size was observed to decrease with increasing deformation. The tensile data show that the increase in flow stress (0.2 pct offset) by drawing from 10 to 95 pct depends on the reduction in area, not on the composition of the materials. Dispersion strengthening and subgrain bowzdary strengtlzening contribute to the flow stress, and these strengthening processes have been found to be linearly additive. The flow stress (0) can be related to the subgrain size &) by the Petclz relation = uo + k . t, where go is dependent on the composition of the products and k is approximately the same far all materials. THE microstructure of dispersion-strengthened aluminum aluminum-oxide products consists of small oxide plates distributed in an aluminum matrix. The matrix structure depends on the manufacturing history, and in hot-worked as well as cold-worked products the matrix is divided by subgrain (or dislocation) boundaries. For hot-extruded products it has been shown1 that dispersion strengthening and subgrain boundary strengthening are linearly additive, and the flow stress (0.2 pct offset.) at room temperature has been related to the subgrain size (ts) by a Petch equation,2,3 s = so + k . ts-1/2, where s0, increases with increasing oxide content. For cold-worked products containing subgrains no systematic work has been reported, and it was the aim of the present study to examine the microstructure and the relationship between the flow stress and the subgrain size for such products. The behavior of&apos; aluminum aluminum-oxide products depends on the purity of the aluminum matrix, and aluminum of the matrix purity (99.5 pct) was included in the investigation. The literature contains few data about the behavior of this impure aluminum, and aluminum of a higher purity (99.998 pct) was therefore also examined. As regards the relationship between the flow stress and the subgrain size in cold-worked dispersion-strengthened products, no systematic work has been reported. For aged cold-worked structures containing fine precipitates (Fe-Mo carbide) a Petch relation has been found,4 and it has been shown that the k value NlELS HANSEN is Head, Metallurgy Department, Danish Atomic Energy Commission, Research Establishment Riso, Denmark. Manuscriot submitted January 9, 1969. IMD is approximately the same as in iron, whereas the s0 value is higher owing to the presence of the precipi-tates. Investigations of metals such as tungsten,&apos; ferrous metals,4,6 and molybdenum7 cold drawn or swaged at room temperature have shown that the flow stress can be related to the subgrain size by a Petch relation when ts is taken as the subgrain size perpendicular to the direction of deformation. For aluminum no work has been reported on the relationship between the flow stress and the subgrain size after deformation at room temperature, whereas for aluminum tensile strained at different temperatures in the range -183" to 375°C a Petch relation has been found by taking ts equal to the subgrain size.&apos; In the present study two aluminum materials (99.998 and 99.5 pct) and three aluminum aluminum-oxide products (containing 0.2, 1.0, and 4.7 wt pct oxide) were drawn at room temperature to reductions in area from about 10 to about 95 pct. The structures were studied by transmission electron microscopy, and the flow stress (0.2 pct offset) was measured at room temperature. EXPERIMENTAL Materials. The materials are given in Table I together with the chemical analysis. The three aluminum aluminum-oxide products were manufactured from aluminum powder that had been compacted and Table I. Chemical Analysis of Materials Al203 Fe SI Material wt pct wt pct wt pct 99.998 pct* - 0.0004 0.0012 Aluminum 99.5 pctt - 0.36 0.16 Aluminum AlMD13† 0.2 0.16 0.12 Aluminum- -Oxide AlMD105† 1.0 0.26 0.18 Products SAPISML960s† 4.7 0.22 0.19 *Other impurities: O.0004 pct max each of Cu and Zn (supplier&apos;s analysis). †Other impurities: 0.03 pct max Cu. 0.02 pct max each of Mn, Mg, Zn, Ti. Table 11. Mean Diameter of Aluminum-Oxide Particles in Extruded and in Cold--Drawn Aluminum Aluminum-Oxide Products Mean Diam. of A1203-Plates* Material State A AlMD105 Extruded 540 Cold Drawn 97 pct 510 SAP ISML 960 Extruded 770 Cold Drawn 95 pct 820 *The standard deviation of the mean is approx. 5 ±pct.

Jan 1, 1970

By G. A. Colligan, G. L. F. Powell

A new experimental technique has been developed to study nucleation behavior in eutectic alloys. It is somewhat similar to that applied by Sundquist and Mondolfo1 but with the advantages that: 1) bulk samples are undercooled instead of small droplets thus allowing the thermal behavior to be monitored by a thermocouple immersed in the sample, and 2) nucleation behavior is investigated in the same sample on either side of the eutectic composition by adding additional component to the sample under controlled conditions which preclude the addition of nu-cleation contaminants. Sundquist and Mondolfo carried out ]nucleation ex-periments on a large number of eutectic alloy sys-tems and concluded that nonreciprocal nucleation operated. If one phase a was a good nucleant for the other phase 0, then B was a poor nucleant for a. This was determined experinlentally by comparing the nucleation temperatures of 100 to 300 u diameter droplets of hypereutectic and hypoeutectic composition cooled from above the liquidus and from a temperature between the liquidus and the eutectic temperature. Primary phase a was concluded to be an efficient nucleant for the other phase B, if the following experimental result was obtained. Referring to Fig. 1, the temperature TI at which a drop of hypereutectic alloy of composition B froze when cooled from above the B liquidus was noted. This was the nucleation temperature for B in the absence of a. A drop of hypoeutectic alloy of composition A was then frozen from temperature T2 between the a liquidus and the eutectic temperature. The temperature T3 at which the eutectic nucleated in the presence of the primary or proeutec-tic a was noted. If this temperature T3 was higher than the temperature TI at which the B nucleated in a hypereutectic alloy, it was concluded that the primary a had nucleated the 6. This temperature T3, representing a certain undercooling below the equilibrium eutectic temperature Te , was designated ?TB by a> the undercooling below T, for nucleation of 13 by a. If there was no substantial difference in nucleation temperature between the hypereutectic drop cooled from above the /3 liquidus and the hypo-eutectic drop cooled from a temperature between the a liquidus and the eutectic temperature, it was considered that the a nucleated B at an undercooling equal to or greater than that at which P nucleated from a hypereutectic alloy. Sundquist and Mondolfo1 found that faceted primary crystals were good nucle-ants for metals that grow as orthogonal dendrites when present as the primary phase. Jackson2 has questioned Sundquist and Mondolfo&apos;s technique and proposed that in Sundquist and Mon-dolfo&apos;s samples, such as composition A, primary a retained B in reentrant grooves at their surfaces when heated to a temperature above the eutectic but below the a liquidus. This objection was suggested by experiments with organic eutectics where reten-

Jan 1, 1970

By N. S. Stoloff, K. R. Jordan

The temperatwe and grain size dependence of the mechanical avoperties of ordered and disordered Fe-49 pct Co-2 Pct V were investigated. The yield and flow stresses obeyed the Hall-Petch relationship u = ai + kd-&apos;I2. Ohdering reduced the intercept stress cjj and raised the Petch slope, k, at all temperatures. Ordering also increased the temperatwe dependence of k. The ductile to brittle transition temperature increased with order and grair~ size. Cleavage fracture was nucleation limited and the fracture stress did not zlary linearly with d-&apos;". A quantitative test of the Cottrell-Petch fracture theory (and recent modifications which consider the influence of slip mode), demonstvated that this theory is not applicable to FeCo-V. COTTRELL&apos; and etch&apos; independently suggested that a criterion for cleavage failure at the yield point, a,, based on dislocation pileups at a grain boundary or other obstacle to dislocat.ion motion, is: aYYkd&apos;I2 1 opy [ll or, equivalently, aikz,d112 +k:)bpy [2] where a, and ky are the Hall-Petch intercept and slope, respectively, 2d is the grain diameter, P is a geometric factor dependent on the macroscopic ratio between shear and tensile stress, p is the shear modulus, and y is the true elastic surface energy. When the product of quantities on the left side of the equation is equal to or exceeds that on the right, cracks should be able to nucleate and propagate at the yield stress, as shown schematically in Fig. 1. Therefore a high intercept stress, high Petch slope, or coarse grain size favors brittleness. petch3 associated the existence of a ductile to brittle transition in ferrous alloys with the temperature dependence of ai. One of the earliest modifications of the Cottrell-Petch theory was presented by ~rmstrong,~ who derived an expression for transition temperature in terms of several measurable flow and fracture parameters. The latter paper was able to rationalize situations in which the transition temperature increases with decl-easing grain size, as in the case of molybdenum,&apos; and also suggested that Ppy should be a function of grain size as well as temperature. More recently Johnston et a1.6 and Smith and worthington7 have suggested that the temperature or composition dependence ol&apos; ky must also be taken into account if there is any cha.nge in deformation mode, as from wavy to planar slip, or wavy slip to twinning, with change in temperature or solute content. Armstrong %as suggested that for hcp metals changes in o;k,dw> o;k,d1/2< / is / ^^^^ / / y_______________________________________ d-"2 Fig. l—Schematic representation of grain size dependence of yield stress, cry, and fracture stress, CTF. Intersection defined by Cottrell-Petch equation. slip mode should be incorporated in the theory through changes in the critical resolved shear stress for the slip system which controls ky. The purpose of the present investigation was to critically test the modified677 Cottrell-Petch theory of fracture in the superlattice alloy Fe-49 pct Co-2 pct V, by studying the grain size dependence of the yield and fracture stresses over a range of temperatures, in conjunction with an investigation of slip mode and fracture behavior. Previous work has shown that long range order results in a sharp decrease in flow stress, a small increase in work hardening rate and a drastic upward shift in the ductile-brittle transition temperature of F~CO-V.~&apos;~ The only comprehensive study of slip character in this alloy has been reported in a preliminary account of the present investigation.10 EXPERIMENTAL PROCEDURE The experimental work was carried out on material produced from a 10 lb vacuum melted ingot, of composition 49.32 wt pct Co, 2.09 wt pct V, balance Fe. 30-mil thick sheet samples with a 1; in. gage section were machined from cold rolled stock. The degree of cold work ranged from 85 pct for the finest grained samples to 5 pct for the coarsest grain size. Details of ingot fabrication are reported elsewhere." Equi-axed grain sizes in the range 12.7 to 75.4 p were obtained by annealing for varying times at 850°C. (Re-crystallization annealing time, rather than temperature , was varied to control grain size to insure that samples of all grain sizes contained equivalent quenched-in vacancy and interstitial concentrations.) Grain sizes were measured by the line intercept method on several specimens of each grain size. Following recrystallization, all samples were disordered by quenching into iced brine.

Jan 1, 1970

By D. T. Peters, S. Floreen

The age hardening behavior of an Fe-8Ni-13Mo alloy was studied after the matrix had been varied to produce either ferrite, cold u~orked ferrite, or nzassive nzartensite. The aging behavior of the cold worked ferrite and murtensite structures were very similar. The martensite aging kinetics were much different from those observed in earlier studies of aging of maraging steels, even though the martensite wzatri.r had the same dislocation structure as those found in maraging steels. The results suggest that the previously observed precipitation kinetics of maraging steels ?nay have been controlled by the nucleation be-haviov, which in turn were dictated by the alloy compositions and the resultant identities of the precipitating phases. IT is well known that the rate of precipitation from solid solution depends not only on the degree of super-saturation, but also on the density and distribution of dislocations in the matrix structure. These imperfections often act as nucleation sites, and may also enhance atomic mobility. &apos;Thus, the presence of dislocations is important since the type and distribution of precipitates may be determined by them. The precipitate density and morphology in turn affects the mechanical properties of the alloy. A number of studies have been devoted to the precipitation characteristics in various types of maraging steels.&apos;-" These are iron-base alloys containing 10 to 25 pct Ni along with other substitutional elements such as Mo, Ti, Al, and so forth, that are used to produce age hardening. The carbon contents of these steels are quite low, and carbide precipitation is not believed to play any significant role in the aging reactions. After solution annealing and cooling these alloys generally transfclrm to a bcc lath or massive martensite structure characterized by elongated martensite platelets that are separated from each other by low angle boundaries, and that contain a very high dislocation den~it~.~~~~~~~~-~~ Age hardening is then conducted at temperatures on the order of 800" to 1000°F to produce substitutional element precipitation within the massive martensite matrix. Most of the aging studies to date have revealed several common traits in these alloys, regardless of the particular identity of the precipitation elements. Generally hardening has been found to be extremely rapid, with incubation times that approach zero. The agng kinetics, at least up to the time when reversion of the martensite matrix to austenite begins to predominate, frequently follow a AX/~~ = ktn type law, where x is hardness or electrical resistivity, t is the time, and k and n are constants. The values of n are frequently on the order of 0.2 to 0.5, which are well below the idealized values of n based on diffusion controlled precipitate growth models. Finally, the observed activation energy values are typically on the order of 30 kcal per mole, and thus are well below the nominal value of about 60 kcal per mole found for substitutional element diffusion in ferrite. The common explanation of these observations is that the precipitation kinetics are controlled by the massive martensite matrix structure. Thus, the absence of any noticeable incubation time has been attributed, after ~ahn," to the fact that the precipitate nucleation on dislocations may occur without a finite activation energy barrier. The low values of the activation energy are generally assumed to be due to enhanced diffusivity in the highly faulted structure. If this explanation that the precipitation kinetics are dominated by the matrix structure is correct then one should observe a distinct difference in lunetics between aging in a martensitic matrix and aging the same alloy when it has a ferritic matrix. Such a comparison cannot be made with conventional maraging compositions, but could be made with the alloy used in the present study. In addition, the ferritic structure of the present alloy could be cold worked to produce a high dislocation density so that one could determine whether ferrite in this condition would age similarly to martensite. EXPERIMENTAL PROCEDURE The composition of the alloy used in this study was 8.1 pct Ni, 13.0 pct Mo, 0.10 pct Al, 0.13 pct Ti, 0.012 pct C, bal Fe. The alloy was prepared as a 40 lb vacuum induction melt. The heat was homogenized and hot forged at 2100°F to 2 by 2 in. bar, and then hot rolled at 1900°F to $ in. bar stock. The aging lunetics were followed by Rockwell C hardness and electrical resistivity measurements. Samples for hardness testing were prepared as small strips approximately 2 by $ by 4 in. thick. Electrical resistivity was studied on cylindrical samples approximately 2 in. long by 0.1 in. diam. The method for making the alloy either martensitic or ferritic was based on the fact that the alloy showed a closed y loop type of phase diagram. At high temperatures, above approximately 24003F, the alloy was entirely ferritic. Small samples on the order of the dimensions described above remained entirely ferritic after iced-brine quenching from this temperature. In practice, a heat treatment of 1 hr in an inert atmosphere at 2500°F followed by water quenching was used to produce the ferritic microstructure. These samples were quite coarse grained and usually en-

Jan 1, 1970

By P. N. Richards, M. K. Ormay

The present Paper extends the previous work on cold reduced, low carbon steels to preferred orientations developed after various heat treatments. In recrystal-lized rimmed steel, cube-on-comer orientations increased with cold reductions up to 80 pct. Above that {111}<112> and a partial fiber texture with (1,6,11) in the rolling direction dominated. During grain growth, cube-on-corner orientations have been observed to grow at the expense of {210}<00l>. In re-crystallized Si-Fe (111) (112) and cube-on-edge type orientations are dominant near the surface and the (1,6,11) texture near the midplane for reductions up to 60 pct. With larger reductions {111)}<112> and the (1,6,11) texture are dominant. In cross rolled capped steel a relationship of 30 deg rotation was observed between the (100)[011] of the rolling texture and the main orientations after re crystallization. Most orientations present in recrystallized specimens can be related to components of the rolling texture by one of the following rotations: a) 25 to 35 deg about a (110) b) 55 deg about a (110) C) 30 deg about a (Ill) THE orientation texture of recrystallized steel is of interest where the product is to be deep drawn, because preferred orientation is related to anisotropy of mechanical properties such as the plastic strain ratio (r value);1,2 and in electrical steel applications where a high concentration of [loo] directions in the plane of the sheet improves the magnetic properties of the material. It is interesting to note that both these aims are to a large extent achieved commercially, even though the orientation texture of cold rolled steel does not show large variation3 and the recrystallized orientations are generally given as being related to the as rolled orientations mostly by 25 to 35 deg rotations about common (110) directions.4-6 There is, as yet, no single completely accepted theory on recrystallization. The three mechanisms that have been investigated and discussed are: a) Oriented growth b) Oriented nucleation c) Oriented nucleation, selective growth Largely from the observations of the recrystalliza-tion process by means of the electron microscope,7-11 there is now considerable evidence that the "nucleus" of the recrystallized grain is produced by the coalescence of a few subgrains to form a larger composite subgrain, which finally grows by high angle boundary migration into the deformed matrix. From the intensive work on the recrystallization of rolled single crystals of iron, Fe-A1 and Fe-Si al-loys4-" he following observations have been made: 1) The change in orientation during primary recrys-tallization can usually be described as a rotation of 25 to 36 deg about one of the (110) directions. 2) The (110) axes of rotation often coincide with poles of active (110) slip planes. 3) If several orientations are present in the cold rolled structure, the (110) axis of rotation will preferably be a (110) direction that is common to two or more of the orientations. 4) With larger amounts of cold reduction (70 pct or more) departure from these observations became more frequent. 5) After larger cold reductions, rotations on re-crystallization about (111) and (100) directions have been observed. K. Detert12 infers that a rotation relationship of 55 deg about (110) directions is also possible, by stating that the recrystallized orientation {111}<112> can form from the orientation {100}<011> of cold reduced partial fiber texture A.3 The observation by Michalak and schoone13 that (lll)[l10] formed during recrys-tallization in fully killed steel containing (111)[112],— as well as (001)[ 110] which is related to the {111}<011> by a 55 deg rotation about <110>-implies a possible 30 deg rotation relationship about the common [Ill]. Heyer, McCabe, and Elias14 have recrystallized rimmed steel after various amounts of cold reduction, by a rapid and by a slow heating cycle and found that the preferred orientations strengthened with increased cold reduction. The most pronounced orientation up to about 70 pct cold reduction was found to be {1 11}< 110>, after 80 pct cold reduction both {111}<110> and {111}<112>, after 85 and 90 pct cold reduction, {111}<112>, and after 97.5 pct cold reduction it was {111}<112> and (100)(012). In the present work, the orientation textures of the recrystallized specimens are examined under various conditions of steel composition, amount and method of cold reduction, and method of recrystallization. The relationships between the preferred orientations of the as rolled and recrystallized specimens, and the conditions for the formation of the various orientations during recrystallization are investigated.

Jan 1, 1970

By L. T. Larson

The spectral reflectivity of zirconium in light of 441 to 668 nanometers (nm) wavelengths and air immersion has been determined. Bireflectance and apparent-angle -of-rotation measurements show zirconium to be optically isotropic when examined in light of approximately 484 nm wavelength. There is a direct relationship between bireflectance and the tilt of the basal pole of zirconium from the surface normal. This relationship allows the determination of the spatial orientation of the basal pole of an individual single crystal within a coarse-grained poly crystalline section to within± 2 to 3 deg for angles of basal pole tilt from 0 to 90 deg. In recent years considerable attention has been given to the quantitative determination of optical properties of opaque minerals by use of vertically incident, plane-polarized light. In particular, Cameron&apos; and Cameron et a1.2 have developed criteria for the identification of a large number of anisotropic ore minerals based upon measurement of the apparent angle of rotation and the ellipticity or phase difference of the reflected light. It was shown by Larson and Pickle-simer3 that apparent-angle-of-rotation measurements may also be used to determine crystallographic orientations of grains of noncubic metals. In particular, it was shown that the basa.1 pole orientation in space of zirconium grains can be determined to ±3 deg for those grains with basal pole tilts of 10 to 90 deg from the plane of the section. Another, even more widely studied, optical property is reflectivity. cameron4 has commented upon measurement of the reflectance of plane-polarized, vertically incident light and Bowie and Taylor5 have made such measurements an integral part of their system of ore-mineral identification. Leow6 has reported on the spectral reflectivity of molybdenite and has used reflectivity values to calculate refractive indices and absorption coefficients. Cameron7 has made use of reflectivity values to ascertain aniso-tropic ore mineral symmetry and Piller and v. Gehlen8 have evaluated sources and importance of errors in reflectivity measurements as applied to calculation of optical constants. cambon9 has shown that reflectivity measurements using vertically incident, plane-polarized light are useful in the investigation of metals and in the identification of phases present in alloys. Bronson10 has made preliminary measurements on the optical anisotropy of beryIlium and Mott and Haines11 have published qualitative data on the intensity of light reflected from sections of bismuth, tin, and aluminum when these metals are microscopically examined under crossed polarizing plates. Koritnig12 has correlated the reflectivity of homogeneous solid solutions with their chemical compositions. From the above work and investigations in progress by this author, it is apparent that accurately determined values for the reflectance of vertically incident, plane-polarized monochromatic light from carefully polished surfaces of noncubic metals can prove useful in identification, composition determinations, and crystallographic orientation applications. Finally, reflectivity values, when measured in two media of differing refraction index and related to standards whose spectral reflectivities in these media are known, can be used to calculate optical constants such as refractive index and absorption coefficient. These constants may prove of use to those concerned with problems of electron band configuration. This paper reports the spectral reflectivity of zirconium measured in light of 441 to 668 nanometers (nm) wavelengths and air immersion. It also gives maximum bireflectance values for a prism section of zirconium in these wavelengths and shows how bire-flectance may be used to determine the crystallographic orientation of zirconium single crystals. Because of the lack of information on the reflectivities of the standards in oil immersion, no attempt is made to calculate the refractive indices or absorption coefficients although it is recognized that such values may be of fundamental importance. METHOD Single crystals of zirconium were cut by electro-discharge machining from a single-crystal rod grown from iodide bar by an electron-beam zone-melting process.13 The crystal sections were mounted in cold-setting epoxy resin and mechanically polished to a plane, uniform, bright surface. Each crystal was then chemically polished in a 26/26/43/5 mixture (by vol) of water, nitric, lactic, and hydrofluoric acids to remove the mechanically damaged and smeared surface layer. Final polish was obtained by electropolishing at 30 v in a bath of methyl alcohol and perchloric acid (98/2 by vol) at -70oc.14 Reflectivity measurements were made using a photometer system designed and developed at Oak Ridge National Laboratory and described in detail by Larson.15 Briefly, the reflectivity measuring system consists of a reflecting microscope; a double-beam, null-balancing photometer array; a mechanically driven microscope stage; and a direct X-Y readout of the reflectivity of the specimen relative to its orientation on the microscope stage. The measuring photometer receives its signal from the specimen through a slotted Wright occular placed on top of the photovisual head of the microscope. The reference photometer receives light through a flexible glass "light pipe" from a mirror in the reflecting system of the microscope. Monochromatic light is attained through use of interference filters (15-nm half-peak width pass bands) placed in front of a stabilized Vickers 12 v, 100 w, tungsten-filament, quartz-iodide lamp.

Jan 1, 1970