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By J. H. Swisher

The solubility of graphite in CaO-S2O2-Al,O3 slags was measured by equilibrating slag samples with graphite crucibles and CO gas. Carbon contents as high as 2 ut pct were obtained in CaO-saturated, CaO-A1,O3 slags, and 1.3 wt pct in slags of the composition CaO.Si0,. Although the observed conditions for Sic formation were in agreement with those predicted from thermodynamic data, CaC, was found to form at a lower temperature than predicted frotn thermodynamic data. From measurements of the equilibrium carbon content as a function of CO Partial pressure, it was found that carbide ions dissolve in CaO-A12O3 melts with a valence of minus two. The carbon content increased with CaO concentration in Ca0-Al,O3 melts and increased with SiO, content along the CaO'AlO3-CaOSi0 join in the ternary system. When solid CaC2 was added to CaO-A12O3 and CaO-SiO2-A12O3 slags, it was found that one of the oxides in the slag was reduced by the carbide (Al2O3 in the forrner and SiOz in the latter). In electric furnace steelmaking, a double-slag practice is frequently used to meet alloy specifications. Initially a flush slag, which is oxidizing in nature, is used to remove phosphorus and carbon from the steel bath. Later in the refining period, the flush slag is replaced by a highly reducing carbidic slag. When calcium carbide is formed in or added to a finishing slag, the slag is effective as a desulfurizing agent and also permits alloying elements such as chromium, vanadium, and tungsten to be added to the slag in the form of oxides. The oxides are readily reduced by calcium carbide, thereby minimizing the use of expensive ferroalloys. More work has been done on the thermodynamics of silicon carbide in slags than on calcium carbide. Baird and alor' and Kay and alor' determined the free energy of formation of Sic by measuring the partial pressure of CO in equilibrium with solid silica, silicon carbide, and graphite. Using a similar technique, they determined SiOz activities in CaO-SiOz and Ca0-Si0,-A1203 slags. Rein and chipman3 also determined the free energy of formation of Sic using slag-metal equilibrium measurements. A literature survey has uncovered only one experimental study of the behavior of CaC, in slag systems. Shanahan and cooke4 report the results of some preliminary experiments on the solubility and stability of CaC, in a CaO-A1,03 and a Ca0-Si0-A1,03 slag at a temperature of about 1500". The carbon solubility as CaC, in a slag containing 50 pct CaO and 50 pct A1203 was reported to be 0.6 pct. They also review earlier work on the binary CaO-CaC, system. A eutectic exists in this system, but various investigators disagree on the eutectic temperature and composition. eal has given an explanation for carbide furnace erruptions in terms of the thermodynamic properties of CaC,; his analysis is not based on experimental data, but on compiled data for the free energies of formation of CaC, and CO.' , These data for steel-making temperatures are all extrapolated from the results of low-temperature measurements. In the experiments described in this paper, slag samples were equilibrated with graphite crucibles and with mixtures of CO and argon or with CO gas at 1 atm total pressure for measurement of the carbon solubility. Most of the work was done on Ca0-A1203 binary slags, although in some experiments CaO-SiO, and Ca0-Si0,-A1,03 slags were used. EXPERIMENTAL Slag samples of the desired composition for the solubility measurements were obtained by blending pre-fused master slags. The master slags were prepared by fusing mixtures of reagent-grade CaC03 with either A1,03 or Si0, in a graphite crucible. The master slags were crushed, then decarburized in air in a muffle furnace at 1200O C. A schematic diagram of the apparatus is shown in Fig. 1. The source of carbon for the solubility meas-

Jan 1, 1969

By K. J. Anusavice, R. T. DeHoff, H. Oikawa, J. J. Pinajian

STUDIES of nickel self-diffusion and impurity diffusion in pure metals and alloys have, for the past two decades, employed predominantly the nickel radio-However, because of the low energy of the emitted particle, careful and time-consuming techniques must be used to obtain reproducible measurements. In our studies of nickel diffusion into copper, we have recently used Ni66 [Td1/2: 55 hr; : 0.20 Mev (100 pet)] which decays to it much more suitable as a tracer because of the presence of the high-energy y radiation from the cu66 daughter. Although the half-life of Ni66 is appreciably shorter than that of Ni63, the useful working lifetime of a small quantity, " 10 mc, is about 1 month. preparation bf Ni66. he Nis6 radioisotope was produced at Oak Ridge National Laboratory by means of a double (n,y) reaction:

Jan 1, 1969

By P. K. Strangway, H. U. Ross

Briquets consisting of pure artificial magnetite, pure artificial hematite, and mixtures of the two were reduced by hydrogen in a loss-in-weight furnace at temperatures in the range 500° to 1000° . The rate of reduction of the pure hematite briquets increased continuously with increased temperature. In contrast, the pure nmgnetite briquets exhibited a pronounced rate ninimutn at about 700°C. Metallographic studies of partially reduced briquets rerlealed that, at this temperature, the he.matite samples reduced in a topo-chemical manner while the magnetite ones reduced uniformly throughout, and after partial reduction their cross sections contained a mixture of iron and unreacted wustite grains. No iron shells could be detected on the surfices of any of these uwstite grains. X-ray diffraction investigations indicated that these grains had a rzinimum lattice parameter when they had been formed at the rate rninimum temperature. Also, it was found that an activation energy of 41,000 cal per mole zoas required for reduction when only these wustite grains were present. Thus, it is suggested that the overall reduction rate of the rnagnetile su?nples at temperatures in the range influenced by the rate nzinirnum phenomenon was limited by the rate qf iron ion diffusion in the unreacted wustite grains. THE rate minimum phenomenon, which has often been observed when reducing iron oxides at a temperature of about 700°C, is one of the most interesting, yet unresolved, problems in the field of reduction kinetics. Basic principles of chemical kinetics and 'In some instance, a second rate minimum has been observed at about 900°C. Since most investigators are in agreement that this minimum is directly related to the transformation from a to y iron (which takes place at 911°C) and since it was not encountered during the present reduction tests, it will not be referred to in this vaver. fundamental laws of diffusion all agree that, as the temperature is increased, the rate of reduction should also increase. However, with certain ores, it has been found that their reduction rate actually decreases with an increase in temperature up to some value X where a minimum reduction rate is reached. With further temperature increases beyond X the rate becomes more rapid again. Temperature X is usually referred to as the "rate minimum temperature", while the overall type of behavior constitutes the "rate minimum phenomenon". This phenomenon has been reported by numerous investigators. They have found rate minima during the reduction of both artifiial' and natural374 magnetites and artificia15j6 and natural5" hematites. Rate minima have been observed when reducing high-purity material2 or low-grade ores,3'4 when studying particles in the micronsize range5 or relatively large agglomerates,g10 and during reduction with either hydrogen7 or carbon monoxide.11"2 Previously, this phenomenon has been attributed to many factors; these include sintering and recrystallization of the iron formed during reduction374 changes in microporosity of the ore upon redction,"" formation of dense iron shells around retained wustite grains,11716 and chem-isorption,17 to name only a few. However, most investigators who have reported a rate minimum merely speculated as to what seemed to influence it and they did not examine the fundamental causes. Consequently, the present experimental study was initiated in order to evaluate the basic factors which could be associated with this phenomenon. MATERIALS AND METHODS The experimental techniques, followed during this investigation, are similar to those which have been described previously.18 The chemically pure magnetic powder was prepared by partially reducing Fisher reagent-grade hematite with a gaseous mixture of carbon monoxide and carbon dioxide in a rotating-drum furnace. Three-quarter-inch diam cylindrical briquets which weighed about 12 g were formed from this magnetite powder and pure hematite powder. All of the briquets were sintered while they were slowly raised through the 1200°C hot zone of a vertical tube furnace. An argon stream was continually flushed through this furnace in order to prevent oxidation of the magnetite briquets, while in the case of the pure hematite briquets sintering was carried out in air. The sintered hematite briquets had a density of 5.06 g per cu cm while the density of the sintered magnetite briquets was 4.27 g per cu cm. The sintered briquets were reduced by purified hydrogen in a loss-in-weight furnace at temperatures in the range 500" to 1000°C. In all instances, the critical reducing gas velocity was exceeded and, in order to ensure that the results were reproducible, duplicate briquets of each type were reduced under each set of experimental conditions. A continuous record of the weight loss during reduction was obtained with the aid of a Statham transducer. The present experimental setup was capable of detecting a change in weight as small as 10 mg. Since a weight loss of over 2 g usually occurred during each reduction test, an accuracy of better than 0.5 pct of the total weight loss could be achieved. RESULTS AND DISCUSSION Reducibility Tests. In the first set of experiments, pure hematite and pure magnetite briquets were used.

Jan 1, 1969

By David V. Ragone, James A. Craig, Richard E. Balzhiser

The Gibbs free energies of formation of UC2 and UC were measured by equilibrating two-phase mixtures of UC2 + C and UC, + UC with liquid bismuth. The measured equilibrium concentrations of uranium in the bismuth combined with available activity coefficient information yielded uranium activities in these two-phase regions. Measurements on UC2 were performed over the range 1015 to 1160 K and on UC over the range 1115° to 1165°K. The values obtained for UC2 are in excellent agveement with values determined using combustton calorimetry and low-temperature heat capacity measurements. The UC values are in fair agreement with the calorimetric values, differing by about 10 pct from the calorimetric determination. MUCH interest has been shown in the uranium carbides in recent years because of their potential as nuclear fuels. As nuclear reactor operating temperatures have been raised to increase thermal efficiency, new fuels have been required. The uranium carbides are of interest because of their high melting points, >2000°C, high thermal conductivity, and resistance to irradiation damage. The manufacture and use of uranium carbides are aided by a knowledge of their stability and reactivity under various conditions. In this regard the thermo-chemical properties of the carbides, i.e., heat capacity, heat of formation, free energy of formation, and so forth, are particularly important. A great amount of work has recently been done on the thermodynamics of the U-C system. Unfortunately, however, there has not been good agreement among the various investigations. This study of the free energies of formation of uranium monocarbide and uranium di-carbide in the temperature region 1100°-1200° K was undertaken to help clarify the situation. It should be noted that in the temperature range of this investigation, 1100°- 1200° K, the thermodynam-ically stable phase in equilibrium with graphite is U2C3, not UC2, Fig. 1. However, U2C3 is reported to be stable only under extremely low oxygen and nitrogen pressure. Although UC2 is metastable below 150O°C, it exists under most experimental conditions. It should also be noted that "UC," never exists as UC2 but with compositions near UC1.9. However, "UC2" will be used to designate the dicarbide phase except when the stoi-chiometry is necessary for clarity. METHOD The approach taken in this study of the free energies of formation of UC and UC2 was to determine the thermo- dynamic activities of uranium in the two-phase regions UC, + C and UC + UC, by equilibrating the two-phase mixtures with the liquid bismuth. When a mixture of solid UC2 + C is brought to equilibrium with liquid bismuth, the reaction that occurs is: Neither carbon nor UC, could be detected as dissolved material in the bismuth. The standard free energy for this reaction may be written: In the two-phase region UC, + C, Fig. 1, the thermo-dynamic activities of UC2 and carbon are unity. The activity of uranium in this region was determined by measuring the concentration of uranium in a liquid bismuth melt in equilibrium with the two-phase mixture. This concentration was then used in conjunction with the activity coefficient data of uranium in bismuth reported by Tien et al.' to determine the activity of uranium in the two-phase region, UC, + C. All of the quantities in Eq. [2] were then known, and the AG; (uc,) was evaluated. UC + UC2. For the studies involving UC + UC,, the reaction taking place when the two-phase mixture is brought to equilibrium with liquid bismuth is: The standard free-energy change for this reaction is given by:

Jan 1, 1969

By A. U. Seybolt

Experiments on both suljidation and hot corrosion have been carried out using ternary Ni-Cr-X alloys and commercial nickel-base superalloys. It has been shown that lhere are certain micro structural similarities between sulfidation using H,S/H2 mixtures and hot corvosion using Na,S04 in "crucible" experiments or hot corrosion tests using a flame tunnel apparatus. It is proposed that two key processes in the hot cowosion process are: 1) formation of chromium sulfides which deplete the alloy matrix, and 2) oxidation which can be accelerated because of chromium depletion. Other processes play an important role in the hot corrosion process, such as accelerated oxidation attack due to the presence of a N& S04 or N&SO,- NaC2 film which inhibits the formation of a protective external oxide scale. However, this latter phenomenon was not studied in this work. THE term hot corrosion has come to mean a combination of sulfur and oxygen attack on nickel-base or cobalt-base superalloys used as gas turbine blades or partitions. This attack can be initiated by any combustion process in air involving fuel containing sulfur if the sulfur level is sufficiently high. Levels of 5 pet SO2l for example, in the combusting gas have been observed to produce hot corrosion attack on nickel-base alloys. The important immediate corroding medium in aircraft gas turbines, however, has been established to be Na2S04, formed from reaction between NaCl from sea air and sulfur in the fuel.' The Na2S04 concentrates the sulfur sufficiently so that superalloy parts heated in the range 1400" to 1900°F can become sulfided by reducing the Na2S04 film which forms on the parts, and this reaction allows sulfur to gain access to the alloy. The sulfur thus released diffuses into the superalloy and forms primarily chromium sulfides of various compositions, but frequently Cr2S, has been identified. Figs. 1 and 2 show the morphology typical of hot corrosion of a cobalt-base superalloy X-45 (25 Cr, 10 Ni, 7.5 W, 0.25 C) and a nickel-base alloy, Udimet 500 (19 Cr, 19 Co, 4 Mo, 3 Ti, 2.9 Al, 0.07 C). Both alloy samples were subjected to the same hot corrosion conditions: 616 hr at 1600°F in a combusted 2.9 pct S distillate oil containing 125 ppm Na as NaC1. It will be noted at once that the nickel-base alloy is much more severely attacked. The depth of corrosion is much greater and the number and size of the sulfides present are much greater. Both alloys show a duplex oxide scale, which is more noticeable in the X-45 alloy. The external scale is probably a spinel in both cases, with CrQ3 lying next to the alloy. Many investigators1 -"ve been concerned with hot corrosion phenomena, but there has been a lack of unanimity of opinion as to the details of the hot corrosion mechanism. More than one definition of hot corrosion is possible. Some investigators con- sider as a measure of hot corrosion only the weight gain due to an accelerated oxidation. However another point of view is that the total depth of affected alloy may be used as a measure. While it is recognized that surface oxidation attack is greatly accelerated by the presence of salts like Na2S04 or Na2S04-NaC1 mixtures, sulfur penetration into the alloy also undoubtedly produces very important effects. The region of sul-fide penetration which is so prominent in Fig. 2 is one of the outstanding characteristics of hot corrosion. For highly stressed parts, such as first-stage buckets, this sulfur-penetrated region can be more significant in mechanical property loss than the reduction of cross section produced by the formation of the massive external scale. In addition, evidence will be presented that this sulfided region can be less resistant to subsequent oxidation attack. Since it appears that the sulfided region below the surface oxide scale plays an important role in the overall corrosion process,

Jan 1, 1969

By J. D. Verhoeven

In the past 15 years a considerable amount of experimental and theoretical work has been done concerning the onset of convection in liquids as a result of interm1 density gradients. This work, which has been doue in many different fields, is reviewed here and extended slightly to give a rrlore quantitative understanding to the probletrz of conzection in liquid metal dlffusion experinletzts. In liquid metal systems the capillary reservoir technique is currently used, almost exclusively, to measure diffusion coefficients. In this technique it is necessary that the liquid be stagnant in order to avoid mixing by means of convection currents. Convective mixing may result from: 1) convection produced as a result of the initial immersion of the capillary; 2) convection produced in the region of the capillary mouth as the result of the stirring frequency used to avoid solute buildup in the reservoir near the capillary mouth; 3) convection produced during solidification as a result of the volume change; and 4) convection produced as a result of local density differences within the liquid in the capillary. The first three types of convection have been discussed elsewhere1-a and are only mentioned for completeness here. This work is concerned only with the fourth type of convection. Local density differences will arise within the liquid as a result of either a temperature gradient or a concentration gradient. It is usually, but not always, recognized by those employing the capillary reservoir technique that the top of the capillary should be kept slightly hotter than the bottom and that the light element should be made to migrate downward in order to avoid convection. In the past 15 years a considerable amount of work, both theoretical and experimental, has been done in a number of different fields which bear on this problem. This work is reviewed here and extended slightly in an effort to give a more quantitative understanding of the convective motion produced in vertical capillaries by local density differences. The Stokes-Navier equations for an incompressible fluid of constant viscosity in a gravitational field may be written as: %L + (v?)v = - ?£ + Wv - g£ [1] where F is the velocity, t the time, P the pressure, p the density, v the kinematic viscosity, g the gravitational acceleration, and k a unit vector in the vertical direction. A successful diffusion experiment requires the liquid to be motionless, and under this condition Eq. [I] becomes: where a is the thermal expansion coefficient [a =-(l/po)(dp/d)], a' is a solute expansion coefficient [a' = -(l/po)(dp/d)], and the solute is taken as that component which makes a' a positive number. Combining with Eq. [3] the following restriction is obtained: Since there is no fixed relation between VT and VC in a binary diffusion experiment, Eq. [5] shows that the condition of fluid motionlessness requires both the temperature gradient and the concentration gradient to be vertically directed. Given this condition of a density gradient in the vertical direction only, it is obvious that, as this vertical density gradient increases from negative to positive values, the motionless liquid will eventually become unstable and convective movement will begin. The classical treatment of this type of instability problem was given by aleih' in 1916 for the case of a thin fluid film of infinite horizontal extent; and a very comprehensive text has recently been written on the subject by handrasekhar.' It is found that convective motion does not begin until a dimensionless number involving the density gradient exceeds a certain critical value. This dimensionless number is generally referred to as the Rayleigh number, R, and it is equal to the product of the Prandtl and Grashof numbers. For the sake of clarity a distinction will be made between two types of free convection produced by internal density gradients. In the first case a density gradient is present in the vertical direction only, and, since the convection begins only after a critical gradient is attained, this case will be called threshold convection. In the second case a horizontal density gradient is present and in this case a finite convection velocity is produced by a finite density gradient so that it will be termed thresholdless convection. Some experimentalists have performed diffusion experiments using capillaries which were placed in a horizontal or inclined position in order to avoid convection. These positions do put the small capillary dimension in the vertical direction and, consequently, they would be less prone to threshold convection than the vertical position. However, if the diffusion process produced a density variation, as it usually does, it would not be theoretically possible to avoid thresh-

Jan 1, 1969

By J. R. Hauber, N. R. Borch

A study uras made on the creep behavior of cast and extruded SR grade beryllium. It is shown that, for stresses below about 1000 psi in the temperature range 760" to 85o° c, the creep behatior is nearly exactly described by the Nabarro-Herring mechanism. The activation energy is apparently that for self-diffusion, 42 2 kcal per mole, below 1000 psi, but it rises to 88.6' kcal per mole at higher stresses. The slress exponent is 4.5 at the higher stresses. Tertiary creep in this material is clearly related to void formation apparently caused by grain boundary sliding. BERYLLIUM is becoming an increasingly important technological material. A search of the literature has revealed a lack of fundamental studies on the creep of beryllium. This investigation was therefore undertaken to gain insight into the creep behavior of this material. EXPERIMENTAL PROCEDURE Tensile creep samples were prepared from cast and extruded SR grade beryllium. The vendor's chemical analysis of the beryllium tested is shown in Table I. The test specimens were machined as shown in Fig. 1 from i -in.-diam rods. The machined creep specimens were annealed to remove surface damage and to establish a variation in grain size. The heat treatments and their resulting grain diameters are shown in Table 11. The average grain diameters were determined by the intercept method. True average grain diameters were estimated by multiplying the measured average grain diameters by 1.5.' The creep tests were performed at temperatures from 700" to 850°C in a vacuum of 105 Torr or better in a tantalum-element resistance furnace. Loads were applied by an Instron testing machine such that the stress was held constant to within 20 psi. The test temperature was measured by thermocouples on the sample. With one exception the deviation from the desired test temperature was 2"C, and in that case the deviation was 4"C. Elongations were measured by an extensometer within the vacuum chamber which was fastened to the creep specimens at the grooves in the grip ends, as shown in Fig. 1. The precision of measurement of elongation was 1 X loe4 in. The creep tests were begun only after thermal equilibrium had been established in the sample and the extensometer to insure that there was no strain rate component due to transient thermal effects. Two kinds of creep experiments were performed. First, at constant grain size, the effects of varying stress and temperature were studied. In the second set of experiments, the temperature was held constant and the grain size was varied. The activation energy for creep was determined by varying the temperature at constant stress, as described by orn, during the first set of experiments. The variable grain size experiments revealed that creep at low stress apparently occurred by the abarro-errin' mechanism. In all of the creep tests, the stress was held constant only until sufficient strain had occurred to accurately determine the creep rate. The stress was then raised to a new value and the new creep rate determined. This process was reported until tertiary creep occurred. In this manner several data points were obtained from each specimen. The assumption was made that the structure was not changing appreciably between the incremental stress levels. This was verified by reducing stresses to previously tested levels and comparing the creep rates with the creep rates obtained at the lower strains. The re-producibility was within experimental error over strains on the order of 1 pct. EXPERIMENTAL RESULTS A typical series of creep tests is shown in Fig. 2. Primary creep was not observed in any test. Transient creep, which we define as creep rates that are nonlinear with time, was not observed for any change in stress except where tertiary creep occurred. The absence of both primary and transient creep has been previously reported for hot-pressed powder beryllium.= The data for the creep behavior at constant grain size are summarized in Fig. 3. The data show two distinctly different stress dependencies. At stresses below about 1000 psi, in the equation:

Jan 1, 1969

By M. Kitada, U. Kawabe, F. Ishida, T. Doi

The relations between micros tructures and critical current density in transverse magnetic field were experimentally investigated due to each transformation of the 0 to 0' + P" phases at 700' C for superconductmainly examined using replication electron microscopy. The ß' or a precipitates were found to pin down magnetic flux lines in these alloys. The effects of precipitation upon the critical current density were discussed in relation with the size, spacing, and characler of these precipitates. HIGH magnetic field superconductors, such as Nb-Zr, Nb-Ti, and Nb-Zr-Ti alloys, have been recently put to extensive practical use as winding materials for superconducting magnets.13 The critical current density of these hard superconductors under an applied magnetic field is an important characteristic for magnet materials and is very sensitive to metallurgical structure. It is generally known that the critical current density is increased by introducing dislocations and precipitates into a superconductor; that is, dislocations and precipitates are presumed to be barriers that hinder quantized flux lines from moving.4'5 Theoretical6'7 and experimental analyses of the motion of flux lines and the interaction between flux lines and various defects have already been reported by many authors. Metallographic analysis of high magnetic field superconductors such as Nb-Zr and Nb-Ti is difficult, so that no quantitative relationship between microstruc-ture and critical current density has been established yet. In this paper, the effect of precipitation on the critical current density in magnetic field was investigated for two superconducting alloys, Nb-40Zr-10Ti and Nb-5Zr-60Ti. In these alloys the resistive critical field H, at 4.2oK was about 100 kG and the critical current density Jc at 80 kG was of the order of 104 amp per sq cm.13-l5 The superconducting properties were examined in relation to the microstructural changes due to transformation of i) the ß to ß' + ß" phases at 700°C for Nb-40Zr-10Ti alloy and ii) the ß to a + ß phases at 500°C for Nb-5Zr-6OTi alloy. The effect of size, spacing, and character of precipitates on flux line pinning was in particular examined. The microstructures were studied by means of residual resistivity, microhardness, and tensile strength measurements as well as by X-ray diffraction, optical, and replication electron microscopies. I) EXPERIMENTAL PROCEDURE Pure niobium, zirconium, and titanium, in the form of rods 0.8 cm in diam, served as raw materials. Results of chemical analyses of these rods are given in Table I. Ingots of the alloys, 0.4 cm in diam and 3 cm in length, were prepared by means of levitation melting, utilizing a copper mold in an argon-gas atmosphere. Samples from the ingot then were cold-worked by grooved mill to 0.2 cm in diam, heat-treated homogeneously (in the ß phase region) for 5 hr at 1100° in a vacuum of 1 x 106 Torr, and finally cold-drawn to 0.025 cm in diam. For heat treatments, samples were wrapped in niobium foil and sealed in an argon-gas atmosphere in fused quartz capsules. Water quenching was done after each heat treatment. Subsequently H-J, were performed at 4.2° by slowly transporting the current through the samples 4 cm long, under transverse magnetic field, until the least detectable resistive terminal voltage was observed. The resistive critical field H, was taken as the field at which 100 pv appeared at 4.2°K across a sample 3 cm in length, with a current of 5 ma. The critical temperature T, was measured by means of a conventional four-probe resistivity technique and taken as the temperature at which the sample resistance reached one-half of full restoration of the normal-state resistance with a current l ma flowing through a sample 2 cm in length. Precipitates were observed by means of optical microscopy and carbon replication electron microscopy. The etching solution consisted of 5 ml HF, 10 ml H2SO4 10 ml H2O2, and 50 ml H2O, and shadowed carbon replicas were examined in a itachi HU-11 electron microscope operated at 50 kv. X-ray diffraction photographs were taken by a 11.46-cm-diam Debye-Scher-rer camera using copper Ka radiation. The micro-hardness was measured under a load of 200 g using

Jan 1, 1969

By R. D. Nelson, S. D. Dahlgren

The conditions of temperature, strain rate, and total strain favoring deformation by grain boundary sliding, slip, or deformation with concurrent recrystallization were evaluated for alpha plutonium. Grain boundary sliding and slip were studied by examining structures formed on polished surfaces with 4.5 pct compressive deformation. The conditions required for recrystallization were determined from compressive deformation us time curves. At 110" C and at a strain rate of 10&apos;per min, deformation was almost exclusively by grain boundary sliding whereas slip was the predominant deformation mode at -10°C and lo-&apos; per min. Defarmation at intermediate tenzperatures and strain rates produced structures showing mixtures of grain boundary sliding and slip. Recrystallization occurred concurrently with deformation only after a critical strain was reached. About 14, 6, and 3 pct strain was required at 105", llO°, and lZO°C, respectively, before recrystallization started, irrespective of the strain rate in the range of lo-&apos;1 to 10&apos;4 per nzin. L HE temperature and strain-rate dependency of the modes of plastic deformation were evaluated for high-purity as-cast alpha plutonium. The techniques used to study slip and grain boundary sliding were similar to those employed previously for alpha plutonium by Bronisz and Gorum,&apos; and spriet.&apos; Recrystallization was investigated using the methods reported by Nelson.3 Bronisz and Gorum&apos; found that slip occurred on more than one slip system at room temperature, and suggested that grain boundary sliding also contributed to the deformation. spriet2 found that deformation was predominantly by slip at room temperature, and observed one to three orientations of slip traces in individual grains. In addition, he deformed polished samples at 10O° C, but concluded that the deformation character of alpha plutonium at 100° C and at room temperature were not essentially different. Several investigators reported that twinning was only occasionally observed.1&apos;2&apos;4 Nelson3 recently found in creep tests that high-purity alpha plutonium would recrystallize concurrently with compressive deformation at temperatures between 25" and 115°C. EXPERIMENTAL PROCEDURE Electrorefined plutonium having less than 300 ppm total impurities was received from Los Alamos Scientific Laboratory in the form of +-in. diarn cast rods. Major impurities were americium, <I00 ppm, and tungsten, (60 ppm. Less than 25 ppm each of other impurities were present. The rods were cut into right half-cylinders 0.35 in. long and 0.25 in. in diam, and the flat faces along the cylinder axes were metal-lographically polished. To avoid loss of the metallo-graphic polish by oxidation, the polished samples were deformed in a silicone fluid heat treating medium contained in a chamber evacuated to a pressure of lo-&apos; torr. Deadweight loading was used to compress the samples between 4.5 and 20 pct at strain rates between 10"4 and lo- &apos; min-&apos;. Strain rates were determined by dividing the total deformation by the elapsed time of the test, even though the strain rate was not constant during deformation. Curves of strain vs time for samples deformed with a constant compressive stress3 show that the strain rate changes by less than a factor of four during the testing of a given sample, which is small compared to the three orders of magnitude change in strain rate investigated. Two samples were loaded into an ordinary metallographic mounting mold and impacted by striking the mold piston with one blow of a 2-lb hammer. Deformation temperatures for the two impact samples were 25" and 90°C. The samples, following deformation, were washed in carbon tetrachloride and their polished and deformed surfaces were immediately inspected metallographi-cally. Subsequently, the deformation structures were replicated with acetate replicating tape for later electron microscope examination, and the samples were then repolished and etched to reveal the microstruc-tures of the deformed metal. Second-stage carbon replicas were prepared from decontaminated acetate replicas using the procedure developed by Miller, Bierlein, and astel.&apos; Additional samples, which were 0.35 in. long by 0.25 in. in diam, were used to obtain constant load deformation vs time curves. These samples were deformed 10 to 20 pct with loads of 15 and 20,000 psi at 120°C; 30, 45, and 55,000 psi at 110°C; and 20 and 30,000 psi at 105°C. Samples were polished and etched to determine whether or not recrystallization or twinning had occurred during deformation. RESULTS AND DISCUSSION The experiments showed that alpha plutonium deforms by grain boundary sliding, slip, and deformation with concurrent recrystallization. Deformation by twinning was insignificant. Metallographic examination of polished and deformed surfaces revealed grain boundary sliding and slip. The start of recrystallization was ascertained from constant load deformation vs time curves. Deformed surface structures of samples compressed 4.5 pct under four different conditions of temperature and strain rate, Fig. 1, show how the deformation mode changes from predominantly grain boundary sliding to predominantly slip with increasing strain rate and decreasing temperature. Deformation at 110°C and 10" 4 min-&apos;, Fig. l(a), was predominantly by grain boundary sliding. Only a few slip traces can be seen in Fig. l(a).

Jan 1, 1969

By Luc Delaey, Horace Pops

The structure and morphology of thermoelastic and burst type martensitic phases that form upon cooling in Cu-Zn-Si p phase alloys have been studied by transmission electron microscopy. The martensitic phases are composed of a lamellar mixture of two close-packed structures with different stacking sequence, namely ABCBCACAB (orthorhombic) and ABC (fcc). Striations within thermoelastic martensite are most likely produced during interaction with impinging burst-type martensite and not as a consequence of secondary shears. In a study of the martensitic transformation in ternary Cu-Zn based 0 phase alloys1 the dependence of the martensitic transformation temperature, M,, with composition shows variations for elements within a constant valence subgroup and between different subgroups. Such variations are not reflected in a change in habit plane, which is approximately the same for each ternary alloy, namely in the vicinity of (2, 11, 12 Ip. The fact that the habit plane remained constant, despite large differences in M, temperature and electron concentration, suggested2 that the crystal structures of the martensitic phases could be nearly the same. Crystal structures of ternary Cu-Zn based martensites have been determined recently for alloys containing the three-valent elements gallium3, 4 and aluminm. The present studies have been made to examine the structures and morphology of the martensitic phase in ternary Cu-Zn based alloys containing a four-valent element, silicon. I) PROCEDURE Two alloys were prepared by melting and casting weighed quantities of the component high-purity metals in sealed quartz tubes under half an atmosphere of argon. They were subsequently remelted by levitation under a protective atmosphere of argon. After allowing for losses of zinc as determined by the difference in weight before and after casting, the compositions in atomic percent of both alloys were established to be Cu-33.5 Zn-1.8 Si and Cu-27 Zn-5.0 Si. These alloys were homogenized in the P-phase field for 2 days at 800" C. Bulk samples consisted of a martensite phase at room temperature, the M, temperature being approximately 30&apos; and 200" for the 1.8 and the 5 pct Si alloys, respectively. Thin disks were cut from the ingots using a spark machine, and they were heated for 5 min at 800&apos; and quenched into water in order to obtain martensite. These slices were thinned chemically at room temperature in a solution consisting of 40 parts HN03, 50 part H3PO4, and 10 parts HC1 and thinned further electrolytically by the Window technique, using a voltage of 15 to 25 v and a mixture of 1 part HN03 and 2 parts methanol, which was kept at a temperature near -30° c. Foils were examined by transmission electron microscopy using a Philips EM 200 electron microscope. 11) RESULTS AND DISCUSSION 1) Structure and Morphology. Fig. 1 shows the martensitic phase in the alloy containing 1.8 at. pct Si. This phase is composed of contiguous platelets, each containing striations. The direction of the striations changes at the boundary between individual platelets. These internal markings resemble the striations that are usually identified as stacking faults, as for example in Cu-A1 martensites6-a or the lamellar mixture of two close-packed phases in Cu-Zn-Ga marten-sites.3p &apos;9 lo In the present alloys, selected-area diffraction experiments have been obtained in order to determine the nature of the striations. Figs. 2(a), (61, and (c) are electron diffraction patterns of an area inside a single martensite plate. Fig. 2(a) contains diffraction spots which correspond to two close-packed structures with different stacking sequences, namely ABCBCACAB (orthorhombic) and ABC (fcc). Spots belonging only to the fcc structure are indicated by arrows. By tilting the foil either the orthorhombic structure, Fig. 2(b), or the cubic structure shown in Fig. 2(c) may be obtained. When the foil is oriented so that only the diffraction spots of the orthorhornbic structure are present, bright-field illumination shows small lamellae, as seen in Fig. 3. In this figure the lamellae that belong to the fcc structure are bright bands inside the dark extinction contours of the orthorhombic structure. The boundaries of the lamellae are parallel to the basal planes of the orthorhombic structure and to the {Ill} planes of the cubic structure, the close-packed directions of both structures being parallel. The 5 pct Si alloy shows similar features as those described for the 1.8 at. pct Si alloy.

Jan 1, 1969

By William D. Klopp, Joseph R. Stephens

A substantial reduction in the 300°F ductile-to-brittle transition temperature for unalloyed chromium was achieved in alloys from systems which resemble the Cr-Re system. These alloy systems include Cr-Ru, Cr-Co, and Cr-Fe. Transition temperatures ranged from -300° F for Cr-35 at. pct Re to -75°F for 0-50 at. pct Fe. The ductile alloys have high grain gvowth rates at elevated temperatures. Also, Cr-24 at. pct Ru exhibited enhanced tensile ductility at elevated temperatures, characteristic of superplas-ticity. It is concluded that phase relations play an importarlt role in the rhenium ductilizing effect. The ductile alloys have compositions near the solubility limit in systems with a high terminal solubility and which contain an intermediate o phase. The importance of enhanced high-temperature ductility to the rhenium ductilizing effect is not well understood although both may have common basic features. CHROMIUM alloys are currently being investigated for advanced air-breathing engine applications, primarily as turbine buckets and/or stator vanes. The inherent advantages of chromium as a high-temperature structural material are well-known1 and include its high melting point relative to superalloys, moderately high modulus of elasticity, low density, good thermal shock resistance, and superior oxidation resistance as compared to the other refractory metals. Additionally, it is capable of being strengthened by conventional alloying techniques. The major disadvantage of chromium is its poor ductility at ambient temperatures, a problem which it shares with the other two Group VI-A metals, molybdenum and tungsten. For chromium, the problem is further amplified by its susceptibility to nitrogen em-brittlement during high-temperature air exposure. In cases of severe nitrogen embrittlement, the ductile-to-brittle transition temperature might exceed the steady-state operating temperature of the component. The low ductility of chromium would make stator vanes and turbine buckets prone to foreign object damage. The present work was directed towards improvement of the ductility of chromium through alloying, with the anticipation that any improvements so obtained might be additive to strengthening improvements achieved through different types of alloying. The alloying additions for ductility were selected on the basis of the similarity of their phase relations with chromium to that of Cr-Re. The reduction in the ductile-to-brittle transition temperatures of the Group VI-A metals as a result of alloying with 25 to 35 pct Re is well established.a4 the temperature range -300" to 750° F. This phenomenon is commonly referred to as the &apos;<rhenium ductilizing effect"; this term is also used to describe systems in which the ductilizing element is not rhenium. Other alloy systems which have recently been shown to exhibit the rhenium ductilizing effect include Cr-Co and c-Ru.= In order to explore the generality of this effect, alloys were selected from systems having phase relations similar to that of Cr-Re, primarily a high solubility in chromium and an intermediate o phase. The following compositions were prepared: Cr-35 and -40Re; Cr-10, -15, -18, -21, -24, and -27 pct Ru; Cr-25 and -30 pct Co; Cr-30, -40, and -50 pct Fe; Cr-45, -55, and -65 pct Mn. Seven other systems were also studied which partially resemble Cr-Re. These systems have extensive chromium solid solutions or a complex intermediate phase, not necessarily o. The compositions evaluated include the following: Cr-20 pct Ti; Cr-15, -30, and -45 pct V; Cr-2.5 pct Cb; Cr-2.5 pct Ta; Cr-20 pct Ni; Cr-6, -9, -12, and -15 pct 0s; Cr-10 pct Ir. The compositions of alloys in these systems were chosen near the solubility limit for the chromium-base solid solutions, since in the Group VI-A Re systems, the saturated alloys are the most ductile. These alloys were evaluated on the basis of hardness, fabricability, and ductile-to-brittle transition temperatures. In addition to the studies of alloying effects on ductility, an exploratory investigation was conducted on mechanical properties at high temperatures in Cr-Ru alloys EXPERIMENTAL PROCEDURE High-purity chromium prepared by the iodide deposition process was employed for all studies. An analysis of this chromium is given in Table I. Alloying elements were obtained in the following forms: Commercially pure powder — iridium, osmium, rhenium, and ruthenium. Arc-melted ingot — titanium and vanadium. Electrolytic flake — iron, manganese, and nickel. Sheet rolled from electron-bearn-melted ingot — columbium and tantalum. Electron-beam-melted ingot — cobalt. Sheet rolled from arc-melted ingot — rhenium. All alloys were initially consolidated by triple arc melting into 60-g button ingots on a water-cooled hearth using a nonconsumable tungsten electrode. The melting atmosphere was Ti-gettered Ar at a pressure of 20 torr. The ingots were drop cast into rectangular slabs and fabricated by heating at 1470" to 2800° F in argon followed by rolling in air. Bend specimens measuring 0.3 by 0.9 in. were cut from the 0.035-in. sheet parallel to the rolling direction. The specimens were annealed for 1 hr in argon, furnace cooled or water quenched, and electropolished prior to testing. Three-point loading bend tests were conducted at a crosshead speed of l-in. per min over

Jan 1, 1969

By S. G. Epstein

Electromigration has been measured in dilute liquid alloys of lead in antimony and antimony in lead. In these alloys antimony migrates with the electron current; lead migrates in the opposite direction. These results, which contradict the mass criterion, were predicted by the electron drag model for electromigration in liquid alloys. The existing experimental data are shown to correlate with the difference in electrical resistivities of the alloy components. FOR many years investigators have attempted to relate observed electromigration phenomena in liquid alloys to the physical properties of the alloy components. The most successful correlation was found by Angus et&apos; al.,1 who in 1959 proposed an empirical criterion for predicting the relative direction of motion of the components of a liquid alloy in an electric field: the component with the smallest atomic mass concentrates at the cathode. While this criterion is obeyed in nearly all the alloy systems which had been investigated, the physical basis for such an effect was not understood. It was also disturbing that the mass criterion predicted the wrong sign for the Haeffner effect; observations with pure liquid metals revealed that in every instance the lighter isotope was transported to the anode.2 Klemm3 explained these isotopic separations by suggesting that the lighter isotopes were more mobile and more easily carried to the anode with the electron stream. Additionally, several deviations from the mass criterion have been found in liquid alloys, notably involving transition metals such as chromium, nickel, palladium, and zirconium, which migrate to the anode in liquid bismuth.4&apos;5 Recently, a model has been proposed6 in which electromigration in liquid alloys is attributed primarily to the interaction between the electron stream and the metal ions. In essence, this model predicts that the component with the greater electron-ion scattering cross section will be preferentially transported to the anode, displacing the other component to the cathode. The electrical resistivity of each pure component at its melting point is taken as the measure of its scattering cross section. This model was developed from the results of systematic studies with various solutes in liquid mercury,7&apos;8 bismuth,9 and sodium.10 In every alloy, the component with the greater resistivity has centrates at the anode. Coincidentally, in every instance the component with the greater resistivity has also the greater mass, apparently satisfying the mass criterion. In order to differentiate between electron-ion coupling and atomic mass as the relevant physical prop- erty influencing electromigration, measurements were made with Pb-Sb alloys. Lead has an atomic mass nearly twice that of antimony, but lead has an electrical resistivity of 91 microhm-cm while antimony has a value of 113.5 microhm-cm at their respective melting points. The mass criterion predicts that in an alloy of the two antimony will concentrate at the cathode; the electron drag model predicts that antimony will concentrate at the anode. EXPERIMENTAL To conclusively determine the relative motion of lead and antimony in each other, solute electromigration was measured in dilute liquid alloys of antimony in lead and lead in antimony. Both starting materials were 99.999+ pct pure. The measurements were made with the same capillary-reservoir technique previously used for measuring electromigration in liquid bismuth alloys.11 Several changes in the experimental apparatus were necessary, however, to accommodate liquid antimony, which has a higher melting point than bismuth. The modified apparatus is depicted in Fig. 1. In each experiment four quartz capillaries were filled with the molten alloy. A direct current was passed through two of the capillaries; the electrode in one of these capillaries was made the cathode, and the electrode in the other was made the anode. The remaining two capillaries sampled the alloy in the reser-

Jan 1, 1969

By H. E. Cline, J. L. Walter

Grain boundary sliding and migration were studied in pure aluminum bicrystal and polycrystal samples with two-dimensional grain structure. Scratches, 50 P apart, were used for measurement of sliding and migration distanceso. Samples were deformed at constant rate at 315C and events recorded continuously on wrotion picture film. Electron micrograPhs of boundary-scratch intersections were obtained. Yield and flow stress values were measured. The sequence of sliding and migration events for a three-grain junction is described in detail. Sliding depended only on the resolved shear stress imparted to the boundary. Sliding was accowmodated by formation of shear zones in grains opposite triple points and adjacent to curved boundaries. These shear zones provided the driving force for grain boundary migration. Migration caused rumpling of the boundaries, decreasing the sliding rate. Sliding and migration generally began at the same time, occurred simultaneously and ended at the same time. In the bicrystal, sliding and migration rates were proportional. Initial sliding rules of 5 X joe cm per sec. were measured for the polycrystal and bicrystal samples. These sliding rates agree wilh the internal friction experirnents of K;. The observations seem consistent with a viscous boundary sliding nzechanism. GRAIN boundary sliding is the translation of one grain relative to its neighbor by a shear motion along their common boundary. Sliding is thought to be an important mode of deformation at elevated temperatures and at low strain rates such as prevail in creep,&apos; and perhaps in the area of superplastic behavior.2"4 Although much work has been done to investigate grain boundary sliding, the effort has not led to the identification of a mehanism. KG showed that grain boundaries in aluminum exhibit a viscous nature under very small displacements of internal friction measrements. Various dislocation mechanisms have been proposed but are without conclusive experimental support. Attempts to relate sliding to 6&apos;s viscous boundaries have been unsuccessful in that measured rates of sliding are always several orders of magnitude lower than KG&apos;S results would predict.= In bi crystals7and polycrystalsR of aluminum tested under constant load, the grain boundary sliding was found to be proportional to the total creep elongation which indicated that sliding might be controlled by deformation of the grains. Shear zones were observed to extend beyond grain boundaries at triple points to accommodate the sliding.8 Surface observations brought forth the opinion that sliding and migration occurred alternately, in sequence.&apos; Measurements of sliding at the surface have been criticized because they might not be representative of the interior of the sample. Generally speaking, it seemed that much of the previous work and knowledge was based on observations made at relatively low magnification and examination of samples after deformation had been accomplished. Thus, it was the purpose of the present study to continuously record, at high magnification, the events occurring during the deformation of pure aluminum. Samples with two-dimensional grain structures were used to simplify interpretation of the results. The sliding and migration of small areas of many samples were continuously recorded by time-lapse motion pictures. Replicas of the surface were used to provide high-resolution electron micrographs. These observations, coupled with tmsile strength data, provide sufficient information to arrive at an understanding of the phenomenon. EXPERIMENTAL PROCEDURE An ingot of 99.999 pct A1 was rolled to sheet, 0.127-cm thick. Tensile specimens, with a gage length of 0.85 cm, were machined from the sheet. Bicrystal tensile specimens, of the same dimensions, were spark cut from a large bicrystal ingot. The grain boundary was oriented at 45 deg to the tensile axis. The surfaces of the tensile samples were ground flat on fine metallographic paper and were then electropolished in a solution of 75 parts absolute alcohol and 25 parts of perchloric acid. The solution was cooled in an ice-water bath. Using a weighted sewing needle suspended from a small pivot on a precision milling machine, a grid of fine scratches, 50 p apart, was scribed on one surface of the sample. The polycrystalline samples were then annealed in hydrogen for 15 min at 350" to 400°C to produce a two-dimensional grain structure of about 0.2-cm average grain diameter which would not undergo further growth at the test temperature, 315OC. Examination of both surfaces of the samples showed that the grain boundaries were perpendicular to the surface of the polycrystal and bicrystal samples. A hot-stage tensile machine was constructed for use with an optical microscope as shown in Fig. 1. The specimen is shown mounted in the grips. The grips ride in V-ways so that the sample can be mounted without damage. The rear grip is free to slide so that when the sample expands during heating it is not put under a compressive stress. When the grips and samples are at temperature, the rear grip is locked in place by two set-screws. The other grip is connected to a synchronous drive motor which, through a worm gear and a fine-threaded rod, deforms the

Jan 1, 1969

By Hansheinz Portisch, Harold Margolin

A surface expansion was found to occur sometime after etching in Ti-A1 alloys containing 9.5 to 12.5 wt pct Al. The structure formed, grew, and disappeared with tzrrze. The surface expansion was followed by microscope observations and interferometric and lattice parameter measurements. Activation energy measurements for the growth of the "expansion structure" and chemical analysis indicated that the phenomenon occurred as a result of hydrogen pzckup during etching. It is proposed that hydrogen initially enters octahedral sites of Ti3Al coherent with a Ti and later shifts to the tetrahedral sites. It is postulated that expansion occurs when hydrogen enters the tetrahedral sites. The expansion structure disappeared, it is proposed, because of diffusion of hydrogen from the surface into the body of the alloy and because of loss of coherency of Ti3Al. In examining Ti-A1 alloys, Ence and arolinl observed markings on the surface of specimens. These markings did not appear after electropolishing only, but rather appeared only after etching. The markings appeared to grow as a function of time after etching and later seemed to disappear. Although the markings had some similarity to precipitates, showing, frequently, a Widmanstatten type of arrangement, the observation that other microstructural markings continue to be seen within the new structure suggested that it was actually not a precipitate. The source of this structure was unknown and an attempt was made in the present investigation to develop some understanding of its nature. It has been labeled expansion structure. 1) EXPERIMENTAL PROCEDURE A) Alloys. Alloys in the range 6.5 to 14.5 wt. pct A1 were studied. Bars, 4 in. sq, forged from Bureau of Mines (73 Bhn) titanium consumably arc-melted 4-lb ingots,&apos; as well as 50-g arc-melted buttons of desired aluminum contents were used. The 50-g buttons also used Bureau of Mines titanium (73 Bhn) and aluminum of 99.99 pct purity. Buttons containing up to 8.5 wt pct A1 were hot-rolled from a furnace at 900&apos; . Those with higher aluminum contents were hand-forged on a titanium anvil, and heated with an oxygen-hydrogen torch in the region of 1200" to 1300°c. Frequent reheating kept the samples at the desired temperature range. After a reduction of about 30 pct, the samples were water-quenched. To eliminate any contamination picked up either during hot rolling or forging, at least 1 mil of the surface of the sample was taken off. B) Heat Treatment. Prior to heat treatment all alloys were vacuum-annealed to remove hydrogen. Samples were annealed at 900&apos; until a vacuum of 10&apos;5 mm Hg was established. After this treatment, the samples were wrapped in molybdenum sheet and heat-treated in argon-filled quartz capsules, which were broken under water or iced brine at the conclusion of the heat treatment. All heat treatments under dynamic vacuum were performed in a rapid-quench furnace. This consisted of a molybdenum-lined quartz tube attached to a vacuum system and through a stopcock to a beaker of water. At the completion of the heat treatment the vacuum stopcock was closed, the furnace shut off, and dropped below the quartz tube. Then immediately the inlet stopcock was opened and water admitted until the tube was filled. The steam formed was allowed to escape through the inlet stopcock. This method was used in heat treatments up to llOO°C. C) Metallography. Specimens for metallographic examination were ground, then electropolished using a Disa Electropol machine with a perchloric acid electr01te. Specimens were etched with R-etch.3 A standard etching time of 3 min was used, with the specimen being agitated during immersion. D) Sample Preparation for X-ray Analysis. Samples 0.2 to 0.5 mm in diam were produced from heat-treated rods which were turned to 2 mm diam on a lathe and then rotation-etched. An etchant consisting of 1 pt HF, 7 pt HN03, and 12 pt HzO was satisfactory. With the rod rotating in a vertical position at 50 to 100 rpm, a needle with uniform dimensions could be obtained. Care had to be taken to insure that the rod was at the center of rotation, otherwise cavitation developed. If a small unevenness developed, it was possible to grind it off with a fine emery paper. E) X-ray Diffraction. All X-ray work was done on a North American Phillips X-ray diffraction apparatus and a Jarrell Ash microfocus X-ray unit. The Phillips unit was used with a copper target and nickel filter. The Jarrell Ash unit was fitted with a cobalt target and iron filter. For the Phillips unit 35 kva and 20 ma were used, whereas for the microfocus unit with the 100-p fixed-focus gun 40 kv and 1.5 ma were used. It was found that alignment of cameras on the Jarre11 Ash unit was very critical. The X-ray beam contains an intense area which is not the beam center. The cameras were aligned with the intense region by monitoring the beam coming out of the camera with a Geiger counter. Adjustments were made until a maximum intensity was obtained. A Phillips diffractometer with a Brown chart recorder furnished some of the lattice parameter data. The divergence slit up to 80 deg 28 was I deg; above 80 deg, a 4-deg opening was used, while the scatter slit was1 deg and the receiving slit had a 0.003-in. opening. The general scanning rate was 1 deg per min, while peaks of special interest were rescanned at -j deg per min. For elevated-temperature X-ray diffraction a Uni-cam High Temperature Camera with a film diameter

Jan 1, 1969

By J. Brett, L. Seigle, L. Castleman, T. Montelbano

Impurity-induced low-temperature recrystallization of cold-worked tungsten was inuestigated with emphasis on the influence of nickel on the reaction. Palladium, nickel, aluminum, manganese, platinum, and iron greatly lower the recrystallization temperature of doped tungsten, which zs normally very high, but the recrystallization temperature of electron-be am zone-refined tungsten wzre is slightly raised by conlacl with nickel. Recrystallization can be induced at low temperature by the presence of solid nickel on the surface of doped tungsten wire, but apparently not by exposure to nickel vapors alone. Approximately 200 ppm of Ni dijjused into 10-mil wires at 1200 from a deposit of nickel on the surface produced total recrystallization, whereas more than 600 ppm of Ni could be absorbed frotn a vapor source without altering the fibrous structure of cold-worked tungsten. Once initiated, nickel-induced recrystallization required a continued source of&apos; nickel for propagation of the recrystallization front. The solubility of nickel in fibrous 10-mil W wire was approximalely 500 ppm at 1150&apos; C, and the activation energy for penetration of the recrystallization front was 52 kcal per mole. In many applications the usefulness of tungsten depends on critical control of its structure. Cold-worked tungsten with the fibrous structure developed by suitable thermo-mechanical treatment has a low, but technologically significant, ductility. It has long been known1 that traces of nickel, and perhaps other metals, are profoundly deleterious in doped tungsten, because they induce recrystallization at low temperature, which produces a brittle, equiaxed grain structure. This effect appears to be an exception to the general observation that recrystallization is impeded and the recrystallization temperature raised by the presence of impurities.2"9 Previous studies7-&apos;&apos; of the annealing and recrystallization of tungsten wire have divided the phenomenon into prior recovery stages, primary recrystallization and secondary recrystallization. The present investigation is concerned principally with primary recrystallization which is defined here as the replacement of the fibrous structure of deformed tungsten by equiaxed grains. The objective of this study was to explore the nickel-induced recrystallization reaction in tungsten and attempt to elucidate its mechanism. As well, an effort to define which other elements give rise to low-temperature-induced recrystallization was carried out. EXPERIMENTAL PROCEDURE The procedure adopted for these experiments was essentially to bring nickel and other elements into diffusive contact with cold-worked tungsten wires. The process of recrystallization was followed as a function of time and temperature by light and electron microscopic observations. First the influence of nickel on the recrystallization temperature of arc-melted, zone-refined, and variously doped tungsten wire was determined by electroplating a deposit of nickel on the surface of the wire and annealing at a variety of temperatures for 3 hr. The chemical analyses of the tungsten wires used in this investigation are given in Table I. The surface of the tungsten wire was etched with Murakami&apos;s slution&apos; and approximately 0.005 in, of Ni was deposited from a Watts-type low pH bath14 for the conditions of these experiments. Variations in plating thickness from about 0.001 to 0.005 in. had no discernible influence on the resulting structures. The wires were then annealed in an atmosphere of dry hydrogen to establish the recrystallization temperature. Concurrently, un-plated specimens were annealed to establish the recrystallization characteristics of nickel-free wire. The criterion of recrystallization was that the fibrous structure be completely replaced by equiaxed grains after a 3-hr treatment of temperature. This provided more reproducible results than use of the first recrystallized grain or a fixed proportion of re-crystallized structure as the critical observation. The structures encountered in longitudinal and transverse sections were examined by both light and electron microscopy at magnifications up to X32,000 using parlo-dion-carbon replicas shadowed with platinum for the latter method. Second, the influence of a variety of metals on the recrystallization temperature of 0.010 in. D alumina-silica doped tungsten wire, AW136-64, was determined. The elements were applied by electroplating whenever possible. Alternatively, they were vapor-plated on the tungsten wire and a greater thickness built up by coating with a dispersion of metal powder in nitrocellulose lacquer. Elements not amenable to either of these procedures were merely slurry coated on the tungsten. The recrystallization temperature was determined as above. Third, the nickel-induced recrystallization process in doped wire was studied more closely by electroplating 8 mils of Ni on 65-mil alumina-silica doped tungsten wire, AW153-NS10, and exposing the wire to temperatures of llOO°, 1200°, or 1300°C for various times in a hydrogen atmosphere. A circular recrystallization front, &apos;Onsisting of equiaxed grains, developed at the periphery Of the coated tungsten wire, and the advance of this front into the fibrous interior was studied. These experiments employed relatively coarse 0.065 in. D wire because the 0.010 in. D wire recrystallized too quickly to permit observation of the pene-

Jan 1, 1969

By E. S. Machlin

The wzodel of Blandin and Diplunt;, generalized to include a phase factor, is applied to the carbon-carbon interaction in iron. Darken&apos;s "energetic" model is generalized to include not only first neighbor interactions but further neighbor interactions as well. On the bases of these generalized models relations are derived for the activity of carbon in both austenite and ferrite in terms of the carbon-carbon Pair interaction energies. A single function then yields the pair interaction energies consistent with the experimental activities of carbon in both ferrite and austenite. Thus, a simple explanation is given for the observation that the nearest-neighbor interaction between carbon is repulsive in austenite and attractive in ferrite. Certain consequences of this approach are explored. OnE object of the present paper is to attempt to take into account the consequences of electrostatic contributions to the carbon-carbon pair interaction energy for carbon as a solute in iron. Friedel&apos; has shown that oscillations in electrostatic potential are to be expected about a solute atom in a metallic solution. Blandin and 6lant6&apos; have shown that such oscillations yield an interaction energy between pairs of solute atoms that obeys the relation: W{ = A cos(2ftFri + 4>)/(kFri)3 [l] where kF = Fermi wave vector, ri = distance between solute atoms comprising the pair7 <p = phase factor dependent only on electronic nature of solute and solvent, A = coefficient dependent only on electronic nature of solute and solvent. Machlin3 found that Eq. [I] accurately described the pair interaction energy derived from short-range order measurements based on field ion microscope observations of dilute alloys of platinum. He also found that the value of the phase factor $ derived from residual resistivity measurements agreed well with that obtained from the analysis of the short-range order data. Harrison and paskin4 were able to predict the long-range ordering energy of 0 brass using Relation [I] and residual resistivity values to predict the value of the phase factor $. Machlin5 has repeated their analysis and applied it to the prediction of the long-range ordering energy in AgZn and AgCd with excellent agreement between prediction and experiment. Both A and $ are independent of the crystal structure. The Fermi wave vector depends uniquely upon the conduction electron concentration per unit volume in the spherical approximation of the Fermi surface. Thus, Eq. [I] is expected to apply to both fer- rite and austenite with only one set of values of A and $. Mossbauer studies6 yield the result that iron has one 4s electron. We shall make an assumption found to hold previously for platinum3&apos;7 and nikel, which is that only the s electrons are involved in shielding the perturbing potential of carbon. With this assumption, kF = 1.35 A-l. Although A and $ may be obtained from certain mdels&apos;&apos;&apos; we shall take A and $ to be empirical constants in the spirit of Kohn and osko.&apos; Thus, Eq. [I] involves two adjustible parameters. Consequently, two independent relations in A and $I are required in order to evaluate them for carbon as a solute in iron. We may use a recent analysis of Aaronson, Domain, and poundg who showed that Darken&apos;s energetic model,1° as well as others, can be used to describe the activity-temperature data for carbon in iron in both the aus-tenitic and ferritic phases. Darken&apos;s model takes into account only first neighbor pair interactions. For our needs, all neighbor pairs need to be taken into account. It is convenient to generalize Darken&apos;s model. The result for the partition function for austenite is: over the temperature range 800" to 1200°C and where the uncertainty corresponds to one standard deviation. Eq. [4] effectively yields only one relation. Another relation is required to obtain unique values for A and $. One property of Eq. [4] is that it is independent of crystal structure. Hence, data for a iron can be used to obtain another relation. To arrive at this relation we must generalize Eqs. [2] and [3] so that they may be applied to the bcc a iron. The result is that:

Jan 1, 1969

By B. W. Christ, P. M. Giles

Mossbauer effect measurewents have been made on I-mil-thick foils of commercial 1 wt pct C steel and Fe-2 wt pct C alloy. The experimental method required about 3 to 5 vol pct of a phase in the nzultiphase steel sample for detection. Room-temperature Md&apos;ssbauer patterns obtained on austenitized atid quenched samples exhibit fifteen, and possibly twenty-one, lines. A sharp parama&tetic singlet and a quadrupole doublet, poorly resolued from the singlet, are attributed to austenite. Remaining lines are due to tnartensite. Accurate evaluation of austenite line paranzeters is not feasible if significant amounts of other phases such as carbides or martensite occur simultaneously with austenite. This is demonstrated by comparison of hyperfine interactions determined for austenite in multiphase high-carbon samples with those reported for Fe-C austenite in a nearly 100 pct austenitic sanple. Lines from carbides are incompletely resolced from austenite lines, as demonstrated by comparison of austenite line positions with carbide line positions calculated frow published values of hyperfine interactions. One martensite line overlaps an austenite line in the pattern for commercial 1 wt pct C steel. Results of this study suggest that the usefulness of e M6ssbauer pectroscopy for quantitatizle analysis of austenite in bulk samples of quenched and tempered high-carbon steels is restricted by poor resolution. Use of Mossbauer spectroscopy for phase identification and for evaluation of atomic and electronic structures appears quite feasible, however, The Mijssbauer effect has been widely discssed,&apos;-and e Mossbauer effect measurements have been reported on materials of metallurgical interest.7"20 In particular, it has been proposed that e Mossbauer patterns of commercial steels and laboratory-made Fe-C alloys, in the quenched condition, are composed of lines originating in two phases, Fe-C austenite and Fe-C martenite.-&apos; Evidence accumulated in this study demonstrates that three absorption lines found in the central region of the e Mossbauer pattern obtained on quenched steels are attributable to retained austenite. This interpretation is supported by parallel decreases in the intensity of these three lines caused by subambient cooling of commercial 1 wt pct C steel samples after water quenching to room temperature. A second result of this study is to clarify effects of line resolution and sensitivity in the Mossbauer patterns of multiphase steels on the accu- rate determination of austenite line parameters. Experimental line widths (full width at half height) are generally 1.5 to 3 times larger than the natural line width of 0.19 mm per sec. At least two lines, and sometimes more, from a single phase such as cementite (Fe3C), other carbides, martensite, and austenite fall in the energy band, i0.85 mm per sec. hhis band width is employed simply for convenient reference. It represents approximately the energy interval between the + 112 to 112 transitions in ferrite and is expressed as the velocity needed to Doppler shift a 14.4kev 7 ray to the aforementioned ferrite energy levels. This energy band is referred to as "the central region of the Mossbauer atttern:: in this paper. Hence, due to the large number of lines from different phases in a multiphase steel falling in a relatively narrow energy band, absorption lines from the different phases may overlap. Analysis of available data, presented below, indicates that this occurs to a significant extent for phases which commonly occur in quenched and quenched and tempered high-carbon steels. One consequence of limited resolution in the Mdssbauer patterns from multiphase steels is difficulty in accurate determination of such line parameters as position, width, and intensity. In fact, it appears that quantitative analysis for retained austenite in quenched and tempered high-carbon steels is not practical with the present experimental method. Line resolution is influenced to some extent by sensitivity. We point out below that atom or volume fractions of less than about 3 to 5 pct are not detected by the present experimental method. Thus, the presence of a multiplicity of phases does not always lead to impaired resolution. Finally, we report in this paper room-temperature MGssbauer parameters determined for austenite in a freshly quenched, commercial 1 wt pct C steel and in a freshly quenched laboratory heat of an Fe-2 wt pct C alloy. These parameters are compared with others reported in the literature. Three types of hyperfine interactions are detectable in a Mossbauer effect measurement: isomer shift, quadrupole interaction, and magnetic dipole interaction. These interactions are evidenced by one, two, and six line patterns, respectively.&apos;-4 More than one type of interaction has been reported in certain metallurgical phases thus far studied by this method. Isomer shift is the experimentally measured displacement of line position from some arbitrarily defined reference position. In the case of a multiline pattern, isomer shift is given by the displacement of the centroid (center of gravity) of that pattern from the reference position. All isomer shifts measured at finite temperatures contain a second-order Doppler effect characteristic of that temperature. The isomer shift is related to the total s electron density at the nucleus, becoming more negative with increasing s electron density. The first-order quadrupole effect arises from the interaction between the nuclear quadrupole moment and any axially symmetric electric field gradient in

Jan 1, 1969

By Heribert Wiedemeier, Ali Khan

The tetnperature-conposition phase diagram of the syste,n MnS-CdS has been investigated over a range fro)n 600° to 1000° C. The small degree of solid solution on the MnS rich slde cornpared to the large CdS rich single-plzase region could be esplained by the difference in strzrctures of the cotnponents and the relative sizes of the metal ions. The change in lattice parameter as a function of cot)zposition is linear atzd jollous Vegavd&apos;s rule within experittzental limits of error. Mns and CdS have gained considerable attention in recent years because of their interesting solid state properties. In order to investigate such properties and thermodynamic quantities of mixed compositions of transition metal chalcogenides, it is necessary to establish their phase diagrams. Two earlier publications are concerned with the MnS-CdS system. Schnaase&apos; found complete miscibility when MnS and CdS were co-precipitated in aqueous solutions at room temperature. However, there is evidence that the mixed crystals were not stable over the entire range of composition. roger&apos;s&apos; investigation of the ternary system ZnS-CdS-MnS at 900" C indicates a solution of 48 mole pct MnS in CdS. During the course of this work which covers a temperature range from 600" to 100O° C, emphasis has been placed on the use of high-purity materials and well-defined modifications of starting products. EXPERIMENTAL Starting Materials. The stable green modification of MnS with NaCl structure was prepared by direct fusion of the elements and by chemical transport reaction. Stoichiometric amounts of manganese of 99.99+ pct purity and of sulfur of 99.999 pct purity from Gallard-Schlesinger Corp. were sealed in an evacuated quartz tube at a pressure of 10"5 mm Hg and annealed for 48 to 60 hr at 800°C. The quartz tubes used throughout this work were outgassed under high vacuum at a temperature of 90OU to 1000° C for 12 to 18 hr. For the synthesis of MnS by chemical transport3 stoichiometric ratios of elemental manganese and sulfur and small amounts of iodine were sealed under vacuum in a quartz tube, which was placed in the temperature gradient, 900/800-C, of a two zone furnace. Single crystals of MnS in form of platelets and octahedra were deposited at the cooler end of the tube. The manganese content was determined by EDTA titratin. A typical result of several analyses was 63.05 pct Mn which agreed well with the computed value, 63.14 pct. Commercially available CdS of 99.9+ pct purity, a mixture of the cubic and hexagonal forms, was converted into the hexagonal high-temperature modification by annealing CdS under vacuum in quartz tubes at 700° C for about 36 hr. As a second method, cadmium sulfide was transported in a temperature gradient, 70O° /650" C, with in vacuo sublimed iodine from the hot to the cooler zone of the tube. Large sized crystals in form of hexagonal columns and some platelets were obtained. An average result of the cadmium analysis by EDTA titration4 was 77.93 pct in good agreement with the computed value, 77.81 pct. Only the NaCl modification of MnS and the wurtzite modification of CdS were used for the solid solutions. Preparation of Solid Solutions. Finely powdered MnS and CdS samples were thoroughly mixed in molar ratios and compressed into pellets of about 6 mm diam and 2 mm in height at a pressure of approximately 13,500 atm.

Jan 1, 1969

By G. Baralis, P. Gondi, I. Tangerini, G. Scandola

The precipitation behavior of Zn-0.5 pct A1 alloy single crystals was studied by means of electrical resistivity measurements and by optical and electron microscopy. The single crystals for the resistivity measurements were prepared by an original method in - 100-p -thick sheets. The order of the precipitation kinetics ranged between 1 and 1.5. The dislocations play a relevant role in the first-order kinetics. Precipitation always occurs both on dispersed particles and on dislocations. Statistical examinations have shown that the first-order kinetics can have two different activation energies; i.e., the precipitation can have dz;fferent mechanisnrs which could not be identified, however, in the course of the research. During the tnetallographic exanzination of the precipitation structures a specific process of dislocation decoration was obsereed. The main purpose of this work was to study the contribution of dislocations to the precipitation. A number of authors have observed precipitation on dislocations and reference might be made to several monographs on the ubject.&apos;&apos; The possibility that dislocations also accelerate precipitation has been considered by Turn-bull3 and Fischer et al.4 The studies described in the present paper were carried out on zinc, chosen as a base metal owing to the ease with which dislocations can be introduced into it and because of the absence of excess vacancies after quenching in conditions where phenomena of accelerated precipitation still occur. Aluminum was preferred as alloying element because of the accelerated precipitation phenomena that resulted in a preliminary reearch. EXPERIMENTAL METHODS The observations refer to a Zn-0.5 pct A1 alloy. The zinc was 99.995 pct pure; a typical spectroscopical analysis is given in Table I. As a rule the alloy was subjected to homogenization, quenching, or slow cooling and annealing. Homogenization was carried out by heating at 390" to 410°C for 24 hr. From the homogenization temperature, some specimens were quenched and some slowly cooled at a rate of 2°C per sec. At this rate no precipitate was detectable under the optical microscope just after cooling. Quenching was carried out simply by dropping the specimens into water, aqueous ethylene glycol solution at -30" c, or liquid-nitrogen baths placed close to the homogenization oven. Vaseline oil baths were used with a thermal stabilization of 10-20 for both the aging treatments and the measurements; aging was generally carried out at 90" or 130°C. To avoid oxidation phenomena during heating, the vaseline oil baths had to be frequently renewed. The precipitation kinetics were studied by means of electrical resistivity measurements, using ans potentiometric method (reproducibility ± 5 x 10 5 v, that is 0.5 pct of the total voltage decreases on the specimens during precipitation). First, various types of specimens were tested, i.e., polycrystals, single crystals grown in capillary quartz tubes, and thin single-crystal sheets prepared by means of an original method requiring no container except for the natural oxide. Even if fully annealed, the polycrystals and the capillary grown single crystals showed resistivity in -creases, most probably due to dislocations introduced in the course of the measurements. Similar resistivity increases in pure zinc were noticed by another author. Only the single-crystal sheets showed no resistivity change; thus they were chosen for the subsequent tests. As already mentioned, these single crystals were obtained by using, as a container, the natural oxide on the zinc surface; the oxide strength is sufficient to maintain the original shape during melting with sheets up to 500 p thick. An initial zone melting and subsequent zone leveling, which led also to formation of the single crystals, were thus carried out on rolled sheets of the required thicknesses (- 100 p) and shape, lying on a flat silica surface. The resistivities were first evaluated by measurements at the liquid-nitrogen temperature. This method gave poor reproducibility, however, and this was attributed to the thermal cycles which had to be operated. To avoid cycles and handling, it was therefore decided to make measurements directly in the annealing oil baths; this required thermal stabilization at ilo-&apos; "C. In this way only the resistance changes were measured. Specimens of pure zinc and of completely annealed alloy were always examined as controls together with those under consideration; only those measurement runs were taken into account where the reference samples showed no resistance increases. Again, the main inconvenience was due to oxidation and this was avoided by renewing the oil baths; even so data reproducibility was poor and the observations were therefore carried out on a large number (many hundreds) of specimens so as to provide indications of statistical value. For the transmission observations under the elec-

Jan 1, 1969

By Colin Baker, G. C. Smith

Investigation of the initiation and propagation of ductile failure in OFHC copper was undertaken to determine the role of nonmetallic inclusions. The effect of inclusion initiated voids on the formation of the internal cavity and the final shear separation was studied by metallographic eranzination of strained test pieces. A strain anneal technique was used to enlarge the voids under uniaxial stress conditions to elinzinate triaxial stress effects. Measurements of void size us stress and strain were made to show the point at which void im&apos;tiation begins and becomes an important factor in the deformation process. The work of separation of copper-cuprous oxide was determined to attempt to correlate the breakdown of the matrix inclusion interface with void initiation and propagation. The zloid shape and position relative to the tensile axis suggested an interface breakdown mechanisnz of initiation. Evidence is presented that shows a basic similarity between the central cavity propagation and the 45-deg shear portions of the failure. DUCTILE fracture has been studied by a number of workers1-lo and attention drawn to the importance of hard second phase particles in the initiation of the failure. Holes formed at the matrix-particle interface can elongate by plastic deformation and then subsequently expand sideways to link up and produce a major crack. This is usually observed first in the center of the macroscopically necked region of a test-piece where the hydrostatic stresses are at a maximum. As the crack spreads sideways towards the free surface of the specimen, well defined shear zones develop from the crack tip and the final separation is along a direction at approximately 45 deg to the stress axis. This shear failure may also be associated with voids formed adjacent to second phase particles. In this way a cup and cone type fracture is produced. The stage at which separation takes place between particles and the surrounding matrix has not been clearly identified. In addition, although researchers have dealt with anisotropy of tensile behavior" as a result of material fabrication variables, not much is known about the microstructural features of aniso-tropic behavior. In the present work evidence on these points is presented in relation to the behavior of copper containing second phase particles of cuprous oxide. I. MATERIALS AND PROCEDURES EMPLOYED The material used was +-in. diam or 2-in. sq cold-drawn OFHC copper bar which contained 0.6 pct by volume of cuprous oxide inclusions. These ranged in COLIN BAKER, Junior Member AIME, formerly at -mnF of Metallurgy, University of Cambridge, Cambridge, England, is presently Research Scientist Reynolds Metals Co., Richrnand, Va. G. C. SMITH, Member AIME, is Senior Lecturer, Department of Metallurgy, University of Cambridge. Manuscript submitted June 20, 1967. IMD size from approximately 1 to 6 p in length and 1 to 4 p in width. The shape was generally slightly ovoid. Tensile tests were made on specimens having a gage length of 2.5 cm and diameter of 0.643 cm. Metallographic examination was carried out by sectioning deformed and fractured specimens; in addition fracture surfaces were examined optically and with a scanning electron microscope. Some measurements of the work of separation between copper and cuprous oxide were made, using a sessile drop technique which was a modification of that used by Kingery and umenick." The best metallographic results were obtained by using a vibratory polisher, which minimized smearing of the surface. 11. RESULTS A) Initial Experiments. Specimens from the +-in. diam rod were annealed for 2 hr at 650°C in uacuo, at which temperature complete recrystallization occurred without any change in the form of the inclusion. They were then fractured at temperatures from -190" to 600°C. Cup and cone fractures were obtained at all temperatures from -196" to 400°C. With increase in temperature there was, however, a continuous increase in the extent of the central transverse area and a corresponding decrease in the shear portion of the fracture. Above 400°C, the fractures became intergranular. Sections of specimens tested below 400°C revealed extensive small voids which were always associated with inclusions. However, the voids only reached dimensions greater than the inclusion size in the region of the macroscopic neck, where they were many times longer. Lateral expansion was found only near the fracture surface of the test pieces. As observed by Puttick, the voids were either (a) triangular holes initiated in the direction of the tensile axis and elon-

Jan 1, 1969