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By G. L. Kulcinski, R. D. Leggett

Irradiated uranium containing 635 ppm of carbon, mostly in the form of UC precipitates, was annealed at temperatures from 650" to 900°C under hydrostatic pressures of 0 to 1000 bars. Postirradiation examination revealed that the carbide particles are not stable in the r phase of irradiated material but are stable in unirradiated material annealed under identical conditions. The degree of carbide dissolution appears to be connected with the fission product concentration and independent of annealing pressure. THIS paper describes the change in appearance of carbide particles in irradiated uranium after the uranium has been postirradiation-annealed. It has been proposed by several investigators&apos;-5 that fission gas-induced swelling in irradiated uranium may be reduced by incorporating a fine dispersion of second-phase particles into the metal. Because of the low solubility of carbon in uranium6 and the apparent stability of UC precipitates at high temperatures,6-8 this system has received some attention. The stability of UC particles to low-temperature irradiation has been demonstrated many times, as well as their stability during postirradiation anneals in the high a or B phases.9 Unirradiated uranium containing UC particles has been annealed high in the r phase, and the solubility of carbon was found to be only -115 ppm at 1050ºC.6 Vacuum annealing of irradiated uranium to the same temperature produces a spongelike sample, due to the formation and growth of fission gas bubbles."14 This highly disrupted lattice has made any determination of the stability of UC at these temperatures impossible. Nevertheless, it has always been tacitly assumed that the UC particles were still present. Recently, postirradiation, high pressure-high temperature tests have been performed on irradiated uranium containing a secondary phase of UC. 14 Examination of these samples after 100-hr, 900°C tests revealed that the carbides are not stable, and the results of these tests are presented here. 1) EXPERIMENTAL PROCEDURE The samples, high-pressure equipment, and subsequent analytical techniques are the same as those described elsewhere.14,15 Briefly, cylindrical samples of commercial-purity uranium that had been irradiated at <350°C to 0.37 at. pct B.U. were subjected to 90O°C, 100-hr anneals in NaK at pressures ranging

Jan 1, 1970

By K. Tangri, M. Chaturvedi

The addition of 0.5 wt pct Cu to Zr-2.5 Cb alloy increases the as -quenched hardness of the hexagonal martensitic a&apos; phase, produced by water-quenching bccß-Zr phase, by about 35 pct. This strengthening has been attributed to the solid -solution hardening of the matrix. On aging ternary martensite, a&apos; phase reverts to equilibrium a and Zr2Cu and ß-Cb precipitate out, mainly at the twin and grain boundaries, causing a secondary hardening of the matrix. COLD-worked Zircaloy-2 pressure tubes have been in use in power reactors for a considerable period of time. The search for a better material led to the development of Zr-2.5 wt pct Cb alloy which in the quench-aged condition develops 50 pct more strength than that of cold-worked Zircaloy-2, however, its corrosion resistance in water and steam in the temperature range of 316" to 400°C, in absence of neutron flux, is inferior to that of zircaloy-2.&apos; Work carried out by Ells et al.1 and Dalgaard2 has shown that the corrosion properties of Zr-2.5 wt pct Cb alloy can be considerably improved by the ternary addition of 0.5 wt pct Cu. This paper is concerned with the effect of 0.5 wt pct Cu on the formation of martensitic a and its aging characteristics in a Zr-2.5 wt pct Cb alloy. MATERIALS AND EXPERIMENTAL TECHNIQUES Zr-2.5 Cb-0.5 Cu (referred to as the ternary alloy) and Zr-2.5 Cb (referred to as the binary alloy) alloys, supplied by the Chalk River Nuclear Laboratories of the AECL were used. The detailed chemical analysis is given in Table I. Cold rolling and swagging with frequent intermediate anneal of 1000°C were used for the initial fabrication of the alloys. All the heat treatments were carried out after the specimens were wrapped in zirconium foils and encapsulated in silica tubes under a vacuum of 5 x 10-6 mm of Hg. For optical metallography and hardness measurements specimens were mechanically and then chemically polished in a 45 pct HNOj, 45 pct HzO, and 10 pct HF solution. Hardness was measured on a Vickers hardness tester using a 10-kg load. For each specimen at least fifteen indentations were made in order to obtain a representative value. The phase identification and structural analysis were carried out using X-rays and electron diffraction techniques. Wires of 1.5 mm diam reduced to 0.12 mm diam by chemical etching were used for making Debye-Scherrer powder patterns using Cu Ka radiation in a 114.6 mm diam camera. Carbon extraction replicas were prepared by etching the specimens, after depositing a layer of carbon on the metallographic specimen, in one part HF and thirty parts ethyl alcohol. Thin films were prepared by electropolishing heat-treated 3/4 by 1/2 by 0.005 in. thick strips using a modified Bollman-Window technique. The 10 pct perchloric acid-90 pct methyl alcohol bath was kept at -50°C and polishing was done at 5 to 10 V. The thinned specimens were washed in ethyl alcohol at -30º to -40°C and dried between filter papers. Replicas and thin films were examined in a Phillips 300 G electron microscope. For resistivity measurements thin strip specimens 0.02 by 0.3 by 10.0 cm long were used. The potential leads were spot welded to the specimens in order to maintain a fixed length for the initial and the final resistivity measurements. The resistivity was measured by a Kelvin bridge in a temperature controlled room. The temperature was maintained at 72º ±1°F and the accuracy of the resistivity measurements was 0.03 µa-cm. RESULTS As-Quenched Structures. In order to produce a homogeneous matrix to study the precipitation reaction the solution-treatments of both the alloys were carried out in the -field region. From the Zr-Cb phase diagram due to Lundin and cox3 ß/a + ß phase boundary for Zr-2.5 wt pct Cb alloy is 820°C. Ells et al.1 have reported this boundary for Zr-2.5 Cb alloy containing 1100 ppm 0 to be at 920°C. Also, the addition of 0.5 wt pct Cu reduces this temperature by 50°C. Therefore, the solution-treatments were carried out at 1000°C to ensure that the alloys were in ß-phase region. The soaking time was 1 hr and the specimens were water-quenched. The as-quenched hardness of the binary alloy was 245 Vpn whereas, that of the ternary alloy was 330 Vpn. The X-ray diffraction studies indicated that the as-quenched structure of both the alloys consists of martensitic hexagonal phase a&apos;, with a c/a ratio of 1.591, and some retained ß-Zr. The presence of a&apos; phase was further confirmed by thin film electron microscopy. Electron micrographs of typical ß-quenched structures of the ternary and the binary alloys are shown in Figs. 1 and 2, respectively. Fig. 3 shows the diffraction pattern from an area similar to that shown in Fig. 1. Although, the as-quenched hardness of the ternary alloy is about 35 pct greater than that of the binary alloy, the structure of both the alloys seems to be the same. The matrix of both alloys is heavily twinned and shows very few dislocations. Furthermore, there is no evidence of any precipitation taking place in either of the two specimens during quenching from the solution-treatment temperature. Aging Behavior of Martensitic a&apos;. The aging kinetics of the ternary alloy were followed by resistivity and hardness measurements. The as-quenched values

Jan 1, 1970

By A. U. Seybolt, J. L. Walter

The effects of the addition of 0.5 pct ThO2 (by volume) on the grain structure and texture of heavily rolled tungsten sheet were studied. Powder metallurgy ingots were rolled to sheet, 0.001 in. thick, and samples were annealed at temperatures from 1200" to 2500°C. The heating rate to the anneal temperature was varied from 3°C per min to 6500°C per min. The orientations of the largest grains were determined by X-ray diffraction. The disposition and loss of the ThO2 particles were determined by electron transmission microscopy and the activation energy for remozlal of the thorium was measured by mass spec-troscopy. Heating rates below about 800 C per min produced large, highly elongated grains. Higher heating rates produced much smaller, less elongated grains. The grain structure and texture of the slowly heated samples were identical to the structures and textures of heavily rolled tungsten foil conventionally doped with aluminum, silicon, and potassium but the recrystallization temperature was about 200°C lower. There was stringer-like dispersion of larger ThO2, particles superimposed on a uniform dispersion of fine particles. The particles increased in size and decreased in number with time at temperature. The loss of particles was accompanied by formation of grain boundary voids and surface pits. The activation energy for removal of the ThO2 was about 40 kcal per mole. THE addition of small amounts of aluminum, silicon, and potassium to tungsten has a profound effect on the grain structure of heavily rolled sheet1 or drawn wire."4 Thus, "doped" tungsten sheet, rolled to 0.001 in. and recrystallized, develops a structure consisting of large, highly elongated grains of a specific preferred orientation.&apos; It has been shown that the elongated grain structure was caused by a dispersion of particles, identified as mullite (Al6si2O13),1,4 in strings parallel to the rolling direction in sheet or to the wire axis. Identical results were obtained for iron which was doped with glass and rolled to 99 pct reduction of thickness and recrystallized.5 Again, the glass particles were disposed in strings parallel to the rolling direction. The strings retarded boundary migration in the lateral direction but grain growth was able to proceed relatively unhindered along the direction parallel to the strings.1,5 In both the doped tungsten and the glass-doped iron, the particles were highly plastic during the high-temperature deformation. Since mullite melts at about 1800°C and the glass employed melts at about 810ºC, the particles were probably molten during the recrystallization anneals (above 1800°C for the doped tungsten and 850°C for the glass-doped iron). There are indications in the literature that particles not plastic at hot-working temperatures (up to about 1550°C for tungsten) may also impart elongated grain structures by primary recrystallization of worked alloys. Examples are dispersions of tantalum carbide in chromium,6 and ThO2 in nickel where elongation ratios of recrystallization grains of up to 20:l were obtained.7 Strings of ThO2 particles in W-ThO2 wire have been seen by Rieck.8 In view of the available evidence, it was of interest to extend the previous studies of doped tungsten and glass-doped iron to include W-ThO2 sheet materials. Of specific interest was the grain structure, preferred orientation, recrystallization temperature, and disposition of the thoria particles. EXPERIMENTAL PROCEDURE A) Material Preparation. About 380 g of blue tungsten oxide (approximate composition WO3) was wet with a sufficient amount of aqueous solution of Th(N03)4 to provide 0.5 vol pct ThO2. The wet mixture was stirred to distribute the doping material uniformly throughout the powder. Stirring was continued while the mixture was heated until it was completely dry. The dried, doped mixture was then reduced to tungsten powder by heating at 850°C for 2 hr in a stream of dry hydrogen. The doped tungsten powder was hydropressed in a rubber sack at pressures of 50,000 psi to produce an ingot approximately 2 cm diam by about 5 cm long. Next, the pressed cylinder was heated in hydrogen for 2 hr at 1350°C to render it strong enough for machining. The cylinder was machined to a square cross section of 1.6 by 1.6 cm with rounded corners. Finally, the bar was heated for 2 hr at 2150°C in hydrogen to provide a sufficiently dense mate rial to withstand the hot-rolling operation. Prior to rolling, the ingot was reduced in thickness by about 20 pct by forging at 1550°C. This served to increase the density of the material and to widen it slightly for better rolling characteristics. The forged ingot was then rolled at 1550°C to a reduction of 45 pct of thickness, following which the rolling temperature was reduced to 1300°C and the slab rolled, with several reheats, to 0.050 in. Further reduction was accomplished at 800°C in tungsten sheet packs to a total reduction of about 99.85 pct. B) Annealing Treatment and Observation of Structure. Small samples of the rolled foil were annealed in one of two ways. Some of the samples were suspended in a covered tungsten can and annealed at temperatures from 1200" to 2200°C for various times in vacuum of l0-7 to 10-6 mm Hg. The can was heated by induction and temperatures were determined by optical pyrometry

Jan 1, 1970

By M. B. Bever, A. K. Jena

Equations for the heat effects of additions of mixtures of multicomponent phases to a solution have been derived in terms of the enthalpy interaction coefficients. By these equations and the measured composition dependence of the heat effects on addition of mixtures of Ag-Cd solid solutions and elemental gold to liquid tin-rich solutions, values of the enthalpy in-teraction coefficients in tin-rich solutions at 541°K have been obtained. Analysis of these results in terms of the regular solution theory and the quasichemical theory suggests that near the melting point of the solvent association in the solution becomes important. SEVERAL recent papers have discussed the nature of dilute solutions on the basis of measured enthalpy interaction coefficients. l-3 These coefficients contribute to the understanding of the constitution of solutions and can be used for the evaluation of thermo-dynamic data of multicomponent systems. Their experimental determination, however, is laborious. This communication reports values of the enthalpy interaction coefficients of silver, cadmium, and gold in liquid tin-rich solutions obtained from the measured heat effects of additions of mixtures of Ag-Cd solid solutions and elemental gold to liquid tin-rich solutions. These measurements were made in the course of the determination of the heats of formation of Ag-Cd solid solutions reported in a concurrent publication.4 THE HEAT EFFECT OF AN ADDITION TO A SOLVENT This analysis is concerned with the addition of a mixture of multicomponent phases from the temperature To to a solvent of known composition at temperature T. If Nmixture << Nsolvent, where N designates the gram-atoms involved, the heat effect per g-atom of mixture added can be expressed as (HT - HT )i = difference in heat contents of component element i in the mixture at T and To Q = heat effect on solution of the mixture at temperature T Also1 Q = S Xi [2] where ?Hi ,T,x = relative partial enthalpy per g-atom of i in solution at temperature T and composition of the solution x x = average of the atom fractions of the added material in solution before and after the addition The relative partial enthalpy ?Hi per g-atom of an element i in a dilute solution composed of a solvent 1 and the solutes j = 2, ... m is related to the interaction coefficients by the following equation5 ?Hi - ?Hi-?Hi,x1-1 + S n1ixj+ . . . +S...S...S nrixn2... Xnji...Xnmm+... [3] vhere Xj = atom fraction of solute j in the solution nri = the rth order enthalpy interaction coefficients, which can also be represented by the more general designation5 L(i)n2,n3...nm and nj may have any positive integral value or zero. For identification of various rth order interaction coefficients, nri is written as nn2i2,...nij,...nmm. Eqs. [1], [2], and [3] combine to give the following general equation for the heat effect on addition of a small quantity of a mixture to a large quantity of a dilute solution n = _?ga ?Ha,To + ? Xi(HT - HT o)i a. i + ?xi?Hi,X,i?1 + ??xnjixj + . . . + ???. . .?. . .?xinrix2n2. . . xnji. . . xnmm+ . . . [4] The first term on the right-hand side of this equation is the heat of decomposition at the addition temperature of the phases present in the mixture, the second term is the heat required to raise the temperature of

Jan 1, 1970

By S. Kobayashi, A. E. Armenákas, C. Mylonas

Earlier work1-4 has shown that commercial mild steels under static loading at the lowest natural operating temperatures fracture in a brittle manner only when damaged by a suitable history of straining. Notched and then compressed plates have fractured in subsequent tension at loads as low as 10 pct of the limit load and precompressed smooth bars at a subsequent extensional strain as low as 0.01. The comparison of the average net fracture stress with the flow limit stress was shown to be an excellent criterion of brittle or ductile behavior of mild steel structures when only loads and general stress levels are known. The present investigation shows that the deformation at fracture is a far more sensitive measure of brittleness than the fracture stress. Both criteria, deformation and stress, are used to determine the amount of uniform precompression of two mild steels, ABS-B and Project E-steel, resulting in brittle fracture under the strong constraint of a subsequently machined severe circumferential groove. The fracture stress equaled or exceeded the theoretical flow limit Ól = 2.680., (&apos;based on the elevated yield stress at each prestrain) up to prestrains of about 0.20 and then fell off to about 1 at prestrains of 0.60. Yet a prestrain of only 0.05 reduced the elongation at the shoulders by a factor of about 4. The total plastic elongation of a region surrounding a sharp notch in prestrained steel deternines whether or not fracture will be initiated in large structures, hence is a direct and realistic measure of the remaining ductility and provides an excellent test of the material&apos;s resistance to embrittlement. ALMOST all engineering structures of mild steel which failed in service in a so-called "brittle" manner exhibited appreciable local plastic deformation (more than 1 pct) and a mixture of "cleavage" and "shear" fracture surfaces. Furthermore, the peak local stress in an advancing crack is always high. Such simple criteria as pure cleavage, absence of plasticity, or fracture stress, so useful in other fields, are insufficient to characterize brittleness in engineering structures at ordnary temperatures. The "brittle)&apos; behavior of engineering structures is caused by the limited ductility at cracks or notch regions, as shown by recent work at Brown University summarized and extended in Refs. 1 to 4. It was also shown that the local ductility of mild steel may be catastrophically reduced by a suitable strain and temperature history similar to those which may occur in real structures. Localized yielding begins at the notch roots at low loads but is contained by surrounding elastic regions. The plastic strains are hence small. They increase slowly with the load up to the flow limit or limit load for an ideally plastic material. Unrestricted plastic flow then occurs. At such strains the real material locally st rain-hardens and fractures. With work-hardening materials no flow limit exists, and the transition from low to high plastic strains is gradual but increases more rapidly at loads close to the flow limit of an equivalent perfectly plastic material. When the available ductility is sufficient for reaching the limit load, the behavior is normal or "ductile". With insufficient ductility, fracture will occur at a low load and will be defined as "brittle". Accordingly the sufficiency or not of the ductility at a notch is reflected in the magnitude of the fracture load or average net stress as compared with the limit load or flow limit. The application of this criterion gave surprising results. Service failures under semistatic loading occurred mostly below the limit load, hence were "brittle". On the contrary all static tests with undamaged commercial mild steels reached the limit load in spite of the deepest notches and temperatures below Charpy impact transition (say about -30°F or higher). Notched bars showed no brittleness even under fully dynamic axial loading up to 1.5 x107 psi per sec at -23°F and about 2.5 x l06 psi per sec at -ll0°F, but broke in a brittle manner at -200°F and l03 psi per sec.&apos; To propagate a fracture at low load, experimenters had to trigger it by superimposing a strong dynamic impact at a notch cooled by liquid nitrogen as in the Robertson5 or Esso tests.&apos; Once started the cracks would run through warmer regions of smaller stress. Obviously the ductility of the apparently undamaged commercial steels was "sufficient" in the laboratory tests but not in the service fracture, where it must have been reduced by some embrittling procedure of fabrication or service. These conclusions were confirmed by the achievement of low static stress (brittle) fracture initiation in unwelded steel after a local reduction of ductility by simple prestraining. Symmetrically notched plates of undamaged mild steel cooled below the Charpy V-notch transition range were tested in central static tension: Undamaged plates withstood loads of limit intensity, but when subjected to prior in-plane com-pressive prestraining perpendicular to the notch axis and to accelerated aging, the plates fractured completely or partially at very low static loads, as low as one-tenth of the flow limit.2-4 However, damage could not be easily related to the strongly variable prestrain around a sharp notch. To obtain easier strain measurements, it was decided to use axially precom-pressed bars and bent bars. Final testing was done by

Jan 1, 1970

By P. Shahinian, H. H. Smith, M. R. Achter

Crack growth rates are measured at elevated temperature in a resonant fatigue machine from vibration frequency decreases calibrated in terms of crack depth. Crack growth rates in Type 316 stainless steel at 500º and 800°C show a sharp increase with oxygen pressure in an intermediate pressure range and little or no change at high and low pressures. At 500°c, I torr of oxygen reduces the fatigue life by almost a factor of 100 in comparison to that in vacuum and raises the growth rate of shallow cracks by the same At At 800°C the effects are smaller. Changes in slope in the crack growth rate curves are discussed in terms of a model in which rates of surface production and of surface coverage by gas are compared. The use of a calculation method in which the surface exposure time is equal to X/v, where x is the interatomic spacing and v is the growth rate, makes it possible to obtain order of magnitude agreement at 500°C between the observed pressure and the predicted pressure at these slope changes. At 800°C oxidation becomes a .factor and the data cannot be treated by simple adsorption theory. THE decrease in the fatigue life of metals as a function of gas pressure usually follows a stepped curve with virtually all of the decrease concentrated in a sharp drop in a transition zone at intermediate pressures and little or no change at low and high ranges. A number of models, differing in the details of the mechanism, have been offered to explain the shape of the curve. Measurements of crack growth in aluminum as a function of gas pressure by Bradshaw and Wheeler&apos; and Hordon2 demonstrated opportunities for quantitative comparison to evaluate the proposed models. Since comparable data were lacking at high temperatures, in the present work rates of crack propagation were measured in Type 316 stainless steel at 500" and 800°C as a function of oxygen pressure. Choice of this material was dictated by two considerations; it is stiff enough at these elevated temperatures to resonate with the regenerative drive on our fatigue machine and it is known to display a large effect of environment. A new method of calculation is described to predict the gas pressure at the critical point. EXPERIMENTAL PROCEDURE Because of the difficulty of measuring crack depths directly at high temperatures, an indirect method was developed based on the decrease in the resonant frequency with the growth of a crack. A reversed bending, constant amplitude fatigue machine, described previously,3 vibrates a specimen at its resonant frequency, automatically records any changes in it and shuts itself off after it has reached a preset value of frequency decrease. The record of frequency change is used to determine the rate of crack growth. Sheet type specimens of Type 316 stainless steel, Fig. 1, incorporated a sharp, shallow notch to localize the formation of a single crack. After machining, they were annealed in a vacuum of l0-6 torr either at 1066" (lot A) or 871°C (lot B) and then electropolished in an acetic-chromic acid solution. Bending strains were measured at 500" and 800°C by an optical technique4 and reported as total strain without correction for the notch. At 500°C, the 0.141 pct strain was 0.085 pct elastic and the remainder plastic. At 800°C the 0.062 pct strain was all elastic. To convert frequency decrease to crack length, calibration curves were obtained by interrupting the vibration at stated intervals of frequency decrease. The crack depth was measured microscopically at a magnification of X400 and reported as the average of the measurement on each edge. Some specimens were sectioned for crack measurement while others were returned to the machine and fatigued further. There was good agreement between the two methods. Before beginning the vibration, the vacuum chamber was first evacuated cold to 1 x 1O-6 torr, then heated to the operating temperature and held there until the pressure was again reduced to 1 x10-6 torr at which time oxygen was introduced to the desired pressure. In this investigation the vibration frequency was nominally 10 cps and a decrease of 0.6 cps was taken as the failure point. The choice of the frequency decrease to represent failure has no appreciable effect on the fatigue life because the crack is growing very fast at this point.

Jan 1, 1970

By M. J. Richards, A. Szirmae, G. R. Speich

The formation of austenite from ferrite, ferrite plus retastable carbide, spheroidite, and pearlite has been studied in a series of irons, Fe-C alloys, and plain-carbon steels using fast heating techniques. In the absence of carbide, austenite nucleates at ferrite/ferrite grain boundaries; nucleation is followed by the rapid growth characteristic of a massive transfornation. The trarnsformation occurs at 950°C at heating rates of 106º C per sec and cannot be suppressed. Metastable carbide dissolves before austenite forms and does not influence the transformation kinetics. For spheroidite structures, austenite nucleates preferentially at the jinction between carbides and ferrite grain boundaries. Growth from these centers proceeds until the carbide is completely enveloped; subsequent growth occurs by carbon diffusion through the austenite envelope. For pearlite structures, austenite nucleates preferentially at pearlite colony intersections. Carbide la)?zellae dissolve at the advancing austenite interface but complete solution of carbide does not occur; the residtial carbide is eventually dissolvled or spheroid-ized depending on the carbon cuntent. The magnitude and temperature dependence of the austenite growth rate into Fe-C pearlite when incomplete carbide dissolution is assumed are satisfactorily explained by an approximate colume diffusion model. The impurities present in plain-carbon steel reduce the growth rate of austenite in comparison to that jound in an Fe-C alloy. The formation of austenite has been studied in much less detail than the decomposition of austenite. This is primarily a result of the importance of harden-ability in determining the mechanical properties of steel. Recently, more interest in the kinetics of austenite formation has resulted from the discovery by Grange1 that rapid heating techniques strengthen steel by refining the austenite grain size. Although the strengthening effect is not large, it is accompanied by no loss in ductility. In addition, interest continues in rapid heat treatment of low-carbon steel sheet for tin plate applications.2,3 Among the few systematic studies of austenite formation are the early work of Roberts and Mehl4 on formation of austenite from pearlite and recent work of Molinder5 and of Judd and paxton6 on formation of austenite from spheroidite. Also, Boedtker and Duwez7 and Haworth and paar8 have recently studied the formation of austenite from ferrite in relatively pure iron, Kidin et al.9,10 have studied the formation of austenite in 8 pct Cr steels, and Paxton has recently discussed various aspects of austenite formation in steels." The present work was undertaken to determine the kinetics of austenite formation for a variety of starting structures including ferrite, ferrite plus metastable carbide, ferrite plus spheroidal cementite, and ferrite plus pearlitic cementite. Emphasis was placed on determining the active sites for austenite nucleation, determining the temperature and time range of austenite formation, and in the case of pearlite a careful study of the growth rate of austenite was made in the absence and presence of impurities. By using a variety of heating techniques including laser-pulse heating, it has been possible to study austenite formation in an isothermal fashion over a wide range of temperatures. EXPERIMENTAL PROCEDURE The alloys studied in the present work are a zone-refined iron with 4 pprn C, an Fe-C alloy with 130 pprn C, 2 Fe-C alloys with 0.77 and 0.96 wt pct C, and a plain carbon steel with 0.96 wt pct C. The zone-refined iron and Fe-C alloys contained 60 pprn and 200 pprn total substitutional impurities, respectively. The plain carbon steel contained 2400 pprn Si, 2000 pprn Mn, and 900 pprn Cr. Various heat treatments were given to these alloys to produce different starting structures of equiaxed ferrite, ferrite plus metastable carbide, fine pearlite, and spheroidite. These heat treatments are given in Table I. A wide range of heating rates were employed in this work because many of the reactions occur so quickly at temperatures in the austenite range that they are completed during the initial heating cycle unless very fast heating rates are used. Essentially the same heating techniques employed by Speich et a1.12 and Speich and Fisher13 were used in this work. For time intervals of 2 sec to 20 hr, simple hand immersion of 0.010-in. thick specimens in a Pb-Bi bath was employed. These specimens were quenched in a 10 pct NaC1, 2 pct NaOH aqueous bath. For time intervals of 100 m-sec to 2 sec, an automatic dunking and quenching device was employed with 0.002-in. thick specimens. Again, liquid Pb-Bi baths were used for a heating medium but now helium gas quenching was employed. For time intervals of 2 to 100 m-sec a laser heating device was employed with 0.002-in. thick specimens; a helium plus fine water-droplet spray was now used for quenching. Additional information on heating times shorter than 2 m-sec was obtained by study of the zones around the centrally heated laser spot. Here diffusion of heat from the centrally heated zone raises the temperature of the specimen locally to all temperatures between ambient and the peak temperature, but for times of the order of microseconds. All the heat-treated specimens were examined by

Jan 1, 1970

By R. Schuhmann, G. W. Powell

The concept of local equilibrium is examined and, in particular, the applicability of the concept to two-phase binary diffusion couples is discussed. It is concluded that, if binary solid solutions are treated thermodynamically as ternary solutions, vacancies being the third component, then recent experimental observations of nonequilibrium interface compositions (i.e., compositions different from the phase diagram values) are consistent with a state of complete dynamic equilibrium at the interface. CLASSICAL approaches to diffusion and to other irreversible processes often utilize a postulate of "local equilibrium". That is, one assumes even in the presence of gradients, fluxes, and time changes of properties, a) that the Second Law can be formulated locally, and b) that thermodynamic equations of state among intensive properties are identical with those for equilibrium phases. A direct consequence of this assumption, for example, is that one would calculate the total entropy of a nonequilibrium phase simply by integrating the entropy density (eu per unit volume) over the volume of the phase, assuming that entropy density is the same function of energy and particle density as for equilibrium phases. In the study of diffusion and of diffusion-controlled phase transformations, metallurgists take this concept of local equilibrium for granted and utilize it automatically. In fact, experimental evidence of all kinds is overwhelming that "local equilibrium" is a valid limiting law, approached more and more closely as gradients and rates of change approach zero. On the other hand, we have neither experimental nor statistical thermodynamic proof that this principle of "local equilibrium" should remain rigorously valid at high gradients and for rapid processes. Theoretically, in fact, one would expect deviations because interactions between adjacent volume increments of material affect the evaluation of entropy. Also one observes experimentally structural and small energetic differences between equilibrium and nonequilibrium phases. The purpose of this paper is to present a thermodynamic framework for the study and correlation of deviations from strict local equilibrium in isothermal diffusion and related processes. This procedure, in effect, preserves the principle of local equilibrium by thermodynamically assigning the deviations from static equilibrium properties to a defect component. Although this theory is entirely phenomenological, the possibility does exist of correlating the theory with experimental observations of defects under favorable circumstances. The most immediate application appears to be to the equilibria at the interfaces in two-phase binary diffusion couples. A recent pertinent work by Eifert et al.1 has shown that the concentrations of aluminum in the a(fcc) and B(bcc) phases at the 0-8 interface in Cu:Cu-12.5 wt pct A1 diffusion couples are greater than those given by the phase diagram. It is postulated by these authors that the supersaturation of the o phase at the interface provides the driving force for the a-to-B lattice transformation; the excess free energy of the a phase, ?Gaxs, arising from the greater-than-equilibrium aluminum concentration is about 3 cal per g-atom. On the basis of the schematic free energy-composition diagram shown in Fig. 1, Eifert et al. concluded that the thermodynamic situation at the interface is one of the partial equilibrium; that is, = for the more mobile aluminum whereas will be reexamined in the latter part of this paper. THERMODYNAMIC PROPERTIES OF DEFECTS A rigorous analysis of the thermodynamics of defects requires an added degree of freedom in the Phase Rule sense, because the standard formulations of solution thermodynamics (partial molal properties of components, free energy minimization, equality of chemical potentials, and so forth) involve the implicit

Jan 1, 1970

By R. F. Lynch, J. D. Wood

The Al-1.0 pct Mg alloy 565 7 was studied using optical microscopy and electron microprobe X-ray analysis. Constituent particles were found to exist inter-dendritically in the as-cast material in a region of precipitate free a -aluminum. Five phases besides a fine precipitate and a-Al were identified in the cast structure: Fel3, Fe2Al7, Mg2Al3, CUMgAl2, and Cu2FeAl7. Thermal treatments conducted for 100 hr at 1180°, 1130°, 1080°, 1030°, 980°, and 880° F revealed a general dissolution and spheroidization of the in-terdendritic constituent network observed in the cast structure. The principal constituents present in the thermally treated structures were FeAl3 and Fe2Al7 with the relative amount of Fe2A17 to FeAl3 increasing with a decrease in the treatment temperature. The phases Present in the wrought structure were identical to those observed after the thermal treatments, with the constituent particles strung out in the direction of rolling. ALLOY 5657 is a nonheat-treatable commercial purity Al-1.0 pct Mg alloy utilized extensively because of its bright finishing characteristics. This investigation was conducted to determine the constituents present in 5657 alloy, and to study the effect of extended thermal treatments on morphology. Numerous studies have been carried out to establish the equilibrium diagrams for various aluminum systems,1-3 with phase identification based on X-ray analysis, morphology, and the etching response of relatively large particles. Phragmen4 conducted a study of the phases in aluminum eutectic systems and compiled a "corrected" table of etching responses, drawing on his work plus that of Schrader,5 Keller and Wilcox,6 and Mondolfo.7 A review of the original work of Keller and Wilcox, and Mondolfo, which was concerned with the constituents found in commercial alloys, reveals that in numerous cases their etching responses differ from those reported by Phragmen and from each other. These inconsistencies may occur because a specific constituent will react to a given etch in a varying manner depending upon its size, the elements dissolved in the phase, the other constituents surrounding a phase, and the solute content of the matrix. Work with a commercial orientation was conducted on alloys 2024 and 3003 by Sperry8,9 and on alloy 3003 by Barker,10 where the relationship between the phase diagram and the nonequilibrium structure of an alloy was examined. Backerud11 investigated the A1-Fe binary system and found that at high cooling rates the equilibrium eutectic reaction forming a-A1 and FeA13 is replaced by another lower temperature eutectic reaction forming a-A1 and metastable FeAl6, a constituent first identified by Hollingsworth et al.12 Most of the above mentioned studies were conducted on materials having a significantly greater alloy content than 5657 alloy, where the relatively small size and sparse distribution of second phase particles hinders the process of identifying constituents. EXPERIMENTAL PROCEDURE Material with a composition as given in Table I was examined in the as-direct chill cast, hot rolled and cold rolled conditions, and after thermal treatment of the cast structure. Thermal treatments were terminated by a water quench. Microscopic examination was conducted under various lighting conditions following the application of standard etchants as specified in Table 11. A semi-quantitative electron microprobe X-ray analysis was conducted for Al, Mg, Fe, Cu, Si, Zn, and Ti. RESULTS AND DISCUSSION Microstructure of the As-Cast Material. Particles of second phase material were found to exist inter-dendritically, principally in regions of precipitate free a-Al, as illustrated in Fig. 1. Adjacent to the ingot edge was a region of inverse segregation, resulting in an increased amount of second phase material containing large sized particles which aided in phase identification. Phase Identification. Cast Structure. Five phases besides a-Al and a fine precipitate were identified using optical microscopy and electron microprobe X-ray analysis, as presented in Tables II and III, respectively. FeA13 and Fe2A17 are often found with Fe2A17 forming a sheath around the core of FeAl3, resulting from an incomplete peritectoid reaction. These phases have a nearly identical appearance under white light, although they are easily differentiated under crossed polarizers, as characteristically illustrated in Figs. 2(a) and 2(b), respectively. Microprobe analysis con-

Jan 1, 1970

By M. J. Marcinkowski, Gordon E. Lakso

An extensive investigation has been made of the deformation behavior associated with the Fe3Si super-lattice using transmission electron microscopy techniques. Above 243°K the stress-strain curve exhibits three stages. Stage I occurs at a very low stress level and is related to the generation of perfect superlat-tice dislocations. Stage II is characterized by an extremely rapid rate of work hardening and is associated with the Taylor type locking of these superlattice dislocations. Finally Stage III is related to dynamic recovery processes since the work hardening rate is very small. Below 243ºK, only Stage I is observed, but it occurs at a much higher stress level. This latter observation is related to the generation of imperfect dislocations in Stage I with the consequent production of second nearest neighbor antiphase boundaries. The reason for this is that insufficient thermal energy is available at these low temperatures to generate the complete and perfect superlattice dislocations. It has been shown that the fully ordered FeCo alloys, i.e., those possessing the B2 type structure, exhibit three distinct stages of work hardening whereas the corresponding disordered alloys show only one.&apos;" This difference in behavior between the disordered and ordered alloys has been attributed to the fact that dislocations in the former case travel only as ordinary 1/2ao(111) types whereas in the latter case the move through the lattice as coupled 1/2a0(111) dislocations separated by an antiphase boundary (APB), i.e., the so-called superlattice dislocation. Although some preliminary work has been carried out concerning plastic deformation in ordered alloys possessing the DO3 type superlattice,3 no detailed analysis similar to that described in Refs. 1 and 2 has been attempted. Specifically, it has been suggested that the superlattice dislocation in this particular type structure should consist of four ordinary 1/2ao<111> types bound together by first and second nearest-neighbor APB&apos;s. Fe3A1 and Fe3Si are the two classic alloys possessing the DO3 type lattice; however, because of the somewhat higher ordering energies associated with the FesSi alloy, which in turn assures that dislocations will travel through the lattice as perfect superlattice dislocations under at least some conditions, it was chosen for the present investigation. Because of the extreme brittleness of Fe3Si, all deformation was done in compression. Stress-strain curves were obtained using both polycrystalline samples as well as single crystals. In the latter case the crystals were oriented so that deformation could be controlled either by single or double slip. They were then wafered parallel to and at various angles to the operative slip planes. These wafers were in turn examined by transmission electron microscopy (TEM) techniques in order to determine the extent of the interaction from the dislocation configuration contained therein. EXPERIMENTAL PROCEDURE The alloys used in this investigation were arc melted under helium from electrolytic iron of greater than 99.90 wt pct purity and transistor grade silicon of 99.99 wt pct purity. A typical analysis of interstitial impurities showed 120 ppm 0, 15 ppm N, and 65 ppm C Because of the extremely low ductility of the Fe3Si alloys, it was necessary to spark cut 0.230-in. diam polycrystalline cylinders 0.400 in. long from arc-melted fingers using a thin-walled brass tube as a cutting tool. The polycrystalline alloys could not be recrystallized since very little strain was induced in preparation. However they were annealed at 1273°C for 15 min in evacuated vycor capsules to relieve any cooling stresses that may have developed during solidification and then air cooled. The resulting grain size of the alloy was 0.50 mm. According to warlimont4 1273ºC is just within the single phase field where FesSi possesses the DO3 type lattice. In addition because of this high critical ordering tem-ature, air cooling from this temperature was believed sufficient to fully order all of the Fe3Si samples used in the present investigation. For the same reason, no attempt was made to achieve any degree of disorder by quenching. In fact, rapid quenching from 1123°K caused cracking. Such cracking was first suggested by sato5 with respect to the experimental observations of Glaser and Ivanick.6 Single crystal compression specimens were spark cut from single crystal ingots grown in a Bridgman type furnace. The iron and silicon for the crystals was prealloyed by arc-melting two 130-g buttons which were cut into small pieces before remelting in the furnace. This procedure resulted in a long-range inhomogeneity of 0.5 at. pct Si between the top and bottom of the 2-in.-long single crystal ingot, which was assumed to be negligible in the present investigation. The single crystals, after orienting and spark-cutting, were about 0.37 in. by 0.37 in. in cross section and about 0.5 in. long. True stress-strain curves were obtained using an Instron Tensile Testing machine in conjunction with techniques described previously. 1,7 The strain rate was 0.05 in. per in. per min. Prior to testing, the ends of all the compression cylinders were hand polished using a special jig to insure parallelism after which the sides of the samples were electrochemically polished to eliminate stress risers and to facilitate slip line observations. Test temperatures between 77" and 823°K were obtained using various cooling and heating media as described in Ref. 7 while at the upper end of this temperature range, a mixture of equal

Jan 1, 1970

By N. J. Olson, G. W. Toop

A series of equations previously derived for calculating ternary thermodynamic properties using binary data has been applied to the problem of predicting ternary phase diagrams and quaternary excess free energy. The methods are considered to be rigorous for regular ternary and quaternary systerns and empirical for nonregular systems. The equations have been used to predict ternary phase boundaries in the Pb-Sn-Zn system at 926°K and the Ag-Pd-Cu system at 1000ºK. Calculated quaternary excess free-energy values are presented for the Pb-Sn-Cd-Bi system at 773°K. A method for predicting the location of ternary phase boundaries would be a useful supplement to experimental measurements in ternary systems. This has been recognized with the considerable work that has been done to find models to predict or extend thermodynamic properties and phase diagrams in binary and ternary systems1-18 for which direct experimental measurements are limited. With the access to highspeed digital computers and mechanical plotting devices, it is currently rather easy to compare mathematical models with experimental data. The regular-solution model is consistent with systems which exhibit negative heats of mixing, positive heats of mixing, and miscibility gaps, and therefore it is applicable to simple phase diagrams. The purpose of this paper is to illustrate the use of regular-solution equations to predict, empirically, phase equilibria in some types of nonregular ternary systems. Corresponding equations for regular quaternary systems are given and used to calculate empirical quaternary excess free-energy data. METHOD FOR PREDICTING THE LOCATION OF TERNARY PHASE BOUNDARIES USING BINARY DATA Meijerin1,6 has used the regular-solution model to calculate common tangent points to ternary free energy of mixing surfaces and hence to determine phase boundaries in ternary systems involving miscibility gaps. He used the following equation to calculate ternary excess free energy of mixing values: stants characteristic of the binary solutions, and Ni is the mole fraction of component i. An alternate expression which gives for regular solutions as a function of binary values of along composition paths with constant N1/N2, N2lN3, and N1/N3 may also be derived:15 ternary r xs 1 ?c-*n.Ti*.U*. This expression for is more useful for the empirical calculation of ternary excess free-energy values for nonregular systems because actual binary AFXS data may be used in the expression rather than attempting to find suitable constants for Eq. [I]. The results of this feature of Eq. [2] are illustrated in Table I where calculated excess free-energy values for the Ni-Mn-Fe system at 1232°K are compared with experimental data of Smith, Paxton, and McCabe.19 Although regular-solution equations have been shown to give calculated thermodynamic quantities which agree quite well with experiment for single-phase nonregular ternary systems,14,15 care should be exercised in the use of the equations to predict thermo-dynamic properties of multiphase ternary systems in which strong compound formation is suspected. This precaution is consistent with the simple regular-solution model which for negative values of ai_j will indicate a tendency toward compound formation but even for very large negative values of ai-jwill not give multiphase binary or ternary systems involving a distinct stable compound. Hence, calculated ternary free-energy data using Eq. [2] might be expected to vary between being rigorous and poor, in the following order, for ternary systems which are: a) regular solutions, b) nonregular single-phase liquids in which random mixing is nearly realized, c) nonregular single-phase solids, d) nonregular multiphase systems exhibiting miscibility gaps, e) nonregular multiphase systems with binary compounds but no ternary compounds, f) nonregular multiphase systems with highly stable binary and ternary compounds. The calculated data will be expected to be least accurate for the last two cases. The general method adopted in this paper involves two-dimensional plots of ternary activity curves. The principle used is that tie lines indicating two-phase equilibria join conjugate phases a and B for example, for which a1(a) = a1(B), a2(a) = a2(B), and a3(a) = a3(B). Tie lines may be determined by plotting the ternary activities of two components along an isoactivity line for the third component and the unique points where the above equalities hold may be found graphically.

Jan 1, 1970

By W. J. Maraman, D. R. Harbur, J. W. Anderson

A device for rapidly quenching liquid metals into thin platelets has been developed at the Los Alamos Scientific Laboratory. This rapid quenching equipment is built around the technique of catching a molten drop of metal between a rapidly closing plate and a stationary plate. The design and operation of this unit are described. The closing speed of the smasher plate at impact is 12.6 ft per sec. The quenching rate for this device is controlled by the interface resistance between the plates and the platelet, and is dependent upon the heat content and density of the material being quenched. The initial quenching rate down to the freezing point of the platelet material is lo5º to 106ºC per sec. After an isothermal delay, which is poportional to the heat of fusion of the platelet material, the final cooling rate down to the temperature of the smaslier plates is l04ºto 105cº per sec. RAPID heating of metals by capacitor discharge and other methods has provided the metallurgist with a useful tool for probing into the kinetics of phase changes and the many nonequilibrium phenomena which occur during rapid temperature changes. Equally interesting studies can also be made on metals and alloys which are rapidly cooled from the liquid state.&apos; Studies in this field have been limited, however, because the rates at which metals could be cooled were many orders of magnitude slower than the rates possible for heating. In recent years many new laboratory methods have been developed to rapidly cool metals from the liquid state to ambient temperature and below.2"4 All of these methods involve spreading a liquid drop of metal into a thin foil in a very short time. The methods developed have varied from ejecting a drop of molten metal at the inside surface of a rotating cylinder or stationary curved plate to catching a falling drop of molten metal between rapidly closing plates. The equipment which has been developed at the Los Alamos Scientific Laboratory for rapidly cooling molten materials uses the latter of these two approaches. The basic design, operation, and initial results of this rapid quenching device are given in this report. APPARATUS The drop smasher, which is now being used to obtain rapidly cooled metal foils, is shown in Fig. 1. Basically the device consists of a smasher plate which is driven by a solenoid into a stationary plate. The solenoid is activated by a drop passing through the photoelectric cell and is powered by discharging an adjustable 350-v capacitor bank with a 66-amp peak current into it. This power supply is designed so that the solenoid is powered for 2 m-sec after plate closure to minimize the rebound effect. There is an adjustable time-delay mechanism between the photoelectric cell and the solenoid. Both smasher plates have changeable inserts so that a variety of materials can be used to smash the molten drop. The shaft of the moving plate is guided in an adjustable housing which has ball-bearing walls. The cabinet shown to the left of the drop smasher in Fig. 1 contains the power supply and receiver for the photoelectric cell, the time delay mechanism, and the capacitor bank. The drop smasher can be placed inside a vacuum chamber, for use with radioactive materials, with the upper plate forming the lid, as shown in Fig. 2. On top of the vacuum lid is an induction coil, powered by an Ajax induction generator, which is used to melt drops from the end of the rod extending through the vacuum seal on top the quartz tube. OPERATION The drop smasher shown in Fig. 2 is operated in the following manner. The smasher plates are separated and the unit is lowered into the vacuum chamber using a pressurized cylinder. The induction coil, quartz tube, and lid with sliding vacuum seal are then assembled on top the vacuum chamber. A rod of the material for rapid quenching studies is connected to the rod extending through the sliding vacuum seal. The vacuum chamber is then evacuated and the desired atmosphere established. The photoelectric cell is turned on, and the capacitor bank is charged and armed. Power is supplied to the induction coil, and the rod of material for rapid quenching studies is lowered into the induction field. A molten drop forms on the end of the rod, drops off, falls through the light beam of the photoelectric cell, and is then caught between the smasher plates. .

Jan 1, 1970

By Frank M. Monroe, James R. Cost

The solubility of nitrogen in vanadium is determined from 275" to 575°C by measuring the height of the nitrogen internal friction peak of equilibrated V-N alloys. The proportionality constant at 275°C between the internal friction peak height (Q- 1) and the atom percent nitrogen in solution is found to be 0.095 per at. pct for nitrogen concentrations up to 0.8 at. pct. The heat of solution of the nitride in vanadium is 5500 cal per mole. The solubility of nitrogen in the Group V metals is discussed. LITTLE work has been performed on the vanadium-nitrogen terminal solid solution. Hahn1 found the solubility for nitrogen to be very small and reported the existence of a hexagonal phase of composition near that of V2N at the solubility limit. Rostoker and Yamarnoto2 reported the solubility to be at least 3.5 at. pct at the melting point and to be less than this value at 900°C. In addition, they reported from X-ray diffraction studies that nitrogen in solution produces tetragonality in the vanadium lattice. An X-ray study by Schonberg3 has confirmed the results of Hahn but indicated that the tetragonality observed by Rostoker and Yamamoto was due to the presence of oxygen in their specimens. Beatty4 has performed lattice parameter and hardness measurements on terminal solid solutions and found the upper limit of the solubility to be at least 0.66 at. pct N. No measurements have been made of the pressure-temperature-composition relationships (P-T-X) for the terminal solid solution. As a part of a research program on gas-metal equilibrium, an attempt was made to study the P-T-X relationships in the V-N system using both the internal friction and the gas equilibration methods which have been successful with the Nb(Cb)-N and Ta-N systems (see Ref. 5 for a review of this work). Extensive investigation, using the gas equilibration methods, showed this method not to be applicable with vanadium This was presumably due to the gettering action of vanadium sublimed on the walls of the Sieverts apparatus. Thus, the nitrogen pressure relationships with temperature and composition were not obtained. The internal friction methods were, however, found to be applicable, and the temperature-composition relationships are reported in this paper and compared with similar results for the Nb-N6 and Ta-N7 systems. The existence of a Snoek internal friction peak due to nitrogen in solution in vanadium has been clearly demonstrated. 8-10 Powers and Doyle found the peak to be at approximately 275°C for frequencies near 1 cps.8 In a subsequent paper10 they reported the proportionality constant at 275°C between the internal friction peak height (Q-1) and the concentration of ni- trogen in solution (in atom percent) as 0.06 per at. pct. The studies of Stanley and wert9 indicated qualitatively that the height of the Snoek peak decreased with aging at the peak temperature and thus suggested that internal friction methods were suitable for study of the solubility. EXPERIMENTAL METHOD The vanadium for this investigation was of particularly high purity. It was obtained from the Ames Laboratory of the U.S. Atomic Energy Commission, Ames, Iowa in the form of a 1/2-in. diam, three pass zone-refined ingot. The electrical resistivity ratio (p300ºk/p4ºk) was 160. The initial composition was determined as follows: Carbon 200 ppm Oxygen 150 ppm Chromium <50 pprn Iron 125 ppm Silicon <50 ppm Other metallic 100 pprn The initial vanadium ingot was fabricated to 30-mil wire by swaging and wire drawing without the need of intermediate annealing. Lengths of this wire were then further purified (particularly for oxygen) by outgassing at 10-6 torr at 1400°C for 4 hr. The outgassing treatment resulted in specimens with a bamboo grain structure and a lustrous appearance. Desired amounts of nitrogen were added to the outgassed wires in a Sieverts apparatus in which known amounts of nitrogen were equilibrated with the wire at 1300°C. Nitrogen concentrations were produced in the desired range from less than 1 to 10 at. pct N. Monitoring of the partial pressure of nitrogen in the Sieverts apparatus indicated that at 1300°C equilibrium between the nitrogen gas and the vanadium was obtained within 10 min. Relatively rapid cooling from the nitrogen addition temperature was obtained simply by turning off the specimen heating current and cooling to room temperature in the partial pressure of nitrogen. Internal friction measurements of wire specimens were made under forepump vacuum in a torsional pendulum at frequencies near 1 cps. The torsional pendulum was of low thermal inertia and was designed so that specimens could be heated both by a conventional tube furnace and by the joule heating of a separate current through the wire specimen." Use of a static atmosphere of helium gas as a quenching medium made it possible to cut the specimen current, rapidly cool the specimen to the measurement temperature, and make a measurement of the internal friction in less than 1 min. Because of the large solubility of vanadium for nitrogen, the internal friction peak heights were in some cases greater than Q-1 = 0.1. This high damping resulted in an estimated relative uncertainty in the damping measurements of approximately 10 pct. X-ray analyses made to identify the precipitated ni-

Jan 1, 1970

By W. A. Young

Polynomial functions of temperature were obtained for the specific heats, thermal diffusivities, and thermal conductivities of zirconium hydrides containing 4 at. pct U. Three hydrides (H/Zr atom ratios of 1.58, 1.65, and 1.70) were studied over the range a" to 900°C and a fourth (H/Zr = 1.81) was studied over the range 0° to 760°C. The specific heats were determined from enthalpy measurements which were obtained using a unique drop calorimeter specifically designed for use with materials in which high temperature phase transitions and/or high dissociation pressures occur. Thermal diffusivities were measured by the flash method using a pulsed laser. The thermal conductiuities were obtained as the product of specific heat, thermal diffusivity, and density. The specific heats agree, within 10 pct, with values derived using a theoretical model in which the hydrogen and zirconium atoms are treated as Einstein and Debye oscillators, respectively. RELIABLE values of the thermophysical properties of the fuel are required to predict the operating temperatures and temperature response of SNAP nuclear reactors. Among the most important of these properties are the thermal conductivity, specific heat, and thermal diffusivity. A considerable number of investigations1-4 have been made of these properties for the Zr-H and Zr-H-U systems.* However, little of the drides, however, this direct method cannot yield meaningful results, since the hydrogen will redistribute under the influence of the thermal gradient, thus forming a concentration gradient; hence, one has a spectrum of compositions, rather than a homogenous alloy. Although the "average" composition of the material may be identical to the initial uniform concentration, the directly measured value of conductivity will be dependent on the thickness of the specimen, due to the highly sensitive dependence of transport properties on hydrogen content. This dependence is strikingly illustrated by the work of Bickel,5 who found that the electrical conduction of zirconium hydrides ranges from primarily hole conduction to primarily electronic conduction, depending upon the hydrogen content. Fortunately, the direct measurement of thermal conductivity is unnecessary, since it can be expressed as the product of the specific heat, thermal diffusivity, and density, all of which can be directly measured with considerable accuracy. EXPERIMENTAL Specimen Preparation. The combined fuel-moderator material used in SNAP reactors is a hydrided zirconium-uranium alloy containing -10 wt pct U. The alloy used in this work was representative of that used in nuclear reactors except that normal uranium was substituted for the enriched uranium required for reactor usage. It was produced by a triple-arc-melt and double-extrusion process. All specimens were prepared from a single cylindrical extrusion which contained 10.30 pet U, 89,35 pct Zr, and 0.35 pct impurities, The specimens for each composition were hydrided simultaneously with ultrapure hydrogen (10 ppm total impurities) using standard fuel production techniques which routinely yield homogeneous, crack-free fuel with negligible increases in the impurity levels. The hydrogen content of each specimen was determined from its weight gain and the density was measured by liquid displacement, Chemical analyses yielded hydrogen concentrations which agreed with the weight gain data within ±0.02 in H/Zr atom ratio) the concentrations of all other elements agreed almost exactly with the initial values after adjustment for the added hydrogen. The specimens used for the determination of specific heat were centerless ground to 2.00 cm diam after hydriding. A thin slice was carefully removed From each end for metallographic examination. In every case, this examination revealed a uniform structure as evidenced by the appearance and distribution of the two phases present in the fuel at the hydrogen concentrations used. TWO specimens (H/Zr = 1.600 and 1.632) appeared to be entirely 6 phase with equi-axed grains; the specimen with H/Zr = 1.756 showed

Jan 1, 1970

Jan 1, 1970

By B. A. Wilcox, A. H. Clauer

The tensile and creep deformation characteristics of fiber reinforced composites have been studied, primarily at room temperature. The matrix was an alloy of Mg-14 wt pct Li-1 wt pct Al (LA141A alloy) and the reinforcing fiber consisted of continuous wires of a high strength precipitation hardening stainless steel (AFC-77 alloy). The ultimate tensile strength and strength-to-density ratio of composites were much improved over that of the mmix, both at room ternperatwe and up to 200°C. Creep studies at room temperature revealed logarithmic weep behavior for wires and composites and steady state creep for the nonreinforced matrix. It was concluded that creep of the fibers controlled composite creep. The instantaneous logarithmic weep rate of the composite, 6, was related to the average tensile stress on the fibers, where n = 3.4. Mg-Li alloys are the lightest structural metals commercially available, e.g., the alloy LA141A (Mg-14 wt pct Li-1 wt pct Al) is 27 pct less dense than beryllium Although Mg-Li alloys have moderate tensile strengths at normal strain rates and ambient temperature, their creep strength is relatively poor, even at room temperature. Reinforcement by fibers offers a means of increasing the tensile strength as well as overcoming the limitations of low creep strength. With a proper choice of reinforcing filament, composites could be designed with higher strength-to-density and modulus-to-density ratios than the matrix alloy. This communication reports a study on the tensile and creep characteristics of alloy LA141A reinforced with continuous wires of a high-strength precipitation hardening stainless steel (AFC-77 alloy). The matrix has a bcc structure, with possible precipitates of AlLi and MgLi2A1,3 and is ductile at room temperature Stainless steel wire was chosen as the -reinforcing filament since previous work at Battelle4 showed that a good bond between wire and matrix could be produced in this system. For all volume fractions of reinforcing wire, the theoretical composite strength-to-density ratio is greater than that of the matrix and the modulus-to-density ratio is somewhat lower than that of the matrix. EXPERIMENTAL PROCEDURES The 0.004-in. diam AFC-77 wire was obtained from two suppliers: National-Standard Co.* and Crucible 0.13 Si, 0.18 V, 0.011 P, 0.012 S, balance Fe. In the as-received condition, wires from both sources had room-temperature ultimate tensile strengths of 585,000 to 590,000 psi with approximately 2 pct total elongation and 40 pct reduction in area. Composite preparation was accomplished by the vacuum infiltration technique. This involved placing the continuous wires in a mild steel tube (1/8-in. ID), capping one end of the tube with a sheet of the matrix alloy, and evacuating the other end of the tube. When the capped end was placed in a crucible of the molten matrix alloy and held for 31/2 min at 70O°C, the liquid metal was drawn up the tube approximately 7 to 8 in. A cross-sectional view of a typical composite is shown in Fig. 1. This preparation technique promoted excellent bonding between the matrix and wires, and porosity was rarely observed. Test specimens for both creep and tension studies were prepared by machining off the steel tube. Tensile tests on the wires and composite specimens were made in an Instron using a cross-head speed of 0.01 in. per min. The composite specimens had no reduced section and were held in self-tightening grooved serrated grips. Most of the specimens broke in the effective 1-in. gage section. Even though several tests fractured in the grip section, their ultimate strengths were essentially the same as those of specimens which fractured in the gage section. Creep specimens of the composite were gripped in a similar manner, and

Jan 1, 1970

By H. C. Fiedler

Heats of high purity iron containing 3.1 pct Si and be -tween 0.0003 and 0.0295 pct N were prepared by vacuum melting ad then pouring while in a nitrogen atmosphere with the pressure between 0 and 90 psi. Strip from a heat with 0.0184 pct N underwent complete secondary recrystallization during the final anneal. Heats with less nitrogen had too few Si3N4 particles to restrain normal grain growth, and the heat with higher nitrogen had too many particles to allow complete secondary recrystallization. In the hot-rolled structure, Si3N4 precipitates only at the grain boundaries, with the consequence that annealing after hot-rolling diminishes the ability to subsequently undergo secondary recrystallization. In contrast to this behavior, ALNprecipitates uniformly in the hot-rolled structure. Under 1 atm of nitrogen, Si3N, in 3.1 pct Si-Fe dissociates between 900" and 950°C; the solubility of nitrogen increases from 0.0010 pct at 900" to 0.0030 pct at 1200°C. The solubility of nitrogen in Si-Fe has been the subject of many investigations. Corney and Turkdogan1 heated a 2.83 pct Si alloy in nitrogen and found the solubility, under 1 atrn of nitrogen, to be 0.0019 pct at 900°C. They claimed that Si3N4 did not form in the alloy above 705°C in 1 atrn of nitrogen. Fryxell et al.2 heated samples of 3.25 pct Si-Fe containing 0.0025 pct N over a range of temperatures and then analyzed for total nitrogen by vacuum fusion and for nitrogen in solution by a modified Kjeldahl technique. At 900°C, they reported the solubility of nitrogen in equilibrium with Si3N4 to be 0.0011 pct. pearce9 found the solubility of nitrogen at 900°C under 0.95 atrn of nitrogen to be 0.0017 pct in a 3.06 pct Si alloy. He reported that Si3N4 does not form above 770°C in 1 atrn of nitrogen. Although internal friction measurements have given somewhat higher values for the solubility,4-6 if the solubility of nitrogen is as low as has been reported by most investigators, and if Si3N4 is stable up to at least 945°C at 1 atrn pressure of nitrogen as reported by Seybolt,7 a small amount of nitrogen in properly processed Si-Fe should be effective in promoting secondary recrystallization. The requirement is that in the final heat treatment there be enough small, well-dispersed particles of Si3N4 to restrain normal grain growth. Fast8 has obtained secondary recrystallization by nitriding high-purity 3 pct Si-Fe after hot-rolling to a thickness of 0.118 in., followed by processing to 0.012 in., and annealing. A large amount of nitrogen, 0.076 pct. was introduced during the nitriding heat treatment, but he has since reported9 that "a few hundredths of a percent" is sufficient. Small amounts of aluminum10 or vanadium" nitride are capable of promoting secondary recrystallization. Heats containing as little as 0.010 pct A1 or 0.042 pct V and from 0.006 to 0.009 pct N underwent complete secondary recrystallization at final gage, whereas heats with lesser amounts of aluminum or vanadium did not.l2 To be reported is the behavior of nitrogen in high-purity 3.1 pct Si-Fe, and the relation of this behavior to the ability to undergo secondary recrystallization. PROCEDURE Ingots weighing 1 lb were made by vacuum melting high-purity electrolytic iron (A104, Glidden Co.) and high-purity silicon (Monsanto Co.). The latter was used in preference to ferrosilicon to insure a low aluminum content. The design of the melting furnace permitted pouring with the furnace atmosphere either below or above atmospheric pressure. Accordingly, at the completion of melting, nitrogen was admitted to the desired pressure and the heat then immediately poured. The ingots were sound, with no indication of porosity. In Table I are listed the heats investigated, the nitrogen pressure at pour, and the nitrogen and oxygen contents as determined by vacuum fusion with a platinum bath at 1850°C, a procedure which insures measurement of the total nitrogen.13 In addition, all heats contained 3.1 pct Si and not more than 0.002 pct C, 0.003 pct S or 0.005 pct Al. It was subsequently found that the quantity of nitrogen contained in the heats in Table I does not necessarily represent that obtained under equilibrium conditions. For example, the ingot poured immediately after 1 atrn of nitrogen was admitted to the chamber contained 0.0093 pct N, whereas an ingot poured 3 min after the nitrogen was admitted contained 0.021 pct N and another poured after a 6-min delay contained 0.029 pct N. While some bleeding of the hot top occurred in the latter instance, the ingot when examined in cross section appeared sound. The ingots were heated to 1325°C in hydrogen and rapidly rolled to 0.080 in. in 3 passes. The roll speed of the final pass was reduced so as to increase the quenching effect of the rolls. The hot-rolled pieces were processed both as-hot-rolled and after heating for 3 min at 900°C in hydrogen. After cold-rolling to 0.026 in., the strips were heated for 2 min at 900°C in hydrogen, then cold-rolled to the final gage of 0.012 in. The loss of nitrogen in going from the ingot to cold-rolled strip was no more than 10 pct. The final heat treatment, which was for the purpose of develop-

Jan 1, 1970

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

Evidence has been found for a (010)a?(111)B[102]a /,11[341]/B crystallographic relationship between the monoclinic a and B phases of plutonium during the a?B transformation. The results of an X-ray diffraction study, where [010] fiber textured a samples were used in the absence of suitable single crystals indicate that the (OIO)a planes become (111)B planes upon transformation under near-equilibrium conditions. The transformation strain along the fiber axis, which was the [010] direction, was measured dila-tomekically; the measured 8.5 pct expansion compares favorably with the 8.44 pct expansion in the in-terplanar spacing represented by the (010)a?(111)B relationship. From plots of the atom positions in each of the related planes, a correspondence was deduced between the [102]a, direction and the [341]B direction. Further analysis of the two lattice structures in the light of this relationship revealed a rotation about the [102] direction of 1 deg 43 min and a slight shearing in this same direction of about 30 min. THIS paper discusses the (B crystal structure of plutonium and the orientation relationship existing between the monoclinic a and B phases during the a?ß transformation. The kinetics of the a?ß and (3 — a transformations have received extensive consideration, and because of the crystallographic complexity of these phases, the question of the mechanisms by which these transformations occur is especially intriguing. Nelson and Shyne1 evaluated the existing experimental evidence and concluded, from the indirect evidence available, that both the ß ? a and a ? ß transformations occur by a martensitic process. Their data reveal the anisotropic nature of these transformations which suggests the existence of specific crystallographic relationships between the parent and product phases. In this paper, we are concerned with the confirmation of the existence of such a relationship resulting from the a ? ß transformation and the derivation of the crystallographic details necessary to specify it. EXPERIMENTAL RESULTS X-ray diffraction and dilatometric data were obtained from samples of a plutonium having a [010] fiber texture. These cylindrical specimens, approximately 1 cm in diam, were prepared by transforming the ß phase to a under the influence of a uniaxially applied compressive load.&apos; The [0l0] direction is parallel to the direction of applied stress; it is also perpendicular to the (010) planes. This correspondence between the plane normal and the direction having the same indices is, in the monoclinic a plutonium structure, restricted solely to this (010)[010] combination. Such a specimen was mounted in an evacuated, elevated temperature specimen holder on an X-ray dif-fractometer so that the diffracting surface was perpendicular to the fiber axis. The a diffraction pattern, Fig. 1, taken at about 115ºC, revealed the predominance of the (020) reflection. This monoclinic, P 21/rn space group yields no (0k0) reflections when k is odd. The temperature was raised slowly to 160°C to effect the complete transformation to the phase; then it was lowered to 120°C so that a diffraction pattern of the ß could be obtained near the a = ß equilibrium temperature for direct comparison with the a at the same temperature. The (3 diffraction pattern, Fig. 2, obtained under these conditions showed a (222) reflection relatively much more intense than in the random pattern. The other reflections appearing with sig-

Jan 1, 1970

By R. L. Stephenson

The effect of fabrication variables on the creep-rupture properties of TZM (Mo-0.5 pct Ti-0.08 pct Zr-0.03 pct C), Cb-TZM [columbium-modified TZM (7140-1.5 pct Nb-0.5 pct Ti-0.8 pct Zr-0.05 pct C)], and TZC (Mo-1.2 pct Ti-0.25 pct Zr-0.15 pct C) has been studied at 982º. 1093º, 1204º, and 1315°C for rupture times up to 1000 hr. The creep tests were performed in vacuum creep furnaces, employing cold-trapped oil-diffusion pumps, operating at pressures 2 X 10-7 tory. After-test chemical analyses showed no significant changes in interstitial content. The creep-rupture properties of TZM, fabricated according to current mill practice, were determined in the stress-relieved and in the re crystallized conditions to provide control data. Specimens of TZM, Cb-TZM, and TZC fabricated according to each of two experimental fabrication schedules were then tested. The schedules differed in terms of in-process annealing temperatures and warm -working temperatures. The data make several conclusions evident. Fabrication variables do indeed have a profound effect on the long-time creep-rupture properties of molybdenum alloys. Strengths of these alloys compare very favorably with those of other refractory metal alloys in the temperature range studied. FOR several years we have been engaged in the evaluation of the creep-rupture properties of promising refractory metal alloys. We consider the determination of these properties to 1000 hr at several temperatures necessary for a valid comparison. Such an evaluation indicated that the creep strengths of Mo-0.5 pct Ti and TZM (Mo-0.5 pct Ti-0.08 pct Zr-0.03 pct C) compare favorably with those of other refractory metal alloys. Tensile and recrystallization data of other investigators1,2 show an effect of fabrication variables. More specifically, those fabrication schedules which produce high strength through work hardening exhibit the least thermal stability. A similar conclusion was reported by perkins3 for Cb-TZM. This would lead one to expect that, in terms of creep, those materials showing higher strength at short times and low temperatures would exhibit lower strength at long times and high temperatures. If these expectations were fact, a substantial improvement could be made in these alloys by optimizing their fabrication schedule in terms of their anticipated service temperature. We therefore undertook a study of the effect of fabrication variables on the long-time creep properties of TZM, Cb-TZM (Mo-1.5 pct Cb-0.5 pct Ti-0.08 pct Zr-0.05pct C) and TZC (Mo-1.2 pct Ti-0.25 pct Zr-0.15 pct C). MATERIALS All materials used were supplied by the Climax Molybdenum Co. of Mich. Our original intention was to test the same heat of each alloy in different conditions. Fabrication difficulties prevented this; however, heats with nearly identical analysis were selected. The compositions of the materials used are listed in Table I. All materials were supplied in the

Jan 1, 1970

By L. Leibowitz, M. G. Chasanov, L. W. Mishler

A drop calorimeter system is described for use in measuring enthalpies to 3600°K. Data are presented for tungsten between 2800" and 3600°K. The enthalpy of tungsten in cal per mole between 2000° and 3600°K can be represented by the equation HºT- Hº298 = - 1.7622 X 103 + 5.7772T + 8.9861 where T is in degrees Kelvin. A tabulation of com -puted values is presented for heat capacity, entropy, and free energy function. A drop calorimeter has been constructed to carry out enthalpy measurements at temperatures to 3600°K. Samples are heated by induction1 and dropped into a commercial adiabatic calorimeter, modified for this purpose. The experimental temperature is limited by the melting point of container materials and compatibility of the container and its contents. Several high-temperature drop calorimeters have been described in the literature1-5 but none has been used at temperatures as high as those in the present work; our measurements of the enthalpy of tungsten range from 2800" to 3600°K. DESCRIPTION OF EQUIPMENT An overall schematic view of the equipment is shown in Fig. 1. Power for the induction coil is supplied by a 25-kw 250 kHz Ther-Monic generator coupled to an iron core RF transformer. The Sample capsule is suspended in the work coil by 10-mil diam tungsten wires which are wrapped around a horizontal 5-mil diam tungsten wire. The horizontal suspension wire is clamped between two massive copper electrodes which are fixed in an x-y motion device that allows adjustment of the position of the heated capsule from outside the vacuum chamber. The copper electrodes are connected by flexible copper straps to a 1250-joule (5 kv, 100 pfarad) condenser bank. When it is desired to release the capsule, the condensers are discharged through the horizontal suspension wire causing it to vaporize rapidly. Very reliable and precise release of the capsule is achieved in this manner. Experiments have shown that no heat correction is required for this discharge energy. As part of the temperature measuring system, two prism holders have been incorporated in the apparatus. The upper prism holder is in the main vacuum chamber itself, whereas the lower one is in a side arm attached to the drop tube below the gate valve. The upper prism is mounted on a rotary vacuum feed-through, and may be moved under a protective shield when not in use. This prevents deposition of vapors on the prism surfaces when temperature measurements are not being made. Similarly, the lower prism is mounted on a push-pull vacuum feed-through, and when not in use may be pulled into its side tube. The prism mountings are fitted with guides and stops so that they may be moved precisely into the desired position. The aim throughout is to minimize the time the prisms are exposed to vapors from the hot samples. At the high temperatures reported in this paper, only the lower prism was used. The upper prism holder in these cases was fitted with an additional radiation shield. By using a prism and viewport, the lower surface of the samples can be observed by an optical pyrometer. The measurements discussed in this paper were obtained with a Leeds and Northrup 8622-C-S series manual pyrometer which is estimated to be accurate to 0.5 pct. Pyrometer calibrations and prism and window corrections were carried out in the conventional manner6 using tungsten strip lamps calibrated by the National Physical Laboratory, Teddington, England. Prism corrections were rechecked after each use. All work to date has been done in vacuum, and no measurable change has been observed in the prism correction below -2300°K for the upper prism and below -2800°K for the lower one. The total time of exposure of the prisms is about 50 sec per run. At high temperature, the final temperature reading is corrected by using the final A value for the prism; see Ref. 6 for details of this procedure. The calorimeter is a modified Parr Instrument Co. (Moline, lll.), Series 1230 adiabatic calorimeter with automatic jacket control. Other authors5 have used a similar calorimeter with good results. The calorimeter jacket cover and calorimeter cover are attached to the drop tube which contains a radiation shield. This shield is a gold-plated copper disc which can be operated manually from outside the calorimeter. The receiver is attached below the radiation shield and is lined with tungsten. In a typical experiment, the calorimeter and its jacket water temperatures were adjusted to 0.000°K temperature difference. The sample was allowed to equilibrate in the furnace at the desired temperature for about 20 min. The initial calorimeter temperature was then recorded, the sample dropped, and appropriate shutters closed. After about 3 min, the drop tube and receiver were filled with helium to 60 torr. The final calorimeter temperature was recorded after it had remained constant over a 5-min period. The equilibration time in the calorimeter was about 25 min. Thermistor probes are used to operate a hot and cold water supply system to maintain the jacket temperature equal to the calorimeter temperature. For actual measurements of the calorimeter temperatures, a quartz thermometer was used (Hewlett Packard Dymec Thermometer, Model #2801A). This thermome-

Jan 1, 1970