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By J. B. Wagner, p. Hembree

The iron tracer diffusion coefficient of umstite has been measured at 110(fC across the phase field and at a single composition at 800°C. Assuming a simple cation vacancy model the tracer diffusion coefficient was found to be a linear function of the cation vacancy concentration at 1100°C. The equation is D = 3 x 20 29 where denotes the concentration of vacancies in numbers per cc. The tracer work at 800°C was carried out to investigate the reported "pinning" of tracer to the wustite surface at low temperatures. No evidence for the "pinning" of the tracer was found at 800°C in COz-CO gas mixtures. HIMMEL, Mehl, and Birchenall,&apos; Carter and Richardson,2 and Desmarescaux and La combe3 have measured the diffusion of iron tracer in wustite at several temperatures and compositions. The present work was undertaken to extend the measurements over a large composition range at 1100°C and to resolve certain apparent discrepancies in the data, expecially at lower temperatures. EXPERIMENTAL Wustite was prepared by oxidizing rectangular iron plates* in C02-CO mixtures. The samples were •The iron was supplied by the Battelle Memorial Institute courtesy of the American Iron and Steel Institute. The analysis is presented in Table I. quenched. Due to the inward flow of cation vacancies during oxidation, the center of the sample contained a thin void. The edges of the wustite slab were sanded until the sample could be split into two parts. Each part was then sanded on the front and back flat area until a smooth surface was obtained. The specimens were then replaced in the furnace and equilibrated at llOO°C in a predetermined COa-CO mixture by methods described elsewhere.4"6 The specimens were again quenched and the surfaces were lightly sanded to remove any roughness following the first equilibration. The specimens were then reequi lib rated in the same C02-CO mixture for thirty minutes in order to relieve any mechanical damage on the surface due to the polishing. The specimens were then quenched and the tracer was applied by an electroplating technique. The work of Carter and ~ichardson&apos; demonstrated that there was no systematic difference in the iron tracer diffusion coefficient in wustite if the tracer was plated, dried, or evaporated on the specimen. In the present study a piece of filter paper was saturated with an iron chloride solution of pH <* 3 that contained the tracer FeS5. The wustite was placed on the filter paper and made the cathode. A current density of 0.4 to 0.6 ma per sq cm was passed for about five to ten minutes. The thickness of the tracer layer was estimated to be about 7 x lom6 cm. This estimate was made by considering the area plated, the current flow, and time for plating and the activity of the iron in the plating solution. Different areas of the specimen were counted using a collimator to determine the uniformity of the tracer. Any specimen which exhibited a variation from the initial count rate (about 1500 cpm) by more than 15 pct was rejected. An estimate of the time necessary to convert the thin layer of iron tracer to wustite was made using the data of Pettit and wagner." he estimated time was 1 sec at 1100°C assuming linear oxidation kinetics. The shortest diffusion anneals were 1800 sec. The samples were suspended in the hot zone of a furnace by two platinum wires. Two separate specimens were run at the same time. Only the edges of each sample were in contact with the wires. The C02-CO gas of the same composition as that used in the pre-diffusion anneals flowed freely around the samples at a linear velocity of 0.9 cm per sec. To initiate a run, the specimens were lowered from the cold zone of a furnace to the hot zone by a magnetic lowering device." bout 60 sec were required for lowering. To terminate a run, the sample was withdrawn from the hot zone to the cold zone. Time zero for the beginning of the experiment was taken when the sample blended into the red glow of the furnace and conversely for the end of the experiment. The surface decrease method of measuring the tracer diffusion coefficient was used to collect the data. This method requires that counting geometry be reproducible because the specimen is counted before the diffusion anneal and after the anneal. A special jig was constructed for each specimen so the specimen could be removed from the jig and returned to the jig such that the well geometry was reproducible.

Jan 1, 1970

By James S. Foster, Paul G. Shewmon, Frank V. Nolfi

Analytical expressions are developed for the kinetics of dissolution or growth of a spheroidized, solute rich stoichiometric Precipitate in the surrounding matrix. There are two limiting cases; in one the rate of dissolution or growth is limited by long range solute diffusion through the matrix and in the other by the transfer of atoms across the mrdrix-precipitate interface. In the former case local interfacial equilibrium exists while in the latter it does not and the rate of dissolution or growth is controlled by an interfacial reaction. The analysis treats both limiting cases as well as mixed control in a single development, where it is found that the thermodynamic state of the interface is completely specified by a single parameter, o, defined by where K is the reaction rate constant, D is the matrix solute diffusivity, and R, is the precipitate radiz~s. If K is infinite then a is zero and local equilibrium prevails; if K deviates infinitesimally from zero, then a is very near unity and an interfacial reaction is rate controlling. Mixed control occurs for intermediate values of o. From the analytical results, numbers are computed which are useful in determining the duration of interfacial reaction or mixed control; following this time period, long range diffusion is rate controlling. THE rate controlling process or processes governing phase boundary migration has been the subject of much speculation and investigation. Traditionally, the most widely assumed boundary condition in quantitative treatments of this problem has been that of local interfacial equilibrium. This condition implies that long range diffusion of one or more elements controls the migration and is referred to as "diffusion controlled migration" (herein DCM). In contrast to the above view is the proposition that local interfacial equilibrium does not exist and that transport of atoms across the interface is rate controlling. Consequently, this mechanism is referred to as "interface controlled migration" (herein ICM). In processes of the latter type, the activity, a, of one or more elements is discontinuous at the phase bound- ary and the flux, J, across the boundary of a given element is some function of its activity discontinuity, a. One of the most comprehensive contributions to a mathematical description of phase boundary migration is due to am.&apos; His analyses are applicable to precipitation in binary systems in which a) the precipitates are spherical* solute rich compounds of constant

Jan 1, 1970

By A. Raman, P. P. Singh

The constitution of the La-Rh system was studied by powder X-ray diffraction, metallopaphic, and differential thermal analysis techniques and an equilibrium diagram is presented. Eleven intermediate phases occur in the system and the crystal structural data for nine of them were determined. La3Rh crystallizes in an orthorhombic structure of undetermined type, whose unit cell is obtained by doubling the &apos;a; and &apos;c,,&apos; edges of an FesC type unit cell. The other intermediate phases of the system are LarRh-3( undetermined structures also occur in the system. LaRh, undergoes a polymorphic phase transformation at 1240°C. LaRh3 and La2Rh7 also exhibit polymorphisnz. The phases Laah and LazRh7 melt congruently. The latter undergoes a eutectoid transformation into LaRh, and Rh at 1205°C. Laah3 is formed by a peritectoid reaction between Laah and La,Rh,,. The other Phases result from peritectic reactions between the liquid and the adjacent rhodium-rich phases. The intermediate Phases of the La-Rh system are compared with those of the La-Co and La-Ni systems. DURING the course of a detailed investigation to study the occurrence of CrB, FeB, A1B2, and related structures in the rare earth alloys it was found that much information is lacking for the rare earth noble metal systems. Although the structures of several rare earth alloys containing the noble metals at the AB and AB2 stoichiometries have been reported, the occurrence of related structures at other stoichiometries has not been studied. We have initiated a project to study the crystal structural features of selected rare earth-rhodium alloys and to map the equilibrium diagrams of representative systems with conventional methods. The results of our investigation in the La-Rh system are presented in this paper. Two phases were known in the La-Rh system. LaRh has the CrB-type structure.&apos; LaRhz is a MgCu2-type Laves phase.z EXPERIMENTAL PROCEDURE Alloys weighing less than 1 g were prepared from commercially pure lanthanum (99.9 pct +), supplied by Lunex Company, Pleasant Valley, Iowa, and rhodium (99.92 pct +), supplied by Engelhardt Industries, Newark, N.J., in a conventional arc melting furnace under argon atmosphere. The buttons were turned upside down and remelted three times to insure homogeneity in the samples. Since negligible loss of material was encountered during melting, a chemical analysis of the alloy buttons was not undertaken. Powder specimens for X-ray diffraction studies in the as cast state were then prepared. The buttons were wrapped in thin molybdenum foils and homogenized by heating in vacuum at suitable high temperatures for more than 1 week. They were then broken into three or four pieces for annealing experiments. The pieces were wrapped in molybdenum foils and annealed at various temperatures in evacuated quartz capsules. The annealing was carried out for 2 hr at or above 1200°C, 1 day at temperatures close to llOO°C, 2 days at 1000°C, and for 1 week at temperatures below 1000°C. After annealing the alloy pieces were again broken and powder specimens for X-ray diffraction were prepared. The powders of the lanthanum rich alloys with more than 80 at. pct La were prepared by filing. The filings were sealed in molybdenum tubings and stress-relieved at 600°C in vacuum. It was not deemed necessary to stress-relieve the powders of the other alloys, since the alloys were very brittle and were ground easily. POWDER X-RAY DIFFRACTION X-ray diffraction photographs of powders (-325 mesh size) of the alloys in the as cast and annealed states were prepared in a Guinier-de Wolff focussing camera with copper K, X radiations. These patterns were studied to identify the stoichiometries and the crystal structures of the intermediate phases. The lattice parameters of the phases were calculated after minimizing the differences between the observed sin2 6 values, calculated from the diffraction angles 8, and the sin2 8 values, calculated using approximate lattice constants obtained from a few lines. These differences were minimized manually to less than 0.0005. The latLice constants are judged to be accurate to *0.005A for values less thp about 10A and to k0.01~ for values greater than 10A. The relative intensities of the lines were calculated using a computer program written by Jeitschko and Parthk.~ No attempt was made to refine the atomic positional parameters in the phases. METALLOGRAPHY The phase equilibria in the investigated alloys in the as cast and annealed states were also studied by metallographic examination. The polished specimen surfaces were etched with 10 pct picric acid in alcohol (alloys up to 25 pct Rh), concentrated picric acid (from 25 to 37.5 pct Rh), 2 pct nital (40 to 50 pct Rh), 10 pct nital (from 50 to 66.7 pct Rh) and with concentrated 48 pct HF for the other rhodium-rich alloys. Selected microstruture~ were then photographed using a Po-laroid Land camera. THERMAL ANALYSIS Differential thermal analysis of the alloys was carried out in DTA-668 Stone differential thermal ana-

Jan 1, 1970

By J. R. Cahoon, H. W. Paxton

The mechanical properties of unidirectionally solidified A1(rich)-Mg and A1(rich)-Cu castings containing up to 15 wt pct solute have been determined with re -spect to the volume fraction of interdendritic eutectic. Pioperties were determined in the directions pumllel and Perpendicular to that of solidification; the volume fraction of eutectic was varied between the "as-cast" and equilibrizcm amounts by approperiate heat treatment following solidification. The principles of fiber strengthened composites and dispersion strengthened materials are adapted to explain the mechanical properties of these castings. It is generally accepted that castings often have inferior mechanical properties when con~pared to wrought products. However, there is little quantitative data available concerning the factors which make apparently sound castings weak and/or brittle. The relative ease and inexpensiveness of the casting process have always been attractive and, therefore, an understanding of the factors which contribute to the mechanical properties of castings would seem desirable. Such an understanding may lead to an improvement in the mechanical properties to an extent where castings would become competitive in applications where presently only wrought products are considered to have the requisite properties. Such an understanding could also improve the reliability of present cast products. Much of the recent research on castings has centered about determining the extent of segregation in cast alloys. Macrosegregation, particularly inverse segregation, has been studied in some detail 1-8 and a considerable understanding of microsegregation has been obtained.9&apos;10 The effect of solidification rate on dendrite spacing and on the amount of interdendritic eutectic in binary alloys has been established, particularly for Al(rich)-Cu alloys.""0 However, the extension of these ideas to relate the amount of interdendritic eutectic, concentration gradients, micro-segregation, dendrite spacings, and so forth, to the rnechanical properties has been limited. Dean and spear" have related the mechanical properties of an Al-Si-Mg alloy, A356-T62, to the dendrite spacing and have shown that the mechanical properties improve with decreasing dendrite spacing. Passmore et al.12 have shown that annealing at high temperature improves the mechanical properties of Al(rich)-Cu al- loys and Archer and Kempf 13 have shown that an Al-1 pct Mg-1.75 pct Si alloy behaves in a similar manner. Ahearn and Quigley 14 have shown that high temperature homogenization also enhances the mechanical properties of an SAE 4330 steel. However, in the above investigations, no underlying reasons were suggested for the improvement in mechanical properties. The purpose of the present investigation is to relate the mechanical properties of castings to some of the solichfication variables and to derive some equations by which calculations of the mechanical properties may be attempted. In particular, the effect of the amount of interdendritic eutectic and the effect of stress direction with respect to that of solidification on the mechanical properties will be considered. The Al(rich)-Mg and Al(rich)-Cu binary alloy systems were chosen for study. The A1-Mg system was chosen because its constitutional relationships are such that large volunles of eutectic (up to 24 vol pct) may be obtained in the as-cast condition and then be completely dissolved by subsequent heat treatment at about 440°C. This allows a comprehensive study relating the mechanical properties of castings to the amount of interdendritic eutectic. Also the Al(rich)-Mg eutectic is almost a single phase 15 which should make the experimental results more amenable to theoretical interpretation and calculation. The A1-Cu system was chosen for study because of the large amount of related information available concerning segregation, dendrite spacing, and so forth. Unidirectionally solidified castings were used throughout the investigation so that the effect of solidification direction with respect to the direction of applied stress could be determined. THEORETICAL It is well known that upon solidification of binary alloy castings, the nonequilibrium amount of eutectic which forms is given by 10 where fe o is the weight fraction of eutectic, Cs is the solid solubility of solute at the eutectic temperature, k is the equilibrium partition coefficient, and C, is the average composition of the alloy. In the development of Eq. [I], it is assumed that the effects of inverse segregation and diffusion in the solid are negligible, and that no porosity is present. If the casting is homogenized at a high temperature for a long period of time, some (or all) of the eutectic is dissolved and the amount of eutectic for this "equilibrium" condition may be calculated directly from the constitutional diagram. By appropriate intermediate annealing, the

Jan 1, 1970

By J. R. Cahoon, H. W. Paxton

The possibility of using unidirectionally solidified, two-phase alloys as an approximation to fiber composite materials is investigated. The short-term me.chanical properties and failure modes of unidirectionully solidified A1 (rich)-Cu alloys containing ap -Proximately 0, 17.5, and 27.7 vol pct of 0 phase &apos;fibers" are determined at temperatures from 25" to 500" and compared with those obtained for conventionul SAP alloys. In a previous publication,&apos; hereafter referred to as I, the possibility of understanding some of the room-temperature mechanical properties of unidirectionally solidified castings was explored. For Al(rich)-Cu and Al(rich)-Mg two-phase alloys over a substantial range of compositions, the yield and ultimate strengths and common ductility measures were very adequately predicted from the principles of fiber strengthening4 and the analysis of ductility outlined by Gurland and Plateau." The results obtained in I suggest the possibility of using unidirectionally solidified, two-phase alloys to simulate fiber composite materials where the inter-dendritic second phase or constituent acts as the reinforcing material. Recent attempts concerning the fabrication of fiber conlposites have concentrated on producing composites with a good bond between fiber and matrix and with very long fibers so that their maximum contribution to the strength of the composite may be realized. However, these objectives are difficult to attain in practice and present fabrication processes are either extremely laborious or costly.13 The slow, unidirectional solidification of eutectics has received considerable attention as a method for producing composite materials. 5,6 This method can fulfill both of the above objectives but it is currently laborious, expensive, and has the additional disadvantage that the volume fraction of reinforcing phase cannot be easily varied. On the other hand, unidirectionally solidified, two-phase alloys, also with a good bond between the phases, are relatively easy to make and the volume fraction of reinforcing "fibers" can be easily varied by changing the average composition of the alloy. The disadvantage of the cast alloys is that the mechanical effectiveness of the "elongated interdendritic reinforcements" (EIR)* may be reduced due to their rela- tively short lengths, the w factor in Eq. [2] of I. However, if the EIR have a high strength their contribution can be considerable. For composite materials containing discontinuous cylindrical fibers of various lengths the ultimate strength is given by1 where it is assumed that the composite fractures when the fibers fail. In Eq. [I], a, is the stress in the matrix just prior to failure of the composite, Vf is the total volume fraction of fiber reinforcing constituent, Vf(l+) is the volume fraction of fibers whose lengths exceed the critical length, I,, which is defined as the shortest length of fiber in which the stress can build up sufficiently to break the fiber. af is the fracture strength of the fiber material, w is a factor accounting for the discontinuity of those fibers whose lengths exceed I,, 1-/d is the average aspect ratio of those fibers whose lengths are shorter than I,, and t is the shear stress in the matrix at the fiber-matrix interface. The factor w is dependent on the length of the fibers and also on whether deformation of the matrix occurs plastically or elastically. However, for a given length of fiber, w is smaller when elastic deformation of the matrix is assumed.&apos; It is of interest to consider the properties of simple unidirectionally solidified, two-phase alloys at elevated temperatures in view of the possibility of using suitable modifications for high temperature service. Knowledge of the creep behavior of these materials is still rudimentary (although under active investigation) and the present paper concerns itself with short time tensile properties of some alloys similar to those investigated in I (i.e., unidirectionally solidified Al(rich)-Cu alloys). Unidirectionally solidified alloys containing 5.6, 17, and 23 wt pct Cu were tested parallel to the direction of solidification at temperatures from 25" to 500°C. In the present investigation, the alloys were homogenized for 2 days at 535°C giving a matrix of homogeneous a phase (5.2 wt pct Cu) and an interdendritic constituent (EIR) which was completely Q phase (53 wt pct Cu). EXPERIMENTAL Alloys of nominal composition 5.6, 17, and 23 wt pct Cu (containing approximately 0, 17.5, and 27.7 vol pct 8 phase, respectively, after homogenization at 535°C) were prepared by melting 1200 g of A1 (99.99 pct) in a high purity graphite crucible and adding the appropriate amount of freshly cleaned copper chips (99.9 pct). The molten alloy (at 700°C) was poured into a preheated graphite mold (also at 700°C) and the ingot unidirectionally solidified by impinging water on the steel baseplate of the mold. The alloy was degassed immediately

Jan 1, 1970

By E. Teghtsoonian, E. M. Schulson

The tensile behavior of bcc ordered P&apos; AuZn single crystals (CsCl structure) has been investigated under varying conditions of temperature, composition, and orientation. Between -0.2 and 0.4 T, multi-stage hardening occurs fm stoichiometric and nonstoichio-metric crystals oriented near the middle of the primary stereographic triangle. At higher and lower temperatures, parabolic type hardening occurs, followed by work - softening at the higher temperatwes. Deviations from stoichiometry give rise to increased flow stresses. Multi-stage hardening was observed for most orientations, except along the [loll-[lll] boundary and near the [001] corner of the stereo -graphic triangle, where parabolic type hardening occurs. Along two slip systems, (hk0)[001] and (, operate simultaneously while in the [001] comer, slip occurs mainly on the system. Electron microscopy of deformed crystals revealed bundles of edge dislocations forming walls approximately Perpendicular to the glide plane. In general the plasticity of 4&apos; AuZn closely resembles the plasticity of bcc crystals. In recent years, considerable interest has arisen concerning the mechanical properties of the CsCl type intermetallic compounds Ag Mg,&apos;- Fe co,&apos; and Ni Al.&apos;-&apos; The compound P&apos;AuZn is structurally similar. It has a low and congruent melting point of 725"~,&apos;" remains ordered up to the melting point,16 and pos-esses a range of solid solubility from 47.5 to 52.0 at. pct Au at room temperature.15 The present paper reports the results of an investigation on the general tensile behavior of material in single crystal form. Some dislocation configurations characteristic of the deformed state are also reported. The results of a detailed study of the slip geometry in AuZn are presented in a separate paper.17 PROCEDURE Alloy preparation, crystal growing techniques, and the procedure followed in selecting specimens of minimum composition variation are reported elsewhere.17 Dumb-bell shaped tensile specimens were prepared by carefully machining single crystals in a jewellers&apos; lathe to a gage length of 0.80 in. and diam of 0.090 in. Back-reflection Laue X-ray patterns and room temperature tensile tests revealed that machining damage could be eliminated by electrochemically polishing 0.005 in. from the machined surface followed by annealing at 300°C for 1 hr. Specimens were polished in fresh 5 pct KCN solution (40°C, 12 v). Experiments were performed by gripping specimens in a self-aligning pin-chuck and threaded collet system, then straining in a floor model Instron tensile machine. All tests were performed in duplicate. Experimental variables included temperature, composition, and orientation. Unless otherwise stated the strain rate was 2.5 x 10"3 per sec. Liquid testing environments included nitrogen (WOK), nitrogen cooled petroleum ether (133" to 293"K), and silicone oil (293" to 488°K). Resolved shear stress-shear strain curves were electronically computed from autographically recorded load-elongation curves. Stress and strain were resolved on the macroscopic noncrystallographic (hkO) [001] system operative under the specific test conditions of temperature, strain rate, and orientation reported earlier.17 RESULTS The temperature dependence of the work-hardening curves is shown in Fig. 1 for gold-rich crystals of 51.0 at. pct Au oriented near the center of the stereo-graphic triangle. Over the range of intermediate temperatures from -200" to 400°K, they are very similar to those classically observed for fcc metals (reviewed by Nabarro et al.).&apos;&apos; The beginning of deformation is characterized by a region of decreasing hardening rate, stage 0, which is followed by a region of low linear hardening, stage I, and then a region of higher linear hardening, stage 11. At the higher temperatures, stage 111 is observed, a region of decreasing hardening rate. Over the intermediate temperature range, the extent of stage 0 and of the slow transition between stages I and I1 decreases with increasing temperature. Total ductility is large, often greater than 300 pct shear. As the temperature is either increased or decreased, the extent of stage I is decreased, giving rise to parabolic type flow and reduced ductility. Similar temperature effects have been reported for bcc ~r~stals.~~-~~ Below -14O°K, hardening is terminated in brittle fracture while above -400°K. initial hardening is followed first by work-softening and then by chisel-edge type ductile fracture. Stoichiometric (50.0 at. pct Au) and Zn-rich (51.0 at. pct Zn) crystals were also tested from 77" to -500°K. The effect of composition on the flow behavior is illus-

Jan 1, 1970

By A. W. D. Hills, M. R. Moore

An apparatus has been developed in which metals can bc solidified under closely controlled unidirectional heat flow conditions. The metals are cooled by a multiple-air jet system, designed so that the heat transfer coefficient is uniformly distributed over the cooled surface. They are contained in a special furnace system of low thermal mass which enables unidirectional heat flow conditions to be rigorously maintained for certain specific cooling rates. This apparatus has been used to study the solidijication of pure lead and pure tin at zero superheat, solid metal thicknesses being determined by thermal analysis, and by dipstick readings. Detailed thermal balances have been drawn up on the experiments in order to determzne the cooling conditions that most rigorously correspond to unidirectional heat flow. Solid metal thicknesses, measured experimentally for these conditions, have beetz shown to agree closely with the theoretical wedictzons of different integml-profile methods. lt is concluded that any errors inherent in the integval-profile method are no greater than the errors inherent in experimental investigations of solidification. A knowledge of the influence of heat transfer rates on the solidification of metals is essential to the understanding and control of industrial casting processes. Since very few formal methods are available for solving the heat conduction equation under solidification conditions several authors have developed approximate techniques for doing so. One of the most promising is the integral-profile technique that has been used by Goodman,1 Hills,2,3 Tien4 and Hills and ~oore&apos; to predict solidification rates under certain specific heat transfer coniditions. In the first of this present series of papers6 Hills has further generalized the method and developed a universal integral-profile technique that can be used to predict solidification rates under a wide variety of unidirectional heat flow conditions. Since the method is approximate it is necessary to investigate the accuracy with which it predicts actual solidification rates. A review of the literature7 shows that solidification rates have seldom been measured under accurately known heat transfer conditions and it was therefore decided to develop experimental techniques that would enable this to be done. Results obtained would then be available as a check on the approximate solutions already developed, and in the development of further solutions that would be applicable under more complicated conditions. The initial work in this experimental program which is described here, is concerned with the solidification of pure metals at zero superheat under unidirectional heat flow conditions. Subsequent experiments have been concerned with the solidification of pure metals at appreciable superheats, under varying unidirectional heat flow conditions and under two dimensional heat flow conditions. In a series of experiments recently initiated, the solidification of binary alloys is also being investigated. The results of these subsequent experiments, together with relevant theory, will be described in later papers. The solidifying metal has been cooled in all the experiments, by a multiple air jet system designed so that the heat transfer coefficient to the cooled surface is constant and is uniformly distributed over the surface. This type of system has been chosen since only one parameter is needed to specify the heat transfer conditions and since these conditions are analogous to those met in certain continuous casting processes.&apos; Air cooling was chosen in preference to water cooling, however, since it offers a wider range of heat transfer conditions, and since it can be investigated by analogous mass transfer techniques. The first part of this paper discusses the existing integral-profile solutions that correspond to the heat transfer conditions used in the experiments, and describes the development and use of the experimental apparatus. In subsequent sections the heat transfer and solidification results are presented, and the various theoretical predictions are compared with them, and with one another.

Jan 1, 1970

By E. J. Rapperport, J. P. Pemsler

The thermodynamic activities of zinc in six solid solution Cu-Zn alloys ranging from 5 to 35 at. pct Zn were determined experimentally in the temperature range 400° to 600°C. This low temperature investigation was canducted in order to evaluate techniques developed to utilize the inherently high sensitivity of atomic absorption flocesses in the measurement of thermodynamic activities. Analytical expressions ,for the activity and actizlity coeflcient are given for the six alloys in the temperature ranges investigated. RELATIVELY few experimental methods are available for investigation of thermodynamic activities of alloys, especially in the solid state. The techniques most frequently used have been the electrochemical potential and the effusion methods, both of which have severe limitations in many instances. It is therefore desirable to expand the ability to perform such measurements in order to obtain new information as well as to provide an additional independent verification capability. In this work, we present a significant improvement in the spectrophotometric method for sensing small vapor pressures in static absorption cells. Similar techniques have been used previously;1"5 however, applications had been limited to relatively high pressures, often greater than 1 torr. Prior investigators have, for the most part, used broad spectral sources such as xenon or mercury lamps, and high intensity arcs. Hollow cathode sources were first suggested in 1956 6 and were used soon afterwards.4&apos;5 These sources offer significant improvements in sensitivity and freedom from interfering spectral lines.&apos;-&apos; EXPERIMENTAL High purity zinc was obtained from Cominco Products, Inc., and copper from American Smelting and Refining Co. Both elements were of 99.999 pct purity. Copper-zinc alloys were vacuum melted in a high fired carbon crucible with each alloy pulled from the melt as a 4 -in. diam bar. The bars were swaged to -1/4 in. rods and vacuum annealed for 160 hr at 800° + 1°C. Samples for gross chemical analysis were taken at intervals along the length of the rods to ascertain the axial zinc gradient. Electron microprobe analysis of homogenized specimens indicated that the alloys had uniform compositions over their cross sections on a macro (200 p) and micro (1 u) scale to better than *1 pct (20) of the gross composition. This tolerance was determined by counting statistics, rather than assured composition fluctuations. All SiO 2 windows were high-ultraviolet-transmission grade to minimize intensity losses. Silica absorption cells were scrupulously cleaned consecutively in organic solvents, dilute HF, and distilled water before use. The empty cells were then flamed while under a dynamic vacuum, cooled, and removed to an argon-filled glove bag. Alloy pieces were cut and filed in the glove bag to produce fresh surfaces, and then loaded into the cells. The loaded cells were temporarily sealed, removed from the glove bag, reevacuated to 10-5 torr or better, and permanently sealed. The instrument used is schematically shown in Fig. 1. The spectral emission from a commercially made hollow cathode lamp (A) of a selected element is focused through an absorption cell (B) inside a well-controlled furnace (C). The intensity of the transmitted beam is measured using the spectrometer* (D) &apos;Techtron model AA4 atomic absorption spectrometer. which contains a grating (E) that disperses the light prior to impingement on the photomultiplier (F). The monochromator grating is adjusted so that only the wavelength of interest is measured. The power supply delivered an interrupted voltage to the lamp, causing a chopped radiation output to be transmitted. The detector read only the intermittent component of radiation incident upon it, so that all continuous noise signals (furnace radiation, and so forth) were eliminated. Three recording thermocouples contained in the muffle furnace were positioned along the length of the absorption cell: one at each end and one at the center. An effort was made to keep the ends of the cell several degrees hotter than the center to avoid window condensate. Appropriate thermal corrections were then necessary to relate cell pressure to radiation attenuation. Water-cooled heat shields, as shown in Fig. 1, were found to aid signal stability by protecting the hollow cathode and the photomultiplier from furnace radiation. The furnace had a 2-in. diam muffle, Kan-thal wound, with SiO 2 windows at its ends to minimize convective effects. The hollow cathode radiation was masked and focused to form a conic beam that was a maximum of { in. diam within the furnace. Thus, the 1.5 in. diam absorption cell easily contained the entire beam. The furnace was mounted on ball-bearing slides with positive positioning detents. This arrangement allowed the removal of the entire furnace assembly from the radiation path, position [I], Fig. 1, so that frequent sampling of the unattenuated beam intensity could be obtained. In all cases the beam intensity was kept constant to 0.1 pct as judged by readings taken immediately before and immediately after data collection. Only data for absorptions of less than 80 pct were utilized, as systematic deviations from linearity were found for greater absorptions.

Jan 1, 1970

By M. B. Kasen

eralized strain equation appear quite different they are really identical. This identity can be shown in a simple mathematical rearrangement. Referring to Eq. [I], the substitution of ln(1 +?E) for ? (where ?E is the engineering strain) yields: a =s8- (s8?so)e?1/?c) ln(1 +s8??E) [4] or s =s8?(s8?so)(l +?E)-1 [5] Replacing (1 + cE) with its equivalent, (l/lo): s=s8?(s8?so)l/€c [6] Adding and subtracting the quantity (s8 - so) yields: s=s8?(s8?so)+ (s8-so) l-(^)l/£c [7] = s0+(s8?so)ri-(^0)1/^l [8] Letting n = 1/?c it follows that: This equation will be seen to be identical to the generalized strain expression in Eq. [3], the coefficients a and b being equal to so and (s8?so)/?c or n(s8?so), respectively. Confirmation of the relationship noted above was provided by fitting experimental stress-strain data5 for 304 stainless steel (total strain from 0.072 to 1.15) at room temperature at a true total strain rate of 4 x 10-3 sec-1 to Eqs. [I] and [3]. In this study nonlinear regression analyses were used to evaluate the equation constants. The results of this evaluation are presented in Table I. When these constants are used in Eqs. [I] and [3] the curves obtained are coincident. It will also be noted that the value of n is equal to YE,, the value of a is equal to so, and the value of b is equal to (s8 - so)/Ec. These equalities are illustrated in Table I where the Voce constants in parentheses were calculated from a, b, and n values. Excellent agreement is seen to exist. It is concluded, therefore, that the Voce equation is, indeed, identical to the linear expression involving generalized strain. In applying the generalized strain concept to stress-strain data, it has been noted3 that data within what was termed the transition region (first few points in the plastic flow region) must be excluded from the analysis in order to obtain the linearity in Eq. [3]. A similar exclusion applies in the use of the Voce equation since an expression which would describe the strain-hardening region would usually be found to be not too effective in the elastic-plastic fillet2 which connects the elastic line to the strain-hardening region. These considerations further substantiate that Eqs. [I] and [3] do indeed describe identical behavior. Note added in proof. Since this manuscript was submitted for publication, correspondence with Professor S. R. Davies, University of Edinburgh, (of Ref. 3) indicated that his associates have also confirmed the identity between the Voce equation and the generalized strain concept. It is sometimes desirable to obtain a small grain size in super-purity metals. Unfortunately, the absence of impurities, the low recrystallization temperatures, and the low activation energies for boundary motion result in rapid growth of relatively few grains when conventional recrystallization practices are used. For example, Arajs et al.1 were unable to obtain a mean grain diameter less than about 0.4 mm in iron containing 38 at. ppm of impurity. The <1 at. ppm purity range in many modern superpurity metals results in yet larger limiting grain sizes. It is the purpose of this communication to describe a technique by which mean grain diameters as small as 30 µ have been produced in aluminum having an impurity content < 0.5 at. ppm. The technique should be applicable to superpurity metals other than aluminum and has potential applications to grain refinement of commercial alloys. The necessary and sufficient requirements for production of a small grain size are as follows: a) a large number of potential nucleating sites must be created randomly within the cold worked material, b) sufficient thermal energy must be provided at a rate that will simultaneously activate a large fraction of the potential nuclei, and c) the grain growth must be stopped shortly after grain impingement.&apos; A high density of potential grain nuclei may be cre-

Jan 1, 1970

By T. T. Field, M. Gell

MUCH has been learned about plastic deformation behavior in crystals through the use of dislocation and slip band etchants. Slip in nickel and nickel-base alloys has previously been revealed by various etching techniques.l-5 The techniques for nickel-base super-alloys4,5 were successful only in the Udimet 700 composition in specific heat-treated conditions. The objective of this work was to develop a more generally applicable slip-band etching procedure. The nominal compositions of the alloys used in this study are listed in Table I. The low carbon Mar-M2OO alloy referred to in the text is the same as listed in Table I with the exception that the carbon content is less than 100 ppm. Mar-M200 and Udimet 700 were solutionized at 2250" and 2150°F, respectively. The aging treatment for both cast alloys was 32 hr at 1600°F and for wrought Udimet 700 was 4 hr at 1975"F, 24 hr at 1550°F, and 16 hr at 1400°F. The new slip-band etching technique consists of a chemical etch followed by a short electropolish, Table 11. Fig. l(a) shows the best result obtained on an internal section of a plastically deformed single crystal of Mar-M2OO when using a conventional slip-band etching procedure which consists of electropolishing followed by etching. Ghostlike traces corresponding to planar slip bands are observed, but the contrast between the bands and the background is weak. Fig. l(b) shows the same field using the new slip-band etching technique. After the etching step of this technique, the same ghostlike traces of Fig. l(a) are observed, but the subsequent electropolishing accentuates the slip bands and the subgrain boundaries while the rest of the matrix is being polished. Longer electropolishing obliterates the slip bands. The new slip-band etching technique makes use of the etchants and electrolytes that are normally used for a given material. Because of this, it should be possible to slip-band etch other nickel-base superal-loys by using existing etchants and electrolytes for a material and following the procedures outlined in the "Comments" section of Table 11. All the illustrative examples given below show internal plastic deformation in single crystals of regular and low carbon Mar-M200 in the solutionized and

Jan 1, 1970

By H. L. Marcus, P. W. Palmberg

As can be seen from the phase diagram A1-W1 the equilibrium solubility of tungsten in aluminum is practically nil at room temperature. By quenching from the liquid state (50,000°C per sec), Varic, Burov, and Kolesnicenko2 obtained A1-W solid solutions up to 0.15 at. pct W. The quenched alloys were in the form of foils, 0.2 to 0.3 mm thick. Considering the results of Duwez and Willens,3 it is obvious that this thickness, which makes impossible a sufficiently rapid quenching, was the main reason for the relatively low content of tungsten dissolved in aluminum found by Varic.2 he present note shows that the metastable solubility of tungsten in aluminum can be appreciably extended in aluminum-rich A1-W alloys. The quenching technique and the procedure employed for the preparation of the alloys have been described previously.475 The resulting quenched flakes varied in thickness from 1 to 20 µm from experiment to experiment. However, the measurements of the lattice parameters were carried out only with flakes thinner than 5 µm. The areas of quenched flakes were between 0.1 and 15 mm2. The quenched flakes were placed into a 0.3-mm glass capillary tube which was then mounted in a 114.6-mm-diam Debye-Scherrer camera. Straumanis asymmetric film position and nickel-filtered CuKa radiation were used. The lattice spacings were computed taking X(CuKa1) = 1.54050A for resolved and ?(CuKa) = 1.54178A for unresolved doublets. All specimens were rotated at room temperature, 26" +2°C. The lattice parameters were estimated from extrapolation against the Nelson-Riley function. It was estimated that the error in the lattice parameter of the measurements on a single film lies within +0.0004A for lower and about +0.001A for higher concentrations of tungsten. The lattice parameters of the metastable solid solutions A1-W are plotted vs the concentration of tungsten in Fig. 1 together with the parameters measured by previous investigators.&apos; Each point of the present measurements represents a determination of the lattice spacing on different quenched flakes, for a given concentration of tungsten. With experimental accuracy, the lattice parameters of the metastable solid solutions fall on the straight line passing through the already known data.&apos; As estimated from the uncertainties in the lattice spacings of the solid solutions, the alloys were homogeneous within 0.1 at. pct W. The solubility of tungsten in aluminum-rich A1-W solid solutions obtained by a very rapid quenching technique is increased to about 0.95 at. pct W. This value is 6 times greater than the amount known up to now. -he lattice parameters of the resultant aluminum solid solutions with higher concentrations of tungsten than 0.95 at. pct W did not remain constant AUGER electron spectroscopy has been used to clarify the role of impurities in the embrittlement of AISI 3340 steel. Analysis of fracture surfaces has shown that the embrittled condition is correlated with appreciable antimony segregation at grain boundaries. The low temperature (400" to 600°C) temper embrittlement of low alloy steels containing various combinations of Cr, Ni, Sb, Mn, P, Sn, and As has been examined extensively for many years. General reviews of the area have been made by McMahon1 in 1968, LOW&apos; in 1959, woodfine3 in 1953, and Holloman4 in 1946. Recent work by Low, Stein, Turkalo, and LaForce5 has done much in separating the alloy and

Jan 1, 1970

By G. P. Tiwari

Recrystallization and grain growth in thoria dispersed nickel and nichrome were recently studied by Webster as a function of temperature and deformation. The unexpected part of these results was that specimens which had received heavier deformation developed greater resistance to recrystallization. Retardation of recrystallization was accompanied by the formation of voids around thoria dispersion. To explain these results, Webster suggested that the formation of void around the particles increased the effective size of thoria particles. This resulted in greater impediment to the grain-boundary migration and as a consequence the recrystallization of the matrix is retarded. In the present note an alternative and more probable explanation for the effect of voids on recrystallization is presented. The exact mechanism of void formation in thoria dispersed nickel or nichrome is not known. However, it is reasonably certain that it must be preceded by the stress concentration in the matrix around thoria dispersion during the deformation.&apos;&apos; The resulting stress concentration must be sufficient enough to supply the surface energy for the new surfaces created. Further, the decrease in the strain energy of the matrix surrounding the potential void nucleus must be larger than the surface energy of the newly created surface. The release of strain energy due to formation of crack results in a strain free cylinder of the material around the voids.13 If the void formation is not localized, at few points only (as is the case here), this process may lead to considerable amount of release of strain energy of the matrix. The pattern of recrystallization behavior of single phase homogeneous matrix as well as the matrix having a second phase dispersion is same except for the fact recovery and recrystallization are more clearly delineated.14 In general, the recrystallization temperature is lowered (i.e., recrystallization is easier) with increase in the amount of cold work. This is due to the increase in stored energy in the matrix with increasing amount of deformation. If somehow there is a relaxation of strain energy in the matrix, the recrystallization should become difficult because of the decrease in the amount of stored energy available for recrystallization. Since the formation of voids leads to a decrease in the strain energy of matrix, the recrystallization of the matrix would be inhibited due to the formation of voids during deformation prior to recrystallization. It has been observed by earlier workers15&apos;16 that the presence of preexisting voids in a matrix retards the recrystallization. The essential issue here is how do the voids act to produce this effect. If the voids influence recrystallization only by blocking the grain boundary migration, then the effect should be maximum when they are present almost exclusively along grain boundary. These conditions are obtained during high temperature deformation. However, the voids produced due to creep along grain boundary are not able to prevent recrystallization17 suggesting that they are not effective in blocking grain boundary movement. Recently it was shown by Davies and Williams that the voids can act as sinks for vacancies." As a result the processes dependent on vacancy diffusion like recovery, recrystallization, dislocation climb, and so forth, will be hindered. This fact may be responsible for inhibition of recrystallization during subsequent deformation and annealing cycles. It is to be noted here that there is a large difference between the density of voids in creep experiments and the other experiments where retarding effect of voids on recrystallization is seen. The voids in former may number up to l04 to l05 per sq cm whereas in latter cases the voids density is typically around 1010 to 1013 per sq cm. It appears that the decrease in supply of vacancies in creep is insufficient to adversely affect the recrystallization due to low void population. The author is grateful to P. Das Gupta and S. P. Ray for helpful discussions. Author&apos;s Reply D. Webster Tiwari appears to have misunderstood the nature of grain boundary-particle interactions. Tiwari (quoting Cahn) states that second phase particles become more effective as they become smaller, therefore as the voids in TDNiC make the thoria particles effectively bigger their ability to resist grain boundary movement is impaired. This particle size argument was originally proposed in the form of an equation by Zener 20 years agol9 and is not necessarily valid as is discussed below. However, assuming it is valid, it predicts a greater boundary restraining effect by smaller particles simply because their combined cross sectional area is greater at a constant volume. If the number of particles remains the same and their effective size increases, as in the present case, Zener&apos;s equation predicts a greatly reduced grain size. This is because the effect

Jan 1, 1970

By R. D. Nelson, F. E. Bowman

Assumptions are made of ideal mixing and that the density of silver can be obtained by extrapolating reported liquid density-temperature data through the freezing point back to the temperature range of interest. The results of this procedure using liquid silver density data of Kirshenbaum et al.5 are presented in Table I1 where it is observed that agreement is everywhere within <0.1 pct and generally is within 0.05 pct. Because the Sn-Ag alloys are dilute, the assumption of ideal behavior is, therefore, probably justified. In conclusion, the densities of dilute liquid solutions of silver in tin have been determined. Even for concentrations as low as 0.1 pct, the effect of silver on the density of liquid tin is clearly measurable. This work also suggests that for dilute alloys at temperatures far below the freezing point of the solute metal, densities may be accurately calculated by extrapolation of the pure metal data without having recourse to physical measurement on the alloy itself. plutonium having a grain size of about 100 µ. This paper presents data showing that large elongations of fine-grained a Pu can be obtained by using slow deformation rates. Large plasticity, however, of a Pu in compression has been observed.4 Reductions in thickness of 90 pct have been observed with no edge cracking. These large reductions are accompanied by concurrent re-crystallization. The deformation modes, which are quite complex, have been studied extensively by observing the deformation microstructures of polished surfaces that had been deformed in compression.5-7 Although slip apparently is a predominant mode of deformation at room temperature, grain boundary sliding and concurrent recrystallization become more predominant at high a temperatures.4&apos;7 Although recovery occurs,8,9 no grain growth has been reported in a Pu even at temperatures near the a =ß equilibrium temperature (-115oC), which is 0.7 of the calculated melting temperature of a Pu.10 From studies on other materials, it appears that high elongations can be obtained in alloys when the THE purpose of this technical note is to present briefly some data revealing high ductility of a Pu, which is normally considered brittle. The very low ductility of a Pu in tension has been reported by many investigators.&apos;-3 Gardner,1 for example, reported that the total elongation of a Pu at a testing speed of 0.015 ipm is less than 0.1 pct at room temperature and only about 1 pct at 100°C. The only tensile creep studies that have been reported&apos; indicate no large ductility, but they were performed on relatively low purity

Jan 1, 1970

By A. Tonejc, A. Bonefacic

As can be seen from the phase diagram A1-W1 the equilibrium solubility of tungsten in aluminum is practically nil at room temperature. By quenching from the liquid state (50,000°C per sec), Varic, Burov, and Kolesnicenko2 obtained A1-W solid solutions up to 0.15 at. pct W. The quenched alloys were in the form of foils, 0.2 to 0.3 mm thick. Considering the results of Duwez and Willens,3 it is obvious that this thickness, which makes impossible a sufficiently rapid quenching, was the main reason for the relatively low content of tungsten dissolved in aluminum found by varic.2 he present note shows that the metastable solubility of tungsten in aluminum can be appreciably extended in aluminum-rich A1-W alloys. The quenching technique and the procedure employed for the preparation of the alloys have been described previously.475 The resulting quenched flakes varied in thickness from 1 to 20 µm from experiment to experiment. However, the measurements of the lattice parameters were carried out only with flakes thinner than 5 µm. The areas of quenched flakes were between 0.1 and 15 mm2. The quenched flakes were placed into a 0.3-mm glass capillary tube which was then mounted in a 114.6-mm-diam Debye-Scherrer camera. Straumanis asymmetric film position and nickel-filtered CuKa radiation were used. The lattice spacings were computed taking X(CuKa1) = 1.54050A for resolved and ?(CuKa) = 1.54178A for unresolved doublets. All specimens were rotated at room temperature, 26o +2°C. The lattice parameters were estimated from extrapolation against the Nelson-Riley function. It was estimated that the error in the lattice parameter of the measurements on a single film lies within +0.0004A for lower and about +0.001A for higher concentrations of tungsten. The lattice parameters of the metastable solid solutions A1-W are plotted vs the concentration of tungsten in Fig. 1 together with the parameters measured by previous investigators.&apos; Each point of the present measurements represents a determination of the lattice spacing on different quenched flakes, for a given concentration of tungsten. With experimental accuracy, the lattice parameters of the metastable solid solutions fall on the straight line passing through the already known data.&apos; As estimated from the uncertainties in the lattice spacings of the solid solutions, the alloys were homogeneous within 0.1 at. pct W. The solubility of tungsten in aluminum-rich A1-W solid solutions obtained by a very rapid quenching technique is increased to about 0.95 at. pct W. This value is 6 times greater than the amount known up to now. -he lattice parameters of the resultant aluminum solid solutions with higher concentrations of tungsten than 0.95 at. pct W did not remain constant AUGER electron spectroscopy has been used to clarify the role of impurities in the embrittlement of AISI 3340 steel. Analysis of fracture surfaces has shown that the embrittled condition is correlated with appreciable antimony segregation at grain boundaries. The low temperature (400" to 600°C) temper embrittlement of low alloy steels containing various combinations of Cr , Ni , Sb , Mn , P , Sn , and As has been examined extensively for many years. General reviews of the area have been made by McMahon1 in 1968, LOW&apos; in 1959, woodfine3 in 1953, and Holloman4 in 1946. Recent work by Low, Stein, Turkalo, and LaForce5 has done much in separating the alloy and

Jan 1, 1970

By Takeyasu Ito, Mayumi Someno, Kazuhiro Goto

SINCE the pioneering work by Kiukkola and Wagner,1 many experiments have been reported on solid electrochemistry at elevated temperatures. However, the studies have been confined to experiments under isothermal conditions. One may conceive many situations under nonisothermal conditions. With two different temperatures T1, and T2 at the two electrodes, the electromotive force, E of a Galvanic cell will be expressed by the following equation under a steady state heat transfer in solid electrolytes of zirconia-lime and thoria-lime. E = ^ $ l&-dGO2+a(T2-Ti) [1] where tO2- is the transference number of oxygen ions in the electrolyte, Go, is the chemical potential of oxygen, and a is the coefficient of the thermoelec-tromotive force due to the temperature difference. The objective of the present study was to evaluate the coefficient of the thermoelectromotive force for zirconia-lime and thoria-lime under isobaric condition. The physical meaning of this coefficient is out of the scope of the present communication. The experimental cell assembly is schematically shown in Fig. 1. The zirconia-lime electrolyte tube and thoria-lime electrolyte tube were 8.0 mm OD and 5.0 ID, from commercial sources with chemical analyses of 94.8 wt pct ZrO2, 3.85 pct CaO, 0.83 pct SiO2, 0.25 pct TiO2, and 0.05 pct Fe2O3; and 95.0 pct ThO2, 4.0 pct CaO and rare earth metal oxides, respectively. The specific gravity was 5.5 g per cu cm for zirconia-lime and 9.8 g per cu cm for thoria-lime. Original powder size before shaping and sintering the tube was several microns for both electrolytes. The distance separating the two electrodes was 4.0 or 5.0 cm. Platinum wire of 0.5 mm diam was used for the electrodes. The temperature gradient was controlled by heating one electrode with a small heating coil of nichrome wire. The temperatures at the two electrodes were measured with two calibrated Pt-13 pct Rh:Pt thermocouples, directly contacting the two platinum electrodes. The atmosphere was either air or pure oxygen. The partial pressure of oxygen in air was considered equal at the vicinities of the two electrodes, with negligibly small thermal segregation in the gas phase. The difference of the chemical potential of oxygen was controlled only by the temperature difference at the two electrodes and not by the oxygen pressure difference. The temperature ranges were 600" to 1200°C for zirconia-lime and 850" to 1200°C for thoria-lime electrolytes. Fig. 2 shows the relation of the measured electromotive force and the difference of the oxygen chemical potential at the two electrodes for zirconia-lime and thoria-lime electrolytes. The electromotive forces in the figure were measured by a *0.05 mv potentiometer. The chemical potential difference was calculated by the following equations.&apos;

Jan 1, 1970

By Joshua Pelleg, G. M. Lindberg

THERE are three reported investigations of self-diffusion in niobium. Lundy et al.1 found their self-diffusion data well represented by the equation

Jan 1, 1970

By R. R. Hart, B. C. Wonsiewicz, G. Y. Chin

In recent years there has been increased miniaturization of electromechanical devices to keep pace with current trends toward smaller electronic components. A major problem facing the designer, however, is the higher stresses encountered by the material as a result of shorter springs. Hence an improvement in the elastic limit, as approximated by the 0.01 pct offset yield strength, would be highly desirable. An increase of 25 pct in the yield strength, for example, will permit a 20 pct reduction in both the length and thickness of a cantilever-type spring while maintaining the same compliance. One technique of improving the yield strength that has received little commercial attention is crystal-lographic texture strengthening.1,2 Texture strengthening is expected to be most beneficial in materials of hcp structure, but considerable gain can also be expected in cubic materials. A wire with a (111) fiber texture, for example, is expected to be 20 pct stronger than randomly oriented material, and 50 pct stronger than wire with a (100) fiber texture.293 For sheet specimens with a {110}(112) texture, characteristic of many heavily rolled fcc alloys, the (111) transverse direction is expected to be the maximum yield strength direction, about 20 pct higher than that in the (112) rolling direction.&apos; In addition, the (111) direction is the direction of maximum modulus of elasticity for most cubic alloys. A large value of the elastic modulus could be desirable in designs where stiffer springs are required. To test the above idea, a 0.090 in. (-2.3 mm) thick commercial grade A (5 pct Sn) phosphor bronze sheet, a widely-used material for relay springs, was rolled from the spring-tempered condition (60.5 pct reduction) to various additional reductions up to a total reduction of 95 pct. Subsequently, additional material was obtained with a total thickness reduction of 97.3 pct Standard tensile specimens were prepared from the sheet material with the tensile axis parallel to and at 90 deg to the rolling direction. Tests were run on an Instron testing machine at a strain rate of about 0.050 min-l. Textures were determined by the use of the reflection pole-figure technique. Data were obtained using nickel-filtered CuKa radiation and with the aid of a Siemens pole figure goniometer. The X-ray pole figure studies show an incrzasing development of the texture toward the {110}(112) ideal

Jan 1, 1970

By A. F. Crawley

THIS communication reports measurements of the densities of dilute liquid alloys of 0.1 and 0.5 pct Ag in Sn over temperature ranges of 170" and 210°C, respectively, above the melting point of pure tin (232°C). The work was earried out to provide accurate density data for some liquid diffusion studies performed by Davis.1 Densities were measured using a pycnometric technique established in this laboratory. Earlier papers2, 4 attest to the accuracy of ±0.05 pct and the reliability of the method. Tin, 99.999 pct pure, and silver 99.99 pct pure, were melted in a graphite crucible in a vacuum furnace and held at temperature for 10 hr to ensure homogenization. Ingots suitable for machining

Jan 1, 1970

By J. W. Edington

THE Hopkinson bar has become a popular technique for the measurement of the mechanical properties of materials deformed at high strain rate. Maximum use of the equipment is made in the arrangement first used by Kolskyl in which a short compression specimen is sandwiched between two pressure bars and is loaded by a single pulse travelling through the system. The pressure bars are used both to apply the load to the specimen and as transducers to obtain continuous strain-time histories of three pulses, incident on, reflected, and transmitted by the specimen. The data measured by the pressure bars can be analyzed in terms of the stress/strain behavior of the specimen.2&apos;3 However, one of the assumptions of the analysis of the observed pulses is that the total stress and total strain do not vary significantly from point to point within the specimen at any given instant during the deformation process. Although this assumption is generally justified for very short disc-like specimens2 the situation is uncertain for larger specimens. For example, at small plastic strains (-0.01) Hauser et al.2 have some evidence of small flucations in the total stress within the crystal during deformation, even in relatively short aluminum specimens. In addition, Karnes4 has shown that the plastic strain, and by inference strain rate, is different at each end of a compression specimen tested in a Hopkinson bar, although the length of the specimen was not specified. Recently, the mechanical properties and the dislocation substructure have been investigated in single crystals of columbium5 (length 0.25 in., diam 0.19 in.), and copper6 (length 0.5 in., diam 0.5 in.) deformed at high strain rates. As part of this research program the assumption that the plastic strain is constant throughout the specimen has been checked by measuring the total dislocation density as a function of position in the specimen. Compression specimens of the same orientations and dimensions were tested as described previously5,6 sing a split Hopkinson bar. Since any discontinuity in strain distribution is most likely to arise during the initial stages of deformation the investigation was performed on specimens deformed to plastic shear strains of 0.054 (copper) at a strain rate 1.2 x l03 sec-1, and 0.06 (columbium) at a strain rate 1.5 X l03 sec-1. The orientation of the single crystals is shown in Figs. 1 and 3. Thin foils were taken parallel to the most highly stressed slip plane, i.e., (111) in copper and (011) in columbium, using conventional disc techniques. The dislocation densities were measured using first order reflections with compensation for invisible dislocations.5&apos;6 In the copper single crystals the discs were randomly distributed throughout the cross section of the specimen. However, the dislocation density obtained from each disc was plotted vs the disc positions relative to the ends of the specimen. The results for the copper specimens are shown in Fig. 1. Clearly the dislocation density is constant throughout the main portion of specimen within the experimental error. The error bars on the dislocation densities correspond to a shear strain variation of 0.015 on the basis of previous measurements% ± of the rate of increase of dislocation density with strain in copper single crystals of the same geometry. Thus within this experimental error the plastic strain can be concluded to be constant within the specimen and the assumptions used in the analysis of the stress/time curves are therefore reasonably valid. The higher measured dslocation density near the impact end and the lower dislocation density at the bar end of the copper specimen is in agreement with the results of Karnes4 who showed that this strain/time curve rose to a maximum more rapidly at the impact end compared with the bar end. Hauser et al.2 have also pointed out that at small plastic strains (-0.01) the strain at the impact end of the specimen may be greater than that at the bar end. Thin foils taken from different points within the columbium single crystals demonstrated that the dislocation density could vary significantly within the specimen, see Fig. 2. Large areas of some thin foils up to 30 µ sq contained very few dislocations, see Fig. 2(a). However, in other parts of the compression specimen dislocation configurations like those shown in Fig. 2(b) existed over large areas (-30 µ sq). As a result, when the average dislocation density in a thin foil is plotted as a function of the position of the thin foil relative to the ends of the specimen, considerable scatter is observed, see Fig. 3. In this material then, the local dislocation density, and consequently the

Jan 1, 1970

By L. H. Sjodahl, J. B. Conway

of each particle on grain boundary movement is proportional to the area it occupies on the grain boundary and this increases with the square of the particle radius. In contrast to the impression gained by Tiwari the effectiveness of a particle, as a grain boundary obstacle, increases rapidly as the particle size increases. The counterbalancing factor in a dispersion of constant volume (e.g., those considered by Zener) is of course the rapidly diminishing number of particles, a situation which does not exist in thoria dispersed materials where the volume fraction of thoria remains constant. Although it has been assumed that the Zener approach is valid for the sake of the above argument, it is open to the following objections: 1) It assumes that the effect of many small particles along a grain boundary is cumulative and does not take into account the possibility of each small particle being overcome separately. In this case the boundary will not be able to move forward until the largest particle on the boundary has been overcome. This means that the rate controlling factor will be the rate at which a few relatively large particles are overcome with the remaining small particles playing a negligible role. 2) When the dispersion consists of very small particles the interparticle spacing is usually small compared to the grain size and most particles are located away from grain boundaries where they can play no part. The most efficient dispersion, from a purely geometrical viewpoint, is one where the particle spacing is equal to the grain size so that all the particles are on grain boundaries. Tiwari&apos;s second point that voids cannot prevent re-crystallization seems to be unfounded as several workes20-23 have shown that voids alone can retard grain boundary movement and recrystallization. To further convince Tiwari, Fig. 17 shows a void in deformed TD Nichrome holding back a recrystallization interface. Tiwari&apos;s explanation for the effect of voids on recrystallization, i.e., they reduce local strain energy and hence lower the driving force for recrystallization may be valid in itself but is irrelevant to the present case where even complete recrystallization after ONE of the more recently proposed expressions for describing stress-strain behavior is that due to Voce.1,2 This equation is usually written: s =s8 ?(s8?so)e??/?c [l] where s is the true stress, ? is true strain, cC is a constant called the characteristic strain, s8 is the asymptotic stress approached at high strain values, and so is the threshold stress at which the plastic deformation begins. While this expression has not been universally accepted as yet it does contain certain features which are consistent with experimental stress-strain behavior. In a more recent publication Hsu, Davies, and Royles3 employed the concept of generalized strain proposed by seth4 and identified a method for linearizing the stress-strain plot. In this approach the generalized strain was given by: where 7 is the generalized strain, 1 is the instantaneous length, 1, the datum length, and n is a constant called the "coefficient of strain measure". A value of n was said to exist which would yield the linearity: s —s+ S[.-(tf] [3] In recent studies of both these approaches, it has been found that while the Voce equation and the gen-

Jan 1, 1970