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By L. F. Bryant, J. P. Hirth, R. Speiser

The surface, gain boundary, and twin boundary energies, as well as the surface diffusion coefficient, of cobalt were determined from tests at 1354°C in pure hydrogen. A value of 1970 ergs per sq cm was calculated for the surface energy, using the zero creep method. It was possible to measure the creep strains at room temperature because the phase transformation was accompanied by negligible irreversible strain and no kinking. Established techniques based on interference microscopy were used to obtain values for the other three properties. The gain boundary and twin boundary energies were 650 ad 12.7 ergs per sq cm, respectively, while a value of 2.75 x l0 sq cm per sec was determined for the surface dufusion coefficient. In the course of a general study of cobalt and cobalt-base alloys, information was required about the surface energy of cobalt. Hence, the present program was undertaken to measure the interfacial free energy, or, briefly, the surface energy, of the solid-vapor interface of cobalt. The microcreep method was selected for this measurement because other surface properties could also be determined from the accompanying thermal grooving at grain boundaries and twin boundaries. A brief summary of the methods for determining the various surface properties follows. At very high temperatures and under applied stresses too small to initiate slip, small-diameter wires will change in length by the process of diffu-sional creep described by Herring.1 The wires acquire the familiar bamboo structure and increase or decrease in length in direct proportion to the net force on the specimen. For a specimen experiencing a zero creep rate, the applied load, wo, necessary to offset the effects of the surface energy, y,, and grain boundary energy, y b, is given by the relation: where r is the wire radius and n is the number of grains per unit length of wire. The first results obtained from wire specimens were reported by Udin, Shaler, and Wulff.' udin3 later corrected these results for the effect of grain boundary energy. The grain boundary energy is determined from measurements of the dihedral angle 8 of the groove which develops by thermal etching at the grain boundary-free surface junction. For an equilibrium configuration: Measurements of the angle 8 can be made on the creep specimens4'5 or on sheet material, as was done in this investigation by a method employing interference microscopy.= If the vapor pressure is low, the rate at which grain boundary grooves widen is determined primarily by surface diffusion and, to a lesser extent, by bulk diffusion. The surface diffusion coefficient, D,, is obtained from interferometric measurements of the groove width as a function of the annealing time, t. As predicted by Mullins~ and verified by experiment, the distance, w,, between the maxima of the humps formed on either side of the grain boundary increases in proportion to if grooving proceeds by surface diffusion alone. For this case: where fl is the atomic volume and n is the number of atoms per square centimeter of surface. When volume diffusion also contributes to the widening, the surface diffusion contribution can be extracted from the data by the method described by Mullins and shewmon.8 Where a pair of twin boundaries intersects a free surface, a groove with an included angle of A + B (using the groove figure and notations of Robertson and shewmong) forms by thermal etching at one twin boundary-free surface junction. If the "torque terms", i.e., the terms in the Herring10 equations describing the orientation dependence of the surface energy, are sufficiently large, an "inverted groove" with an included angle of 360 deg-A'-B' develops at the other intersection. The angles A + B and A' + B' are measured interferometrically. When the angle, , between the twinning plane and the macroscopic surface plane is near 90 deg, the twin boundary energy is calculated from the relation: 1) EXPERIMENTAL TECHNIQUES Five-mil-diam wire containing 56 parts per million impurities was used for making ten creep specimens. These specimens had about 15 mm gage lengths with appended loops of wire and carried loads (the specimen weight below the midpoint of the gage length) ranging from 3.7 to 149.8 mg. The wires were hung inside a can made from 99.6 pct pure cobalt sheet. Beneath the wires were placed small specimens of 20-mil-thick, 99.9982 pct pure cobalt sheet from which the relative twin boundary and grain boundary energies and the surface diffusion coefficient were measured. All the specimens were annealed at a temperature of 1354" i 3°C which is 92 pct of the absolute melting point of cobalt. The furnace atmosphere was 99.9 pct pure hydrogen that was purified further by a Deoxo catalytic unit, magnesium perchlorate, and a liquid-nitrogen cold trap. As a precautionary measure the gas was then passed through titanium alloy turnings which were heated to 280" to 420°C and replaced after every test period. The hydrogen was maintained at a

Jan 1, 1969

By R. L. Pober, L. Kaufman, E. V. Clougherty

Composite structure of hafnium, zirconium, and titanium diboride with additions of metals and/or compound phases were prepared by reactive high-pressure hot pvessing and evaluated in air and in mixtures of oxygen and helium at temperatures up to 2400°K and at linear flow rates of 0.1 to 0.2 ft per sec stp. Oxidation characteristics, principally depth of conversion of diboride to dioxide, were determined by a gas analysis method and by postoxidation metallo-graphic analyses. The best oxidation resistance was observed for hafnium diboride-silicon carbide composite which exhibited a 6-mil conversion to dioxide for a 1-hv oxidation in air at 2200°K compared to a 20-mil recession for hafnium diboride with no additive. Analogous improvements in oxidation resistance were observed for the addition of silicon carbide to zirconium. EARLIER investigationof the oxidation behavior of the diborides of the transition elements of Groups IVA and VA in flowing gas mixtures have produced a ranking of these compounds according to which HfB2 is the most oxidation-resistant followed in turn by ZrB2 > TiB2 > TaBz > NbB2. Other ~tudies~-~ have examined the physical, thermal, and thermodynamic properties of these diborides to provide a sound basis for the more detailed and specialized investigations which are required to generate the information needed to assess the usefulness of such materials in high-temperature oxidizing environments. Recent oxidation studies7 have examined the effect of variations of metal and boron content on the oxidation characteristics of zirconium and hafnium diboride in flowing gas mixtures including air and helium plus oxygen. Results obtained in the latter investigation confirmed the superior oxidation resistance of HfB2 over ZrB2. Moreover, metal-rich compositions of hafnium diboride showed improved oxidation resistance over boron-rich compositions at temperatures up to 2000°K; at higher temperatures the differences are not distinguishable. In particular HfBI.7 exhibited a diboride to dioxide conversion depth of 4 mils in 1 hr at 2000°K; HfB2. 2 exhibited a conversion depth of 16 mils for the same exposure.~ Specimens for the study of metal and boron stoichiometry on the oxidation characteristics of HfB2 and ZrB2 were prepared by high-pressure hot pressing, a specialized type of fabrication which produced dense crack-free bodies of the desired compositions with no significant impurity introductions. The purpose of the present investigation was to explore the possibility of further improving the oxidation resistance of the metal-rich ZrB, and HfB2. The plan to accomplish this objective was based in the formulation of several diboride compositions containing other compounds and phases which are generally known to have good oxidation resistance in one or more types of test environment. Ideally, such additives would also enhance or at least not diminish other boride property values principally mechanical strength and those parameters related to thermal stress resistance. The additions selected for HfBz included zirconium, aluminum, and (Ta + TaB2) designed to produce ternary metal diborides, hafnium to form a discrete HfB phase, chromium to provide a metal skeletal phase, (Hf + Si) to form a discrete hafnium silicide phase, and Sic to provide a discrete second phase. Additions to ZrB2 included A1 + B designed to produce a ternary metal diboride, Zr + Si to form a discrete zirconium silicide phase, and Sic to provide a discrete second phase. All the specimens were prepared by high-pressure hot pressing which was used to advantage to fabricate billets of the variety of compositions desired and suitable for oxidation testing. The present investigation also included the evaluation of high-pressure hot-pressed TiB2and TiB2-20 vol pct Sic, conventionally hot-pressed Boride 2,' and KT silicon carbide. Boride

Jan 1, 1969

By Rees D. Rawlings, C. W. A. Newey

The aging characteristics of an Fe-11 at. pct Mo alloy have been studied by means of light metallography together with density, Young&apos;s modulus, and hardness measurements. The results were consistent with the precipitation of a single intermetallic compound during aging; overaging was slow relative to that in other iron-based binary alloys. The solution treatment temperature had a small effect on the rate of hardening whereas deformation prior to aging had a marked effect on both the rate of hardening and the peak hardness. The density data indicate that the compound precipitated is Fe3MO2 and not the Laves phase Fe2Mo. Analysis of the modulus and density results gave values for the time exponent for precipitate growth of approximately 1.0 and 1.5 for the alloy aged with and without prior deformation, respectively. DETAILED studies of precipitation hardening in bcc matrices have been confined largely to the effects of carbides and nitrides. In view of this and the growing technological interest in intermetallic compound strengthening, e.g., in maraging steels, a study of precipitation in iron-based alloys with a low interstitial content has been undertaken. This paper is concerned with the aging behavior of an Fe-11 at. pct Mo alloy; the mechanical behavior of the alloy will be reported later. The early work of sykes on Fe-Mo alloys showed that precipitation of the intermetallic compound was accompanied by an increase in hardness and a decrease in volume of the material. More recent surveys of the strengthening associated with precipitation have been made3-5 and, in particular, Elsen and wassermann4 showed that deformation prior to aging increased the rate of hardening. These latter workers also followed the precipitation process by means of dilatometry, electrical resistivity, and lattice parameter measurements. Their results confirmed that there is a decrease in volume on aging. Except for the work of Hornbogen on an Fe-20 at. pct Mo alloy, neither clustering nor the precipitation of a nonequilibrium phase has been observed in Fe-Mo alloys. Studies of alloys of lower molybdenum content475 indicate that the equilibrium intermetallic compound is precipitated during aging. However, there is some doubt concerning the nature of the equilibrium precipitate phase. According to the phase diagram constructed by Hansen,8 the phase should be precipitated. This phase has a rhombohedra1 crystal structure which is characterized by the formula Fe706,&apos; although the composition of the molybdenum-rich boundary corresponds approximately to Fe3Mo2. The version of the diagram proposed by Sinha, Buckley, and Hume-Rother indicates that the A phase, a Laves phase Fe2Mo, should be precipitated. Their observation of a Laves phase supports the earlier findings of Bechtoldt and Vacher,13 although, in a recent study of the system by means of diffusion couples, Rawlings and Newey did not detect the phase. The work presented here describes the effect of solution-treatment temperature, aging temperature, and prior deformation on the aging characteristics of the alloy as revealed by light metallography together with hardness, density, and Young&apos;s modulus measurements. In addition the density data are used in an attempt to determine the compound precipitated during aging. EXPERIMENTAL PROCEDURE A 29-kg ingot of the alloy was cast at R.A.R.D.E., Fort Halstead, from deoxidized, Japanese electrolytic iron and sintered molybdenum. The ingot was homogenized for 6 hr at 1473°K and then worked, with intermediate anneals, into 6- and 16-mm-diam rods and 6-mm plate. Chemical analysis of the alloy gave, wt pct: Mo, 17.5 (11 at. pct); C, 0.003; Si, 0.002; S, 0.005; P, <0.002; and02, 0.0098. Solution treatments were carried out under a dynamic argon atmosphere in a vertical, "crusilite" element, furnace which had a facility for rapid quenching into iced water. Except for the study of the effect of solution treatment temperature, all specimens were solution-treated at 1573" * 2°K for 1 hr. Salt baths were used for the aging treatments. Specimens for hardness, density, and Young&apos;s modulus measurements were produced, after heat treatment, from the stock rod or bar using a precision silicon carbide slitting wheel. As described later, the quenching treatment produced local plastic strain in the stock material; consequently, care was taken to ensure that the specimens were not prepared from these regions. Those specimens used in the studies of the effects of prior deformation on the aging behavior were strained in compression in a Denison universal testing machine. Specimens for light metallographic observations were mechanically polished on successively finer grades of diamond paste down to and then etched in either alcoholic ferric chloride or in a 2 pct nital solution. Vickers diamond pyramid hardness data were obtained using a 30-kg load. At least five impressions were averaged for each determination. Density measurements were made using a displacement technique in which each specimen was weighed in air and in dibromoethane at 296°K. The specimens were cylindrical and weighed 3 to 4 g; all weighings were made on a balance reading to 1 x 10"5 g. For each specimen the mean value of five weighings was used to calculate the density. The density of the dibromoethane was determined using the displacement procedure and a standard nickel specimen. The error in an absolute density value was estimated to be HI.01 pct. To obtain the density as a function of aging time a single specimen was used and the density meas-

Jan 1, 1969

By John C. Gifford, Charles L. Thomas

A unique and reproducible method is presented for the determination of water vapor in tough pitch wire bar copper. The procedure involves reduction of the water vapor with molten aluminum to form hydrogen, which is subsequently measured by mass spectroscopy. Average water vapor pressures within the porosities of the wire bar samples are calculated. Correlation is to exist between the specific gravities of the samples and their measured water vapor contents. The method should find application as a very sensitive means of detecting hydrogen embrittlement in copper. The nature and quantity of gases evolved and retained during the horizontal casting of tough pitch wire bar copper have long been of interest to the metallurgist. Considerable work has been done at this laboratory on the determination of these gases. The work has involved not only qualitative but also quantitative analysis, so as to provide a basis for a total accounting of the porosity which is associated with the cast product. From a knowledge of the gas-forming elements within the copper, and the practice of melting and protecting it with a reducing flame followed by contact with a charcoal cover in the casting ladle, the gases which one might expect to find in the pores of the cast product are sulfur dioxide, carbon monoxide, carbon dioxide, hydrogen, and water vapor. Hydrogen sulfide, nitrogen, and hydrocarbons would be other possibilities; however vacuum fusion-mass spectroscopy techniques employed at this laboratory have shown that no hydrogen sulfide and only traces of nitrogen and methane are present. It is highly improbable according to phillipsl that any sulfur dioxide could be evolved in wire bar copper with 10 ppm or less sulfur under normal freezing conditions. Mackay and smith2 have noted that porosity due to sulfur dioxide only becomes noticeable at concentrations above 20 ppm S. Investigation of carbon monoxide and carbon dioxide by a variation in the method of Bever and Floe showed that these two gases could only account, at 760 mm and 1064°C (Cu-Cua eutectic temperature), for a maximum of about 25 pct of the total porosity in a wire bar having a specific gravity of 8.40 g per cu cm. phillips&apos; has noted that no normal furnace atmosphere is ever sufficiently rich in hydrogen to cause porosity in copper from hydrogen alone. In addition, using a hot vacuum extraction technique for hydrogen,4 values have never been observed in excess of 10 ppb in tough pitch wire bar. On the basis of the preceding considerations of gases in tough pitch wire bar, only water vapor is left to account for the major portion of the porosity. Direct determinations of water vapor are virtually impossible at low concentrations by any presently known technique, due to adsorption and desorption within the walls of the apparatus used.5 The present investigation deals with a method for the determination of water vapor by an indirect procedure, using molten aluminum as a reducing agent to form hydrogen according to the reaction: 2A1 + 3H2O — A12O3 + 3H2 The evolved hydrogen can then be measured quantitatively by mass spectroscopy. EXPERIMENTAL A 10-g piece of 99.9+ pct A1 was charged into a porous alumina crucible (Laboratory Equipment Co., No. 528-30). Fig. 1 shows the crucible in place at the bottom of an 8-in.-long quartz thimble. A funnel tube with two l1/8-in.-OD sidearms extending at a 90-deg angle from each other was attached to the top of the thimble. One of the sidearms was joined to the inlet system of the mass spectrometer (Consolidated Electrodynamics Corp. Model 21-620A) via a mercury diffusion pump situated between two dry-ice traps. The copper samples were placed in the other sidearm, followed by a glass-enclosed magnetic stirring bar for pushing the samples into the crucible. All ground joints were sealed with vacuum-grade wax. The entire system was evacuated and the aluminum was heated with a T-2.5 Lepel High Frequency Induction Furnace for 21/2 hr at a temperature visually estimated to be 900°C. The temperature was then lowered and the hydrogen was monitored on the mass spectrometer until it was given off at a constant rate of about 4 to 5 1 per hr. This rate corresponded to a slope of 2 to 3 divisions per min on the X3 attenuation of a 10-mv recorder at a hydrogen sensitivity of approximately 100 divisions per 1. A micromanometer (Consolidated Electrodynamics Corp. Model 23-105)

Jan 1, 1969

By J. Szekely, Robert G. Lee

Calculations are presented for the prediction of the combined radiative-convective heat loss from molten steel held in a ladle, covered by initially molten slag. A mathematical formulation is given and numerical solutions are presented of the resultant partial differential equation. It is shown that a slag layer of about 2 to 3 in. thick would prevent any significant heat loss from the top metal surface for Periods of up to 1 hr. For thinner slag layers (or in the absence of the protective slag) appreciable heat losses would occur; plots given in the paper allow the quantitative evaluation of the fall in the metal temperature due to this heat loss. The ironmaking-steel processing operation involves several intermediate steps where the molten metal is held or transfered in ladles. The quantitative assessment of the heat losses occurring under these conditions is of considerable importance in process design considerations since the temperature of the metal may have to meet rigid specifications in any given part of the processing sequence. While the metal is held in a ladle, heat is lost by two mechanisms: i) by conduction into the ladle walls; ii) by radiation and convection from the top surface. Calculations relating to the conductive heat loss, are readily made and information may be found in the literature both on data pertaining to metallurgical situations and on the techniques that are available for performing additional computations.&apos;-3 The evaluation of the combined convective-radiative heat loss is less straightforward, especially when there exists a protective slag layer covering the metal. In this latter case, as the top slag surface loses heat partial solidification may occur and the latent heat thus given up by the slag may represent an effective barrier to the heat loss from the metal. A semiquantitative assessment of the role played by the slag in preventing heat loss from the metal has been made in a previous paper,4 where it was shown that a slag layer 6 in. thick would act as a near-perfect insulator for periods of up to 2 hr. However, this first paper reported on an essentially preliminary investigation that considered only one slag layer thickness; furthermore, the boundary conditions used for the calculations were somewhat restrictive since no allowance was made for changes in the metal temperature. The purpose of this second paper is to extend the scope of the preliminary investigation previously reported by: i) considering several slag layer thicknesses; ii) allowing for variations in the metal temperature; and finally iii) by performing calculations on the net loss from the metal rather than from the slag surface. FORMULATION Consider a slag phase extending from y = 0 to y = L1, covering a metal phase that occupies the region extending from y = Ll to y = L, as illustrated in Fig. 1. Denote the slag and metal temperatures by TS and Tm and assume that initially both slag and metal are molten, having a uniform temperature Ti. At time = zero the surface represented by the y = 0 plane (top slag surface) is brought into contact with cold air, the temperature of which is given as T Thus for time > zero, heat will be transfered from the slag to the air by natural convection and thermal radiation; as a result of this heat loss the slag temperature will fall and after some time a solid phase is formed and a solidification boundary (more realistically described as a zone) will move progressively from y = 0 toward y = L1. Once the region of temperature gradients, moving ahead of the solidification zone, reach the slag-metal interface (y = L1) there will be a net transfer of heat from the metal through the slag to the cold air, across the y = 0 plane. In the formulation of moving boundary problems, involving phase changes that require computer solution, it is convenient to represent both phases by a single equation, making allowance for the latent heat of solidification by assigning an appropriate temperature dependence to the specific heat content. Thus the energy equation for the whole of the slag may be written as follows:

Jan 1, 1969

By J. D. Hunt, D. T. J. Hurle

A uariety of eutectic structures are formed in faceted/nonfaceted eutectics. The various structures are explained in terms of the absence or presence of small facets in the liquid groove. Regular structures are produced when, for purely geometric reasons facels cannot form. The presence of a facet in the liquid groove leads to the formation of an irregular or a cell-like complex regular structure, due to the relative immobility of the groove. A classification of eutectics was proposed by Hunt and jackson, based on the presence or absence of facets on the primary phases (the absence of facets may be predicted from the dimensionless entropy of melting2). Eutectics were divided into three groups: 1) eutectics in which both phases grow in a nonfaceted manner; 2) eutectics in which one phase grows faceted, the other nonfaceted; 3) eutectics in which both phases grow faceted. It was suggested that regular1 rodlike or lamellar structures1 should be formed in the first group, that irregular or complex regular structures1 should be formed in the&apos; second, and that irregular structures1 should be formed in the third. Recently it has been shown that the structural classification is incomplete. Regular rodlike structures (InSb-NiSb eutectic3), or broken lamellar structure (Bi-Zn eutectic, Fig. 8), are formed in alloys of the second group when the faceted phase has a large volume fraction. Hunt and jackson&apos; argued that regular structures could form in faceted/nonfaceted systems, but that such structures would be unstable in the presence of microfacets on the lamella of the faceting phase, because the growth rate at a point on such a facet would depend on the kinetic undercooling at the point of nu-cleation on the facet, and not on the local kinetic undercooling. In these circumstances it would not be possible to consistently balance the compositional and kinetic undercooling over a lamellar structure and thus obtain a stable isothermal interface. In this paper we discuss in detail the origin of the various structures formed in faceted/nonfaceted systems, pointing out that the most important factor promoting the formation of a regular structure is the absence of a facet in the liquid groove. 1) FACET FORMATION IN SINGLE-PHASE MATERIALS Facets form when there is an energy barrier for the addition of a new solid layer on an existing solid. When a barrier is present,2 growth proceeds by the lateral movement of steps across a crystallographic plane. The rate-controlling stage of the process occurs when the step is first formed. Hulme and Mullin6 have shown that faceting in single-phase materials can only occur when both interface curvatures are convex with respect to the solid and when the surface is tangential to the facet plane. When even one of the curvatures is concave a facet does not form because new layers of solid from adjacent regions can always feed the facet plane, Fig. 1. Growth under these conditions is then as easy as elsewhere. Similar considerations will apply to eutectic growth; consequently the shape of the faceted phase is extremely important. 2) LAMELLAR SPACING CHANGES IN EUTECTICS Jackson and Hunt7 have shown that the interface undercooling AT of a growing lamellar interface (neglecting kinetic undercooling) is related to the lamellar spacing, A, and growth velocity, v, by an expression of the form: where m, Ql, and nL are constants of the system given in Ref. 7. Eq. [I] is plotted for fixed v in Fig. 2. Jackson and Hunt postulate that a regular eutectic grows near, but to the right of the minimum in the AT vs A curve. They argue that the spacing cannot be to the left of the minimum because the interface is then unstable to fluctuations in A. It cannot grow too far to the right, because when the spacing becomes too wide an isothermal interface can no longer be maintained over the large-volume-fraction phase.7 It is argued that during any change in growth rate the lamellar spacing remains in the permitted range by the movement of lamellar faults. When the spacing is too wide, the fault, shown in Fig. 3, moves to the left; when the spacing is too narrow it moves to the right. The faults, however, have to be formed. heir formation has been shown to occur when local regions deviate considerably from the spacing defined by the lamellar When the spacing is locally too narrow (it passes to the left of the minimum, Fig. 2), pinching off of the narrow phase occurs. When the spacing is locally too wide, the interface on the large volume-fraction phase can no longer be maintained as an iso-

Jan 1, 1969

By M. G. Benz

The superconducting performmce of diffusion-processed Nb3Sn is influenced by its micro structure. High isotropic transverse current density may be achieved in this material by a process which forms a precipitate of ZrO, within the Nb3Sn. FOR an ideal type-I1 superconductor, little or no transport current can be carried in the mixed state; i.e., little or no transport current can be carried above the lower critical field H,,, where the field penetrates abruptly in the form of current vortices or fluxoids, even though full transition to the normal state does not occur until the upper critical field H,,.&apos; Fortunately, nonideal type-I1 superconductors can be readily obtained and these carry large transport currents up to the upper critical field H. Both theoretical and experimental investigations have attributed this current-carrying capability for nonideal type-I1 superconductors to pinning of the fluxoid lattice by heterogeneities in the microstructure of the superconducting material. These heterogeneities may take the form of dislocations or dislocation clusters,2"5 grain boundaries: structural imperfections introduced by phase transformations; radiation damage,8"10 or precipitates.11"15 Nb3Sn formed by diffusion processing is a type-I1 superconductor. Heterogeneities are needed for high superconducting critical currents above H,,. This paper will cover: a) what the microstructure of diffusion-processed NbSn looks like; b) what changes in the microstructure take place when the system is doped with precipitates, and c) how these changes in microstructure influence the superconducting critical currents. EXPERIMENTAL Preparation of Samples. Diffusion processing was used to form the Nb3Sn. The procedure used was as follows: a) coat the surface of a niobium tape with tin; b) heat-treat this tape at a temperature above 930°C to form a layer of Nb3Sn at the Sn-Nb interface. Such a layer of NbsSn is shown in Fig. 1 The thickness of the NbsSn layer formed was controlled by the time and temperature of the heat treatment. The same general procedure was used for preparation of both undoped samples and samples doped with a precipitate. An additional step was included in the preparation of the doped samples which consisted of internal oxidation of zirconium to form ZrOn. The details of the doping process will be reported in a later paper. Sample Testing. The Nb3Sn tape samples were soldered to a copper or brass shunt. Current and voltage leads were then attached to the sample in the usual four-probe resistance measurement configuration. The sample was cooled to 42°K. In some cases it was cooled in the presence of a high magnetic field and in other cases with the field turned off. The results were the same for both cases. The samples were oriented in a configuration with field transverse to current but could be rotated such that the angle between the field vector and the wide side of the tape sample could be changed. Measurements up to 100 kG were done in a superconducting solenoid and measurements above 100 kG in a water-cooled copper magnet at the MIT National Magnet Laboratory. Once the test field was reached, the current in the sample was increased until voltage was detected across the sample. The critical current was taken as the current at which voltage was first detected in excess of background noise. In most cases this was 1 to 2 x 10~6 v for a— in.-wide sample carrying several hundred amperes with a in. separation between voltage leads and with a 10 "-ohm shunt resistance. RESULTS AND DISCUSSION Microstructure. Examination of the microstructure of the undoped Nb3Sn shows rather large-diameter (1 to 2 columnar grains growing outward from the niobium surface toward the tin surface. As the layer is made thicker by longer diffusion times, these grains grow longer. Few new grains are started. Transmission electron microscopy shows little or no second-phase material within the bulk of the Nb3Sn layer. The microstructure of a diffusion-processed NbsSn layer changes quite drastically when the system is doped so as to form a precipitate within the NbsSn layer. Instead of large-diameter columnar grains of NbaSn forming, smaller-diameter (0.5 to 1 ) equiaxed grains of Nb3Sn decorated with the precipitate form. Fig. 2 shows a transmission electron micrograph of a Nb3Sn layer doped with zirconium oxide. This layer has been etched so that one may look between the grains

Jan 1, 1969

By P. Chiotti, J. T. Mason

Thermal, X-ray, metallographic, and resistivity data were obtained to establish the phase diagram for the Yb-Zn system. Six intermetallic compounds and five eutectics have been identified. The compounds position at 695°C. No evidence for the compound YbZn,, was observed. Whether this compound is stabilized or inhibited by small amounts of impurities is uncertain. SEVERAL aspects of the Yb-Zn system have been reported in the literature. Much of this work deals with the crystallographic identification of some of the compounds. The YbZn compound has been reported by Iandelli and palenzonal and the YbZn, structure and thermal data for the composition range between YbZn and Yb3Znll have been reported by Michel et al. A compound of uncertain stoichiometry in the range 60 to 68 wt pct Zn with a cubic structure has been reported by Kuz&apos;ma et aL4 The YbzZn17, YbZn,,, and YbZn13 compounds have been reported by both Kuz&apos;ma et a1 and Iandelli and Palenzona.&apos; YbnZn17 has also been identified by Laube. This investigation was undertaken to establish the phase diagram of this system. Ytterbium in many respects behaves as an alkaline earth rather than a rare earth metal6 and it is of interest to note the resemblance between the Yb-Zn system, the Ca-Zn,&apos; and typical rare earth-zinc systems.g&apos;10 MATERIALS AND EXPERIMENTAL PROCEDURES The materials used in this investigation were Ames Laboratory ytterbium and Bunker-Hill slab zinc, 99.99 pct pure. Analyses of the ytterbium showed 38 ppm Ta, 82 ppm 0, and 15 ppm N with Ca, Cu, C, Mg, Al, Si, Cr, Fe, Ni, Sc, Y, Er, Tm, and Lu all less than 50 ppm. The ytterbium was dehydrogenated by heating in tantalum under vacuum for 8 hr at 900°C. The metal was kept under argon except when being cut with shears and when being weighed. Tantalum was found to be a suitable container for alloys in the composition range between ytterbium and Yb2Zn17. With higher zinc concentrations the tantalum was penetrated by the alloy and failed after several days at temperatures of 600" to 700°C. Approximately 20 g of zinc and ytterbium metal were sealed under argon in *-in.-diam tantalum cruci- bles equipped with thermocouple wells. The crucibles were in turn sealed in stainless-steel jackets. The alloys were equilibrated in an oscillating furnace and given various heat treatments in a soaking furnace. The steel jackets were removed and differential thermal analysis data were obtained under an atmosphere of argon. The thermal analysis apparatus was calibrated against the melting points of pure zinc, aluminum, silver, and copper and found to give thermal arrests within 1°C of the accepted melting temperatures for these elements. The thermal analysis apparatus has been described in an earlier paper.g Alloys were further heat-treated as necessary and subjected to metallographic examination and X-ray diffraction analysis. Most alloys were etched with Nital (0.5 to 10 pct nitric acid in alcohol). EXPERIMENTAL RESULTS The results of the thermal analysis are summarized by the points on the phase diagram, Fig. 1. Six compounds and five eutectics were observed. The eutectic temperature and compositions in weight percent zinc are 491°C and 12 pct, 645°C and 32 pct, 687°C and 54 pct, 742°C and 67 pct, and 750°C and 77 pct. The compounds YbZn, YbZn2, Yb2Zng, Yb2Zn17, and YbZnll melt congruently at 650°, 751°, 75Z°, 754", and 755"C, respectively. The compound Yb3Znll undergoes a peritectic decomposition at 695°C. The transformation and melting temperatures for the ytterbium were observed to be 797" and 817°C. re-

Jan 1, 1969

By Charles E. Lundin

The character of the Er-D system was established by determining pressure-temperature-composition relationships. A Sieuerts&apos; apparatus was employed to make measurements in the temperature range, 473" to 1223"K, the composition range of erbium to ErD3, and the pressure range of 10~s to 760 Torr. The system is characterized by three homogeneous phase regions: the nzetal-rich, the dideuteride, and the trideuteride phases. These phases and their solubility boundaries were deduced from the family of isotherms of the system zchich relate the pressure-temperature-composition variables. The equilibrium plateau decomposition relationships in the two-phase regions were determined from can&apos;t Hoff plots to be: The differential heats of reaction in these two regions are AH = - 53.0 * 0.2 and -20.0 *0.1 kcal per mole of D2, respecticely. The differential entropies of reaction are AS = - 36.3 * 0.2 and - 31.0 * 0.2 cal per mole D2. deg, respectively. Relative partial molal and intepal thermodynamic quantities were calculated from the pure metal to the dideuteride phase. The study of the Er-D system was undertaken as a logical complement to an earlier study of the Er-H system.&apos; The primary interest was to compare the characteristics of the two systems and relate the difference to the isotopic effect. Studies of rare earth-deuterium systems by other investigators have been very limited in number and scope. Furthermore, there is even less information available wherein an investigator has systematically compared a binary rare earth-hydrogen system with the corresponding rare earth-deuterium system. The available information consists primarily of dissociation pressure measurements in the plateau pressure region of a few rare earths. Warf and Korst&apos; determined dissociation pressure relationships for the La- and Ce-D systems in the plateau region and several isotherms for each system in the dideuteride region. They compared these data with those of the corresponding hydrided systems. The study of these systems as a whole was very cursory and did not give sufficient data for a thorough comparison of the effect of the hydrogen vs the deuterium in the respective rare earths. The heat capacities and related thermodynamic functions of the intermediate phases, YH, and YD2, were determined by Flotow, Osborne, and Otto,~ and the investigation was again repeated for YH3 and YD3 by Flotow, Osborne, Otto, and Abraham.4 This investigation studied only these specific phases. Jones, Southall, and Goodhead5 surveyed the hydrides and deu-terides of a series of rare earths for thermal stability including erbium. They experimentally determined isotherms of selected hydrides and plateau dissociation pressures for deuterides. These data allowed comparison of the enthalpy and entropies of formation of the dihydrides and dideuterides. To date, no one rare earth has been selected to thoroughly establish the complete pressure-temperature-composition (PTC) relationships of binary solute additions of hydrogen and deuterium, respectively. The objective in this investigation was to provide the first comparison of a complete family of isotherms of a rare earth-deuterium system with those of a rare earth-hydrogen system. This would allow one to determine what differences exist, if any, in the various phase boundaries and the thermodynamic relationships in various regions of the systems. I) EXPERIMENTAL PROCEDURE A Sieverts&apos; apparatus was employed to conduct the experimental measurements. Briefly, it consisted of a source of pure deuterium, a precision gas-measuring buret, a heated reaction chamber, a mercury manometer, and two McLeod gages (a CVC, GMl00A and a CVC, GM110). Pure deuterium was obtained by passing deuterium through a heated Pd-Ag thimble. A 100-ml precision gas buret graduated to 0.1-ml divisions was used to measure and admit deuterium to the reaction chamber. The reaction unit consisted of a quartz tube surrounded by a nichrome-wound furnace. The furnace temperature was controlled by a recorder-controller to . An independent measurement of the sample temperature in the quartz tube was made by means of a chromel-alumel thermocouple situated outside, but adjacent to, the quartz tube near the specimen. Pressure in the manometer range was measured to k0.5 Torr and in the McLeod range (10~4 to 10 Torr) to *3 pct. The deuterium compositions in erbium were calculated in terms of deuterium-to-erbium atomic ratio. These compositions were estimated to be *0.01 D/Er ratio. The erbium metal was obtained from the Lunex Co. in the form of sponge. The metal was nuclear grade with a purity of 99.9+ pct. The oxygen content was reported to be 340 ppm and the nitrogen not detectable. Metallographically the structure was almost free of second phase (<i vol pct). A quantity of sponge was arc-melted for use as charge material. The solid material was compared with the sponge in the PTC relationships. They were found to be identical. Therefore, sponge material was used henceforth, so that equilibrium could be attained more rapidly. The specimen size was about 0.2 gr for each loading of the reaction chamber. The procedure employed to obtain the PTC data was to develop experimentally a family of isothermal curves of composition vs pressure. First, a specimen

Jan 1, 1969

By S. Luszcz, R. W. Vook, Fred Witt

In situ X-ray investigations were made on polycrys-talline silver films deposited by vacuum evaporation on (111) CaF2 and (100) NaCl single-crystal substrates at 80°K. The films were evaporated and annealed in an X-ray diffractometer attachment having a residual gas pressure of 2 x lo-&apos; Torr. All measurements were made without exposing the films to the atmosphere. Measurements were made on the films in the as-deposited state and after various annealing treatments. The intrinsic stacking and twin fault densities, the magnitudes of the uniform and nonuniform strains, and the crystallite sizes were determined. In addition the textures in the films were measured qualitatively. The results obtained for the as-deposited films on single-crystal substrates are in substantial agreement with previously reported results for silver films deposited on glass. Intrinsic stacking and twin faults, as well as uniform and nonuniform strains, were present in these films. During the various annealing treatments (up to 350°C) the faults and nonuniform strains annealed out. Considerable grain growth and texture changes occurred also. The effects were much greater for the NaCl substrate than for the CaFz substrate. The relative magnitudes of the grain growth in the variously oriented grains could be explained qualitatively in terms of the thermal strains and strain energies introduced into the differently oriented grains during the initial, irreversible anneal. These strains were due to the different thermal expansion coefficients of the film and substrate. X-RAY diffraction measurements on evaporated films deposited on substrates at low temperature have the advantage that many of the imperfections introduced into the film during deposition are "frozen in". Thus, the influence of a very important experimental variable, substrate temperature, on the imperfection structure of evaporated metal films may be studied. Moreover, the effects of annealing such films makes possible the study of thermally activated recovery processes in these films. The present study was designed to determine the influence of single-crystal substrates on the resultant film structure relative to the previous results obtained using glass substrates.&apos; To this end great care was taken to keep the experimental variables the same in the two cases. Different experimental conditions would, of course, result in films having different physical properties. Again the initial substrate temperature was in the neighborhood of 80°K and the films were subsequently annealed to 350°C. The pure metal silver was chosen for evaporation, primarily because of its relatively low stacking fault energy and consequent high fault density in the as-deposited state. The silver films were formed by evaporation onto air-cleaved {ill} CaF, and (100) NaCl surfaces cooled to 80°K in an X-ray diffractometer attachment2 having a base residual gas pressure of 2 X l0-&apos; Torr. The films were not exposed to the atmosphere until all of the X-ray data had been recorded. In this way one of the most important experimental variables, environment, could be well-controlled and reproduced. X-ray measurements were made at the temperature of deposition and included determinations of the diffraction line peak positions, line shapes, and integrated intensities. The peak position measurements were used to determine the intrinsic stacking fault densities and the average uniform strain in the film. The shapes of the diffraction lines provided information on the twin fault density, true crystallite size, and average nonuniform strain. The preferred orientation in the film was determined qualitatively from the integrated intensities. I) EXPERIMENTAL PROCEDURE The evaporator attachmentZ was charged with 99.999 pct Ag pellets positioned in a tantalum filament which had been outgassed previously at l0-8 Torr. The CaFz and NaCl single crystals were cleaved in air and then placed in position in the chamber so that their cleavage surfaces were on the diffractometer axis. The chamber was prepumped using a sorption pump, sealed off, and then baked at 150°C for 24 hr. The ion pump operated during the bakeout cycle. The substrate was then heated to 500° C by means of an auxiliary heater and kept hot until the rest of the chamber was cooled slowly to room temperature. This bakeout procedure consistently resulted in an ultimate pressure in the low lo-&apos; Torr range. The substrate was then cooled down on 80°K. Its temperature was monitored by a thermocouple wedged into the rear of the copper substrate holder. The diffracted intensity and peak position of the 111, 222, and 333 CaF, lines were measured prior to evaporation. Nickel-filtered, pulse-height-discriminated copper radiation was used. Similar measurements were made for the 200 and 400 lines from NaC1. These measurements were used as a lattice parameter check and to determine the thickness of the evaporated silver films from the attenuation of the substrate lines. The evaporation rates were approximately 3A per sec for both films while the maximum pressures during evaporation were 3 x lo- &apos; and 7 x 10"8 Torr for the CaF, and NaCl cases, respectively. The film thickness was measured by the attenuation of the CaF, and NaCl substrate lines and by at optical interference method. Values of 1700 and 1500A, respectively, were obtained for the silver

Jan 1, 1969

By M. H. Richman, W. D. Sproul

THE indexing of a field-ion micrograph is in many cases similar to the indexing of the poles of a stereo-graphic projection.* If one has a standard projection as a guide, the task of indexing is relatively simple. In this way, field-ion micrographs of bcc and fcc wires have been oriented from projections available in most any text on X-ray diffraction. These books always illustrate the projections for the bcc and fcc structures and even for a particular hcp structure. There is no "standard" hcp projection because the angles between planes depend on the c/o ratio of the unit cell. In order to index field-ion micrographs of hcp metals, one must compute the angles between various planes—a rather laborious task. In recent work,, we have had to identify the structure and index the orientation of field-ion micrographs of the compounds WC and W,C. To overcome the problem of computing angles by hand or calculator, a program was written in Fortran lV for use on the IBM 360, Model 50 which will compute all angles between planeswith indices (hlklll) and (17,k,l2) in the range from (447) to (444) for any given c/o ratio. The program, which is more specific than that of Camp and clum, was so written as to take advantage of the multiplicity of the hexagonal system, and, for the limits defined above, only 26,649 values out of a possible 265,721 values had to be computed. This is a 90 pct saving in time (and cost) and was accomplished in the following way. Because the lattice parameters of the hexagonal crystal system are defined such that: a = b * c [1] the I index does not enter into the multiplicity (i.e., it cannot be transposed with the h or k indices), and all possible values of h and I, from 4 to 4 must be used—a total of eighty-one combinations. The index h2 varies the most—it must assume values from - Ill,: to 3Ihl. The indices kl and k2 are always equal and vary

Jan 1, 1969

By Raymond D. Daniels, Frank E. Rizzo, James D. Gerber

ThIS discussion describes a method for the addition of small amounts of oxygen to columbium (niobium) in an accurate and reproducible manner. The method is based on the complete reduction by columbium of a carefully weighed amount of another metal oxide. The equilibrium Pq associated with Cb-CbO mixtures is extremely low, e.g., 10"25 atm at 100O°C, and the pressures over Cb-0 solutions are even lower. The equilibrium Pq associated with a given metal-metal oxide mixture can be easily obtained, with the aid of a Richardson-Jeffes chart.&apos; Although columbium should effectively reduce almost any metal-metal oxide combination, the proper choice of a metal-metal oxide system is complicated by the low rate of oxygen transport in the gas phase at low oxygen pressures and the difficulty in reducing any columbium suboxide formed during the reduction of the oxygen source material. Thermodynamically, oxide formation on columbium will be avoided so long as the oxygen partial pressure over the columbium is below the equilibrium pressure associated with the mixture Cb-CbO. The logical choice of a source for oxygen would appear to be a mixture of Cb-CbO, since oxide formation would be precluded by nucleation difficulty. But calculations using the kinetic theory of gasses indicate that, for a temperature of 900°C, the reaction would proceed too JAMES D. GERBER, formerly Research Assistant, University of Oklahoma, Norman, Okla., is Research Metallurgist, Air Force Weapons Test Laboratory, Kirtland Air Force Base, N. Mex. FRANK E. RIZZO, Junior Member AIME, formerly Assistant Professor of Metallurgy, University of Oklahoma, is Associate Professor of Metallurgy, University of Texas at El Paso, El Paso, Tex. RAYMOND D. DANIELS, Member AIME, Professor of Metallurgical Engineering, University of Oklahoma, is an NSF Fellow, Institute de MBtallurgie Structurale, Universite de euch:tel, Neuchitel, Switzerland. Manuscript submitted October 28, 1968. IMD

Jan 1, 1970

By Edward A. Loria

Vanadium is one of the materials being considered for use in fast-breeder nuclear reactors. It is a good heat conductor and nearly transparent to radiation, properties regarded as ideal for nuclear fuel containers. The problem has been the metal lacks ductility needed for forming. In our program at Reno Laboratory the effects of the U.S. Bureau of Mines (previous affiliation) the effects of oxygen, nitrogen, and carbon have been reported21,22 nd most recently the effects of boron and boron with carbon.23 The continuing study by the Ames Laboratory of the effects of hydrogen, the most subtle and fugitive element in its relationship to structure and properties, is commendable. The solubility of oxygen, nitrogen, and hydrogen in vanadium (and other bcc metals as well) is related to material purity. With the available limit on metal purity and the interaction (clustering) of hydrogen with the other interstitial and substitutional elements present in their base metal, would the authors comment on the tolerance of hydrogen in relation to oxy- gen that will avoid intergranular fracture and above what content or how seriously harmful in oxygen at various carbon levels? Understanding the true effects of hydrogen (and other interstitial impurities) in vanadium depends on knowledge of the amount present under various conditions and its distribution between various possible positions. Significant amounts of hydrogen may be in "thermo-dynamic" solution, but not as individual atoms in interstitial positions. It may be in grain boundaries, in subgrain boundaries, in vacancies, or in dislocations. Some of the hydrogen may be paired or in complexes with impurities in substitutional solid solution in vanadium. This makes the analysis of the effect of hydrogen vastly more difficult. It should not be expected that hydrogen in grain boundaries will affect slip in the same manner as hydrogen in interstitial positions, nor will the complexes react to heat treatment the same way as hydrogen in dislocations. It is gratifying that the authors have quoted results from two of our inestiations,&apos; but neglected one2&apos; which applied the Petch theory to electrorefined vanadium of high purity and analyzed the effects of oxygen, nitrogen, and carbon on the ai and ky values obtained by the extrapolation and grain size methods. Details can be found in the paper. Briefly, we obtained a ui value of 10,300 psi (t = 5150 psi) at 273°K. The metal also exhibited profuse twinning with high ductility at 123" and 77°K. Nitrogen was more effective than oxygen in increasing ui, the increase being about twice as much for the same impurity level. Carbon additions resulted in only minimal changes in Ui. The corresponding ky increased as oxygen and nitrogen increased, with nitrogen being more effective. Carbon additions resulted in little change. Although the difference in yield strength of vanadium was explained on the basis of the Cottrell-Bilby model of the tearing away of dislocations from the impurity atoms,

Jan 1, 1970

By P. O. Metz, E. L. Wiehe, J. S. Foster

BASED on their analyses of growth kinetics, ibbs&apos; and Harris et al.&apos; have recently proposed that the rate of subcritical graphitization of steel is controlled by the rate of diffusion of carbon in ferrite. illert has concluded that this is the rate controlling growth mechanism when the growing graphite particles are relatively large. Harris et al.&apos; also propose that the matrix surrounding a growing graphite particle is plastically deformed to make room for the growing particle. If this plastic deformation does occur, then preferred recrystallization may be observed around the larger particles. If diffusion of carbon in ferrite is rate controlling, then a graphite particle growing in a matrix of, say, tempered martensite or pearlite, should be surrounded by a carbide depleted zone. Thus, the simple metallographic experiments reported here are sufficient to determine whether or not diffusion of carbon in ferrite is the dominant mechanism for the growth of graphite in steel. The present investigation considers graphitization in five alloys. The compositions are given in Table I. Graphitization was carried out at three temperatures: 900°K (627"C), 950°K (677"C), and 990°K (&apos;717°C). Samples were reacted in both the martensitic and the pearlitic initial conditions. In the hypoeutectoid steels, Sets 7 and 8, .and in the hypereutectoid Fe-C binary, Set 6, graphitization was very limited after 1000 hr at temperature. In these samples graphite particles observed were less than 10 p in diam. In the hypereutectoid commercial steels, Sets 1 and 3, large graphite particles (100 p) did not appear until after 250 hr at temperature. The limited number of graphite particles observed and the range of sizes obtained prohibited measurement of growth rates in this investigation. However, in all samples showing graphitization, neithe a carbide depleted zone nor recrystallization was observed. illert&apos;s model predicts that diffusion of carbon in ferrite should become dominant for graphite particles larger than about 300 p in diam. The largest graphite particle observed in this investigation was approximately 450 p in diam. No evidence of carbide depletion was noted. Fig. 1 shows a typical graphite particle. This nodule is from an initially pearlitic sample from Set 3 after

Jan 1, 1970

By R. E. Miner, J. K. Jackson, T. L. Wilson

THE nature of the decomposition reactions producing hardening in aluminum-rich A1-Ag alloys is now fairly well understood. The silver is not uniformly dispersed even at temperatures above the solvus line: rather, it is clustered into zones and associated with dislocations.&apos; During quenching, nearly all of the silver segregates into zones&apos; and some is attracted to dislocations, producing stacking faults. Growth of these faults produces the semicoherent y precipitate.1 During aging, the larger zones and the y precipitates grow at the expense of the smaller zones. The large zones persist up to about 350°C; where they redissolve in favor of the y&apos; and y precipitates.&apos; The equilibrium hcp y precipitate occurs both by a cellular reaction at the grain boundaries1 and by growth of the Y&apos; plates to a critical size where incoherency results. Damask and Nowick 4 observed an internal friction peak in an A1-6 at. pct Ag alloy at about 140°C (0.25 cps). The peak was found to exhibit a systematic instability. After aging at successively higher temperatures between 155&apos; and 23Z°C, the peak first migrated to higher temperatures while increasing in height, then returned to lower temperatures and decreased in height. After aging at temperatures above about 200°C, the peak position remained constant while the height decreased very slowly. In quenched specimens, elastic after-effect measurements inhcated a rapid initial transient in peak position from low temperatures up to 155°C. The authors concluded that a stress induced growth and resolution of the clusters and the 7&apos; was the most reasonable mechanism to account for the behavior. It would seem, however, very unlikely that both the clusters and the y&apos; precipitate would provide damping contributions whose relaxation time and activation energies were identical, which is required for them to produce the same internal friction peak. The present investigation was motivated by this apparent anomaly and the development of a very low thermal inertia torsion pendulum5 capable of monitoring transient behavior. Low frequency internal friction measurements were made on four binary A1-Ag alloys nominally containing 5, 10: 15, and 20 at. pct Ag. The results of measurements made on a 10 at. pct Ag alloy in the quenched condition are shown in Fig. 1. There are two peaks apparent in the spectrum, one centered at about 160°C, the second at about 210°C. The two peak spectrum was observed in each alloy, but it was best resolved in the 10 pct Ag specimens. Because of the instability in the internal friction, 4 it seemed possible that the second peak was not a peak at all, but simply a manifestation of a single, sharply transient, peak. This effect has been observed in Au-Ni alloys.6 The existence of the higher tempera-

Jan 1, 1970

By Thomas C. Wilder

ALTHOUGH there is an abundance of thermodynamic information available in the literature today, no experimental data on the standard molar properties of formation of zinc oxide have ever been reported for the temperature range 419.5" to 908°C. This is the temperature range for which zinc metal is a liquid. so that the formation reaction is: Data have been reported for Reaction [I] where zinc is a solid or a gas. Maier. Parks, and nderson&apos; measured the electromotive force of the cell: in order to obtain the free energy of the reaction: over a limited temperature range. With the known properties of H2O, those of ZnO were calculated. These workers found that t;j of ZnO is -75,930 ± 150 cal per gfw and Mtf is-83,000 300 cal per gfw at 25°C. akolkin made similar measurements to obtain ilF7 and AH; of -75,870 and -82,540 cal per dw respectively at the same temperature. Truesdale and arirlg and Kitchener and 1gnatowicz4 measured the equilibrium of the reactions: respectively, in order to determine Ff of ZnO from the known values of CO, CO2, and H/X The thermodynamic properties of ZnO, presumably taken from the above investigations, are tabulated by Kubaschewski and vans&apos; and Wicks and Block" The latter reference also gives values for the range where zinc is a liquid. These numbers are probably acquired from the known extremities of the range plus Cp data of the components. In the present work the electromotive force of the cell: was measured in order to calculate the properties of ZnO from the well known values of NiO for the temperature range where zinc is a liquid. In Cell [B] the cathode reaction is: and at the anode: The overall reaction is: for which the free energy change is: where is the electromotive force in volts of cell [B] after correction for the Pt-Ta thermocouple. The standard molar free energy of formation of NiO is very well known as a function of temperature. Kiukkola and agner&apos;s data are used in most tabulations. The error is probably less than I00 cal per gfw, The latter authors were the first to use solid mixed oxide electrolytes in galvanic cells. Their work with NiO and other oxides was performed with cells similar to Cell [B] using a variety of reference electrodes of fixed oxygen potential. There may be a small composition range for which either NiO, ZnO or both exist. If nonstoichiometry does exist for these oxides, then the properties described herein are those for the metal saturated compositions. The simple cell design was the same as described elsewheres except that the molten metal electrode was about 125 g of pure zinc including a small (0.25 to 0.50 g) amount of ZnO. The mixture of pure nickel and NiO powders making up the reference electrode was contained in a tube of the ZrOl + CaO electrolyte which was immersed in the molten zinc. A platinum contact was made to the reference electrode; tantalum to the zinc. A refractory cement plug was necessary at the open end of the electrolyte tube in order to prevent zinc vapor from contaminating the reference electrode. Experimental details such as the vessel containing the cell, furnace, temperature control and measurement, and electromotive force determinations of the cell have all been outlined previously. The temperature was varied randomly in the range between the freezing and boiling points of zinc. After each temperature change, time was allowed for the drift at the new temperature to be less than +;"c whereupon a series of three cell readings was taken at least 10

Jan 1, 1970

By L. W. Sink, B. H. Kear, S. M. Copley, M. F. Hornbecker

IT is well known that under appropriate conditions of chill casting, many metals and alloys develop a columnar grain structure having a high degree of preferred orientation.&apos; In cubic materials, this principle has been employed to produce shaped castings with a unidirectional cube oriented columnar grain structure as well as shaped single crystals with a cube axis parallel to the growth ais.&apos; "he purpose of this note is to describe how this same principle can be enlployed to produce wires, rods, or more complex crystal Shapes with a variety of conlpositions in cube or random orientations by a single casting operation. The procedure for directional solidification of in Fig. 2. Examination under crossed polarizers indicated that the striations were a second phase (presumably the B19 phase) which frequently forms initially at primary grain boundaries and then grows toward the interior as thin ribbons. X-ray studies on filings of this alloy reannealed at 1300°C for 15 min indicated a strong pattern of the fcc phase together with a substantial pattern of the B19 phase. The un-annealed filings, however, showed only the pattern of a cold-worked, fcc structure. In these two-phase alloys it appears, therefore, that the B19 phase is transformed into a disordered fcc structure by cold-working. The mechanical properties of these alloys would be of some interest since a fcc structure might be expected to possess greater ductility than the or-thorhombic B19 structure from which it forms. The author wishes to thank Mr. Harvey Yakowitz and Mr. Richard Manuszewski for obtaining the photomicrograph in Fig. 2. This research was partially supported by Research Grant DE-02455 from the National Institute of Dental Research. columnar grained ingots involves pouring a melt into a preheated mold having a water-cooled copper chill at its base? and controlling the temperature gradient in the mold so as to maintain columnar grain growth from end to end of the ingot.4 This is illustrated schematically in Fig. l(a). It should be noted that the longitudinal temperature gradient promoting unidirectional columnar grain growth is maintained by heat loss primarily through the solidifying ingot to the chill, so that both the temperature gradient and the growth rate diminish with increasing distance from the chill. As the distance from the chill increases? the columnar structure coarsens, and the perfection in preferred orientation tends to increase progressively. Using this same procedure of gradient solidification, Fig. l(b) shows a simple scheme for producing a batch of crystals having the same cube orientation rather than an assemblage of columnar grains. Wires and rods are produced by cementing ceramic tubes to the wall of the mold. The steep temperature gradient produced in the central chamber is controlled by the mold heater to produce favorable conditions for crystal growth. Clearly the success of the operation lies in the selection of individual growing columnar grains by some kind of orifice at the base of each channel in the mold. Using simple constrictions, experience with nickel-base alloys has shown that 4 -in.-diam holes at a distance of -1 in. from the chill yield crystals within 7 deg of (100); closer control of orientation is possible by placing the crystal selector farther away from the chill.

Jan 1, 1970

By B. C. Wonsiewicz, W. W. Wilkening

Following a procedure proposed by Wheeler and Ireland, Plane stress yield loci were constructed from Knoob hardness numbers. Basically, six differently oriented hardness measurements were made on three orthogml surfaces through pure poly crystalline magnesium sheet, a magnesium single crystal, and sheet of the magnesium alloys: Mg + 0.5 pct Th, Mg + 4 pct Li, AZ31B, and EKOO. Hardness loci were found to be in poor agreement at small strains (E < 0.05) with loci established by a more rigorous technique. At larger strains (E - 0.10) the agreement is fair, but at this stage in deformation the conventional locus has lost much of the asymmetry that characterizes these anisotropic materials. Two effects which will lead to distortions in the Khn locus are discussed with reference to the geometry of plastic flow during a hardness test. DETERMINING a material&apos;s resistance to multiaxial loading is of interest not only from a structural design viewpoint but also from that of deformation processing. Unfortunately, the determination of the yield locus, although simple in principle, involves tedious procedures if the results are to be at all rigorous.&apos; The idea, first proposed by Wheeler and 1reland2 of determining the yield locus by means of six Knoop hardness impressions along the principal directions in a material has obvious appeal. It is simple, quick, and should be applicable to very thin sheets. If such a technique could be demonstrated to produce consistently reliable results, it would be of interest to both researcher and designer. Lee, Jabara, and ackofen have compared the yield locus determined by Knoop hardness measurements (the Khn locus) to a locus determined by more rigorous techniques. They found good agreement for two titanium alloys at a plastic strain of about 1 pct. The purpose of this paper is to investigate if the Khn locus construction is a reasonable approximation to the locus of a highly anisotropic material. Examples of such materials are magnesium and magnesium alloys which have severely distorted yield loci which in turn reflect markedly dfferent yield strength in different directions.&apos; In pure magnesium, for example, the yield stress in tension along the transverse direction may be four times the yield stress in compression in the same direction and twice the tensile yield stress in the rolling direction. Predicting such large differences ought to serve as a severe test of the Khn locus construction. EXPERIMENTAL PROCEDURES Samples of rolled sheet, 0.250 in. (6.35 mm) thick, of pure magnesium and four magnesium alloys (Mg experimental materials. The pure magnesium together with the lithium and thorium alloys were those used in the study of Kelley and Hosford. The grain size was ASTM number 4 for the pure magnesium and number 6 for the alloys. HARDNESS TESTING The materials were sectioned along the rolling and transverse planes, mounted in a quick setting resin, and mechanically polished. Most of the hardness tests were performed on a surface prepared by electro-polishing (30 pct nitric acid in methanol at 0°C and 20 v) with the exception of the AZ31B and EK00 alloys which were made directly on a metallographically polished surface. However, subsequent hardness tests on the same sample after heavily electropolishing, revealed essentially the same hardness as before. At least twenty Knoop hardness impressions under a 100-g load were made in each of the six orientations shown in Fig. 1. The average hardness number and standard deviation were then calculated for each orientation. CONVENTIONAL LOCUS CONSTRUCTION Yield loci were constructed using a technique described in detail by Lee and ackofen,&apos; in which the flow stress (stress at a given plastic strain) fixes the coordinates of a point on the locus and measurements of the strain ratio serve to establish the slope of the locus at that point. The loading paths which correspond to uniaxial tension or compression tests establish the four intercepts of the locus with the coordinate axes plus one point on the balanced biaxial tension line Tensile testing was performed along the rolling and transverse (r, t) directions. Samples had a uniform rectangular gage length 1 by 4 by 4 in. (25.4 by 6.35 by 6.35 mm) and were deformed at a strain rate of 3.33 x 104 sec-&apos;. The tests were interrupted periodically to unload the sample and measure the plastic strains by means of X-Y post yield strain gages. Compression tests in the rolling, transverse, and through-thickness (r, f, z) directions were performed on 1/4 in. (6.35 mm) cubes at an initial strain rate of 8.33 x sec-&apos;. Lubrication was provided by 0.002 in. (51 pm) Teflon sheet which was renewed after unloading for micrometer measurements used to calculate the strains.

Jan 1, 1970

By R. J. Fruehan

The oxygen activity and concentration were measured in Fe-Cr-0 melts in equilibrium with an oxide phase at 1600°C (2912°F). The activity was determined by ,use of the following solid oxide -electrolyte galvanic cell CY-Cr8,(s) I ZrOz(CaO) I Fe-CY-G(saturated)(l) The oxygen concentration decreases with increasing Cr concentration to about 270 ppm 0 at about 7pct CY and then increases gradually. The activity coefficient of oxygen (fo) decreases with increasing Cr. In melts containing up to about 20 pct Cr, log f is approximately a linear function of wt pct Cr with a slope (e q 2) of —0.037. The activity of chromium was calculated and found to exhibit a small negative deviation from Raoult&apos;s law. From the activity and solubility data for low chromium melts, the free energy of formation of chromite, FeCr204, was found to be -79.8kcal per mole where pure liquid chromium and oxygen at I wt pct in Fe are the standard states. ThE effect of chromium on the chemical behavior of dissolved oxygen in liquid iron is of great importance in controlling the deoxidation of steels containing a significant amount of chromium. Chen and chipman&apos; equilibrated Fe-Cr melts in the presence and absence of slag with hydrogen-water vapor mixtures. They concluded that at 1595°C chromite was the oxide phase in equilibrium with Fe-Cr alloys containing less than 5.5 pct Cr while at higher chromium concentration Cr,O, was the stable phase. In the composition range 0 to 10 pct Cr they found that the interaction coefficient, was equal to -0.041. Turk-dogan,&apos; Schenck and Steinmetz,, and pargeter4 measured egr) in a similar manner and found the value to be -0.064,-0.04, and -0.052, respectively. McLean and Be11 evaluated egr) from their data on the equilibrium of Fe-Cr-Al-0 alloys with H2/H20 mixtures and found it to be -0.058. However, McLean and Bell&apos;s value should only be considered an estimate because the effect of aluminum on the activity coefficient of oxygen is about a hundred times greater than that of chromium. Consequently, an error in the value of egl) used, which at the present time is not well-known, or an error in aluminum analysis, which is present in very small quantities, will result in a significant error in egr). Fischer et a1.6 determined the interaction coefficient (eEr) in Fe-Cr-0 melts not in equilibrium with an oxide phase and containing less than 18 wt pct Cr at 1600°C electrochemically. They determined a value of -0.031 for egr). Hilty et aL7 measured the oxygen content of Fe-Cr melts in equilibrium with an oxide phase containing up to 50 pct Cr. They found that the solubility of oxygen decreased as the chromium content increased to about 6 pct Cr and then increased gradually. They concluded that the equilibrium oxide phase was chromite below 3 pct Cr, distorted spinel from 3 to 9 pct Cr, and Cr,04 above 9 pct Cr. Adachi and lwamotoa also investigated this system, but did not find Cr30,. They X-rayed the equilibrium oxide phases and did not find the presence of Cr,O,. They also X-rayed the oxide phase extracted from a 65 pct Cr melt which was heat treated and did not find metallic chromium as would be expected if Cr3O4 were the equilibrium oxide phase as indicated by the reaction : 3Cr3O4 — 4Cr2O:, + Cr [lj It was the purpose of the present investigation to determine the effect of chromium on the activity coefficient of oxygen in Fe-Cr melts by measuring the activity and solubility of oxygen equilibrated with an oxide phase in the composition range 0.18 to 50.5 wt pct Cr at 1600°C (2912°F). The activity of oxygen in the melts was determined by use of the following galvanic cell: The relationship between the partial pressure of oxygen in equilibrium with the melt and the reversible electromotive force of the cell (E) is where 11 = 4, F is the Faraday constant, pb, is the oxygen pressure in equilibrium with the meit and is the oxygen pressure in equilibrium with Cr203 as determined from the free energy data compiled by Elliott et al? The oxide phase in equilibrium with pure chromium was assumed to be Cr If Cr30, were the equilibrium phase the activities derived would be approximately the same, since the best estimated free energy of formation of Cr,O,, if it does exist, is approximately % the free energy of formation of The activity of chromium in Fe-Cr alloys at 1600° C was also determined from the measured electromotive force. The activity of chromium (aCr) is related to the electromotive force as follows: , The oxide phase in equilibrium with pure chromium and Fe-Cr melts from 10 to 52 pct is assumed to be Cr203 so that n equals three. If future work proves the existence of Crs04 in equilibrium with Fe-Cr melts and pure chromium, the experimental results can be reevaluated using a value of $ for n in Eq. 141. A value of ^ for n will make the activities about 10 pct higher. In order for Eqs. 131 and [4J to be valid the electrolyte, ZrOa(CaO), must exhibit predominantly ionic conduction at the temperature and oxygen partial pressure of its use. Previous work1&apos; has demonstrated that ZrOz(Ca0) is predonlinantly an ionic conductor

Jan 1, 1970

By C. D. Williams, C. E. Ells

The susceptibility of quenched and aged Zr-2.5 wt pct Nb alloy to embritt2ement during irradiation has been examined for a number of solution temperatures and aging times. Material quenched from temperatures approximately 40°C below the transus has high tensile ductility, and this ductility is insensitive to aging at 500°C or to irradiation. If, however, the material is quenched from temperatures above the transus it becomes highly susceptible to loss of ductility either from aging at 500 or from irradiation. Inter granular failure is characteristic of the materials having low ductility. The distribution of the equilibrium phase is found to control the susceptibility to embrittlement by restricting 6 grain growth during heat treatment and thus influencing crack propagation. IN zirconium, as in titanium, -stabilizing alloy additions are used to obtain high strengths via quench and age heat treatments, and the Zr-2.5 pct Nb alloy has been developed1 because of its strength advantage over the Zircaloys. Early in the development of the Zr-2.5 pct Nb alloy the problem of 13 embrittlement was appreciated, and for this reason the solution temperature was chosen below the p transus.&apos; In the course of irradiation studies on quenched and aged Zr-2.5 wt pct Nb alloy it was found&apos; that irradiation introduced an important aspect of p embrittlement, riz., material quenched from the phase and aged 24 hr at 500°C was severely embrittled by moderate doses of neutron irradiation. This effect had not been studied in titanium alloys. In titanium the metallurgical features leading to 0 ernbrittlement were found to be structures with: a) coarse a platelets at the grain bondaries, b) finely dispersed a uniformly distributed throughout the (0) matrix,6 c) Widmanstatten a-13 with more than 50 pct P, d) the presence of some metastable p transformation products,3 and e) large prior -phase grain size.5 Alternatively, the presence of a uniform distribution of coarse a was conducive to high ductility and a structure largely of equiaxed a was very dctile. The detailed mechanisms of the embrittlement have not been worked out for all of these conditions, although weakness at either a-matrix boundaries or prior p grain boundaries have been prominent in the eculation. It was proposed that acicular a might act as a mild notch, and low ductility has been associated with easy fracture along its boundary.&apos; There have been two opposing suggestions for the source of the high ductility associated with equiaxed a phase. JaffeeB proposed that this a would accept a large por- tion of the oxygen, thus increasing the ductility of the matrix, whereas after study of a Zr-Nb-Cu alloy Weinstein and oltz proposed that the a phase, softer than the martensitic matrix, acted to blunt cracks formed in the matrix. In the present work we have studied the effect of neutron irradiation on the ductility, particularly the P embrittlement, of the Zr-2.5 wt pct Nb alloy. By a variation of solution temperature and aging time a variety of metallurgical conditions have been examined, and a range of resultant ductilities obtained. The ductility has been related to the material microstructure and mode of fracture. EXPERIMENTAL The alloy used in the present work came from two separate ingots fabricated into rod of 3/8 or i in. diam, Table I. For both batches the P transus temperature was approximately 890° C. Most of the heat treatments were done directly on lengths of the j} in. diam rod, after which the tensile test specimens were machined. Quenching was achieved by dropping rods from a dynamic vacuum into water, the cooling rate estimated to be 2 100°C per sec. For aging the rods were encapsulated in evacuated silica tubes. Round tensile test specimens, with gage diam and length 0.160 and 1.0 in., respectively, were used throughout and pulled at room temperature or 300°C on Instron tensile machines, at a crosshead speed of 0.05 ipm. Specimens were irradiated in the NRX and NRU reactors, in facilities described in previous publications.&apos;0 The metallurgical conditions examined have been: All tensile test specimens were machined with axes in the axial direction of the swaged rod. Although the specimen had a degree of preferred crystallo-graphic orientation with basal plane normals both parallel with and perpendicular to the tensile axis, the material was comparatively isotropic." The techniques of thin foil examination in the electron micro-

Jan 1, 1970