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By A. F. Crawley

The densities of some liquid Pb-Sb alloys up to 11 wt pct Sb and Pb-Sb-& alloys up to 10 pct Sb/10 pct Sh have been determined by a pycnometric technique over a temperature range of about 130°C above their melting points. The data given are accurate within 0.05 pct. Density is shown to vary linearly with temperature , and equations relating these quantities have been formulated. Molar volumes calculated from the density data indicate that volumetric deviations from ideal mixing are undetectable within the limits of experimental error. A continuing research program into some fundamental physical properties of liquid metals is being pursued at the Mines Branch, Department of Energy, Mines and Resources, Ottawa, Canada. This work has received support from the Canadian Zinc and Lead Research Committee in cooperation with the International Lead and Zinc Research Organization. This paper, which reports some density data for Pb-Sb and Pb-Sb-Sn alloys, follows previous work from this laboratory on lead, tin, and Pb-Sn alloys.' Of previous data from others, Greenaway2 and Sato and Munakata3 have reported results on Pb-Sb alloys. No previous work has been published on the ternary Pb-Sb-Sn alloys, reported here. EXPERIMENTAL METHOD Densities were measured by a pycnometric technique which has been described in detail and appraised for accuracy in earlier Mines Branch reports.475 Fig. 1 shows the densitometer with the pycnometer in position for a run. The pycnometer is also shown in some detail. The pycnometer of dense, high-purity graphite, about 14 cu cm in volume, was carefully machined to a uniform, smooth finish. The height was measured by a depth micrometer and the diameter by fitting precision gage blocks between steel balls.' In each case several readings were taken, and the final results were considered accurate within 0.01 pct. The resulting volumetric uncertainty together with small inaccuracies in the coefficients of linear expansion of graphite lead to a maximum systematic uncertainty in the method of ±0.03 pct. As shown in Fig. 1, the pycnometer lid is a threaded cap. Thus, the charge, a cylinder of the alloy, can easily be inserted and the solidified metal can readily be removed after a run. The dimensions of the cylindrical charge are chosen to ensure that, once molten, the metal will not only fill the pycnometer completely but will discharge an excess into the excess-metal float chamber. AS the temperature is increased above the melting point, the volume of metal in the excess chamber increases until the system has equilibrated at the desired temperature. At this point, the excess chamber is moved to one side by twisting the shaft F, leaving a fixed volume of liquid metal in the pycnometer. This volume of fluid is readily calculated using measured coefficients of linear expansion of the graphite which expands anisotropically. The associated weight of fluid is determined as the weight of the solidified metal removed after the furnace has cooled down. Alloys were prepared from 99.997 pct Pb, 99.999 pct Sn, and 99.999 pct Sb, being melted by an electric furnace in a graphite crucible and poured into graphite molds. Several density specimens of the same nominal size were machined from each ingot, and, by comparing specimen weights, relative differences in specimen composition resulting from segregation in the ingots could be detected. In this way, segregation was found to have occurred in Pb-Sb alloys at compositions beyond the eutectic (11.2 pct Sb) and this

Jan 1, 1969

By Charles E. Lundin

Pressure-temperature-composition data were obtainedfor the Er-H system. Measurements werecar-ried out in the temperature range of 473° to 1223°K, the composition range of erbium to ErH,, and the pressure range of 10-5 to 760 Torr. Solubility relationships were established from these data throughout the system. Three solid-solution phases were delineated: metal solid solution, dihydride phase, and trihydride phase. The trihydride Phase decomposes at about 656°K and 1 atm pressure. The dihydride phase is stable to about 1023°K, but becomes more deficient in hydrogen above this temperature. The equilibrium decomposition pressure-temperature relationships in the two-phase regions, erbium solid solution plus dihydride and dihydride plus trihydride, were deter- The differential heats of reaction in these two regions are AH = - 52.6 * 0.3 and - 19.8 i 0.2 kcal per mole of Hz, respectively. The differential entropies of reaction are AS = - 35.2 * 0.3 and - 30.1 * 0.4 cal per mole HZ.deg, respectively. Relative partial molal and integral thermodynamic quuntities were calculated in the system to the dihydride phase. RARE earth metal-hydrogen systems have been the subject of general survey,1"4 and all have been found to form hydride phases. The heavy rare earths, of which erbium is a member, form dihydride and trihydride phases with different crystal structures, whereas the light rare earths form only a single-phase dihydride which expands without structure change, as hydrogen is added, to the trihydride composition. These materials are of interest primarily because of their theoretical properties, such as bonding, defect structure, and thermodynamic and electronic characteristics. Erbium has been studied in several previous investigations.5, 6 It was deemed desirable to more thoroughly and accurately define the system, both for the phase equilibria and the thermodynamic properties. I) EXPERIMENTAL PROCEDURE A Sieverts&apos; apparatus was employed to conduct the experimental measurements. Briefly, it consisted of a source of pure hydrogen, a precision gas-measuring buret, a heated reaction chamber, a mercury manometer, and two McLeod gages (a CVC, GM 100A and CVC, GM 110). Pure hydrogen was obtained by passing hydrogen through a heated Pd-Ag thimble. The hydrogen was analyzed and found to have only a trace of oxygen and nitrogen. A 100-ml precision gas buret graduated to 0.1-ml divisions was used to measure and admit hydrogen 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 ±1°K. 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 ±0.5 Torr and in the McLeod range (10-4 to 10 Torr) to ±3 pct. The hydrogen compositions in erbium were calculated in terms of hydrogen-to-erbium atomic ratio. These compositions were estimated to be ±0.01 H/Er. 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 (<1 vol pct). A quantity of sponge was arc-melted for use as charge material. The solid material was compared with the sponge in the pressure-temperature-composition 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 grain for each loading of the reaction chamber. The procedure employed to obtain the pressure-temperature-composition data was to develop experimentally a family of isothermal curves of composition vs pressure. First, a specimen of erbium was wrapped in a tungsten foil capsule to prevent contact with the quartz tube. After loading the specimen, the system was evacuated to less than l0-6 Torr, flushed several times with high-purity hydrogen, and evacuated again ready for the start of the experiment. The furnace was then brought to the desired temperature. A measured amount of hydrogen was admitted into the chamber. Equilibrium was allowed to be attained, the pressure read, and the process then repeated many times until 1 atm of gas pressure was finally reached. Other isotherms were then developed in the same manner. The partial pressure plateaus were determined by another manner. In the solid solution-dihydride region a composition of approximately 1.0 H/Er was selected on the plateau. The temperature was varied throughout the range of interest. At each temperature level, equilibrium was achieved, the pressure read, and the next temperature attained. The temperature was cycled both up and down. In the dihydride-trihy-dride region, the plateaus were determined in the 473" to 651°K range only by heating to the desired temperature and not by both heating and cooling. The data were much more reproducible in this manner. Equilibrium required long periods of time. Specimens were initially hydrided to 2.8 H/Er, so that at the higher

Jan 1, 1969

By J. W. Martin, L. K. Singhal

Grain boundary M23CB precipitates have been shown to form by a process involving the migration of an austenite grain boundary, and each plate of precipitate is in parallel orientation with one of the austenite grains constituting the boundary. The carbide distribution and morphology appear to be sensitive to grain boundary mis orientation. Some areas of austenite grain bowzdary permit the development of an array of M,C, particles, some of which are in parallel orientation with one grain and some with the other grain constituting the boundary. Massive carbide at grain boundary triple points is also shown to be in parallel orientation with one constituent grain. PREFERENTIAL precipitation during aging of carbides of the type (Fe,Cr)23C6, usually written MZ3C6, in grain boundaries of quenched austenitic stainless steels has been widely recognized. M23C6 has a complex cubic crystal structure&apos; which contains ninety-two metal atoms and twenty-four carbon atoms per unit cell. Less energy is involved in forming grain boundary precipitates than in the formation of intragranular precipitates, and the process is further enhanced by the accelerated diffusion rates in the boundaries and by the probability of segregation of chromium atoms and carbon atoms to the region of the grain boundaries during prior solution heat treatment in order to reduce lattice strain. Early electron micrographic studies2, 3 involving either extraction replica or normal replica techniques established the geometric or dendritic form of the carbide particles, although this approach led to dis- pute as to whether the particles grew within the plane of the boundary or grew into the matrix.4-6 More recent thin-foil studies&apos; have claimed to identify a discontinuous precipitation process involving M23C6 at grain boundaries, and the object of the present work was to attempt to clarify the situation using modern electron micrographic and diffraction techniques. 1) EXPERIMENTAL 1.1) Material. The steel selected for this work had a base composition of 24 pct Ni-25 pct Cr-3 pct Ti and contained about 0.04 pct C. The full analysis if given in Table I. This alloy was in the form of strip which had been hot- and cold-rolled to a thickness of 0.6 mm. 1.2) Heat Treatment. Specimens 4 cm long by 1 cm wide were solution-heat-treated for 3 hr in argon at 1150°C, followed by water-quenching. Specimens were subsequently aged in vacuo at 750°C for periods up to 500 hr. 1.3) Preparation of Electron Microscope Specimens. The heat-treated strips were cut bv spark machining into discs of 3 mm diam and 0.6 mm thickness. he-discs were dished on both sides using an electrolytic jet of 15 pct HCl electrolyte at 80 v. Final electro-polishing of the discs was carried out using 10 pct perchloric acid, 20 pct glycerol, and 70 pct ethanol at 10 v. The current density was kept below 300 ma. cm"2 by cooling the electrolyte to 0" to 5°C. As soon as a small hole appeared, the electropolishing was stopped and the specimen was quickly washed with ethanol.

Jan 1, 1969

By T. H. Alden, H. W. Schadler

The strain rate dependence of the flow stress of the eutectoid Zn-Al alloy has been determined as a function of mechanical processing, microstructure, and temperature. The best superplastic properties result from the ultrafine, equiaxed structure produced by solution treatment and isothermal transformation at 0°C. Lamellar structures produced by isothermal transformation and coarse equiaxed structures produced by annealing also exhibit strain rate sensitivity in excess of 0.5, but at higher stresses and lower strain rates than the finest structure. Solution treatment and isothermal transformation eliminate the effect of prior processing history. Small composition variations in the binary alloy do not influence the mechanical properties. Below the eutectoid transformation temperature (.275C) increasing temperature lowers the flow stress at all strain rates. The data do not favor any of the present proposals for the mechanism of superplastic flow. ALLOYS of zinc and aluminum, near the eutectoid composition, have been investigated for: 1) the flow stress-strain rate and elongation behavior,1, 2) the transformation kinetics,3 and 3) structure,3"5 but the structure sensitivity of the mechanical properties is poorly understood. Using a near eutectoid alloy water-quenched from 380°C, Backofen et aL2 estab- high and increases with increasing strain rate. They found a correlation between strain rate sensitivity and tensile elongation as expected from the increased resistance to necking that a high strain rate sensitivity provides.296 The large elongation at high strain rates is attractive for metal forming. Since most other superplastic alloys7-l3 do not show high strain rate sensitivity at such a high strain rate (for the exception see Ref. 12) there is the possibility of a unique deformation mechanism for this alloy. The sensitivity of the mechanical properties of the eutectoid alloy to thermal history1 suggests a structure sensitivity that has not been demonstrated. Gar-wood and Hopkins3 identified a lamellar product for material transformed between 200" and 260°C. The size of the lamellae decreased with decreasing temperature. They also demonstrated that an unresolved transformation product formed below 200°C. A granular two-phase material was resolved for specimens quenched to below 150°C by Mitbauer and sauerwald4 who observed coarsening of the structure after annealing. The role of grain boundaries in superplastic deformation is suggested by the strong effect of grain refinement in encouraging this phenomenon at high strain rateS7-11, 13 and is emphasized in several proposals about rnechanism7, 8, 12 and in a theory14 of high-temperature deformation. Alden8 showed metallographic evidence that grain boundary sliding is occurring extensively at strain rates where m is large but less at high strain rates where normal plasticity is observed. Holt and Backofen10 have shown that sliding also oc-

Jan 1, 1969

By N. A. D. Parlee, I. D. Shah

The solubilities of oxygen in liquid Ag-Au, Ag-Pt, and Ag-Pd alloys have been determined in the range of 940° to 1200°C at 1 atm pressure of oxygen using an improved Sieverts technique. The additions of gold (0 to 57 pct), platinum (0 to 27 pct), and palladium (0 to 22 pct) to liquid silver continuously decrease the solubility of oxygen in liquid silver. Activity coefficients and interaction coefficients of oxygen in these alloys and have been calculated. The interaction coefficientscan be described by the following equations: Approximate second-order interaction coefficients (pM have been calculated. The contribution of the product, pMxNM, to In yo only becomes significant at high alloy concentrations. RECENTLY several investigators1"3 have redeter-mined the solubility of oxygen in liquid silver. In general the recent findings1" for Po, = 1 atm are in good agreement with the equation:4 log %O = 695.4/T + 1.086 [1] It is established1, 2 that the solubility of oxygen follows Sieverts&apos; law reasonably well, at least up to 1 atm partial pressure of oxygen. It should be noted that a very slight deviation from Sieverts&apos; law has been reported by Lupis and Elliott.3 Only recently has the solubility of oxygen in Ag-X binary liquid systems received much attention, and only the Ag-Cu, Ag-Au, Ag-Pt, and Ag-Pd systems have been studied. Par lee, Sacris, and zoellners reported that the solubility of oxygen in liquid silver increases progressively with the small additions of copper (0 to 0.5 pct) up to the point where the copper oxide phase appears. Lupis and ~lliott~ have reported that the solubilities of oxygen in liquid silver decrease progressively with the additions of gold, platinum, and palladium. However, their investigation was limited to 0 to 5 pct of these alloying elements, a range too limited to satisfy the requirements of the research program of this laboratory, where the solubilities of oxygen in the range of 0 to 30 pct were required for the calculation of chemical diffusion coefficients of oxygen in these alloys. The present paper deals only with the solubilities of oxygen in these alloys while another paper will deal with the diffusion of oxygen in these alloys. EXPERIMENTAL METHOD A Sieverts technique was employed which involved an improved design of the reaction tube, Fig. 1, as described briefly in a previous communication.4 Liquid melts (70 to 100 g) were held in Norton Alun-dum crucibles. The induction furnace used had a maximum output of 2.5 kw with very fine control. This induction system had excellent stability and the final equilibrium temperatures measured by calibrated Pt-Pt, 10 pct Rh thermocouples are believed to be within ±2C. These thermocouples were checked against the melting point of pure gold wire, and the results agreed with standard tables (±l°C). Each run involved a careful sequence of operations. The sample was heated to and held at about 900°C in vacuum for 3 to 4 hr with the thermocouple in a retracted position. After melting, the melts were usually exposed to a small amount of oxygen (0.5 to 2.0 cu cm) and then degassed slowly for 1 to 2 min to remove any oxidizable volatile impurities such as carbon and sulfur as CO, CO2, SO2, and SO forth. Argon gas was then allowed to enter the system. The protection tube containing the thermocouple was then

Jan 1, 1969

By John H. Smith, Michael B. Bever

Pure gold was deformed by wire drawing at room temperature and 78°K. After deformation at room temperature, the stored energy and the resistivity increment reached nearly constant levels at high strains, whereas the yield stress continued to increase with strain. After deformation at 78K, the stored energy, the reszstivity increment, and the yield stress were larger than after deformation at room temperature mzd increased continuously with strain. Annealing at THE stored energy and the changes in properties resulting from cold working of Au-Ag alloys by various processes have been the subject of a series of investigations in this laboratory.&apos;-&apos; The work reported here room temperature after deformation at 78°K did not affect the yield stress appreciably. The stored energy, resistivity increment, and Lncrease in yield stress after deformation at room te-lnperature can be explained primarily in lerrns of dislocations while point defects, as well as dislocations, contribute to the changes in these properties after deformalion at 78°K. extends this research to pure gold. The stored energy, the resistivity increment, and the tensile properties after deformation by wire drawing were measured as functions of the strain at room temperature and at 78°K. The effect of the testing temperature and the effect of intermediate annealing at room temperature before testing at 78°K on the tensile properties of gold deformed at 78°K were also investigated. wire drawing made it possible to use a large range of strains, which was desirable because previous work on the deformation of gold had been carried out mainly at relatively small strains.&apos;-l2 Also, wire specimens

Jan 1, 1969

By O. N. Carlson, W. M. Paulson

A phase diagram is proposed for the Y-C system based on the vesults of thermal analyses, microscopic obsevvations, and X-ray diffraction studies. Three intermediate phases occur in the system: a congru-ently melting fcc phase with a wide range of homogeneity about the composition Y2C, an intermediate solid-solution region between 55 and 58 at. pct C, and a bct dicarbide melting congruently at 2415°C. All three compounds undergo a phase transformation at elezlated temperatures. A continuous serzes of solzd solutions exists between the fcc phase and the high-temperature form of YC2 with a maximum in the solidus at 2000°C and 30 at. pct C and a minimum at 1805°C and 54 at. pct C. THIS investigation of the Y-C system was undertaken as part of a nuclear materials development program. Yttrium-base alloys are of interest as possible containers for liquid metals, and carbides are currently receiving increased attention as high-temperature materials for advanced reactors and other applications. Previous work on this system was limited in scope, and the results were somewhat inconclusive and at times contradictory. Spedding et al.&apos; reported the existence of a triyttrium carbide having an fcc structure with a wide range of homogeneity and Dean et a1.2 reported the existence of a rhombohedra1 phase having the stoichiometry of Y2C. Bachella et a1.3 observed that the latter was the result of ordering of carbon atoms in the fcc solid solution. The ordering range was placed at 800" to 1000°C. Vickery et a1.4 reported a high-melting compound which they identified as yttrium dicarbide, and Spedding and coworkers1 determined the structure of this phase as bct with lattice parameters a = 3.66 and c = 6.17A. Samsonov et al.5 reported the melting point of YC2 as 2300" * 50°C. Recently Bowman et a1.6 found a transformation in the dicarbide from the tetragonal to an fcc form at 1320 20°C. Samsonov and coworkers7 reported a monocarbide of yttrium melting at 1950" * 20°C and also a sesqui-carbide melting at 1800" * 50°C. The existence of the latter has also been indicated by others,1&apos;8 but neither compound has been definitely established. The Y-C phase diagram shown in Fig. 1 was proposed by Chubb and Keller8 in 1964 based on the data available at that time. The tentative nature of this diagram together with the uncertain status of the compounds indicated that additional work on this system was needed. EXPERIMENTAL PROCEDURE Yttrium metal of 99.9 pct purity was prepared for use in this study by the reduction of YCl, with calcium to form a sponge product.9 The major impurities in this material were as follows: 100 ppm C, 150 pprn H, 20 ppm N, 300 to 1000 ppm O, <20 ppm Ca, <100 ppm Cr, <80 ppm Cu, 150 ppm Fe, <30 pprn Mg, <400 ppm Ta, and <100 ppm Ti. Alloys were prepared by arc melting yttrium sponge together with pieces of high-purity graphite rod in a purified argon atmosphere. Homogeneity was insured by repeated melting, inverting the ingot between melts.

Jan 1, 1969

By T. W. Watson, D. R. Flynn

Measurements have been made of the thermal conductivity and electrical resistivity of two specimens of 0.005-cm (2-mil) Be-Cufoil over the temperature range -140° to +200°C. The thermal cmductivity of Be-Cu Alloy 125 was found to be significantly higher than that of Alloy 25, which had a higher impurity content. The thermal conductivity and electrical resistivity values obtained were in concordance with the Smith and Palmer relation for copper alloys which states that ? = 0.0239 (T/p) + 0.075 where A is thermal conductivity (W cm-&apos; deg-&apos;), p is electrical resistivity (microhm-cm), and T is absolute temperature (OK) , indicating that the Smith and Palmer relation can be used to predict the thermal conductivity of this type of Be-Cu alloy over the temperature range -140" to + 200°C to within an accuracy suitable for most engineering applications. THE National Aeronautics and Space Administration, Goddard Space Flight Center, Greenbelt, Md., requested the National Bureau of Standards to measure the thermal conductivity of 0.005-cm Be-Cu foil which was to be used to fabricate antennae for use in Radio Astronomy Explorer space craft. It was felt that measurements had to be made on the actual antenna material, rather than on a thick bar of similar material, since the cold-working and age-hardening properties of the alloy would make it very difficult, if not impossible, to place a thick bar in the same metallurgical state as the 0.005-cm material. As discussed in Section 111 of this paper, the thermal conductivity of many copper alloys can be computed rather accurately from electrical resistivity data using an empirical relation developed by Smith and palmer&apos; and further confirmed by owell.&apos; However, there has been very little work done on correlating thermal and electrical conductivities on Be-Cu alloys. We were reluctant to assume the validity of the Smith-Palmer relation on Be-Cu alloys because of the very large mass difference between beryllium and copper. As will be seen, however, our experimental results indicate that the Smith-Palmer relation is valid for the two alloys on which we made measurements. I) DESCRIPTION OF SAMPLES Samples of Be-Cu Alloy 25 and Be-Cu Alloy 125 were furnished to NBS in the form of rolled strip material, 0.005 cm thick by 5.08 cm wide. The Be-Cu Alloy 25 was purchased by NBS in the form of a continuous length of flat strip. The Be-Cu Alloy 125 was furnished to NBS by Goddard Space Flight Center in the form of two lengths of strip that had been formed into "tubing" of about 1.2 cm diam, with one side of the strip overlapping (but not connected to) the other side by about 90 deg. This "tubing" had been opened up to be flat and then rolled onto spools of about 3 cm diam. When unrolled, the strip would spring back into tubular form. Samples of both of the Be-Cu alloys were chemically analyzed by the NBS Analytical Chemistry Division. The beryllium content was determined quantitatively by the phosphate-gravimetric method to be 1.83 wt pct for Alloy 25 and 1.80 wt pct for Alloy 125. The two alloys were also examined by a general qualitative spectrochemical method for metallic elements. The Alloy 25 specimen contained between 0.1 and 1.0 wt pct Al, Co, Fe, and Si and between 0.01 and 0.1 pct Ni. The Alloy 125 specimen contained between 0.1 and 1.0 pct Co and between 0.01 and 0.1 pct Al, Fe, and Si. Other metallic elements present were in amounts less than 0.01 pct. The NBS Engineering Metallurgy Section measured the tensile strength, elongation, and Knoop hardness of both the Be-Cu Alloy 25 and the Be-Cu Alloy 125. These are given in Table I. The NBS Engineering Metallurgy Section also prepared photomicrographs of the two alloys; these are shown in Figs. 1 and 2.

Jan 1, 1969

By T. W. Watson, D. R. Flynn

,Measurements are reported for the thermal conductivity of four heat-resistant alloys which were measured at the National Bureau of Standards. Data are given for two samples of AISI Type 316 stainless steel covering a combined temperature range from -150° to + 800°C. The thermal conductivities of three samples of AISI Type 347 were measured over the temperature range from -150° to +150C. Thermal conductivity values are given for Carpenter 20 stainless steel from 100" to 800" C. Data are given for Inconel 702, in both the solution-annealed and the age-hardened condition, over the temperature range from -150" to +800C. SINCE 1958 the National Bureau of Standards, at the request of other government agencies or private laboratories, has carried out measurements of the thermal conductivity of a number of metals and alloys. This paper presents available thermal conductivity data obtained in this way on samples of four heat-resistant alloys. The data presented for Carpenter 20* stainless steel are, to the best of our knowledge, the only thermal conductivity values which have been reported for this alloy to date. Although thermal conductivity values for AISI stainless steels 316 and 347 have been reported by previous investigators, the present data are believed to be of particular interest because, for each alloy, the effect on thermal conductivity of small changes in chemical composition can be observed. The data on Inconel 702&apos; are of interest, not only for

Jan 1, 1969

By Y. Kondo, S. Yamazaki, Z. Asaki

Thermal deco7nposition of Pyrite particles in a fluidized bed with inert gas stream was studied. Assuming that heat transfer from the surroundings to the fluidized particles controls the overall decomposition rate, rate equations for the batch process and for the continuous process were derived. In the batch experiment, a linear rate equation satisfies the experimental results and the overall heat transfer coefficient calculated from the rate constant agrees fairly well with that obtained by Leva.l1 For the continuous process, two rate equations were derived, one on the assumption of complete mixing of particles and another on the upward piston flow of particles in a fluidized bed. The former holds for a bed containing a higher fraction of decomposed pyrite realized at lower feeding rates. The latter can be applied for a bed at higher feeding rates. Thus, segregation of particles in the fluidized bed was indicated at higher feeding rates. Bed temperatures also correspond to these conditions. ThERMAL decomposition of pyrite may be represented by Eq. [I]. The pressure of diatomic sulfur gas reaches 1 atm at about 690°C. The thermodynamics,&apos; kinetics,2&apos;3 composition, and properties3-5 of decomposed products of such a reaction have been studied. Pyrite is a very common sul-fide mineral and is often accompanied with other sul-fides. It is of basic interest in nonferrous metallurgy to clarify the behavior of pyrite in the pyrometallur-gical processes of sulfide minerals of metals such as copper, lead, zinc, nickel, and so forth. Interest in this reaction increased recently because of possible elimination of arsenic from pyrite in processing highly purified iron oxide pellets. Producing elemental sulfur from pyrite, instead of sulfuric acid, also aroused interest in this reaction. It is indicated that the thermal decomposition of solid particles, such as calcium carbonate, proceeds through three major sequential steps: heat transfer, interfacial chemical reaction, and mass transfer.637 It is known that the decomposed product of pyrite is very porous2, 3 and the diatomic sulfur gas evolved can easily escape through this layer of decomposed product. It depends upon the circumstances, therefore, whether the heat transfer to the interface within particles or the chemical reaction at the interface determines the overall decomposition rate. The enthalpy change in the decomposition of pyrite is about 33 kcal per mole FeS2 which is comparable to that of calcium carbonate. The decomposition of calcium car- bonate becomes more and more dependent on the rate of transport of heat when reaction temperature increases, such as occurs in a fluidized bed.6&apos;7 It is reasonable to presume, therefore, that the thermal decomposition of pyrite, an endothermic process, carried out in a fluidized bed may be analyzed according to the heat transfer controlling model. This work intends, first, to propose a mathematical model that determines the overall rate in a fluidized bed for the decomposition process and, second, to investigate a few characteristics of the fluidized bed based upon the experimental results obtained. KINETICS OF THERMAL DECOMPOSITION IN A FLUIDIZED BED It is intended in this section to obtain rate equations for thermal decomposition of pyrite in a fluidized bed by assuming that the overall rate is determined by heat transfer from the surroundings to the particles. Both batch and continuous processes are considered. 1) Batch Process. To obtain the rate equation in the batch process, the following two additional assumptions are made. First, the temperature of preheated inert gas, tg, blown into the fluidized bed is assumed to be the same as the temperature of the fluidized bed, tf. Thus, no heat exchange occurs between the gas and particles in the bed and only the heat transfer from the reactor wall kept at tw to the particles is to be considered. Second, the decomposition is assumed to start at the outer surface of the particles and to proceed toward the center. At any given time during decomposition, undecomposed pyrite remains in the tori at a temperature: td. The decomposed shell is composed of FeS1+x whose outer surface is at tp Diatomic sulfur gas evolving at the interface is heated to tf during its escape through the decomposed shell. This is illustrated in Fig. 1. With the above-mentioned assumptions of heat transfer, we have:

Jan 1, 1969

By P. L. Raffo, T. E. Mitchell

Single crystals of Ta-Re alloys have been deformed in tension and compression as a function of solute concentration and temperature. The temperature dependence of the yield stress is decreased by alloying. At low temperatures there is a minimum in the yield stress (at about 2 at. pct) as a function of concentration. Three-stage hardening was not observed in the alloys. Linear hardening rates, where observed, were characteristic of stage II in pure tantalum. At low temperatures and high concentrations, work softening was often prominent at high strains. Electron microscopy revealed that dislocations are mostly of screw orientation, although heavily jogged and cusped, and often occurring in dipole pairs. The alloys become more prone to cleavage with increasing rhenium content, due mostly to an increasing yield stress rather than a change in cleavage strength. Alloying apparently decreases the Peierls stress of bcc metals at low temperatures by facilitating kink nucleation at solule atoms on screw dislocations. Higher solute concentrations further increase the yield stress. Quantitative calculations and comparisons with other bcc alloy systems are made to show that the predominant hardening mechanism is due to the interaction of dislocations with misfitting solute atoms close to their slip planes. The interaction is so localized that the core dilatation of dislocations could be important. CONSIDERABLE interest has arisen in recent years concerning the mechanical properties of unalloyed bcc metal single crystals.&apos;-7 These and similar studies on polycrystalline materials have resulted in a considerable understanding of the macroscopic yielding characteristics8, 9 and the process of work hardening.&apos;&apos; This latter advance is due in a large part to the increased use of transmission electron microscopy in P I RAFFO junior Membar AlMF is Metallyureist Iewis such studies and the general observance of three stages of work hardening in the shear stress-shear strain curves. The properties of substitutional alloy single crystals of bcc metals have not been determined in as much detail as in the pure metals. Insufficient systematic studies have been made on the effect of alloying on the magnitude and temperature dependence of the yield stress or the stress-strain curves. The alloy systems which have been studied to some extent have been Ta-W,11, 12 Ta-Mo," Ta-Nb,12&apos;14 Mo-Re,15 W-Re,16 and alloys of iron with nickel,17 platinum,17 vanadium,18 and aluminum.18 A large body of data exists on Fe-Si alloys, but these have mainly been a result of the experimental convenience of using this material in place of unalloyed iron, rather than a comprehensive study of the mechanical properties of the alloy system per se. The present authors have previously reported additional data on the properties of Ta-Re, Ta-W, and Ta-Mo alloy single crystals.1g Some of the data on Ta-Re alloys will be described later in this paper. Briefly, single crystals of Ta-Re (1.2 to 10.6 pct), Ta-W (6.2 and 10.2 pct), and Ta-Mo (2.9 and 9.0 pct) were grown by the floating zone method in vacuum. Compression tests were performed in the temperature range 77" to 623°K. Slip was found to occur in Ta-Re alloys at 77&apos; and 298°K on the (~ll)[lil] system and slip lines were coarser and straighter than in unalloyed tantalum. No three-stage hardening was observed in any of the alloy systems and the curves were nearly parabolic. At temperatures above 175°K the yield stress* increased monotonically with in- creasing composition while at 77" and 175°K the yield stress initially passed through a minimum after which it began to increase again for concentrations greater than about 2 pct Re. Similar minima were observed in Ta-Mo alloys and to a lesser extent in Ta-W alloys. The minimum was interpreted as being a result of a

Jan 1, 1969

By T. S. Lundy

Anand and Agarwala recently determined diffusion coefficients by the residual activity (Gruzin) method for several tracers in large-grained, high-purity aluminum. D values at any particular temperature in the range of 400" to 630°C were about four orders of magnitude lower for cd115, 1n114, sn113, and pdlm than for Ag. Corresponding values for Do and Q in the Arrhenius equation were also quite small. It was pointed out previously that unusually low diffusion coefficients within the region of a specimen near a free surface may be the major cause of such anomalous results for impurity diffusion in silver and in aluminum.44 Anand and Agarwala considered this possibility but rejected it because their penetration profiles were "homogeneous" and "yielded diffusion coefficients obeying the Arrhenius plot". Neither of these two criteria satisfactorily prove or disprove the presence of a near-surface effect. Such can be accomplished only by direct serial sectioning in which the chips ground from the specimen are assayed for tracer content. In fact, such experiments always should be done prior to use of the somewhat indirect Gruzin method where the finer details of the transport process cannot be determined. There have been several other reports of unusually low D, Do, and Q values for impurity diffusion in silver and aluminum.1"4 It is interesting to note that all of these studies made use of the Gruzin method. Also, in all cases where the same systems were examined by use of a direct serial sectioning technique, large near-surface effects were observed. One must conclude therefore that the reported anomalous diffusion parameters for cd, In114, sn113, and pd in aluminum are due to some near-surface effect, while the results for Agl10 indicate that no such effect was encountered for this system.

Jan 1, 1969

By K. R. Carson, J. Weertman

THE fatigue-hardening curve has received much attention in recent years. This curve is obtained by plotting the peak stress required to maintain a given plastic strain per cycle vs the number of cycles. It

Jan 1, 1969

By Niels Hansen

Dispersion-strengthened aluminum products consist of an aluminum matrix containing finely distributed ceramic or intermetallic particles. Examples of the two types of product are SAP, in which the dispersed phase is aluminum oxide, and materials made from atomized aluminum alloy powder, in which the dispersed phase can be FeA1, particles.&apos; A fundamental difference between the two types of product is that the elongation of aluminum/aluminum oxide products decreases with increasing temperature, whereas the elongation of aluminum- FeA13 products, like that of aluminum alloys, increases with increasing temperature. As regards the structural stability, aluminum/aluminum oxide products are stable to temperatures above 600° C as aluminum oxide does not react with aluminum, whereas prolonged heating at above 400°C of aluminum-FeA1, products leads to coarsening of the intermetallic phase and loss of strength.&apos; On the basis of these results it is supposed that a dispersion-strengthened product combining strength, ductility, and stability at elevated temperatures may be obtained if the dispersed phase reacts with the matrix in such a way that the reaction does not proceed at any significant rate at the application temperature. Different ceramic or intermetallic compounds may be selected as the dispersed phase, and, as alloying of the matrix phase may also influence the reaction, many possibilities exist for each metal. In the present study, aluminum products containing different oxides have been examined. For a reaction to take place between the dispersed oxide and the aluminum the free energy of formation of the oxide (MeO) must be greater than that of aluminum oxide; the difference should, however, not be too great in order to limit the reaction rate. Furthermore the aluminum alloy formed when aluminum reacts with the dispersed oxide should have a melting point near

Jan 1, 1969

By E. Rudy, St. Windisch

The only complete phase diagram investigation of the Ti-W system is by Maykuth and coworkers,&apos; Fig. 1. Although previous work by Gonser2 indicated complete miscibility, later investigations3°5 essentially confirmed the diagram depicted in Fig. 1. The present study was undertaken because preliminary results on metal-rich ternary Ti-W-C alloys indicated complete solid solubility between 0 titanium and tungsten at temperatures above 1300°C—in contradiction to the presently accepted diagram. The powdered elements, as well as crystal bar titanium and tungsten sheet, were used in the preparation of the experimental alloys. The iodide titanium, obtained from Foote Mineral Co., Exton, Pa., had a total impurity content of less than 410 ppm, of which 150 ppm were interstitials (H, O, N, C). The overall purity of the titanium powder (Var-Lac-Oid Chemical Co., New York) was better than 99.7 pct. Major contaminants, in ppm, included: 0, 800; N, 10; H, 1500; Fe + Co + Ni + Cu + Zn, 50; C1, 200. The measured lattice parameters of the titanium were a = 2.94A and c = 4.68,A. The tungsten sheet and the tungsten powder (Wah Chang Corp., Albany, Ore.) contained the following impurities (in ppm, values in parentheses refer to the sheet tungsten): Mo, 50 (70); 0, 140 (110); Fe, 20 (60); Ni, 20 (not determined); N, 110 (not determined); sum of other impurities, <60 (<100). Samples from the iodide titanium bar stock and from tungsten sheet were prepared by repeated melting of the chipped materials in a nonconsumable electrode arc furnace under high-purity helium. The melted alloys were heavily cored, and homogeneity of the alloys could only be achieved after prolonged heat treatments at subsolidus temperatures. The majority of the alloys were therefore prepared by cold compacting the well-mixed powders in steel dies and pre-homogenizing the compacts for 6 hr at 1300°C in a tungsten-element furnace. The vacuum was better than 10"6 Torr, but for additional protection the sample container was wrapped in zirconium foil. Both preparation methods led to identical results. The measurements of the solidus temperatures were carried oat in the Pirani-type furnace described in a previous paper.6 Incipient melting in alloys containing between 20 and 90 at. pct W was rather difficult to detect visually, and therefore a photoelectric transducer system7 was employed to indicate the phase change. For the investigation of the solid-state equilibria, the specimens were first homogenized for 2 hr at slightly subsolidus temperatures in the Pirani fur- nace and then reequilibrated at, and rapidly cooled (-100°C per sec) from, the selected equilibrium temperatures. After the runs, the alloys were analyzed microscopically and by X-ray diffraction. With the exception of spot checks for oxygen and nitrogen in processed alloys, no other chemical analyses were performed. However, as the weight changes of the alloys during processing were within 0.05 pct and the lattice parameters of indeqendently prepared alloy series agreed within 0.0015A, it is reasonable to assume that no significant concentration shifts with respect to the nominal compositions had occurred. The measured solidus temperatures, shown together with literature data in Fig. 2, ascend smoothly from

Jan 1, 1969

By R. K. Govila, E. H. Parkison

THE interplanar angles for hcp metals vary with c/a ratio, and therefore must be computed separately for each particular metal or alloy. Manual computation of these angles is laborious and time consuming, and for this reason computer programs have been developed to accomplish this task.1"3 However, these programs have certain disadvantages. For example, they require prior knowledge and understanding of ALGOL or FORTRAN languages. Further, they will not print out specific angles but instead give all angles between given limits—thus program2 prints out a total of 26,649 angles between planes with indices and in the range from (4 4 4) to (4 4 4) for any given c/a ratio. The purpose of this note is to present a simple and inexpensive computer program for accomplishing this task. This program is written in BASIC language4 which does not require any prior knowledge of computer programming, and is ideally suited for nonprofessional programmers. It also provides flexibility for the user by allowing him to select any indices for as many or few planes as desired for any given c/a ratio. The computer program proposed below is based on the relationship in which + is the angle between any two planes and . TO illustrate use of the program, consider the problem of calculating the interplanar an-

Jan 1, 1970

By J. T. Berling, J. B. Conway

MANY studies have been devoted to the correlation of low-cycle fatigue behavior. Several of these have also been concerned with the identification of an effective approach to the prediction of low-cycle fatigue behavior from short-term tensile data. Perhaps the first such approach was that reported by coffin1 in the form: where is the plastic strain range, Nf is the number of cycles to failure, and c is a constant characteristic of a material. In this analysis by Coffin it was reasoned that in a short-term tensile test the value of Nf could be considered as equal to a , in which case the value of c is interpreted as the tensile ductility, f, measured in such a test. If, therefore, the Coffin equation is assumed to be applicable to a given material, it is a simple matter to predict the low-cycle fatigue behavior. Once the tensile ductility is known, this point is located at Nf = 1/4 on a log-log plot of vs Nf and a line is drawn through this point with a slope of to yield a prediction for the fatigue life. Actually, while this equation is quite useful it is not generally applicable, for experiment has shown that the value of —$ does not reflect the relationship between and Nf for all materials or even for a given material over all temperature ranges. An equation similar to the Coffin equation was prepared almost simultaneously by Manson.2 This expression had the form: In this case the exponent on Nf was not assigned any particular numerical value in accord with the various values of this exponent which had been observed for different materials and at different test conditions. Because of this characteristic it will be recognized that little use can be made of this expression in predicting low-cycle fatigue results. A fairly effective expression for use in predicting fatigue behavior was proposed by Manson3 based on a study of numerous sets of experimental results. This relation (Method of Universal Slopes) makes use of modulus of elasticity, ultimate strength, and tensile ductility, and assumes an exponent on Nf equal to 0.6 in representing the plastic strain range contribution to total strain range. While this equation of Man-Son does not yield completely accurate results it must be recognized as being the best means available at

Jan 1, 1970

By E. S. Tankins

The main purpose of this work was to study the effect of gold on the activity coefficient of oxygen in the liquid Fe-Au alloy and to determine how copper and silver change the activity coefficient of oxygen. A preliminary investigation has been made of equilibrium in the reaction of hydrogen with oxygen in some of the liquid gold alloys. The experimental method, which has been described in detail elsewhere,&apos; consisted of bubbling accurately known H-A-water vapor mixtures through the Fe-Au alloys contained in alumina crucibles within a vertical closed furnace. When equilibrium was reached, the samples were quenched by rapidly lowering the crucible under an atmosphere of argon to a water cooled brass fixture at the bottom of the furnace tube. The melts were found to freeze from the top in less than 4 sec. The heats were carefully prepared for oxygen analysis. The oxygen content was determined by vacuum fusion analysis.&apos; Only high purity electrolytic materials were used in this investigation. The activity and free energy of oxygen in the liquid iron alloys were studied by means of the reaction; The data for the 80 Fe-Au alloys, obtained as a function of temperature, are summarized in Table I and presented in Fig. 1, where log is plotted against . The results can be expressed by: The data were obtained using water vapor-hydrogen ratios between 0.04 and 0.30, and a 25 pct H2-75 pct A mixture. An oxygen content between 0.030 and 0.060

Jan 1, 1970

By J. Winter, W. C. Setzer, A. J. Goldman

ANISOTROPY in cold worked tempers of commercial aluminum alloys is manifested in deep drawn products as protuberances or ears 45 deg to the rolling direction. This reflects the {123}(412) rolling texture.&apos; In fully annealed material, 0 to 90 deg ears in and per-

Jan 1, 1970

By David L. Holt, Walter A. Backofen, Anwar-ul Karirn

ANNEALING the binary alloy, Mg-0.5 wt pct Zr in a hydrogen atmosphere results in extensive precipitation of zirconium hydride. The morphology of these precipitates has already been investigated.lm3 Squires, Weiner, and phillips4 found, following creep testing of the hydrided alloy at 450" and 500°C, that hydride denuded zones formed along grain boundaries that were aligned approximately normal to the tensile axis. Zone formation was attributed to diffusional creep by magnesium transport down the prevailing stress gradients.4&apos;5 Recently, electron microprobe analysis by Karim, Holt, and Backofen6 showed the zones indeed to be zirconium-free and furthermore it was shown that in compression, zones formed along boundaries approximately parallel to the stress axis. Thus it was confirmed that the zones are formed by diffusional creep. Typical zone-formation is shown in Fig. 1. Karim, Holt, and Backofen also measured the con- tribution to the total strain, from diffusional flow, slip creep, and grain boundary shear: results showed that diffusional strain tends to saturate with increasing imposed strain, while grain boundary shear eventually becomes the dominant deformation mode. It was suggested in explanation that the precipitate-denuded zones are soft and easily sheared, such deformation contributing to the grain boundary shear measurement. A point to be emphasized is that the Mg-0.5 Zr alloy was not superplastic for the index of strain rate sensitivity of flow stress, m = a log log 6 was only 0.25. It was recognized that diffusional creep in a poly crystalline aggregate must be accompanied by boundary shearing.&apos; The suggestion was that the non Newtonian-viscous character of diffusional creep in the Mg-0.5 wt pct Zr alloy is due to resistance to sliding of boundaries lying approximately parallel to the tensile axis.= The work described in the present note should be seen against the above background for it represents initial efforts to observe in a similar way diffusional creep in a superplastic alloy. Previous work with the ternary-alloy Mg-6 Zn-0.5 Zr, pellet extruded, showed it to be superplastic however it does not contain resolvable precipitates to act as internal markers for diffusional creep. Also the fine grain size of the alloy (0.5 p) made conventional metallography rather difficult. Solubility relationships in the Mg-Zn-Zr system are not well known, however making reasonable guesses about the probable phase diagram of the ternary, Mg-Zn-Zr, various heat treatments were attempted to produce hydride precipitation. Finally a 16-hr anneal at 495&apos; in hydrogen was found to pro-

Jan 1, 1970