Search Documents

By G. R. Leverant

RECENT investigations1,2 of the low-cycle fatigue behavior of pure copper under strain cycling conditions have shown that a unique saturation stress level is eventually attained for each value of applied plastic strain amplitude. The dislocation substructure of copper at the saturation stress level is in the form of cells whose diameter decreases with increasing saturation stress level, i.e., plastic strain amplitude. In addition, both the saturation stress level and the cellular substructure are completely reversible. That is, the saturation stress level and accompanying cell size are determined solely by the present conditions of testing and are, therefore, independent of any previous cyclic history. The mechanical and substructural reversibility observed in pure copper, which has a relatively high stacking fault energy, is not observedz for Cu-7.5A1 which has a much lower stacking fault energy. This implies that easy cross slip (wavy slip) is a prerequisite for reversible fatigue behavior. A dispersion of fine, nondeformable particles of a second phase in a metal matrix tends to stabilize substruc- tures introduced by forming operations during subsequent elevated-temperature heat treatments.3 This raises the question as to whether a finely dispersed second phase can induce an element of irre-versibility into the cyclic deformation behavior of a wavy slip material at room temperature, due to partial stabilization of the initially introduced substructure. Since nickel has a higher stacking fault energy than copper,6 pure nickel should be characterized by cyclic reversibility. Therefore, TD-nickel* (Ni-2ThO.r) was

Jan 1, 1968

By John R. Hutchins

1ms is a report of nickel (wire) oxidation studies designed to test the validity of Valensi's1 equation developed for the kinetics of a reaction controlled by diffusion in a continuously growing product layer on cylindrical surfaces. The equation is:

Jan 1, 1968

By S. F. Bartram, G. A. Chase

COMPUTED X-ray diffraction powder patterns of YNi3, YNi5, and CbBe3 are available on request from either author.

Jan 1, 1968

By Arnulf Muan, R. E. Johnson

Equilibrium CO2 /CO ratios of a gas phase coexisting with selected oxide phase assemblages of the system CaO-"Fe0"-SiOz and vnetallic iron have been determined at 1080°C. The data obtained are used to calculate activity-conzposition relations for metasili-cute, orthosilicate, and CaO- "FeO" solid solutions, and to determine a new value for the free energy of formation of C&S&0,. The metasilicate solution is practically ideal, whereas large deviations from ideality exist in the othe,r two solid solutions. BECAUSE of the geochemical and metallurgical importance of the oxides CaO, "FeO", and SiOz, the system CaO-"FeO"-SiO2 has been the subject of several experimental studies during the past 30 years. Following the delineation of phase relations at liquidus temperatures by a group of investigators at the Geophysical Laboratory of the Carnegie Institution of Washington in 1933,1 Chipman and associates in the early forties2,3 determined activities of FeO in liquids of this system. Since that time, many attempts have been made to interpret the data of Chipman et al. in terms of the constitution of the silicate liquids and the interaction parameters among the various constituents of the system (see for instance papers by Richardson4 and by Flood and coworkers5). One of the assumptions made in some of these interpretations4 is that the binary silicate systems CaSiO3-FeSiO3 and CazSi04-Fe2SiO4 mix ideally in the solid state. The objective of the present study is to provide experimental data on activity-com position relations in solid solutions of the system CaO-"FeO"-SiO2. Such data will contribute toward an understanding of the thermodynamics of silicate solid-solution phases in general, and will serve specifically to confirm or refute some of the assumptions made in interpreting liquid slag behavior. PREVIOUS WORK Phase relations in the system CaO-"FeO"-SiO2 in contact with metallic iron were determined by Bowen, Schairer, and Posnjak,1 and additional phase-equilibrium data for this system have been presented by Allen and snow.' A reproduction of the most up-to-date phase diagram for this system is shown in Fig. 1.7'8 Of particular interest in the present investigation are the relations among the various crystalline phases slightly below the lowest solidus temperature in the system, as shown in Fig. 2. The present work will be concerned primarily with some of the composition

Jan 1, 1968

By A. G. Guy, T. B. Lindemer

A second intepation of the Fick law has been developed and applied to three-place data generated from the Gosting and Fujita solution of the diffusion equation. This integration provides new mathematical techniques for the analysis of experimental data. Through use of the synthetic data it is shown that for concentration-independent interdifiusion coefficients these techniques permit a more accurate determination of the coefficients than does the usual Boltzmann-Alatano analysis. Another technique, applicable to the most general concentration-dependent diffusion coefficients , can be used to determine whether given sets of coefficients are consistent with the experimental ternary concentration-distance curves. DURING the past 10 years the subject of three-component diffusion has advanced from the stage of a laboratory curiosity to the status of an accepted portion of physical metallurgy.1 In the course of this development the underlying treatment for two-component sys- tems was extended and generalized to accommodate the added component, but fundamentally the analyses currently employed for ternary systems are analogous to those previously developed for binary systems. There are several indications that an improved analysis is needed for the ternary case. First, the two cross coefficients, D312 and D321 are typically an order of magnitude smaller than the direct coefficients and consequently are difficult to determine with adequate precision. Second, instead of a single concentration-penetration curve (as in binary diffusion), there are four such curves in the usual determination of ternary diffusion coefficients. These curves have definite theoretical interrelationships, but actual experimental curves exhibit significant departures from these relationships. Finally, the amount of data needed to adequately describe the diffusion behavior of a ternary system is so large that radically new methods are needed to facilitate the gathering of these data. ICirkaldy2j4 has proposed several possible analyses of ternary diffusion data, including some of the methods in current use. A "second-integration" procedure proposed by him4 differed in important respects from that presented here and was not carried to the point of application. Two other methods have been explored by the authors and will be published separately; these are a numerical analysis technique and a method for the analysis of a single ternary diffusion couple. Still other analyses are being explored by various investigators. At present it seems likely that the final analysis of ternary diffusion that evolves will be a composite

Jan 1, 1968

By Victor A. Phillips

A series of strips of a Ni-12.7 at. pct A1 alloy were Prepared containing cubical y'(NisAl) precipitates with edge lengths from 60 to 500A. A particle-free solution-tveated strip was included for cornparison. They weve cold-rolled 95 pct and the effects of particle size on the isochronal (1/2 hr) annealing behavior between 300° and 950°C studied (by hardness and light and electron microscopy). It ulas inferred that the particles deformed with the lnatvix becoming lamellae which remained coherent. Comparison with published data fov pure nickel showed that aluminum greatly re-tavded softening and recrystallization, but it made little difference whether or not particles were present. The presence of pakticles led to a heterogeneous distribution of precipitates after annealing at 700" to 750°C. Recovery was not detected. Recrystallization occurred by the growth of new grains into unrecrys-tallized material. In a previous study by the author,' the growth of Ll2-type ordered yl(Ni3Al) precipitates was followed in Ni-12.7 at. pct A1 alloy as a function of aging at 600" and 700°C. The particles were showo to be cubical in shape in all sizes from 50 to 3000A and remained coherent. This work was used as a guide in preparing the starting structures for the present study of the effect of these particles on the annealing behavior of heavily cold-rolled strip. Another question of present interest was whether dislocation and particle hardening were additive, since the structures before rolling ranged from solution-treated to peak-aged to overaged. Also, precipitation might occur on annealing after cold-rolling. Reference may be made to other papers2"5 for previous work in this relatively unexplored field and only some recent work will be mentioned her:. phillips2 studied the effect of deformable 0 to 590A-diam cobalt particles on a Cu-3.23 pct Co alloy rolled 95 pct and found that the particles, which rolled out into thin lamellae, impeded softening and recrystallization. Tanner and servi3 likewise studied the annealing of cold-swaged Cu-2 pct Co alloy containing 150A-diam particles and found impeding effects. Haessner et a1.,4 on the other hand, found that incoherent 2-p-diam non-deformable particles of B4C (0.04 vol pct) tended to increase the rate of recrystallization of copper rolled up to 95 pct reduction. They attributed this to the formation of new grains at the particle interfaces. Humphreys and artin' found that nondeformable silica particles in copper rolled to 30 pct reduction accelerated recrystallization if the particle spacing was large and retarded it if the spacing was smaller. Haessner et a1 4 also studied a rolled Ni-Cr-A1 alloy; however, the particles of y'(Ni3Al)-type precipitate were not put in before rolling, but separated during the isothermal annealing at 750°C. No previous work appears to have been carried out on the effect of y' (Ni3A1) particles on the annealing of Ni-A1 alloy. Hornbogen and ICreye7 redetermined the solubility c of aluminum in nickel as a function of temperature T and showed that it was given by c = 32.6 exp(-1940/RT). This relation gives aluminum solubilities of 15.1, 14.2, 12.0, and 10.7 at. pct at 1000°, 900°, 700°, and 600°C, respectively. The phase precipitated from the nickel-rich solid solution is fcc y1 (Ni3A1) which has a Cu3Au -type ordered structure8 and remains ordered up to 1000°C.B EXPERIMENTAL PROCEDURE The alloy used was identical with that used before. Chemical analysis showed 6.27 wt pct (12.71 at. pct) Al, the principle impurities being 0.065 pct Fe, 0.022 pct Co, 0.020 pct Cu, and 0.004 pct C. Bar stock of 1 in. diam was cold-swaged to % in. diam, cold-rolled to 0.300-in.-thick strip, and annealed at 900°C in dry hydrogen. It was cold-rolled to 0.100-in. thickness and solution-treated for 1 hr at 1000°C while sealed in a quartz tube in argon, quenching in iced brine with the aid of a device to snap off the nose of the tube. Lineal analysis gave an average grain size of 0.055 mm. Pieces of strip were aged at 700°C in vacuo for 30 min, 51/4 hr, and 1 week to produce nominal average particle widths of 60, 150, and 500A, respectively, as known from the previous work.' The average diamond pyramid hardness was determined. The heat-treated strips were rolled from 0.100 to 0.005 in., a reduction of 95 pct, and the rolled strips stored at about -5°C. Small pieces were annealed within 1 week for 30 min at temperatures from 300° to 950° ±2°C in a horizontal vacuum furnace. Strips were withdrawn into a cooling zone, giving an estimated initial cooling rate from 950°C of about 50°C per sec. Average diamond pyramid hardnesses were determined on a lightly electropolished spot on the surface of each strip using 300-g load. Each point on the softening curves represents a separate annealed specimen. Sections containing the rolling direction were examined by optical metallography. Selected specimens were electrothinned to the center plane' and examined by transmission at 100 kv in a Siemens Elmiskop I electron microscope. It is well-known that changes in the structure tend to occur when a deformed strip is electrothinned below a thickness of a few hundred angstroms, although this is less serious with a material such as nickel which has a high melting point, and also is apt to be less serious when particles are present. Observations were nevertheless confined to thicker regions of the foils with estimated thicknesses over 1000A. No changes were observed due to beam exposure.

Jan 1, 1968

By John L. Walter

A sintered compact of iron containing 0.007 vol fraction of glass , prepared 6). powder rnetullurgtcal lechniques, was rolled lo foil, 0.001 in. /hick. The foil sullrples were anneuled a1 650° to 850°C in hydrogen. Pri,narj recryslullization prodtnced large grains which Lc3ere highly elongnled in the rolling direclion und which had an unusual prgferred orientation. The glass parlicles assumed a stringerlike dispersiorz on working; llie slrinyers were parallel lo the rolling direction and to the long axis of the grains. The same unusual grain structure, preferred orientation, and stringerlike dispersion of purticles are found in heal-ily rolled and annealed foil of tungsten which has heen doped wilh small amounts of aluminum, silicon, and polassiutvt. Both the proper dispersion of the particles and severe working (reductions in excess of 98 pct) are necessary to produce the elongzcted grain structure. RECENTLY, the author reported on the origin of the elongated or "nonsag" grain structure in tungsten foil which was doped with aluminum, silicon, and potassium.' It was observed that particles, identified as mullite (Al6Si2Ol3), were present in the doped ingot (as sintered) and at all stages of processing from ingot to sheet or wire. It was shown that the particles, being plastic at tungsten working temperatures (up to 1550"C), underwent a "stringing out" parallel to the working di-direction. It was concluded that these strings of particles were responsible for the formation of the highly elongated interlocking grains observed in doped tungsten wire or sheet. To give further credence to this explanation of a long-observed but not understood phenomenon, it was decided to design a new system, one which was analogous to the doped-tungsten system. Thus, a bcc metal, iron, was chosen to be doped with glass which would be plastic at reasonable working temperatures for iron. The glass chosen was a #0080 Corning lime glass which melts at about 810°C. This is approximately the same fraction of the melting point of iron (0.6) as the melting temperature of mullite is of tungsten. It will be shown that all the observed unusual features of the doped tungsten are duplicated in the glass. doped iron, even to the preferred orientation of the grains in the recrystallized sheet. In the tungsten sheet the preferred orientation consists of two components, (1i3)(691) and (013)(362), neither of which has been observed as a component in textures of primary recrystallized bcc metals. EXPERIMENTAL PROCEDURE The glass, in the form of fine powder, was added to high-purity electrolytic iron powder and mixed dry. The particular composition chosen was 0.007 vol fraction of glass. After mixing, the powder was mechanically pressed to a disk 0.5 in. diam and 0.15 in. thick at a pressure of 5000 psi. The pellet was sintered, in pure dry hydrogen, for 2 hr at 8 50°C. The sintered pellet was then heated to 750°C and rolled to 50 pct reduction of thickness in two passes, with reheating between passes. The rolling temperature was then reduced to 600°C and the slab was rolled to a thickness of 0.050 in. Rolling to 0.010 in. was accomplished in several passes at 300°C. Final reductions to 0.003 and 0.001 in. were taken at room temperature. This rolling temperature schedule was similar, in terms of the fraction of the melting point, to that used in the rolling of the doped tungsten. The total reduction of thickness was in excess of 99 pct. Samples of the rolled foil were lightly electro-polished and annealed for 1 to 6 hr at temperatures of 650" to 85O°C in hydrogen. Samples for transmission electron microscopy were thinned on a Disa Electropol using AC-1 electrolyte.

Jan 1, 1968

By L. C. Brown, E. B. Hawbolt

The formation of grain boundary precipitates has been studied in Ag-5.64 wt pcl Al alloys at 688°C. Large-grain specinzerzs were used and the boundary misorientation measured by X-ray diffraction. At low-angle grain boundrrries Primary sideplates form. u)hile abore a 17-deg misorientation lenticular precipitates predominate. Growth of the lenticular precipitates was studied on individual grain boundaries using a statistical technique. The thickening and lengthening rates appeared to be independent of &apos;pain boundary misorientation, indicating that grain boundary diffusion was not significant in this system. The precipitates grew urith constant shape, with both the length and thickness increasing parabolically with time. The parabolic lengthening rates were unexpected since previous theory and experimerztal results had indicated linear growth. By approximating the shape of the precipitate to that of an oblate spheroid grouling with constant shape an equivalent diffusion coefficienl was calculated. The zlalue obtained was in good agreement with nleasurements obtained fron, diffusiorz couples. IF a single-phase alloy is heated or cooled to a temperature such that the phase becomes supersaturated, there is a tendency for a second phase to precipitate from it in order to remove the supersaturation. Precipitation takes place initially on grain boundaries due to preferred heterogeneous nucleation, but subsequently Widmans kitten plates may form in the grain interiors if the grain size and supersaturation are sufficient. The type of grain boundary precipitate formed depends on the nature of the boundary. Aaronson1 and clark2 have shown that grain boundary misorientation can be characterized by the simple parameter R, where and X, Y, and Z represent the minimum rotations about three orthogonal axes required to bring the two lattices forming the grain boundary into coincidence. The maximum value for R is 60 deg. In using this parameter the orientation of the grain boundary itself is, of course, neglected. However it was found in both Fe-si3 and A1-Ag2 that the precipitate shape depended only on the parameter R. Clark found that the vast majority of precipitates formed were allo-triomorphs— lens-shaped precipitates that grew along the grain boundaries. At low-angle boundaries, however, (R < 15 deg) Widmanstatten sideplates nucleated at the grain boundaries and grew into the adjacent grains. It has been reported that the rate of growth of grain boundary precipitates is controlled by diffusion within the supersaturated phase.&apos; The theories which have been developed for growth rates have assumed the diffusion coefficient constant over the composition range of the supersaturated phase. This is a fairly good approximation if the composition range involved is not large. Thickening rates have been calculated using the theory developed by Zener4 and by Frank5 for the growth of planar precipitates. A parabolic growth law

Jan 1, 1968

By Frank Woolley, John F. Elliott

The high-temperatzrre solulion calorimeter has been modified and an extension dynamic analysis of i/s transient behavior has provided an improved basis for interpretation of the experimental data. The partial molar heats of mixing, Him, of aluminum, copper, and silicon in the corresponding binary liquid-iron alloys haz,e been measured directly at 1600°C. The resulls in kcal per g-alom are: THE high-temperature1,2 solution calorimeter was planned and designed to obtain directly the partial molar heat of solution of solute elements in a variety of liquid metals that might serve as solvents. Results obtained in the temperature range of 1000° to 1200°C were described in the two earlier publications. However, a long-term goal in the program has been to obtain measurements at 1600°C of the heats of solution of elements in liquid iron. Hence, subsequent to the work last reported,2 and based on the experience of the first two studies, the calorimeter system has been modified and operated at 1600°C to obtain measurements on the Fe-Si, Fe-A1, and Fe-Cu systems. This paper reports the results of the work. THE MODIFIED SYSTEM It was clear from the earlier results that the most precise measurements can be obtained with the high-temperature solution calorimeter when the solution time is less than approximately 30 sec. This can be achieved only when the bath temperature, Tb, is above the melting (liquidus) temperature of the solute material being dropped. A second point of importance is that the refractories used earlier liberated considerable water so that, although the oxygen potential of the atmosphere in the system was satisfactory for work with nickel and copper, it was too high for work with iron, silicon, and so forth. Third, for work at 1550" to 1650°C, an improved temperature-sensing unit is needed. The modified calorimeter in its latest form is shown schematically in Fig. 1. The refractory brick and the Kanthal-Super heating elements which formed the furnace for heating the solute addition have been replaced by a smaller resistance-heated tube furnace which is insulated with bubble-grain alumina. A more elaborate gas purification system was installed to maintain a satisfactorily low oxygen potential in the atmosphere of the calorinieter chamber and of the solute addition furnace. As was the case in the earlier work, at the beginning of a run the calorimeter chamber is evacuated and then filled with purified argon so that a total pressure slightly in excess of 1 atm is maintained during the run. When either of the furnaces within the enclosure attains a red heat, 6 pct H2 is added to the atmosphere. Throughout the run, gas from the calorimeter is circulated through a de-oxidation system at the rate of approximately 5 standard liters per min; the changeover time for the gas within the calorimeter enclosure is approximately 1 hr. The essential stages of the deoxidation system are: a copper furnace at 600°C, a drying tube of anhydrite, and a titanium furnace at 800°C. The oxygen potential of the gas stream in the purification system can be monitored at several points by a stabilized zirconia oxygen cell. This cell is invaluable in detecting the development of leaks in the container vessel and the gas circulating system. The installation of the solute-addition furnace allowed either of two types of temperature-sensing units to be mounted on a water-cooled probe. The first was a small optical device using a silicon diode that was

Jan 1, 1968

By J. C. Scully, G. Sanderson

The electrolytic formation of y hydride in thin foils of Ti-5Al-Z.5Sn alloy and four Ti-A1 binary alloys has been studied by electron microscopy and electron diffraction. Two orientation relationships have been found: THE adsorption of hydrogen by titanium alloys from aqueous solutions has been widely reported. This can occur, for example, in both alkaline&apos; and acidic2 pickling baths, in chemical polishing374 and electro-polishing Solutions,3,4 during cathodic polarization5" and under certain corrosion conditions,7,8 Etching reagents may also produce visible precipitates, sometimes after an aging period.9 During an investigation into the stress corrosion susceptibility of a titanium alloys by thin foil electron microscopy many observations have been made of hydride precipitation which has been deliberately promoted by techniques that are described below. The characteristics of hydride precipitation are reported and the observed crystallographic orientation relationships are discussed with reference to distortion in the titanium lattice created by the presence of the hydride. EXPERIMENTAL TECHNIQUE One grade of commercial titanium and five alloys were examined. Their composition and hardness values are shown in Table I. All the materials were in the form of thin sheet, 0.05 to 0.065 cm thick, which had been annealed after cold rolling. Foils suitable for transmission electron microscopy were made in two ways: a) by chemical polishing; and b) by elec-tropolishing. The solution used for chemical polishing was a mixture of 44 pct HF and 73 pct HNO3 in the volumetric ratio 2:3. During this polishing specimens were manually moved up and down in the solution. The reaction was veFy rapid, specimens thinning to foil thickness (2000A) in 5 min. Since chemical polishing solutions tend not to cause hydride contamination if they are kept cool3 no attempt was made to prevent the solution from becoming hot during the thinning operation. Electropolishing was performed at -30° C with a mixture3 composed of 295 cu cm methyl alcohol, 175 cu cm n-butyl alcohol, and 30 cu cm perchloric acid with an applied voltage of 40 v after chemically thinning specimens to approximately 0.017 cm thickness in a cool solution of 44 pct HF, 40 vol H2O2, and water in the volumetric ratio 1:6:3. EXPERIMENTAL RESULTS 1) Ti-5A1-2.5Sn Alloy. The Ti-5A1-2.5Sn alloy was severely contaminated by hydrogen during the chemical polishing. Foils obtained in this way contained large amounts of the y hydride phase. A typical micrograph is shown in Fig. l. The laths were identified as the hydride phase by selected-area diffraction of a large number of foils examined in a tilting stage that could be turned through 40 deg. Using the lattice spac-ings of the alloy obtained by X-ray diffraction as a standard the a value of the hydride was determined fromo the electron diffraction patterns to be 4.38 to 4.40A. The accuracy of this figure is only about ±2 pct. Further evidence of the identification was obtained by vacuum annealing chemically polished foils of the alloy at 500°C. This resulted in the dissociation of the hydride with the production of dislocations and possibly vacancy loops as shown in Fig. 2. The hydride

Jan 1, 1968

By E. A. von Hahn, T. R. lngraham

Cementation rates ulere studied by rotating an elec-tropolished or etched copper strip in aqueous solutions, of either perchloric acid or alkaline cyanide, containing silver ions. The rates of cementation were more rapid in acidic media than in cyanide media. In both, the rates varied with the rate of rotation of the copper strip. The deposits formed in the acidic solutions were finely divided, loosely adhering powders. Those formed in the cyanide solutions were dense and adherent. The presence of the deposits influenced the cementation rates. In the acidic solutions the rate was enhanced, possibly because of the increased cathodic area. In the alkaline solutions the rates were decreased in the presence of the deposits. This has been attributed to restricting the diffusion of the copper ion from the rnetal outward into the bulk of the solution. In an earlier paper1 the authors described a kinetic study of the cementation of palladium on copper in perchloric acid solutions. That work indicated that there were two stages in the palladium cementation process. The first, more rapid stage was consistent with rate control by the diffusion of Pd11 ions to the copper surface and/or by chemical reaction at the surface. The second stage was consistent with rate control by the diffusion of copper ions from the copper surface, through the deposit, out into the main body of solution. The effect of the type of deposit on the rate of cementation is of particular interest because it may be one of the primary features involved when large quantities of metal are to be cemented from solution. No substantial investigations of the effect seem to have been made. Accordingly, an extension of the previous work was arranged to study the cementation of silver on copper. This system was selected because of the convenience of the analytical methods, the previously established technology with copper, and the fact that the system could be studied in both acidic and alkaline media. By selecting perchloric acid and alkaline cyanide solutions as the media, it was hoped that some assessment might be made of the effects, on cementation, of having the silver ion present in a virtually uncomplexed state and in a highly complexed state. EXPERIMENTAL The cementation rates were studied, as previously described,&apos; by rotating a copper strip (1.0 by 23.2 cm) clamped to the peripheral surface of a lucite cylinder. The solutions were kept at constant temperatures (±0.05°C) under an atmosphere of purified nitrogen, and samples were taken periodically for analysis. The initial solution volume was 1000 ml and the sample volume 5 ml. The initial silver(1) ion concentrations were made low (0.5 to 1.0 x 10-4 moles per liter) to minimize the influence of the cemented deposit on rates. The solutions were prepared by dilution of suitable aliquots of silver perchlorate and silver cyanide stock solutions. Both stock solutions were prepared from purified silver powder (Johnson, Matthey, and Mallory Ltd.) with redistilled deoxygenated water, and they were kept under an atmosphere of purified nitrogen. To prepare the stock solutions, weighed amounts of silver powder were dissolved with nitric acid. For the AgC104 stock solution the silver nitrate solution was evaporated twice to near dryness with perchloric acid and then made up to volume: For the NaAg(cN)2 stock solution, the silver ions were precipitated with sodium hydroxide solution. The precipitate was filtered, washed thoroughly with redistilled water, dissolved with 1.1 times the required stoichiometric amount of sodium cyanide solution, and made up to volume. The small amounts of free perchloric acid and sodium cyanide present in the stock solutions were disregarded in the preparation of the solutions. The copper strips were cut accurately from 0.025-in. sheet (American Metal Climax OFHC brand) and annealed for 1.5 hr at 470°C in a stream of nitrogen. Analyses of the solution samples for silver and copper were done with a Techtron Model AA-3 atomic absorption spectrophotometer. Calibration standards of the same composition as the experimental solutions were prepared and analyzed simultaneously with the samples. No difficulty was experienced in the analyses, and the reproducibility was within 1 to 2 pct in both alkaline cyanide and perchloric acid solutions.

Jan 1, 1968

By G. R. Heckman, H. J. Murphy, C. T. Sims

An incestigation has been made of the effects of heat treatment and alloy composition on the long-time stress-rupture properties and structural stability of the similar nickel-base alloys Udimet-500, Lrdimet-520, and Udimet-700. Rupture test data are presented at stresses ranging from 4 to 50 ksi at temperatures from 1450° to 1900°F for times up to 14,000 hr. Ductility response is emphasized. Optical and electron tnicroscopy were complemented by X-ray diffraction analyses of extracted phases to relate microstructural stability to the observed rupture properties. Particular attention is paid to Udimet-520 since structural characteristics of this alloy appear to vary somewhat from its sister alloys. Both cast and wrought performance of Lrdimet-500 are discussed. The computerized PHACOMP calculational technique, based on electron-vacuncy theory, is discussed and related to structural stability where appropriate. Electron microscopy and microprobe techniques were used to conduct evaluation of the oxidation characteristics of Udimet-500 exposed in air for 16,100 hr. The steady advance in strength and reliability of nickel-base superalloys continues to be one of the high points of modern metallurgy. The stress capability of these materials has increased steadily, allowing higher and higher operating temperatures in the highly sophisticated aircraft and industrial gas turbines now on the market. The attendant increase in efficiency, of course, means greatly improved power output. Gas turbines for industrial and marine use have long been designed with these objectives paramount the usual design requirements in terms of time of service being 100,000 hr. High-efficiency, long-life aircraft such as the supersonic transport require superalloy engine materials with high-strength and long-time structural stability. Thus, materials studied for and operating experience from industrial gas turbines provide a good reservoir from which technology of high value to the SST program can be drawn. This study is one such case. Three prominent nickel-base super alloys—Udimet 500, Udimet 520, and Udimet 700 were extensively evaluated for industrial gas turbine bucket use. Particular attention was directed toward structural stability as a requisite property. Within the present context, structural stability is defined as freedom from the propensity to form strength-robbing or embrittling phases such as u,p,x,or Laves, and the ability to maintain useful rupture strength and ductility throughout design life. MATERIALS The three alloys, cast Udimet 500 (U-500C), Udimet 520, and Udimet 700, were chosen for detailed evaluation based on preliminary studies which indicated that U-500C and U-520 possessed comparable rupture strength capabilities, and that U -700 had a greater strength capability but somewhat poorer ductility than wrought U-500. The nominal compositions of the three alloys, along with the compositions of the heats investigated, are presented in Table I. PROCEDURE Dimensionally rejected U-520 buckets from Special Metals Corp. heat 63370 were heat-treated using the four cycles delineated in Table 11. Cycle A was investigated to determine the effects of a shortened 1700°F primary age. Cycle B was considered a "standard" treatment. Cycle C investigated a higher solution temperature in combination with a shortened primary age, while cycle D assessed the effect of the higher solution temperature alone. These heat treatments were designed to produce optimum combinations of rupture strength and ductility through maximum y&apos; development, the development of a y&apos; grain boundary cushion, promotion of MC carbide degeneration reactions, and agglomeration of resultant M23CB. Since one of the premises of the evaluation of U-520 was that rupture strength would be equivalent to U-500, forged U-500 buckets from Special Metals Corp. heat 62916 were heat-treated with cycles A, B, and C to provide comparison. The heat-treated structures of U-520 and U-500 are illustrated in the 8700 times electron micrographs of Fig. l. The U-700 tested was all from 3-in.-diam hot-rolled and centerless-ground rod from Special Metals Corp. heat 2-1426. Two heat-treatment cycles were employed, E and F of Table 11. Cycle E is a standard four-step, triple-age treatment intended to provide an optimum match of strength and ductility through well-developed matrix and grain boundary y&apos;, as recommended by U-700 vendors. Treatment F is a shortened , single-age cycle which could provide a significant processing cost reduction should adequate strength and ductility be maintained. Following heat treatment, rupture specimens of U-500 and U-520 were machined from the buckets and tested. Standard rupture bars of U -700 were machined from the heat-treated rod and rupture-tested. Failed and withdrawn rupture bars were prepared and examined by optical and electron microscopy. Select specimens were electrolytically digested, and the residues analyzed for carbide and topologically close-packed phases using CrKa or CoKo radiation. Of the six different U-500C heats evaluated, five were cast by Misco Precision Casting Co. and one was cast by Haynes Stellite Co. Cast-to-size rupture bars

Jan 1, 1968

By D. T. Peters

To better understand the Co-Mo interaction in maraging steels, the precipitate reversion behavior of two alloys closely related to the 18 Ni-250 grade has been studied. The reversion experiment is carried out by aging at a low temperature, T1 (preaging temperature), for some period of time and then aging at a higher temperature, T2, called the reversion tetnperature. Aging and reversion tmzperatures used were in the range 679 to 1050°F. Reversion is marked by an increase in resistivity and a decrease in hardness. It teas found that some reversion took place at all cornbinations of T1 and T2 but that pronounced rei3ersion resulfed for an Fe-18 pct Ni-5 pct Mo-8 pcl Co alloy exposed to preagz&apos;ng&apos; temperatures at or below 850°F. A similar alloy not containing cobalt exhibited no such discontinuity in reversion behazior with TI. The results are interpreted in terms of two types of molybdenum-rich precipitates, one nucleated at dislocations and the other in the matrix. The increased supersaturation resulting from the presence oj- cobalt evidently provides sufficient energy to nucleate the matrix phase. Anotnalies in the temperature dependence of the resistivity decrease and peak hurdness in the Fe-18 pct Ni-5 pct Mo-8 pct Co alloy as a junction of aging temperature noted in an earlier study are explained on this basis. SEVERAL investigatorsl-9 have studied the details of the precipitation-hardening reaction of the maraging steels. The great majority of conclusions have been drawn from transmission electron microscopy. Although much has been learned by this method, alternate techniques which will give information earlier in the aging process are needed for a more complete understanding of the series of precipitation steps probably involved in the aging reaction. Peters and cupp&apos;&apos; have recently shown, by measurements of the kinetics of precipitation, that an 18 pct Ni-Co-Mo maraging steel shows a distinct change in precipitation behavior at aging temperatures below 850°F. The results were interpreted in terms of the existence of two types of precipitates at low aging temperatures. Only one precipitate type is present at higher aging temperatures. The low-temperature precipitate was found to be a particularly effective strengthener. No evidence for the additional low-temperature precipitate was found in the 18 pct Ni-5 pct Mo ternary alloy. The object of this investigation was to study further the characteristics of the two types of precipitates and the interaction between cobalt and molybdenum characterizing this system. Some preliminary experiments indicated a difference in reversion behavior in specimens aged above and below 850°F. This suggested that knowledge of the reversion behavior might shed some light on these two questions. Hardy and Heal11 have defined reversion as the loss of hardness, electrical conductivity, or other properties caused by heating for a very short time at temperatures above the aging temperature. The precipitate reversion referred to in this paper is entirely distinct from "austenite reversion" often referred to in maraging steel literature. This latter phenomenon could more accurately be called the diffusion-controlled formation of austenite. Much has been written about reversion in several of the aluminum-base binary and ternary alloys.&apos;2-16 Two explanations for reversion have been advanced. Based on the classical nucleation theory of Volmer-Weber-Becker-Doring,17 Konobeevski18 suggested that reversion was due to the size of the precipitate particles

Jan 1, 1968

Jan 1, 1968

By R. H. Tien

This paper presents an analytical solution of the problem of freezing of a semi-infinite slab with constant surface temperature; in this analysis accoz~nt is taken of the heat evolution during the solid-state transformations in the frozen skin. The regions where transformations occur are treated as plane isothermal heat sources; i.e., the rates of transformations are assumed to be infinite. In the model considered, three plane heat sources are assumed to be present in the frozen solid. The solution yields the temperature distribution in the solid, the rates of movement of the heat sources , and the rate of movement of the solidification front. It is shown that, although the sum of the heats of transformations in the solid is about 20 or 43 pct of the heat of fusion of iron or manganese, respectively, the effect of the heat evolution in solid-state transformations on the rate of solidification is insignzficant. IN several recent mathematical studies of solidification of liquid metals&apos;-3 no account was taken of the heat evolution accompanying the solid-state transformations. In the case of, for example, steel, there are several phase transformations 6 -y, y -a, and the magnetic transformation. Whether or not a significant error is introduced into the mathematical simulation of solidification processes by the omission of the heat effects associated with these phase transformations is not known. The purpose of the present study is to investigate the effect of these phase transformations on the temperature distribution and the rate of solidification based solely on the heat transfer point of view. That is, for the sake of simplicity, freezing of a pure metal with solid-state transformations will be considered. The mathematical model which represents the present problem includes four moving heat sources representing freezing and phase transformations, 6— y — a — ferromagnetic. The thermal properties such as conductivity and specific heat, and so forth, are different from one phase to the other. But they are considered to be uniform over any particular phase. The usual Fourier heat flow law is employed. The concept of conservation of energy is applied at every heat source in order to estimate their rate of movement. The temperature distribution in the solid and the positions where transformations occur are expressed analytically in terms of error function solutions and four coefficients which are determined from four nonlinear algebraic equations. These coefficients can be calculated either by trial and error or by any numerical method. MATHEMATICAL ANALYSIS Fig. 1 is a schematic diagram showing the zones of different phases 1, 2, 3, and 4 in the solidified portion of a semi-infinite pure liquid metal. The heat is subtracted from the system at x = 0 which is maintained

Jan 1, 1968

By Robert Maes, Robert de Strycker

The Fe-Ni-As phase diagram has been established by the study of about a hundred alloys, by microscopic observation, and by thermal analysis, with arsenic contents up to 50 pct. The iron and nickel arsenides present extensive solid-solution fields, owing to the substitution of nickel by iron and vice versa; the extent of the solubility field of each compound has been determined with an accuracy of ±1 pct. In the investigated range of compositions, the solidification reactions were established, and the temperatures of the invariant reaclions detevmined with a preciston of iZ°C in the most favorable and ±5°C in the least favorable cases. The isothermal lines of the liquidus surface have also been drazum, with an accuracy estimated at i5°C. Reactions in the solid state, which take place for the formation or the decomposition of certain phases , were investigated in detail. ThE constitution diagram of the Fe-Ni-As system is fundamental for the understanding of the properties of nickel speiss; these by-products of the extraction of certain nonferrous metals indeed often contain the three elements iron, nickel, and arsenic as main constituents. The Fe-Ni-As system has already been the object of earlier investigations. In 1932, Guertler and Savels-berg&apos; have presented some elements of the ternary phase diagram, for arsenic contents up to 55 pct (all percentages in this paper are given in weight percent), including the vertical section FezAs-Ni&s2. This investigation is, however, incomplete and certain anomalies suggested the necessity to verify the results published by these authors: the section Fe2As-Ni5AsZ, for example, is presented as quasi-binary, with a field of complete miscibility in the solid state, even though these compounds do not have the same structure. Recently, ~useck&apos; established an isothermal section at 800°C in the Fe-Ni-As system by X-ray diffraction and microscopic examination of water-quenched alloys. These techniques are sometimes inaccurate for the determination of the fields where alloys are liquid at the investigated temperature, and they may lead to erroneous conclusions when a compound exists at the investigated temperature but is not stable at room temperature and cannot be maintained by quenching. LIMITING BINARY PHASE DIAGRAMS The Fe-As constitution diagram has been the object of several investigations which have been reviewed by Hansen and Anderko.3 For the Ni-As phase diagram, a recent study has been effected by Yund.4 In this system, Heyding and calvert5 have determined the existence of a compound of unidentified structure at arsenic contents slightly higher than those corresponding to Ni5As2 and at temperatures lower than about 200°C; by analogy with iron and cobalt arsenides, this compound could correspond to the formula Ni2As, as suggested by Kulle-rud; although this is not definitely established. In the region of arsenic contents from 35 to 55 pct, Fried-rich7 detected anomalies in the solidification reactions; an interpretation of these anomalies was given by Hansen ,8 which assumed that the solidification reactions in practice are not in equilibrium, but are meta-stable. The main features of the Fe-Ni constitution diagram are the existence of a complete miscibility field, at least at high temperatures, for the fcc phase (which will be designated by My in the remainder of this work) and of a limited solubility field for the bcc phase (designated by Ma). EXPERIMENTAL METHODS The fundamental technique used in this investigation was microscopic observation, which allowed the determination of the reactions occurring during solidification of the alloys, and possible reactions in the solid state.

Jan 1, 1968

By H. E. Cline

Mechanical properties of the eutectic between CoAl and cobalt were measured over a range of- temnperatures and strain rates for a variety of microstructures produced by directional solidification and by thermo-mechanical processing. Directional solidification led to rodlike, lamellar, and irregular microstructures. The unusually high volume fraction of the cobalt-rich rods and the lurge spacing of the rods were explained by the phase diagram. The hot-worked structure consisted of fibers of COAL in a cobalt-rich matrix. The roonl- tevlperature strength of the uvrought material increased with decreasing grain size but the 1000°C strength decreased with decreasing pain size. At high temperatures the directionally solidified tnaterial was stronger and less strain-rate-sensitice than the hot-rolled material. The fine-grained hot-worked ma-terial became superplastic at high temperatures, with tensile elongations greater than 850 pct, while at root temperature this material was ductile and impact-resistant because of the ductile matrix. Fracture occurred in the directionally solidified material at elevated temperatures by inter phase separation and at roorn temperature by cracks in the intermetallic phase. Growth of these cracks was impeded by the ductile cobalt-rich phase. It was found that the CoAl intermetallic remains ordered at elevated temperatures. DIRECTIONAL solidification of eutectic alloys has been used to produce structures consisting of parallel rods or lamellae. Although the spacing of the phases depends on the growth rate, it has been observed to be of the order of 1 µ in many eutectics. A strong intermetallic phase has been used to reinforce a ductile matrix in the rod eutectic A1-Al3Ni and the lamellar eutectic Al-Al2cu.1 The microstructure of the eutectics A1-A13Ni and A1-A12Cu remained aligned after samples of these alloys were exposed to temperatures just below their melting points for long times. Stability of the microstructure at elevated temperatures makes directionally solidified eutectics a candidate for high-temperature applications. Recently Thompson4 has developed the Ni-NiMo eutectic containing 40 pct NiMo lamellae, giving a tensile strength superior to nickel-base superalloys. Unfortunately, this eutectic oxidizes rapidly at elevated temperatures. By mechanically processing a two-phase structure, one may reach strengths as high as 700,000 psi, as demonstrated by drawn pearlite.5 In this case the strengthening mechanism was thought to be related to the fine substructure formed during deformation.5 However, a heavily worked structure may recrystallize and coarsen at elevated temperatures. Some worked eutectics such as Al-Al2Cu,6 Pb-Sn,7 and Sn-Bi7 have shown unusually large elongations in tension when tested at elevated temperatures. This phenomenon of large extension, called "superplasticity", was related to the fine grain size of wrought two-phase alloys at elevated temperatures. A mode of deformation of "superplastic" material has been shown to be grain boundary sliding,&apos; which has also been observed during creep of polycrystalline materials.9 The Co-A1 system was chosen for this investigation after examining the phase diagrams of binary eutectics." The high melting point of 1400°C, the aluminum content which was expected to give oxidation resistance, and the properties of the intermetallic CoAl were the chief factors influencing this choice. This eutectic consists of a mixture of the intermetallic CoAl and a cobalt-rich solid solution. The intermetallic CoAl has a large range of solubility and a CsCl structure." From the similarity between CoAl and NiAl one would expect CoAl to be ordered at elevated temperatures; however, specific heat measurements" show a transition at 800°C. West-brookL2 has measured the hot hardness of CoAl and found a rapid decrease in hardness above 600°C. The tensile properties and stress rupture properties of as-cast CoAl-Co eutectic were measured by Ashbrook and wallace13 who report a room-temperature tensile elongation of less than 1 pct. I) EXPERIMENTAL A) Sample Preparation. Experimental materials were prepared by directional solidification, by hot working, and by powder processing. The starting materials were electrolytic 99.9 pct pure cobalt and 99.99 pct pure aluminum. 1) Directional Solidification. A vertical Bridgman apparatus heated by induction was used to directionally solidify cylindrical ingots $ in. in diam and 5 in. long. The apparatus was first evacuated and then an argon atmosphere was introduced to retard evaporation. The ingots were contained in an alumina crucible inside a graphite susceptor that rested on a movable water-cooled base. The base was lowered out of the induction coil at a constant rate. Eight of the ingots were solidified using a drive rate of 2.5 cm per hr, two of the ingots at 1.2 cm per hr, and one ingot at 10 cm per hr. The eutectic composition Co 10 wt pct A1 was used in all but one ingot which had the composition of the stoichiometric CoAl intermetallic, Co 32 wt pct Al. 2) Mechanical Processing. At 1000°C the eutectic Co 10 wt pct A1 is a mixture of an intermetallic phase, Co 21 wt pct Al, and a cobalt-rich phase, Co 5 wt pct Al.10 These phases differ from the stoichiometric CO 32 wt pct A1 and pure cobalt because of the large solubility of this eutectic at elevated temperatures." Four rectangular slab ingots, 4 by 1 by 12 in. high, of Co 10 wt pct Al, Co 5 wt pct Al, Co 21 wt pct Al, and Co 32 wt pct A1 were cast for hot rolling. The cobalt was first vacuum-melted, H2-treated for 20 min,

Jan 1, 1968

By P. S. Rudman

The solubility limit and the diffusivity of carbon in molybdenum have been obtained by duffising carbon into molybdenum rods from a Mo + Mo2C powder mixture. The solubility limit was taken as the long-time asymptotic limit of the rod composition. The diffusiv-ity was obtained from fractionally saturated rods from the rate of change of the average composition. Compositions were determined by chemical analysis. The solubility limit obtained is: WhILE the Mo-C system is important in refractory alloy technology neither the solubility limit nor the diffusivity of carbon in molybdenum is unambiguously known. In Fig. 1 the Mo-C phase diagram is presented. The heavy lines, the terminal solution solubility limit, and the eutectic temperature are results of the present investigation and will be discussed in detail later. However, it is readily seen that the previously published solubility limit determinations, Few and Manning1 and Fromm and ROy2 differ by up to an order of magnitude. The general form of Fig. 1, the Mo2C field, and a eu- tectic temperature -2200°C are due to an early Investigation by Sykes et a1.3 Although they did not determine the solubility limit, they did establish that the maximum at the eutectic temperature was about 1000 ppm. The only other prior data found on the solubility limit is from a lattice-parameter study by Speiser et a1 .,4 from which it can be concluded that the maximum solubility is greater than 1800 ppm. There does not appear to be any data oh the diffusivity of carbon in molybdenum. However, Samsonov and Epik5 have determined, from the rate of growth of an MozC layer, the diffusivity of carbon in Mo2C, and this has been erroneously interpreted, for example by ~c~eil,&apos; as applicable to diffusion of carbon in molybdenum.

Jan 1, 1968

By W. S. Owen, T. Bell

The variation ox the M, temperature with nitrogen concentration has been determined experinzentally. The free-energy difference between martensite and the parent y Phase at the M, temperature,is computed for Fe-C and Fe-N alloys using recent solubility data fm the Fe-N system and new data for the variatim of the activity of the interstitial solute in the y phase with concentration. The "geometric model" is considered also, and the importance of Zener ordering is noted. It is shown that, although at any chosen concentration the M, temperature and the activity are significantly different in the two alloy systems, the free-energy duference is the same within the limits of experimental error, thus Providing further evidence of the very close similarity between the martensite transformations in Fe-C and Fe-N alloys. TO estimate the free-energy change accompanying the martensite transformation in binary interstitial alloys it is necessary to know the variation of the Ms temperature with interstitial solute concentration and some thermodynamic data. To date, only the Fe-C system has been discussed because this was the only system for which relevant experimental measurements had been made, but even in this case the data available are insufficient to permit the free-energy change to be calculated without the assumption of a thermodynamic model for the y and a solid solutions. The last comprehensive discussion of the topic was by Kaufman, Radcliffe, and Cohen in 1.960.&apos; Since that time Ellis, Davidson, and Bodsworth2 have redeter mined the activity of carbon in y iron as a function of carbon content and Atkinson3 has measured the activity of nitrogen in Fe-N austenite. The M, temperature of Fe-N is reported in the present paper. Thus, it is now possible to assess the free-energy change accompanying the martensite transformation in Fe-N alloys on the same basis as that used to assess the change in Fe-C alloys. This comparison is of interest because it has been shown recently4 that the structure of the martensite formed in Fe-N alloys changes with nitrogen content in a manner exactly parallel to the changes in structure in the Fe-C series and that the strain associated with the distortion of the iron lattice in either the y or the a phase by a nitrogen atom is the same as that produced by a carbon atom. The work to be described tests whether or not this close similarity between the two systems extends to the thermodynamics of the martensitic transformations. THE Ms TEMPERATURES FOR Fe-N MARTENSITE Bose and Hawkes5 found the M, temperature of a eutectoid Fe-N alloy (2.35 wt pct N) to be 35°C. This single determination appears to be the only reported measurement of the M, temperature of an Fe-N alloy. In the present work a series of more than fifteen different specimens containing between 0 and 2.7 wt pct N were prepared by controlled nitriding of pure iron wire 0.010 in. diam. The iron was supplied by B.I.S.R.A. and was designated ACN2. The nitriding procedure, all aspects of which are critical, has been described in detail elsewhere.&apos; Each specimen was quenched from the austenitizing temperature into brine at 20°C without removing the specimen from the ammonia-hydrogen atmosphere in which it was ni-trided. Alloys containing up to 0.7 wt pct N were fully martensitic. More concentrated alloys contained progressively more retained austenite. At 2.34 wt pct N the specimen was completely austenitic after quenching to 20°C. The M, temperature of specimens with M, temperature above 20°C (those containing less than 2.35 wt pct N) was determined by a thermal arrest technique. For the more concentrated alloys (2.35 to 2.70 wt pct N) the variation of electrical resistance with temperature down to -196°C was used. Unlike Fe-C alloys, Fe-N alloys cannot be reaus-tenitized in vacuum or in an inert atmosphere because excessive loss of nitrogen occurs, even in short times, at high temperatures. Consequently, the alloys were reaustenitized in the ammonia-hydrogen mixture corresponding to nitrogen equilibrium at the temperatures used. The specimens were quenched in a blast of cold hydrogen gas and the temperature, measured by a thermocouple welded to the 2.5-in.-long specimen, was recorded on a high-speed recorder. In the first experiments 0.002-in.-diam chromel-alumel wire thermocouples were used but it was found that these gave erroneous readings due to contamination by nitrogen pickup. Pt-Pt 13 pct Rh wires of 0.002 in. diam were found to be satisfactory. Further details of the experiments are available in the original thesis.7 The cooling rate was controlled between 400° and 4000°C per sec by adjusting the hydrogen pressure. At least three cooling curves were obtained for each composition. Each specimen was analyzed for nitrogen after quenching. To aid in the accurate location of the martensite arrest points a series of cooling curves of 0.010-in.-diam platinum wire were recorded and these, which did not contain an arrest, were used as comparison standards. Four specimens, each in the form of a 3-in. loop, were prepared from each of the four alloys containing more than 2.35 wt pct N. One specimen was used for nitrogen analysis, one for X-ray diffraction, and two for resistance measurements below 20°C. The latter specimens were quenched from 20°C into constant-temperature baths at selected lower temperatures.

Jan 1, 1968

By F. E. Rizzo, L. R. Bidwell, D. F. Frank

THE poor high-temperature oxidation resistance of the refractory metals becomes an important problem as higher operating temperatures are sought. A meaningful analysis of their oxidation behavior requires a knowledge of the phases that can appear during oxidation as well as their relative stability. Although several extensive investigations have been carried out to obtain this information for the W-0 system,1-10 serious inconsistencies still remain. First, the standard free energies of formation (AG°) determined in recent studies which used the solid electrolyte galvanic cell technique6,7,9 differ significantly from those obtained primarily from gas equilibration measurements.1,3,4,10 The disagreement is especially large for the highest oxides. These data have been used to predict the decomposition temperatures of WO2. 72 and WO2.90.1 A considerable extrapolation is required, resulting in a large uncertainty in the decomposition temperatures. Second, Bousquet and perachon3 have presented convincing evidence, ob- tained by gas equilibration measurements, in support of the long-contested existence of W30. Phillips and chang,ll on the other hand, were not able to observe this phase under similar experimental conditions. The purposes of this work, which is part of a continuing investigation of the W-Mo system, were to resolve the discrepancies between the AGO measured by gas equilibration and solid electrolyte galvanic cell techniques, to extend the latter measurements to lower temperatures, to redetermine the WO2.72 and WO2.90 decomposition temperatures, and to apply the more sensitive electromotive-force method to the question of the existence of W3O. I) EXPERIMENTAL PROCEDURE The measurement of ?G° of reaction by the use of calcia-stabilized zirconia solid electrolyte galvanic cells has been described previously.12 The method is based on the measurement of the difference in chemical potential of oxygen between an electrode containing the two oxides of interest and a reference electrode of known oxygen activity. Two different types of cell holders were used in this study. The first type of apparatus has been described earlier." It consisted of two solid electrodes separated by a disc of electrolyte. Both electrodes were exposed to the same stream of purified helium. With this design a gaseous transport of oxygen between the two electrodes is possible. The second type of apparatus, which has also been described earlier,14 effectively separated the two electrode atmospheres. It utilized a closed-end impervious, calcia-stabilized zirconia tube that was open to the atmosphere. The tube served as an electrolyte for the cell and provided a means for separating the anode compartment, which was held under a static vacuum, from an air reference cathode. The cells and reactions of interest are described in Table I. High-purity tungsten metal was obtained from the Fansteel Metallurgical Corp. and the Allied Chemical Corp. Table II contains an analysis of each material. WO3 was prepared by oxidizing the metal in air at approximately 600°C in high-purity recrystallized alumina boats and by the dehydration of reagent-grade tungstic acid in alundum boats. The two methods of preparing WO3 resulted in slightly different purities.

Jan 1, 1968