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By E. Buehler, R. H. Willens

A Hew melting technique has hem adapted to the rapid quenching of- alloys from the liquid state. The inelting method has no limitations on the alloys investigated for there is no reaction with crucible materials and the most refractory materials are easily melted. The vate of heating is so rapid that alloys which have a high vapor pressure constituent can be melted with a minimal loss in material. Several new superconductovs have been discoveved by vapid quenching of lolten alloys. THE rapid quenching of alloys from the liquid state has led to the discovery of many new metastable phases. The methods initially used were limited to alloys which did not react with crucible materials.1,2 There was also the unmentioned limitation in tem- perature. Alloys with melting points much greater than 2000°C could not be melted in the rapid-quench apparatus. Recently, there have been successful attempts to rapidly quench reactive alloys by Moss et at. and Matthias Moss et al. injected powdered material (325 mesh) into a high-temperature plasma and the high-velocity molten droplets impinged on a cooled copper plate. The technique innovated by Matthias was to melt the alloy in an arc furnace and splatter it against a copper plate by means of a high-velocity gas jet aimed at the melt. I) FAST COOLING APPARATUS The creation of a metastable phase in a given alloy system by rapid cooling from the melt is contingent on the quenching rate. Some alloys require very slow rates while other alloys require the ultimate in quenching rate. At the present time, the vertical-gun technique of Duwez and willens' has demonstrated, in practice, the highest quenching rates and thus the best

Jan 1, 1967

By K. L. Komarek, P. F. J. Landler

Synthetic polycrystals of wustite were reduced ilz H2-H2O mixtures over limited roncentration ranges wiltun the wustite. field and the weight changes were continuously followed with a McBain quartz spiral balance. The reduction was. found to be controlled by a combined surface plus solid-state diffusion reaction. The solid-state diffusion had an activation energy of 38 kcal. Self--diflusioities of iron decreased with itzcreasing vacancy concentration. The activation energy of. the surface reaction runs different tor- different samples. The surface reaction-rate constan increased with increasirzg vacancy concentration. THE reduction of the oxides of iron has been studied for many years. Edstroem' has summarized the early work and has provided much information on the reduction of magnetite and hematite by hydrogen and carbon monoxide. More recent summaries are those by smeltzer2 and Themelis and Gauvin.3 Most investigators have reported that the iron metal which forms the outer layer during gaseous reduction is rather porous. According to Kohl and Engel14 the formation of such a porous iron layer depends on the properties of the underlying wiistite layer, on the reaction of the gas with the wustite surface, and on the transport of matter through the wustite layer. McKewan, Quets, Wadsworth, and Lewis, and Knacke 10 have found that, if a porous iron layer is formed, a surface reaction between gas and wustite at the bottom of the pores controls the rate of reaction. Seth and ROSS 11 and Warner 12 have pointed out that the influence of the gaseous pore diffusion through the porous iron layer cannot be neglected. It has further been shown that the wiistite layer formed during reduction is dense and that transport of matter across the layer occurs only by solid-state diffusion of iron ions.13,14 The solid-state diffusion rates observed by Edstroem and Bitsianis 14 and the surface reaction rates observed by Quets eta1.' show that an interaction of the two steps in controlling the reaction rate has to be considered. In this investigation the reduction of wustite was studied with respect to the interaction of the two steps, isolated from any other effects, by reducing wustite within the wustite field from higher to lower oxygen concentrations with H2-H2O gas mixtures. A similar study with CO-CO2 mixtures has been performed by Levin and wagner.15 Fused synthetic wustite polycrystals were reduced in steps of 0.4 wt pct from 24.4 to 23.2 wt pct 0 and over a temperature range from 700" to 1050°C. A few tests were also conducted with reduction steps from 24.4 to 23.6 wt pct 0 and 24.5 to 23.2 wtpct0. The Fe-O phase diagram is shown in Fig. 1 where the composition of the gas phase in equilibrium with the condensed phases is plotted as pct H2 vs the temperature. A careful study of the literature led to the conclusion that the fully drawn equicomposition curves (in wt pct O) in the wustite field used by Edstroem 1,16 and other authors needed some correction. Based on results by Darken and Gurry17 (shown as open circles) and on some of our own data, four corrected curves for 23.2, 23.6, 24.0, and 24.4 wt pct O were calculated (drawn as dashed lines in Fig. 1) which should replace the fully drawn equicomposition curves. MATERIALS AND APPARATUS Materials and Specimen Preparation. Wustite was prepared from iron sulfate (Fisher Scientific Co., New York) which had a purity of over 99.92 pct, with small amounts of manganese, copper, and zinc adding up to 0.03 pct. From the aqueous solution iron oxalate was precipitated and decomposed to magnetite according to Economos. 18 The magnetite powder was pressed into cylinders and sintered in vacuum at 900°C for several hours. The sintered compacts were placed in a platinum crucible of 2.5 cm diam which was fitted into a high-purity alumina crucible and then inserted into the center of the graphite heating element of an electric resistance furnace.lg The furnace was evacuated to below 1 p Hg and the magnetite sample was slowly heated. The evolution of gases during heating deter-

Jan 1, 1967

By H. M. Davis, T. S. Jones

A methodfor accelerating the reduction of a metal oxide by carbon monoxide is to incorporate in the reduction system a nonreducible oxide which has a strong affinity for carbon dioxide and will remove it from the product gases. The effectiveness of this method was investigated by veduction experiments on specially prepared powder mixtures of SrO-ZnO ("active'.) and SrCO3-ZnO (reference). Measurements at 750o and 677°C showed that the rate of reduction of ZnO by CO was as much as an order of magnitude greater in the presence of SrO. Under the experimental conditions at least as much CO2 as generated by veduction was absorbed when SrO was present. Enlzancernent of the veduction rate by SvO resulted from modification of' gaseous djfitsion processes. THE specific question posed in this investigation was whether the reduction reaction CO + ZnO - Zn(g) + COa [1] could be accelerated by incorporating strontium oxide into the oxide charge undergoing reduction. Provided the strontium oxide was active enough, it could remove carbon dioxide from the product gases of ( 11 and form strontium carbonate, thus modifying Reaction [ 1] to CO + ZnO + SrO = Zn(g) + SrCO3 [ 2] This study of the comparative rates of Reactions [ I] and [2] can be considered as a particular case of a general scheme for increasing the rates of reduction of metal oxides by carbon monoxide. The limits of applicability of this scheme are indicated in the simple thermodynamic analysis presented in the appendix. This analysis primarily dictated the choice of the system, CO-ZnO-SrO, employed in this investigation. In addition, it was thought that a study of this scheme by use of the CO-ZnO-SrO reaction system would be of special interest in view of indications in the literature1-3 that the gaseous reduction of zinc oxide is prone to rate control by diffusion in the gas phase. The distinction should be pointed out between this and other efforts to increase the rates of reduction reactions through the use of addition agents. Additions of a wide range of chemicals have been tried with de- grees of apparent success varying from slightly negative to highly positive. The reasons for making additions have included the use of salts to produce effects akin to catalysis,4, 5 the alteration of the microstruc-tural details of the reduction process (including solid-state diffusion),6-8 and the conversion of an en-dothermic reaction into one that is exothermic or autogenous.9-12 The means used to attempt alteration of the enthalpy change has commonly been to incorporate lime into the charge, so that heat is generated by reaction with either of the reaction products, carbon dioxide or water. The use of lime in this way makes endeavors such as that of Edstrom and Wiberg similar to the present one. Furthermore, the basic principle behind the present work has previously been set forth.13 However, a detailed investigation of the type of reaction described in this work does not appear to have been conducted. EXPERIMENTAL PROCEDURE From both conceptual and physical standpoints, Reaction [2] is to be considered as the sum of two reactions:

Jan 1, 1968

By J. R. Mihalisin

Phase changes in as-cast alloys in the Ni2 CoCr-Ni, Ti-NSAl system containing 0.1 wt pct C were studied after heat treatment at 1650°F. It was found that a vegion of CrCo-type s was developed in this system after I1000 hr. The tendency for s formation was dePendent upon the aluminum and litanium content, the s -forming tendency generally becoming more pro-nounced as the latter two elements are increased. s lended to form in interdendritic regioues and was associated with solutioning- of- carbide phases. Electron- vacancy computations for prediction of s formation on these alloys mere in sufficient agreement with what was observed experimentally to indicate that the method should be of value in assessing a-forming potential in cast alloys. However, the correlation of electrotz- vacancy numbers may not be as favorable in cast as cormpared to wrought alloys. THE increasing use of high-temperature alloys for longer times at higher temperatures has resulted in a real need for obtaining information on the phase changes taking place in these alloys since these changes often have a direct effect on properties. This paper reports on a study of the phase changes in Ni-Cr-Co-Al-Ti alloys after prolonged heating at 1650°F. The alloys were selected from the pseudo-ternary system Ni2CoCr-Ni3Ti-Ni3Al and this system was chosen because it is the basis of many of the newer cast commercial superalloys. The attempt here was not to define accurately the boundaries of s formation in the NizCoCr-Ni3Ti-Ni3Al system but to delineate the phase transformations taking place upon heating alloys covering a wide range of chemistries in this system. An addition of carbon was made to all alloys to further simulate commercial alloys. It was hoped that the information generated in this manner would be of more direct use to superalloy designers than an equilibrium diagram approach since commercial alloys generally have outlived their usefulness when equilibrium is attained. EXPERIMENTAL PROCEDURE The alloys were vacuum-melted from carbonyl-nickel pellet, vacuum-grade chromium, electrolytic cobalt, high-purity aluminum and titanium, and spec-trographic-grade carbon.

Jan 1, 1968

By W. N. Miner, R. O. Elliott

Electrical-resistivity )measurments were made be-trueetz room temperatrive and 1.5 oK on five different stocks of cerium metal, and the results were correlated with the types, amounts, and distribution of the impurities present. Magnesium, which appeared to be distributed as a solute throughout the cerium matrix, was found to have a large effect on the residual resistivity, 1 at. pct Mg being sufficient to increase the residual resistivity by about 10 microhm-cm. The formation of ß by repeated thermal cycling between room temperature and liquid-helium temperature is attributed to the deformation and faulting that occurs during the ? D a transformation. In preparation for starting a proposed study of cerium-rich alloys, we examined samples from severa1 stocks of cerium metal in order to choose the purest stock for future use in making the alloys. Low-temperature electrical-resistivity data were used to gain initial information about the purities of the stocks. Additional information was subsequently obtained from chemical analyses, density measurements, optical metallography, and electron-micro-probe analyses. Cerium that has been annealed at high temperature and cooled to room temperature has the fee crystal structure (? phase) with a = 5.16Å. When cooled further, in the region between about 250" and 150°K, some of the fee phase transforms to the double hcp form (ß phase) with a = 3.68 and c = 11.92Å. The remainder of the room-temperature fee form (and perhaps some of the hexagonal phase) transforms electronically in the vicinity of 100° K to the more dense or "collapsed" fee form (a phase), a - 4.85A, by transferring about 0.5 electron per atom from the 4f level to the valence band. Very little work related specifically to the effects of impurities on the physical properties of cerium has been reported in the literature. Gaume-Mahn1, 2 has studied the effects of calcium, magnesium. iron, silicon, and tantalum on the electrical resistivity and magnetic susceptibility of cerium between 60o and 300°K. Gschneidner, Elliott, and McDonald3 have discussed the effects of total impurity content on the hysteresis of the a —? (reversible) transformation and on the formation of the 4 and "a-? intermediate" phases. Smith and Morrice* have reported the effect of total impurity content on the resistivity of cerium at 4 and 293°K. In none of these reports, however, is it apparent that the distributions of the impurities were determined, L.r., whether the impurities were present in inclusions or in solid solution in the matrix is not mentioned; nor does it appear that the phase purity of the cerium was always considered. In the present study, five different stocks of cerium were involved. One was represented by a single sample of electrowon cerium, which was all that had remained from a stock of high-purity material obtained from the U.S. Bureau of Mines, Reno, Nev., in 1959. The other four stocks were recently purchased from commercial sources and were specified to be 99.9 wt pct pure. EXPERIMENTAL Cerium stocks designated as #1, #2, #4, and #5 were obtained from commercial suppliers for the specific purpose of finding a reliable source of high-purity cerium. Although the purity level of the cerium was specified to be 99.9 pet, the specifications did not include limits as to the amounts of various impurities that would be acceptable. Consequently the chemical analyses of the different stocks varied widely. Stock #3, which had been obtained from the U.S. Bureau of Mines and which was the purest on the basis of chemical analyses, consisted of a single specimen of electrowon cerium. It was included in the examination for purposes of comparison. Table I contains the chemical and spectrographic-

Jan 1, 1968

Jan 1, 1967

Jan 1, 1968

By J. L. Swedlow, M. L. Williams

Two standard techniques for assessing fracture initiatlon in sheet specimens involve measurements of 1) the applied load of fracture which, via linear fuacture mechanics, is used to find the fracture tough/less SC (or SIC), and 2) the velative displacement of fracture of the opposite free faces of the crack (COD). In the past, the quantitative association between these two parameters has not been determined in detail, owing to the mathematical difficulties of computing. the stress and strain fields in the combined elasto-plastic flow near the crack. Using a numerical technique Irecently developed and applied to a 7075- TO' aluminum plane stress specimern, the two parameters noted have been determined and associated quantitatirely. CONSIDERABLE effort has been expended in selecting a rigorous yet practical manner for predicting fracture. The usual point of departure is the modified Griffith criterion in which the mechanism of energy dissipation is reflected in Sc (or SIC), the parameter of "fracture toughness". Sc. differs from the surface energy used by Griffith in perfectly brittle fracture in that it includes the effect of plastic flow in the vicinity of the crack tip. Because plastic flow alters the stresses and displacements predicted from the usual linear theory of fracture mechanics, and because analysis of the nonlinear stress-strain field has presented great obstacles: only estimates of several pertinent quantities have heretofore been available. Nevertheless, two parameters have often been measured experimentally althougll usually just at the point of fracture. These are the energy release rate, or fracture toughness 9, (or I,), and the crack-opening displacement (COD). Such observations have been used in connection with frarture criteria and have been most helpful in design, although their application requires care with respect to changes in geometrical configuration from that upon which the criteria were based 1,2 Recently, however, a reasonably accurate and comprehensive method for analyzing the elasto-plastic flow has been devised and applied to plane stress specimens having arbitrary octahedral stress-strain curves.3 It thus becomes feasible to compute, albeit numerically, both the fracture toughness and crack opening as functions of the applied tensile loading on a typical specimen geometry. As a result, it is now possible to associate these two parameters quantitatively, and thereby to associate data obtained by one method with data pertaining to the other. ELASTIC ANALYSIS For the case of linear elasticity, it is relatively easy to deduce the connection between various measures of crack deformation. Using, for example, the singularity analysis, it is found that the leading term of the Airy stress function x f°r symmetrically applied loadings on an isotropic medium is

Jan 1, 1968

By I. S. Levy, J. L. Brimhall, B. Mastel

Specimens of' Hastelloy X-280, a low-cobalt version of the solid-solution- hardened nickel-base alloy Hastelloy X, were given a series of thermomechanical treatttzents. They were then Lensile-tested at room temperature and 1350°F. The Microstructures of the specimens tested at 1350°F were studied by electron Microscopy. Microscopy showed that dislocation tangling, caused by the cold working, mas still in evidence after aging-for 24 hr to temperatures as high as 1550oF. (Cr, Mo)23 C6, (Fe, Mo)6 C'. as well us an unidentifiable phase precipitale due to the combination of the thermomechanical treatments and subsequent tensile strain. The room -temperature and 1350°F tensile properties show a general increase ill strength and decreccse in ductility with increusing cold-work level. This is due to the dislocation taangling-. PerLurbatiot~s to this general trend occur- due to solid-solution weakening at the higher cold-work levels as a direct result of the preciplitation reactions. THE requirements for corrosion resistance and high-temperature strength place nickel-base alloys among the more promising materials for advanced nuclear reactor applications. However, when these alloys are irradiated at service temperatures, they generally suffer severe embrittlement'" and reduction in rupture life.3 Certain experimental treatments resulted in improvements in the tensile and stress-rupture properties of Hastelloy X-280, a solution-hardened nickel-base alloy.' To provide a basis for understanding these improvements, unirradiated tensile specimens were examined by electron microscopy. The results are reported in this paper. EXPERIMENTAL DETAILS Material. Hastelloy X-280, a low-cobalt version of Hastelloy X, is a member of the solution-hardened class of nickel-base alloys. The Hastelloy X-280 was obtained from 4- and 1-in: thick plates in the mill -annealed condition. Table I gives the chemical composition of the material as reported by the National Spectrographic Laboratories. ~x~erimental Treatments. Plates of suitable size, 12 by 3 by 1 in., or by + in., were cut under a water jet from the stock material and examined ultrasonic -ally for homogeneity of grain size and absence of voids. The acceptable plates were solution-treated at 2150°Ffor 1 hr and air-cooled. These plates were then reduced in thickness by cold rolling 0, 10, 15: or 20 pct along the original rolling direction. The plates were machined into buttonhead tensile specimens with a gage diameter of 0.125 in., with a gage length of 1.125 in., and with their tensile axes parallel to the rolling direction. The specimens were examined for quality of finish with a penetrant dye, ultra son ically checked for voids, and finally given a dimensional tolerance check with an optical comparator. The acceptable specimens were aged for 24 hr at either 1000" or 1500 F and air-cooled. These specimens were then held at 540°F in a water loop for approximately 18 days to qualify as controls for similar specimens irradiated under the same conditions of time, temperature, water chemistry, and flow rate. Table U summarizes the treatments. These treatments were investigated to establish whether prior precipitation and stabilization of carbide phases at strain sites within the matrix could reduce the amount of carbides available for precipitation at grain boundaries during service. Tensile-Test Conditions. Specimens were tested to fracture at room temperature or 1350 F in air on an Instron tensile-testing machine at a crosshead speed of 0.05 in. per min. The time for the furnace to reach equilibrium at 1350°F was approximately 30 min; soak time prior to testing was 15 min; and test duration was approximately 5 min.

Jan 1, 1968

By Robert E. Green, Edmund G. Henneke

Expressions are derived for the orientation factors associated with dislocation damping due to dislocation motion in the basal slip plane. The results of the calculation of these factors for zinc crystals aye pvesepzted and the relevance of these results to ultvasonic-attenuation measuvements is discussed. In this paper expressions are derived for the orientation factors associated with damping of sound waves due to dislocation motion in the basal slip plane of hexagonal crystals. For zinc crystals, the orientation factors for dislocation motion in one slip direction only, as well as for simultaneous motion in all three basal slip directions, have been calculated at 1-deg intervals. The results of these calculations are presented in the form of contour diagrams in a sector of a standard polar coordinate graph. The calculations have been carried out for both the traveling- and the standing-wave conditions. The relevance of these results to ultra sonic-attenuation measurements is discussed. Associated with the calculation of the orientation factors, the modes of elastic-wave calculation were also evaluated, according to the procedure previously employed by Hinton and Green.' The results of these calculations are not presented here since similar results have been reported earlier by Mus-grave.2 However, it should be mentioned that, although the qualitative features of Musgrave's results are preserved, the quantitative values are somewhat altered since different values for the elastic constants of zinc were used. ORIENTATION FACTORS It is convenient to refer to three different sets of coordinate axes, Fig. 1, in the following calculations. First, there are the Miller-Bravais axes which are used in describing the Miller-Bravais indices of planes and directions in a hexagonal crystal. These axes are denoted in the conventional manner by a,, a,, a,, and c. The second set of axes used is a rectangular Cartesian coordinate system located as shown in Fig. 1. Note that the x axis coincides with the close-packed direction al [2110], the z axis coincides with the c axis [0001], and the y axis is orthogonal to these two lying in the [0110 ] direction. Finally, a form of Eulerian angles is used to locate the position of the specimen axis. The angle between the specimen axis and the c axis is denoted by 0 and the angle between the projection of the specimen axis on the basal plane and the a, direction is denoted by ø. The majority of observations on plastic deformation of metal crystals indicates that such deformation is caused by the motion of dislocations on a limited number of crystalline planes and in a close-packed direction. In crystals with hexagonal symmetry the most prominent slip plane is the basal plane (0001) and the slip directiops- are one of the close-packed directions, [2110], [ 12101, or [ 1120]. To properly set the stage for the following work, several points must be clarified. First, we want to consider the contribution to the attenuation of elastic waves by dislocations only. While the Granato-Lucke, model for dislocation damping is presently the one most quoted, it is not necessary to refer the present work to it. The only assumption that need be made is that the motion of dislocations absorbs energy from the elastic wave and therefore attenuates it. It is immaterial here how this energy absorption occurs. However, because dislocations have been observed to move most freely on the (0001) plane for hexagonal crystals undergoing plastic deformation, it will be assumed that it is the dislocation motion on this plane which attributes to the observed attenuation. The basic orientation factor, Ok, is essentially the same as that used by Green and Hinton for fee crystals,4 defined by the equation

Jan 1, 1968

By H. C. Fiedler

The solubility of sulfur in Si-Fe was determined by the metallographic examination of heat-treated and quenched samples. In the absence of manganese, the solubility in 3.1 pct Si-Fe was found to be about 0.010 pct at 1000o C, 0.015 pct at 11000C, and 0.020 pct at 1150°C, which is substatntially less than hitherto reported. Increasing the silicon content was found to decrease the solubility of sulfur, which is consistent with the increase in the activity coefficient of sulfur with increasing silicon content that has been reported for Fe-Si alloys. Manganese additions were studied in alloys containing 3.1 pct Si and between 0.013 and 0.015 pct S. At low manganese levels the solubility product of manganese sulfide was found to be lower than previously reported. THE solubility of sulfur in pure polycrystalline iron has been reported by Rosenquist and Dunicz1 and by Turkdogan et al.2 Samples were equilibrated in atmospheres containing different ratios of H2S/H2. Both groups of investigators found a solubility limit in y iron of 0.013 pct at 1000oC and 0.031 pct at 1200°C. In addition, Rosenquist and Dunicz1 found a solubility limit in a iron of 0.020 pct at 900°C. Ainslie, Hoffman, and seybolt3 found significantly higher sulfur contents in polycrystalline iron samples than in single-crystal samples after heating at 890°C in a sealed tube containing a mixture of powdered iron and FeS made with s35. Whereas the single crystals contained 0.013 and 0.016 pct S (± 0.005 pct), the polycrystalline samples contained between 0.016 and 0.026 pct S. Autoradiographs suggested that the excess sulfur in the polycrystalline samples was due to the segregation of sulfur in solution at grain boundaries. Ainslie and seybolt4 have reported on the solubility of sulfur in 3 pct Si-Fe. Their samples were sealed in capsules containing hydrogen and sufficient sulfur as cobalt sulfide to saturate the sample. After heat treating, the sulfur-rich phase on the surface was removed by abrading, and the sulfur content of the sample was taken as the equilibrium value for that temperature. Before the equilibrating heat treatment, the samples were heated to 1300°C to coarsen the grains. The resulting grain size, which was about 3/18 in. in diam, was considered sufficiently large to preclude a sensible increase in sulfur solubility due to grain boundary segregation. They reported the solubility to be 0.029 pct at 900oC, 0.063 pct at 1000oC, 0.076 pct at 1100°C, 0.122 pct at 1200°C, and 0.098 pct at 1300°C.

Jan 1, 1968

By J. N. Maycock, P. W. M. Jacobs

Previous measurements of the thermoelectric power of ionic crystals are reviewed briefly. It is concluded that, while extensive measurerements are available on systems in which the electrode M has a cation in cornon with the sall MX, there is as yet little modern work on systems in which the metal electrode M' does not haue a calion in common with the salt. We haue now measured the thermoelectric power of- single cryslals of KC1 and of KC1 + SrCl2 between plati.nu?n electrodes over a much wider range of temperature than before. individual ionic heats of transport, which, while probably not very accurate, are of a reasonable order of magnitude, are obtained from this data on the basis of an assumption that charge carriers do not cross the electrode/salt interface. RELATIVELY little work has been done on thermal diffusion in ionic crystals. Reinhold and coworkers1-I measured the thermoelectric power and Soret effect in silver and cuprous salts and their mixed crystals. One electrode was kept at constant temperature and electromotive force was measured as a function of the temperature gradient. This is not a satisfactory technique if the results are to be compared with theory; rather should the electromotive force be measured for small temperature differences as a function of the mean temperature of the two electrodes. They used electrodes having the same cation as the salt. Patrick and Lawsons measured the thermoelectric power of AgBr and of AgBr containing 0.25 mole pct CdBr2 using silver electrodes and temperature gradients of 10°C in the temperature range 100° to 400°C. The results were analyzed using the Teltow9 values of the ratio of the mobility of the two types of charge carrier (cation vacancies and interstitials) found from conductance measurements and the wagnerlo estimate of the heterogeneous contribution to the thermopower, Ohet They obtained values of qi = 0.017 ev and q$ = -0.385 ev for the heats of transport of interstitial Ag ions and cation vacancies, respectively. Their data has been reanalyzed by Haga using the corrections to the Wagner formula for ehet given by Howard andLidiard; Haga found ev. Christy et a1.14 have measured the thermopower of AgBr containing 0.01 to 1.0 mole pct CdBr,. They analyzed their results in terms of the theory of Howard and Lidiard and found that excellent agreement with the theory was obtained if q5 + : + hF was set equal to 0.70 ev at 175°C and equal to 0.58 ev at 250°C. Since Teltow's value for hF, the enthalpy of formation of a Frenkel defect pair, is 1.27 ev, this means that qt + q: increases in magnitude from -0.57 ev at 175°C to -0.69 ev at 250°C. This result is in poor agreement with Patrick and Lawson's value of -0.37 ev for pure AgBr (for which the corrections to the Wagner estimate for ehet are very small). christy1' has also reported thermopower measurements for pure silver halides and for the systems he finds that qr + qt for AgBr increases in magnitude from about -0.55 ev at 150°C to about -1.1 ev at 400°C. The temperature dependence of the sum of the heats of transport in AgCl is very similar in magnitude. The sum qi + q cannot be decomposed into the individual interstitial and vacancy heats of transport without a knowledge of the entropy contribution from the change in the lattice vibrational frequencies around the interstitial and vacancy. Despite this it seems an inescapable conclusion from Christy's analysis that and -6 = Q Ag are quite strongly temperature-de pendent and that -q: is much greater in magnitude than the corresponding activation energy for vacancy migration, +0.37 ev. It remains a mystery as to why the data for pure AgBr are fitted so well by the assumption of temperature-independent heats of transport if association of impurity ions and vacancies is neglected.l The values for q$ and q: so obtained are also much more in line with those expected from a simple kinetic interpretation of the heats of transport due to wirtz.17 Christy and Hsueh have also measured the thermopower of CuCl between copper electrodes; 0 for pure CuCl is comparable with that for the silver halides but, owing to the limited solubility of divalent cation impurities it was not found possible to deduce values for the heats of transport. In contrast to these extensive measurements on cells of the type M MX 1 M, there have been relatively few attempts to measure the thermoelectric power of cells of the form M' 1 MX I M'. (We specifically exclude from discussion cells of this type in which the metal electrodes M' are in contact with gas containing a controlled partial pressure of either M or X,, since in these cells the electrochemical reactions are analogous to those of the first type.) The thermoelectric power of Pb12, PbC12, TlC1, TlBr, TlI, NaNO3, and KNO 3 between platinum electrodes was measured by Thie1e.l3 In discussing these measurements Holtan20 asserts that the thermopotential initially fluctuated wildly and even changed sign before approaching a steady value. A high degree of irreproducibility is also evident in the work of Nikitinskaya and Murin21 who first studied the thermopower of NaCl and KC1 between platinum electrodes. Much better reproduci-bility was achieved in our earlier measurements on KC1;22 these were, however, confined to a relatively narrow temperature range and one of the objects of the work reported in this paper was to extend the temperature range of the measurements of the thermoelectric power 8 of KC1. The only other published

Jan 1, 1967

By M. A. Quader, D. Kuhlmann-Wilsdorf, R. A. Dodd

STACKING fault tetrahedra were first observed in quenched and aged pure gold by Silcox and Hirsch1 and identified as defects originating in the collapse of vacancy discs on {111} planes. It was supposed that sessile loops are the first product of the collapse, and that by a dislocation dissociation/glide sequence these are converted into tetrahedra. Although the tetrahedra can be mechanistically accounted for in this way, recent investigations indicate that their growth occurs by the absorption of individual vacancies on small nuclei involving perhaps as few as six vacancies.2-7 Besides stacking fault tetrahedra, triangular and crystallographic shaped Frank loops, although fewer in number, have always been observed in quenched and aged gold.19798 It is not known definitely whether these loops form from collapsed tetrahedra. The fact that the Frank loops are usually larger than the accompanying tetrahedra might indicate that the loops grow independently by absorbing vacancies, but this does not rule out the possibility of the collapse of tetrahedra into loops under all circumstances. Silcox and Hirsch1 have actually observed under the electron microscope tetrahedra collapsing into loops, probably due to stresses set up by the heating of the specimen by the electron beam. The energy residing in the stacking faults of a tetrahedron is proportional to the square of the edge length, while the energy of a triangular perfect dislocation loop depends on its edge length, L, as const L ln(L/ro). Therefore, beyond some critical size tetrahedra must become unstable with respect to collapse into triangular loops.1,3,8-11 However, it seems that in the absence of strong stresses tetrahedra usually decay by the

Jan 1, 1969

By S. W. Zehr, G. S. Murty, W. A. Backofen

AN observation by Squires, Weiner, and phillipsl has stimulated interest in a mechanism of deformation at high temperature (above -0.5 of the absolute melting point) that is not usually thought to be involved in the creep of metals. They found precipitate-free or "denuded" zones along grain boundaries normal to the stress axis in tensile specimens of a hydrided Mg-1/2 wt pct Zr alloy after slow straining at 450° and 500°C. Their suggestion that the zones were a result of directional diffusion of magnesium atoms was supported with calculations from Harris and Jones2 which also tended to identify the process as Nabarro-Herring (N-H) creep3,4—a process that is characterized by Newtonian viscosity, with stress (o) directly proportional to strain rate (C), and one that proceeds by lattice diffusion. Material transport by diffusion along grain boundaries is an alternative basis for Newtonian viscosity, as demonstrated by Coble,5 and is favored over N-H creep for fine grain size and lower temperature.6 In either case, the strain rate sensitivity of flow stress, defined as m = d log o/d log E (which commonly appears in the empirical a = KEW), is unity. The experiments to be described here gave metallo-graphic indications of diffusional creep which were no less clear than those just cited, but the associated m (as measured by the method of Ref. 7) was much more like that of a Bingham material. For true Bingham behavior, (a — ao) E, where oo is an initial yield stress. Therefore, even if flow after yielding should occur by diffusional transport, m must increase from 0 as < is raised to reach unity only in the limit as One result is that the resistance to tensile necking conferred by Newtonian viscosity is lost, which would become increasingly apparent through the formation of more sharply defined necks as 6 is lowered. That trend appeared in these experiments. Most of the work was done on an extremely finegrained alloy of magnesium with -6 wt pct Zn and ½ wt pct Zr (Mg ZK60); the initial mean-intercept grain diameter, L, was 0.55 µ. Shown in Fig. l(a) is a germanium-shadowed carbon replica of the surface of a specimen that was coated with silicone oil,* heated to 270°C under a helium atmosphere, and then stretched locally -200 pct at an initial E = 3.3 x 10-5 sec-1. Under

Jan 1, 1969

By H. A. McKinstry, F. F. Lange

A vector analysis of orientating single crystals using the Laue back-reflection X-ray technique is given. Briefly, the analysis involves using a few data taken from a Laue photography and defining the crystal co- ordinate axes in a reference coordinate system. After a few matrix multiplications, the proper goniometer angles can then be determined to orient the crystal coincident with the reference frame. This analysis is easily programed for a digital computer to provide a fast, precise, and efficient method of orienting many crystals which are identical. The general procedure is as follows. The crystal is mounted on a goniometer. Laue photographs are taken until an array of diffraction spots is observed that includes a Laue spot that represents a rotational axis of symmetry. The rotation angles of goniometer are recorded. These angles are defined as positive for a counterclockwise rotation. When the axis of symmetry is located on the Laue photograph, the crystal coordinate axes can be defined in the reference coordinate system* as follows. Two Laue spots are chosen, one of which corresponds to the rotational axis of symmetry and the other to a set of planes whose zone axis is a known crystallographic direction and normal to the rotation axis of symmetry. The Laue spots are used to determine these two crystal directions in the reference coordinate frame. This is done by placing the Laue photograph on a sheet of polar coordinate graph paper and determining the polar coordinates (r, o) of these two diffraction spots in the reference coordinate frame. Their third coordinate is the distance between the crystal and the film (-D). The coordinates Xni of the two crystal directions Nn, (n = 1, 2) in the reference frame are then calculated by the following equations: Xn1 = -D X2n = Ancos on X3n = A, sin on where -tan- 1 rn/D An =Dtan(tan-1rp/D/2) By taking the proper cross products of these two directions (normalized to unit vectors), the crystal coordinate axes 3 (i = 1, 2, 3) can be determined in the reference frame. This is illustrated in Fig. 1. The next step is to determine the relation between

Jan 1, 1969

By R. D. Nelson

The purpose of this technical note is to briefly present some data on a phenomenon—recrystallization with concurrent deformation—that has been found to occur in a plutonium. This phenomenon is unusual because a plutonium is considered brittle, not easily deformed, and not easily recrystallized; the a phase is simple monoclinic having 8 atoms per unit cell and it is stable below about 115°C. The properties of the recrystallized metal were different from the as-cast metal. Even though a plutonium is difficult to deform, Ianniello successfully rolled it&apos; and he also observed some recrystallization at 120°C.2 Pavlick and Hanson3 detected some recovery at 109°C but they observed no recrystallization. Gardner4 and Bronisz5 studied the compression properties up to 100°C but they did not report having seen recrystallization. In the present deformation studies of electrorefined plutonium pronounced recrystallization took place concurrently with plastic deformation in compression between 24" and 115°C. The metal contained less than 300 ppm total impurities with the major impurities being 100 ppm Am, 30 ppm C, 40 ppm W, and 25 ppm U; all other impurities totaled less than 100 ppm. The compression specimens were machined to dimensions of 1.2 cm long and 0.8 cm diam from as-cast rods having a density of 19.65 g per cu cm. They were heated to the test temperature in a high-temperature silicone fluid that was evacuated to 10-4 Torr. With this procedure the specimens oxidized a negligible amount, and the temperature was maintained within ±0.2°C for times up to 3 weeks. Deformation and recrystallization

Jan 1, 1969

By A. E. Dwight, A. F. Berndt

ThE published U-Ru equilibrium diagram indicates the existence of six intermetallic compounds in this system.&apos; The structure of only two of the compounds, u2Ru2,3 and URU3,4 have been identified. This communication reports on the crystal structure and density of Uau3, which is formed by a peritectoid transformation at 1025° ± 5°C: U3Ru4 + U3Ru5 = U2Ru3. An alloy with the stoichiometric formula U2Ru3 was prepared by arc melting electrolytic uranium and ruthenium of 99.9 pct purity on a water-cooled copper hearth under an argon atmosphere. After homo-genization at 1000°C for 3 days, a metallographic examination revealed that the peritectoid transformation was complete and less than 5 pct of a second phase was present. A powdered sample, obtained by crushing the brittle compound, was annealed for 1 hr at 1000°C and air-cooled. Debye-Scherrer patterns were obtained with filtered CrKa, FeKa, CoKa, or CuKa radiation. The X-ray patterns of U2Ru3 weFe indexed as an fcc structure with a. = 12.895 0.00lA. The unit-cell constant and its standard deviation were calculated by a computer program described by Mueller, Heaton, and Miller.5 The density, measured by an immersion method, was 14.45 g cm-3. A calculated density of 14.48 g cm-3 was obtained on the assumption that twenty-four formula units (120 atoms) comprise a unit cell. The space group is either oh7 Fd3m, or the less symmetric, T4h, Fd3, since reflections indexed as hk0 with h + k + 4n are absent. All values of h2 + k2 + 12 permitted by both space groups are listed in Table I together with dc, do, and I. values. The calculated d spacings were obtained by the computer program of Mueller, Meyer, and simonsen.6 The observed d spacings above 0.77A were obtained from X-ray" patterns prepared with CuKa radiation, above 0.90A with CoKa radiaaion, above 0.98A with FeKa radiation, and above 1.16A with CrKa radiation. An attempt was made to identify the crystal structure of U2Ru3 by comparison with published data on other A2B3 compounds. A recent compilation7 of intermetallic compounds lists thirty-two structure types with the A2B3 stoichiometry. Only two of the structure types are fcc and they are Sb2O3(r), senarmontite, with 16 Sb2O3 per unit cell, and In2Te3 for which several structures have been proposed.8 However, the two cases cited do not have twenty-four formula units in the unit cell. We therefore, cannot identify UPRU3 with any of the other known A2B3 compounds. Ternary alloys were made in which 5 at. pct Os, Rh, or A1 were substituted for 5 pct of the Ru in U2Ru3. The osmium substitution increased the unit cell constant to 12.899 * .001A, which is to be expected since the atomic volume of osmium is slightly larger than

Jan 1, 1969

By A. Mitchell, T. Bagshaw

A recent paper by Thomas1 has presented new data on the solubility of hydrogen in solid silver at 1 atm pressure in the temperature range 600° to 963°C. However, no data is reported in the literature on hydrogen solubility in liquid silver. The Sieverts technique which has been described previously2,3 was used in the present work. Charges of approximately 160 g were melted in Morgan "purox" recrystallized alumina crucibles and purified helium was used for the determination of the "hot volume" during each experiment. A chemical analysis of the silver indicates that the impurity content (Cu + Al) is less than 0.02 wt pct. Hydrogen solubility in the temperature range 963° to 1200°C was investigated. The results of three experiments are shown in Table I. Fig. 1 shows an Arrhenius plot of the present work together with the solid-state data of Thomas, Steacie, and johnson,4 Eichenauer et al.,5 and Siegelin et al.6 The following expression has been derived from the Arrhenius plot of the present data: log (solubility of hydrogen, cm3 per 100 g) = 2.154-3512.0/ToK The heat of solution derived from Fig. 1 is 31,150 cal per g mole H2 compared with the value of 33,020 cal per g mole H2 obtained by Thomas and 12,000 cal per g mole H2 obtained from the data of Steacie. It was observed that hydrogen evolution took place when the silver melts were solidified under 1 atm of hydrogen, which would not be expected from an extrapolation of the results of Steacie. Schenck and Lange7 have observed that, for several transition metals at their melting points, the ratio of the hydrogen solubility in the liquid to that in the solid lies in the range 2.1 to 3.1. The present results and those of Thomas are in accord in this respect having a ratio of 2.8. &apos;C. L. Thomas: Trans. TMS-AIME, 1967 vol. 239, pp. 485-96. 2T. Bagshaw and A. Mitchell: I. Iron Steel Inst., 1966, vol. 204, p. 87. &apos;M. Weinstein and J. F. Elliott: Trans. TWS-AIME, 1963, vol. 227, p. 382. &apos;E. W. R. Steacie and F. M. G. Johnson: Proc. Roy. Soc. (London), Ser. A, 1928, vol. 117, pp. 662-79. &apos;W. Eichenauer et al.: Z. Metallk., 1958, vol. 49, pp. 220-25. 6W. Siegelin et al.: Z. Elektrochem., 1957, vol. 61, pp. 359-66. &apos;H. Schenck and K. W. Lange: Arch Eisenhuettenw., 1966, vol. 37, no. 9, pp. 739-48.

Jan 1, 1969

By R. W. Jordan, J. Winter, A. J. Goldman

Kirkendall diffusion of copper and nickel atoms across the bond interfaces, as well as oxygen diffusion in the core to the interfaces, are the mechanisms which control the variation in bond strength with annealing time at 1600°to 1800°F in the cupro-nickel clad copper Mint composite. The unequal mass transfer resulting from the high diffusion rate of copper in cupro-nickel compared with that of nickel in copper caused void formation in the core. Small voids also formed in the cladding after short annealing times. These may have been nucleated by nickel oxide particles which are formed by the dissociation of the cuprous oxide in the core and the movement of oxygen to the cupro-nickel interfaces. The bond strength drops to very low values for annealing time up to 3 hr when the void density is greatest. The increase in bond strength after 16 to 72 hr at 1600°F is a result of the decrease in the void density in the cupro-nickel cladding and the growth of grains across the interface. The void density decrease is attributable to grain boundary diffusion of vacancies to the surface. The abnormally large grains in the copper preclude a similar process from taking place in the core. THE solution to many engineering materials problems that cannot be satisfied by using a single metal or alloy is often attained by combining two or more metals in such a way that each component performs a different function, while the composite meets the overall requirements. The Coinage Act of 1965 authorized a changeover from the traditional 90 Ag-10 Cu dimes and quarters to a bimetallic laminate of 75 Cu-25 Ni clad on a copper core. Economic considerations as well as physical, chemical, and mechanical properties provided a basis for the selection of this composite as a substitute for the silver-bearing alloy. An extensive survey of alloys suitable for use as coinage was prepared by Battelle Memorial Institute for the U.S. Mint.1 It was found that the cupro-nickel/cop-per/cupro-nickel composite satisfied the required color, density, mechanical properties, corrosion resistance, electrical properties, and magnetic properties to make it completely acceptable to the general public and the vending machine industry. This investigation is part of a program to determine the feasibility of reclaiming composite scrap by thermally degrading the bond strength of the cupro-nickel clad copper laminate. The composite exhibits bond degradation and subsequent bond improvement during annealing in the temperature range 1600" to 1800°F. A study of the operative diffusion processes and the resultant structural changes was made in order to explain the observed variations in bond strength with annealing time. EXPERIMENTAL PROCEDURES AND RESULTS Bond Degradation. A measurement of the forces required to peel the cupro-nickel cladding from the

Jan 1, 1969

By R. G. Vardiman, M. R. Achter

Observations of dislocation structure in niobium are presented using two techniques. Triangular pits developed by electroetching are confined to orientations in the stereographic triangle between the (111) pole and planes of the (1ll) zone and require the presence of carbon. Some unusual electroetching phenomena at other orientations are noted. A chemical etch of dislocations decorated by the addition of carbon to 50 ppm reveals the complete dislocation line structure in a surface layer up to 30 p deep, with a resolution of less than 1 p. This effect is independent of surface orientation. The structure of subboundary nets may be resolved for misorientations up to about 1&apos;. Dislocation structures found in strain anneal grown crystals, such as helices, prismatic loops, and high-density areas, are observed. The measurement of dislocation density is discussed and values obtained in different ways are compared. IN the course of some work on the response of refractory metals to thermal-mechanical treatments, it was desired to examine the defect structure of relatively low dislocation density crystals of niobium in bulk form. Surface and bulk methods for the observation of dislocations have been reviewed by ~melinckx,&apos; and include etch pitting, decoration, and various X-ray techniques. The dislocation line structure has been developed by decoration in a few metals, although observations were limited to certain orientations, or by the coarseness and nonselectivity of the precipitate. The most commonly used technique is etch pitting. In niobium, etch pits have been developed chemically&apos;0," in material of high impurity content and electrolyti-cally&apos;&apos; in relatively pure material. In this paper, etch pits developed electrolytically, and the dislocation line structure of a surface layer developed by decoration and chemical etching, are examined, and observations are presented from both techniques. EXPERIMENTAL METHODS Our starting material was electron-beam-melted niobium, swaged to 4 or -in.-diam rod. Chemical analysis is given in Table I. Single crystals were grown by a strain anneal technique using 1 to 2.5 pct of strain and growth temperatures of 1700" to 2300"~.&apos;~ Some crystals grown by zone melting were also examined. The desired surface orientation was exposed either by spark machining or by sectioning with a cut-off wheel and prepared for etching by electro-polishing.

Jan 1, 1969