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By E. R. Helderman, C. Y. Ang, C. C. Nealey

Beryllium-base alloys have been successfully p7.-epared by the liquid-phase sintering technique. Depending orz the composition and amount of the intended liquid please, microstructures either single -phase or duplex in feature with randomly oriented grains have been obtained. Qualitative and semi-qualitative determination of distribution of alloying elements md microsegregations in some experi)uzental alloys haue been made by electron-micro-probe analysis in conjunction with microliardness testing and standard metallography. Tensile tests reoealed that some conzpositions possess attractive elastic properties with Young's mot1uli greater than 40 X 10' psi. In powder metallurgy, liquid-phase sintering is a process or phenomenon that has proven to be of practical value. For example, the heavy metals such as tungsten-copper-nickel, high-strength heavy gyro alloys,' heavy-duty electrical contacts,' and tungsten carbide tool materials are all products of liquid-phase sintering. Mechanisms involved in liquid-phase sintering, however, are not completely understood. Questions regarding the exact roles played by rearrangement of particles, liquid/vapor surface energy, solution and precipitation, and so forth, have not been completely answered. Evidence has been cited3 that at least volume shrinkage in the densification process is diffusion-controlled. It is possible that the predominant mechanisms for the complete densification and grain growth in a liquid-phase sintered system depend primarily on the alloy systems involved, in addition to processing conditions. Despite the lack of sound understanding of the mechanisms of the process, liquid-phase sintering has been and is being used to advantage either to synthesize microstructures for their special properties or to prepare alloys which are difficult to form by fusion process. Liquid-phase sintering of beryllium alloys was first attempted by Jones and Williams.4 They first tried infiltrating beryllium with magnesium, and then succeeded in preparing the alloy by sintering Be-Mg powder compact in molten magnesium bath. This investigation resulted in the identification of some Mg-Be intermediate phases. Crossley et a1.5 also used liquid-phase sintering technique in an attempt to produce ductile beryllium alloys for structural applications. The major liquid-phase components investigated by Crossley et al. were aluminum and silver with minor additives of germanium, calcium, lanthanum, cerium, and yttrium. The lack of wetting and the bleeding out of liquid phase were the difficulties encountered during experimentation. According to Hodge,6 the two compositions investigated by Crossley, which showed some promise based on compression tests, involved large amounts (over 35 wt pct) of silver, thus making them too heavy to be of practical interest to the aerospace industry and military users. The present investigation was prompted by the search for light-weight (density less than aluminum) beryllium alloys exhibiting small anisotropy in physical properties for precision inertial navigation instrument applications. In addition to isotropy, good structural properties such as high elastic modulus or desirable combination of mechanical and physical properties are also objectives of this investigation. The technique of liquid-phase sintering was chosen for its versatility in producing either duplex or homogeneous microstructures. This report is concerned with the use of copper and aluminum, with or without silicon addition, as the intended liquid phase, and the resultant micro-structures and some physical properties of the beryllium alloys. Qualitative and semiquantitative electron-microprobe analyses of some of the alloys are presented to illustrate the usefulness of this microanalytical technique for the identification of microconstituents and their distribution. EXPERIMENTAL PROCEDURES The beryllium powder used was -200 mesh Brush Beryllium Co. QMV NP-50 grade. Typical chemical analysis of the powder is shown in Table I. Commercial high-purity copper, aluminum, and silicon powders all screened to —100 mesh were used as additions. Mixed powder compositions were ball-milled in ceramic jars for 1/2 hr to ensure thorough blending. Milled powder was loaded either in 3/4-in.-diam button die or in Metal Powder Association flat tensile specimen die and compacted under top and bottom pressure. No lubricant or organic binder was used. Sintering was carried out in a quartz tube under a vacuum of 50 to 100 µ pressure. Surface hardness and some microhardness readings were taken on sintered specimens. Sintered density was

Jan 1, 1965

By J. H. Scaff, W. G. Pfann

The effects of impurities on the electrical properties of silicon are discussed in a companion paper by Messrs. Scaff, Theuerer, and Schumacher.' It was shown that an ingot of silicon which contained boron and phosphorus in certain concentrations consisted partly of p-silicon and partly of n-silicon2 and that the common boundary between these regions was the source of a photo-voltage. These features were ascribed to the segregation of boron and phosphorus during solidification of the ingot. Because of different rates of segregation the first portion of the ingot to freeze contained a molar excess of boron over phosphorus and hence was p-silicon. The last-solidified region contained a molar excess of phosphorus and was n-silicon. This paper is concerned with the microscopic examination of such ingots. The microstructures are rather unusual in certain respects and their study has helped to show how the segregation of minor elements modifies the electrical properties of silicon. The microstructures of ingots prepared from two lots of silicon, designated 1 and 2, will be described. These lots were obtained from the Electro Metallurgical Co. Both contain 99.8+ pct silicon, but they differ in impurity analysis. For each lot will be shown the microstruc-ture of a slowly cooled ingot, for which the time of solidification is 6 min., and that of a rapidly cooled ingot, for which the time of solidification is 2 min. The ingots were prepared from 45 g charges of silicon. When an alloy freezes a cored structure is generally produced because of insufficient diffusion to remove concentration differences established during freezing. As a result of coring the first portion of a crystal to freeze is usually poorer in solute than equilibrium requires, while the last material to solidify is richer. In a columnar grain, growth is principally unidirectional and coring can produce a concentration gradient along the entire grain. By carrying the picture of the coring process from a single grain to an entire ingot in which columnar grains are aligned more or less radially, one can easily see that a composition gradient could be established between the outside and center of the ingot. This, to a considerable extent, occurs during the solidification of a slowly cooled ingot of silicon. Slowly Cooled Ingot In slowly cooled ingots of both lots of silicon, columnar grains which are approximately radial in direction and longest at the top of the ingot enclose a region in which the shapes and align- ment of the grains are considerably less regular. The central region is last to solidify and contains cavities and inclusions. The sketch of Fig 1 illustrates some of these features, as well as others which will be described below. If a polished section of an ingot is etched in a mixture of 2 parts of 20 pct HF and 98 parts of HNO3 the p-n barrier becomes visible. The overall shape of the barrier in a slowly-cooled ingot is roughly oval, as may be seen in Fig 1. The proportion of n-silicon, that is, the region enclosed by the barrier, is considerably greater in ingots of lot 1 than in those of lot 2. A sample about 34 x 1/8 X 1/8 in. was cut from a slowly cooled ingot of lot 1 with its long direction extending from the top of the ingot to the porous region. Thus its upper half was psilicon, its lower half n-silicon. A longitudinal face was polished and etched in the acid mixture. The areas of interest are identified in Fig 2. A band of parallel markings extends across the sample in the columnar region. These striae are roughly parallel to the upper surface of the ingot and cross grain boundaries with only slight deviations. They are quite distinct in the n-silicon,

Jan 1, 1950

By N. Brown, R. Kossowsky

Plain carbon steels with 0.48 and 0.95 pct C were quenched and tempered at 705°C to produce carbide dispersions with spacings on the order of 1 p. The morphology of the structure consisted of a carbide-dislocation network. The strengthening due to the dispersion was found to vary linearly with M-½ where M is the mean free-ferrite path determined by the entire network. No preyield microstrain preceded the upper yield point. After prestraining, the lowest stress at which dislocation movement could be detected was 104 psi; this frictional stress was independent of the dispersion and prestrains up to 6.5 pct. The Cottrell-Petch equation for grain-size strengthening was used to discuss the dispersion strengthening in this investigation. The results support an impurity mechanism for the upper yield point rather than one based on the Johns ton- Gilman theory. IT was pointed out by Gensamerl that the mean free path in the matrix is the important variable which controls the degree of dispersion strengthening. Gensamer's data on steels showed a linear relationship between the yield point and the logarithm of the mean free-ferrite path. The first theory was by Orowan,2 who suggested the mechanism of dislocations bowing between particles, with the resulting relationship that where a is the yield point, P is the distance between particles, and G is the shear modulus. The Orowan equation applies to that range of dispersion where P is large compared to the particle size and the particles are not coherent, so that the matrix is essentially free of internal stresses. As was pointed out by Orowan, there are different degrees of dispersion which, in turn, will influence the strength-controlling mechanism. However, in this investigation, we wish to confine ourselves to the region of coarse dispersion, where the Orowan mechanism should, intuitively, be applicable. It was soon evident that the data, which existed at about the time that the Orowan theory was proposed, did not agree with the Orowan equation in that the actual strengthening was always greater than the theoretical predictions. Thus, Fisher, Hart, and pry3 modified the Orowan theory by suggesting that the Orowan process took place in the microstrain region preceding macroscopic yielding and the subsequent, rapid work hardening in the form of residual dislocation loops around the particles largely determined the observed macroscopic yield point. The F-H-P theory stated that the increment of strengthening due to the work-hardening mechanism was proportional to f3/2 where f is the volume fraction of the precipitate. F-H-P used data by Shaw, Shepard, Starr, and Dorn4 on A1 3-5 pct Cu to support their theory. Roberts, Carruthers, and Averbach5 were the first to make a microstrain study of dispersion strengthening, and they found that for steel the Gensamer relationship was obeyed. Hayman and Nutting6 suggested that in the case of tempered steel 1) the ferrite grain boundary was the primary obstacle and 2) the carbide particles simply formed part of the grain boundary obstacles. They found that the strength varied as G"" where G is the ferrite grain size. Turkalo and LOW' determined the structure of quenched and tempered plain carbon steel using a replica technique; they concluded that the carbide particles did not necessarily lie in the ferrite grain boundaries. When they defined the mean free-ferrite path as being determined by both particles and the ferrite path boundaries, their data obeyed the Gensamer relationship. Meiklejohn and skoda8 showed that the strengthening from iron particles in mercury was a function of the particle size and the distance between particles. Dew-Hughes9 explained the Meiklejohn and Skoda results by the following theory: 1) grown-in dislocations which surrounded the particles were produced by the thermal stresses during the time the material was cooled to the testing temperature, and 2) the observed strengthening was associated with the cutting of the grown-in dislocations by the glide dislocations. Ansell and Lenel10 proposed a theory in which the glide dislocations pile-up or surround the particle until the number of dislocations in the pile-up is sufficient to yield or fracture the particle. The resulting theory says that the yield point varies as p-1/2, where P is the distance between particles. The Ansell-Lenel theory is almost identical to the

Jan 1, 1965

By Ralph Hultgren

IN solid solutions atoms of differing sizes occupy the same crystalline lattice, requiring that some of them be compressed and others expanded. The energy involved has been called misfit strain energy and is an important concept of crystal chemistry. If the atomic sizes and elastic constants of interatomic bonds are known, the misfit energy may be calculated,' provided certain simplifying assumptions are allowable. Usually, isotropic crystals are assumed and interatomic distances are taken to be the statistical average determined from X-ray diffraction. Such calculations yield values of the misfit energy of the order of 1 or 2 kcal per atom in alloys such as Au-Cu at compositions of 50 atomic pct. However, evidence has accumulated in recent times that atoms change their sizes with composition of alloys, implying electronic rearrangement of the bonds. The size changes have been found particularly by application of the X-ray method developed by Warren, Averbach, and Roberts.' Thus, Averbach, Flinn, and Cohen3 determined radii in Au-Cu alloys. Oriani4 showed that these new radii led to a calculated misfit energy in disordered AuCu, which was decreased from the values calculated by the usual theory more than twenty-fold, to only 80 cal per g atom. Thermodynamic calculations from the phase diagram5 also show misfit energy to be no more than a few hundred calories per g atom in this alloy. The question of what electronic rearrangements are possible therefore becomes compelling in estimating misfit energy. In the following pages the results of certain calculations on the AuCu tetragonal superlattice are submitted. Conclusions drawn from these should be applicable in large degree to disordered solid solutions. As in all ordered states, bonding distances in the superlattice are individually known, rather than being merely average distances as found from lattice constants of disordered states. Moreover, only the Au-Au and Cu-Cu distances are strained; the elastic constants of these are known in the elementary state. In the usual calculation it is necessary to assume elastic constants for Au-Cu bonds. Misfit energy has thus been calculable without the need of many simplifying assumptions usually made. It is still assumed that equilibrium bond lengths and elastic properties of the bonds are the same in the alloy as in the pure metals. As previously discussed, this is probably not correct. Also assumed is that the bonds are not affected by strain of neighboring bonds. A calculation of Young's modulus from compressibility data shows this to be far from true; extensive electronic rearrangements take place. It would seem that misfit energy cannot be calculated from elasticity data for the elements. The usual methods may, however, give an upper limit which is often much higher than the true value. The question of electronic rearrangement is, of course, a complex one. Pauling's theory gives a simple, approximate treatment of the relation between type of bond and bond distance. This has been applied with some success to the Au-Cu system, as will be shown in a later section. Misfit Energy in Au-Cu Alloys Hume-Rothery and Raynor6 discuss the Au-CU system as a type example of strain energy. The gold atom is 12.8 pct larger in diameter than the copper atom, near the size factor limit beyond which solid solubility is severely restricted. They therefore consider the misfit energy to be large, a conclusion for which they believe they find evidence in the phase diagram. Gold and copper are completely miscible in the solid state, but the alloy has a minimum melting point at an intermediate composition. From this Hume-Rothery and Raynor conclude that the strain energy is nearly large enough to prevent miscibility; the phase diagram tends toward a eutec-tic type. In Ag-Cu, which has almost identical size relationships, solid miscibility is quite limited; whereas in Au-Ag, where atomic sizes are nearly the same, there is complete miscibility without a minimum in the melting point. From their arguments the heat of formation of Au-Cu would be expected to be endothermic or only slightly exothermic, that of Ag-Cu to be endothermic, and that of Au-Ag to be exothermic. Deviations, from Ve-gard's law of additivity of atomic radii support these conclusions, since Au-Cu and Ag-Cu both have pronounced positive deviations, and Au-Ag has a negative deviation. Nevertheless, Au-Cu alloys form exothermically; indeed, considerably more exothermically than Au-Ag, Table I. Hence, strain energy must be much less important in this case than Hume-Rothery and Raynor have supposed.

Jan 1, 1958

By J. H. Smith, H. W. Paxton

X HE recent investigation of Butler, McCabe, and paxton' on the vapor pressure of manganese gas in equilibrium with Mn-Fe alloys has been extended to include the iron-rich solutions and alloys in the two phase equilibrium region. The study of the phase equilibrium by Kurnakov and Troneva2 and the extensive reviews of the Mn-Fe system by Hansen,3 and Hellawe114 are not in agreement with regard to the location and extent of the equilibrium between the solid phases of fcc y and complex P in the temperature range above the eutectoid temperature of approximately 975Kwhere 0 decomposes to y and bcc a. An evaluation of the existing equilibrium data is confronted with the conflicting results presented by various investigators who used techniques requiring a quenching treatment to retain the high-temperature equilibrium or encountered temperature hysteresis during thermal analyses. The difficulty of suppressing the transformation of the manganese-rich concentrations of the y-solid solution during quenching has been well etablished.' To avoid this uncertainty the phase equilibrium was investigated at temperature by measuring the partial pressure of manganese gas in equilibrium

Jan 1, 1962

By R. F. Mehl, G. T. Horne

Diffusion coefficients and mobilities were determined as functions of concentration in the a phase of the Cu-Zn system. Use was mode of incremental diffusion couples to determine the Kirkendall effect at various concentrations. Darken's analysis was used to calculate the individual diffusion coefficients and mobilities from these data. The general diffusion coefficient is a single-valued function of the concentration in this system to within the limits of accuracy of the experimental methods used. The form of the various functions (diffusion coefficients and mobilities) of concentration is the same in every case: it is essentially the same as the usual D vs c curve. AS Darken' has pointed out, the knowledge that the movements of different atoms diffusing in the same lattice need not proceed at the same rate is old. Ionic lattices are the classical examples; application of the generalization to lattices with metallic bonding was much more slowly accepted. It remained for Kirkendall'' to show clearly that metallic diffusion need not be symmetrical with respect to both species. Several investigators" have confirmed the initial observation of a "Kirkendall effect:" marker movement accompanying diffusion. They have extended it to other systems and conditions. The theoretical interpretations have been many; ne of the first and simplest of these is that of Darken"' which is essentially mechanism independent. Darken has shown that the Kirkendall experiment permlts a calculation of the individual diffusion coefficients and, coupled with activity data, offers a means of measuring the mobilities of the separateatoms in a binary diffusion process. There is no published information on the effects of concentration and temperature on the individual diffusion coefficients or on the mobility values in binary solid solution; this paper provides such information for zinc and copper in a brass. For purposes of clarity, the overall D value obtained, for example, from the Boltzmann-Matano solution to Fick's law, will be designated as the "general diffusion coefficient;" and the diffusion co- efficients for the separate diffusing species will be designated as the "individual diffusion coefficients." Experimental Procedure The authors have accepted Darken's analysis and have measured mobilities on this basis. The findings of da Silva and Mehl are accepted: that the Matano interface, defined as the origin of coordinates for the Boltzmann-Matano solution to Fick's law, coincides with the original weld interface; that the "shift" of a marker is the distance between the Matano interface and the marker; that the observed porosity is too small sensibly to affect this result; and that the shift is a linear function of the Matano area, the area defined as the absolute magnitude of the area on either side of the Matano interface. Alloys: The a-phase of the Cu-Zn system was chosen for investigation. The measurements were made on incremental couples for two separate reasons: l—it has been questioned whether D, the general diffusion coefficient, is a single-valued function of concentration (a comparison of the D-values for couples with small concentration range, e.g., 10 vs 20 pct Zn, against those from a wide concentration range, e.g., 0 vs 30 pct Zn, will answer that question); and 2—on the Darken analysis, the mobility can be determined only at the concentration at which the marker is observed to lie (this is but one concentration in a single couple) but choosing a series of incremental couples in the range between 0 and 30 pct Zn provides mobility values at several concentrations, thus giving mobility as a function of concentration. Four alloys were chosen; nominally, pure copper, copper with 10 pct Zn, copper with 20 pct Zn, and copper with 30 pct Zn. This allowed six different types of diffusion couples to be prepared, promising mobility determinations at six different concentrations, but having a minimum range of 10 pct Zn. The copper was an especially prepared pure copper supplied through the courtesy of the Ameri-

Jan 1, 1956

By S. W. Kessler, R. B. Pond

Metal specimens were solidified through a measured thermal gradient so a free surface and the liquid-solid interface could be examined. A line structure was observed on the surface and a hexagonal structure on the interface. A model to explain these forms is proposed. NUMEROUS observations of the dendrite form have been made both in nonmetallic and metallic systems. From these, extrapolations have been made as to the probable dendrite form in pure metals. Observations of the dendrite form in pure metals, nevertheless, have been scanty. In general, these observations have been made on the skeleton dendrite after the mother liquid has been drained from around it, and a mechanism of the formation of the dendrite has been postulated from this solid form. Recent investigations have been conducted in an endeavor to make a study of the formation of the dendrite in several pure metals and the effect of several variables on this mechanism and final form. For these investigations, an apparatus was designed and constructed as shown in Fig. 1. It consists of a talc block containing a half-cylindrical depression, the end of which terminates in the conical recess of a copper block having an external attachment for cooling. A heating coil extends the length of the mold just beneath the lower limits of the cavity. The entire cavity for holding metal is coated with a thin film of graphite. Six thermocouples are equally spaced in the cavity and under the graphite, and six microammeters indicate the temperatures at the particular thermocouple stations. Readings were taken of all meters at the same instant time measurements were taken by photographing the panel of microammeters and a stop watch which was started at the beginning of the run. It was possible with this apparatus to solidify metals through a measured thermal gradient and to observe the progression of the liquid-solid interface with time by following the formation of the dendrite markings in the surface of the solid material. These

Jan 1, 1952

By A. Styka, G. Fischer, S. Tour

Described herein are the results obtained during research work involving coating titanium alloys with molybdenum by vapor-deposition methods. Results show that the method can be used successfully to deposit hard adherent wear-resistant coating of methodmetallic molybdenum on titanium or titanium alloys without changing the microstructure of the titanium base. PRODUCTION and use of titanium and its alloys have increased tremendously in the past few years. The physical, mechanical, and chemical properties of this engineering metal have caused considerable enthusiasm among metallurgists and engineers. However, as with all materials, there are some drawbacks. For example, titanium is susceptible to seizing and galling on wearing surfaces. In order to produce a good wear-resistant surface, many investigations have been conducted evaluating oxidizing, carburizing, nitriding, carbonitriding, sili-conizing, and chromizing of titanium. All of these processes require high temperatures for rather extensive periods of time. It has been possible to produce hard surfaces on titanium and its alloys by a number of these processes at the expense of a deterioration of the physical properties of the base material. A practical solution to the problem of providing titanium and titanium alloy parts with a satisfactory wear-resistant nongalling surface must be one that does not involve excessive temperatures for long periods of time. Sam Tour & Co. Inc. has completed a research and development contract for the United States Army Ordnance Corps on vapor deposition of molybdenum on titanium and titanium alloys. On the basis of results obtained from the research program, titanium alloys can be coated successfully with molybdenum to provide a hard wear-resistant surface without harm to their base mechanical properties. The remainder of this article is a description of the techniques used to apply the coating and the results obtained from wear tests on molybdenum-coated titanium. Theory Basically, the technique used was the application of molybdenum by a vapor-deposition method, thermal decomposition of molybdenum hexacarbonyl [Mo(CO)] with hydrogen as the carrier gas. The selection of this method was based chiefly on the following considerations: 1—low plating temperature which would minimize excessive grain growth, 2— low decomposition temperature of the carbonyl, 3— possibilities of controlling the hardness of the plate by adjusting the carbon content using the plating temperature and pressure as the primary variables, 4—use of high vacuum, thereby avoiding unnecessary oxidation and other complex reactions with the atmosphere. Free energy data1 show the strong tendency for titanium to combine with O2 N2 or carbon from normal temperatures to temperatures above its melting point. To maintain the titanium in a film free condition, the use of as high a vacuum as possible is indicated. The literature' indicates that the reaction product of hydrogen with titanium is unstable in vacuum at around 400°C. 5—Although it is indicated from the thermodynamic standpoint that there is little possibility of removing carbon from either titanium or molybdenum, the work of Lander and Germer -ndicates that the use of a suitable H,/CO ratio is somewhat effective in minimizing carbon deposition. 6—Availability of molybdenum carbonyl. In the simplest form, the conditions of equilibrium3 in chemical reactions involving decomposition of carbonyl are as follows: Mo (CO) ? Mo + 6CO 2CO * C + CO,. The plating rate is proportional to the rate of evolution of CO from the decomposed carbonyl, i.e., it is proportional to the pressure of the gaseous decomposition products. Carbon released from CO gas is the significant constituent for the variability of the physical properties of the product. High carbon deposition is favored by increasing pressure. Limitations are imposed in the selection of plating temperature and pressure. Excessive temperature re-

Jan 1, 1956

By C. W. Spencer, Che-Yu Li, R. J. Knight

The usual reaction product for the monotectic reaction in the Bi-Se system consists of rod -shaped particles of selenium-rich liquid embedded in a single crystal matrix of At certain crystallo-graphic orientations of the matrix with respect to the reaction interface, more complex shapes are as -sumed by the liquid particles. This reaction has been examined at different growth rates and relative crystallographic orientations of the matrix with respect to the reaction interface. The uhriation in auerage particle size of the liquid phase with reaction rate has been determined at one crystallograpIzic orientation of the matrix. On a plot of logarithm of average particle diameter vs logarithm of reaction rate, data points for crystals grown at rates of 10- to 1.0 cm per hr fall near a curve of slobe -0.4. MONOTECTIC reactions in binary alloy systems are reactions of the eutectic class in which, as the system is cooled through the three-phase reaction isotherm, one liquid phase (L) decomposes to a solid phase and another liquid phase (LII).' A partial phase diagram, as taken from Hansen, showing the monotectic reaction in the Bi-Se system is given in Fig. 1. This diagram specifies the monotectic point at 618°C and 72 at. pct Se, and the monotectic reaction products as the intermetallic Bi Se3 and a liquid (LII) which contains approximately 98 at. pct Se. At a lower temperature, 217°C, this liquid may undergo a eutectic reaction in which the reaction products are BizSe3 and crystalline selenium. However, under conditions of rapid cooling, or quenching, from above 217°C, this selenium-rich liquid may be partially retained to room temperature in an amorphous or glassy state. The intermetallic BizSe3 is rhombohedral, of the space group jm;' however, for convenience it is usually represented by a hexagonal struture. A pronounced plane of cleavage, which lies perpendicular to the main axis of the rhombohedral unit cell or parallel to the basal plane of the hexagonal cell, exists in the structure. The usual monotectic reaction product consists of rod-like particles of LII embedded in a single-crystal matrix of BizSe3, although at certain crystallographic orientations of the matrix BizSe3 other more complex shapes are assumed by LII. A similar rod-like, or cylindrical, morphology for the carbide phase has been reported by westbrook7 in the a Cr-Crz3Ce eutectic structure. In this paper the morphological characteristics of the LII particles, as retained to room temperature, have been examined under conditions of varying growth rate and crystallographic orientation of the matrix BizSe3 with respect to the growth direction. EXPERIMENTAL PROCEDURE Alloy specimens corresponding to the monotectic composition, 72 at. pct, or 50 w pct Se, were prepared from 99.999 pct pure bismuth and selenium obtained from the American Smelting and Refining Co. The two elements, corresponding to a total specimen weight of approximately 30 g, were encapsulated in 13 mm OD Vycor tubing under a vacuum of 5 x X mm of Hg. The capsules were suspended on a fine platinum wire in a Bridgman-type furnace which exhibited a temperature gradient of

Jan 1, 1963

By J. M. Oblak, R. F. Hehemann, R. H. Goodenow

STUDIES of surface relief and growth kinetics have lead to the concept that widmanstatten ferrite along with upper and lower bainite constitute a continuous series of decomposition products.1-4 Current models4 propose that these products form as plates with a coherent or semicoherent leading edge which propagates at a rate controlled by diffusion of carbon into the surrounding austenite. There are, however, important crystallographic and morphological differences between these products—particularly between upper and lower bainite. For example, upper bainite appears to exhibit a (11lIy orientation habit, whereas lower bainite develops with a more irrational habit near {2251y.5-7 Many of the morphological features of these decomposition products are not yet well-documented. Recent studiess have demonstrated that low-carbon martensites form as sheets of closely spaced needles on {lllly planes while higher-carbon martensites form as plates with {225}? or other orientation habits. The similarity in the crystallography of these two modifications of martensite with upper and lower bainite is striking. Therefore, a study of the morphology of bainite in a series of hypoeutec-toid alloy steels has been initiated to explore these relationships further. The question of immediate interest is whether upper and lower bainite form as plates or needles. A two-surface (approximately perpendicular) metallographic method was employed to study the morphology of bainite in a variety of low and medium alloy steels. Compositions of these steels have been reported elewhere. The behavior of 4340 and 4370 was typical and will be described here. Austenitizing treatments involved 20 min at 2350°F for 4340 and at 2000°F for 4370. Isothermal transformation was conducted in molten-salt baths. Upper bainite was produced at 925°F in the 4340 steel and lower bainite at 575°F in 4370 with transformation times adjusted to produce 10 to 15 pct of the decomposition product. Many of the morphological features of upper bainite have been catalogued in the recent literature.'' The two principal variants observed in the present investigation are illustrated in Fig. l(a). One form appears as long, thin plates or needles and the other as small, frequently irregularly shaped particles. Both variants may occur as isolated forms but more frequently appear in groups as demonstrated in Fig. l(a). Two-surface analysis reveals that these two variants constitute different sections through a single morphological form. To demonstrate this, a number of sections perpendicular to the plane of Fig. l(a) were prepared at various positions along the length of the elongated particles. A section taken at position 1 in Fig. l(a) is presented in Fig. l(b). Here, the dark line represents the edge of the sample and the left-hand portion of this photomicrograph is that from the surface perpendicular to the original plane of polish. Since it was necessary to repolish the original surface after each sectioning, the shape of the bainite particles on this surface, right hand side of Fig. l(b), changes with each sectioning. The disappearance of plate A, Fig. l(a), in Fig. l(b) emphasizes the small cross section of these structures. The group of particles in the lower left-hand

Jan 1, 1964

By W. T. Hicks

Visual observation of the oxidation of columbium shows that the protective behavior noted previously in gravimetric work in the early stages of the reaction below 600°C and throughout the reaction at 640°C is associated with an adherent oxide. The fact that the oxide is seen to move outward from the metal at temperatures from 550° to 935°C implies that the reaction takes place at the oxide-metal interface throughout this temperature range. THE work described in this paper further clarifies the complex oxidation kinetics of Cb revealed, for example, by the continuous gravimetric studies of T. L. Kolski.1 Time-lapse motion picture studies reveal details of the reaction not provided by a study of the combustion products. EXPERIMENTAL PROCEDURE Cb specimens were prepared from material with the following typical analysis: 0, 0.03 pct; N, 0.002 pct; C, 0.006 pct; Ta, 0.04 pct; Fe, 0.01 pct; Ni <0.003 pct; and Cr <0.003 pct. Arc-cast ingots were swaged and cold rolled into slabs. These slabs were machined into blocks 7/16 by 7/16 by 7/16 in; 1/16-in. holes were drilled through the large face of the blocks for suspension. The samples were then de-greased and annealed 1 hr at 1200°C in vacuum. The sample was suspended by a platinum and Pt 10 pct Rh thermocouple inside a 1-in. quartz tube in a Kanthal wound furnace (2 in. OD by 4 in. long) equipped with windows 1/2 in. sq. A Cine-Kodak Special II 16 mm motion picture camera was trained on the sample through a Spencer microscope adjusted so that a magnification of X1.5 resulted on the film. Super Anscochrome film was used to record the events in color. Argon was flushed through the furnace while the sample came to temperature. The argon was then replaced by a stream of dry oxygen at 1 atm. Pictures were taken at the rate of eight per second for about 20 sec during the change of atmosphere. Then by use of a Stevens time-lapse device pictures were taken at the rate of four per minute starting within 1 min of the initial oxygen flow. In this manner continuous visual records of the oxidation of pure Cb

Jan 1, 1962

By H. Fechtig, R. H. Buck, A. G. Guy

MULTIPHASE diffusion has been studied for many years in two-component systems1,2 and many of the experimental aspects are now fairly well understood.314 Although by no means all of the problems connected with the two-component case have been solved,&apos; attention has recently been directed to the more complex situation involving three components. The pioneer work of Clark and Rhines6 yielded a qualitative picture of the types of behavior that can occur, and Clark7 has suggested conventions for describing the various phenomena. Kirkaldy and co-workers8,9 have made quantitative studies in several ternary systems and have offered explanations of the occurrence of isolated and nonisolated precipitates. At present, however, there is no comprehensive theory for the variety of phenomena observed in ternary, multiphase diffusion. By analogy with several studies that have been made of multiphase diffusion in the binary Cu-Zn system,2&apos;10&apos;11 a similar exploratory study was made of Cu-Zn-Ni alloys lying along the line in the ternary diagram from the point 80 Cu-20 Ni to the zinc corner of the diagram, Fig. 1. A principal question to be answered was whether initially plane interfaces would remain plane during the course of one-dimensional diffusion. The diffusion specimens studied are described in Table I. The five separate alloys from which they were made were melted in evacuated Vycor capsules from 99.9 pct purity copper, zinc, and nickel. Since some of the alloys were too brittle to be swaged, all of the alloys were used in the cast condition. To facilitate later homogenization, the molten alloys were solidified by plunging the capsule in water. Homogenization heat treatment was done at 720°C for 20 hr. The five nominal compositions in weight percent zinc and nickel, respectively, were: 37.5, 12.5; 44.0, 11.2; 50.0, 10.0; 55.0, 9.0; 65.0, 7.0. Ln Table I the alloys are identified only by their zinc content. Sandwich-type diffusion specimens were prepared by pressure welding disk specimens, each about 3 mm high by 10 mm in diameter. Welding was done in a special threaded vise which was heated at 500°C for about an hour in an atmosphere of flowing hydrogen. A measurement of the separation of the phase interfaces was made on a polished flat on the welded specimen, and then the specimen was sealed in an evacuated capsule and given the diffusion treatment shown in Table I. The diffused specimen was sectioned longitudinally

Jan 1, 1965

By E. R. Gilbert, D. E. Munson

Creep of copper under 75 to 1.50 kg per sq cm stresses at temperatures near the melting point was found to he a complex reaction controlled by three mechanisms acting in parallel. In order of appearance with decreasing temperature, the auerage activation energies, Qc , are 168, 79, and 24 kcal per mole. Stress dependence of the minimum creep rate was found to he an exponential for the two high-Qc processes and a power law for the low-Qc, process. Transition of control occurs from one mechanism to another. The relative transition temperature depends upon the applied stress, and the range oiler which the transition occurs depends upon the difference in the activation energies of the mechanisms. The creep behavior at high temperature is explained by the climb of dislocations through thermally or mechanically formed jogs, CREEP in pure fcc metals at temperatures in excess of one half the absolute melting point is normally controlled by dislocation c1imb.1,2 A climb model which seems applicable, according to an extensive analysis of data,3 was derived by Weert-man.4 This model assumes jog-saturated dislocations and predicts an activation energy, Qc, nearly equal to that for self-diffusion, USd. Although the requirement of jog saturation is restrictive, agreement between theory and experiment seems adequate. Many other theoretical treatments, including an early model by Mott,5 include detailed consideration of jog formation as an initial requirement for climb. These models predict activation energies for creep which differ from those of self-diffusion. Seeger6,7 postulates an observed activation energy related to the stacking-fault energy. Thus, Usd <Qc<5Usd + Uj where Uj is the jog-formation energy. Seeger incorporated qualitatively the influence of the relative numbers of thermal and athermal jogs. Expanding this concept, Shoeck8 explicitly states a function based on formation mode and relative numbers of vacancies: e r ci exp {-uf/k T} exp {-Um/k T} [ 1 ] where Uf and Um are energies of vacancy formation and migration, respectively. The concentration of jogs, Cj, depends upon the manner of jog production. For intersection jogs, Cj is not sensitive E. R. GILBERT, Junior Member AIME, formerly with De- to temperature; for thermal jogs, Cj is proportional to exp {—Uj /k T}. Schoeck regards each mode as a distinct mechanism; therefore, the mechanisms may act together.299 The diversity predicted by theory, surprisingly, has not been substantiated by experimental results. A significant investigation must include the extremes in stacking-fault energy. Extensive creep studies of aluminum10 and nickel,11,12 high stacking-fault energy metals, have been made. Comparable studies on a low stacking-fault energy metal, such as copper, have not. It is the purpose of this paper to report the results of an investigation of the creep of copper under conditions which favor thermal jogs. EXPERIMENTAL Cylindrical compression creep specimens (0.240 in. in diameter by 0.400 in. long) were machined from cold-drawn rods of electrolytic tough-pitch copper containing 0.0007 Mg, 0.002 Fe, 0.001 Ni, 0.0005 Ag, Cd < 0.005, and Pb < 0.005 wt pct impurities. Undetected spectrographically was a nominal 0.04 wt pct 0, which occurs as a Cu2O constituent distributed discontinuously at grain boundaries. Vacuum annealing at 900°C for 15 min produced a stable 0.03-mm average grain diameter. Testing was carried out using apparatus similar to that described by sherby,13 modified by enclosing platens and a push rod in a vacuum cylinder. Normally this arrangement resulted in pressures less than 10 Only a slight surface tarnish, less than 0.0005 in. in thickness, occurred during the test. The applied stress, corrected for atmospheric pressure, was maintained within 2 pct of the desired true stress by the addition of lead shot at fixed strain increments. Creep strain was measured with dial gages as a relative displacement of the upper and lower platens; accuracy of measurement was 0.0001 in. Two creep-test methods were used, the differential or cyclic temperature14 and the isothermal, to obtain creep data at stress levels of 150, 100, and 75 kg per sq cm over the temperature range of 620° to 1032°C. Minimum creep rates were used from both test methods; this was considered proper because comparable temperature tests or cycling to the same temperature gave the same creep rate, within experimental error. The cold vacuum test chamber, with the unstressed specimen in place, was heated to temperature by placing a preheated furnace over the chamber. Temperature equilibrium was attained within 30 min. For the cyclic tests, the stress was removed during the 5 to 10 min necessary to effect the temperature change and re-

Jan 1, 1965

By E. R. Parker, T. H. Hazlett

An understanding of the mechanism of creep of metals requires an accurate knowledge of shape of the time-deformation curve. An expression is developed which accurately expresses the creep curve for a number of structurally stable metals and alloys. VAST strides have been made in the development of high temperature creep resistant alloys; however, no sound understanding of the physical mechanism of creep exists to date. Consequently, creep resistant alloys are still developed by "cut and try" methods formerly so successful but now yielding returns at a continuously diminishing rate. It is apparent to all workers in the field that if the mechanism of creep were understood, much fruitless labor could be avoided. The dirth of fundamental knowledge has not discouraged the theorists. Speculation has flourished and numerous theories of creep have been proposed. A critical review of these theories reveals that, even though there are some general areas of agreement between the majority of the workers, there are many basic questions yet to be resolved.&apos; It is generally conceded that theoretical speculation is far in advance of experimental evidence. The shortage of reliable creep data greatly hinders more rapid progress in this field. It is essential that the effects of different stresses and temperatures on the creep characteristics of metals be quantitatively determined. Once this has been accomplished, it will then be possible to evaluate the effects of alloying additions and, it is hoped, to provide a firm basis of facts for theoretical treatment of the creep phenomenon. The work reported herein was undertaken to determine the effects of such variables as stress, temperature, alloying, and structure on the creep characteristics of some metals. Material and Equipment Nickel was selected as the base material for the current investigation and an experimental program was initiated to determine the effects of temperature and stress on the creep characteristics of this material. Since a large quantity of high purity nickel was required for the proposed program and such material was not commercially available, it was decided to refine, cast, and prepare the required metal in our own laboratory. The resulting nickel test bars had the following composition, given in percentage by weight: Fe, 0.030 (1); Si, 0.003 (2); Ca, 0.001 (1); Mg, 0.020 (2); and S, 0.002 (2); to make total impurities of 0.056. The nickel (balance by difference) is 99.944 pct. The details of the purification process are described elsewhere.&apos; This

Jan 1, 1954

By R. I. Jaffee, C. M. Craighead, G. A. Lenning

THERE has been considerable discussion among A metallurgists and others interested in the development of titanium alloys as to the nature of the fine line markings which appear in the microstruc-tures of unalloyed titanium and a titanium alloys. These markings have been variously called x phase, etching pits, and twins. Figs. 1 to 3 show typical examples of the line markings as they appear, respectively, in high purity iodide titanium, commercial purity titanium rod, and a high purity a alloy containing 0.2 pct N. The commercial purity titanium sample, shown in Fig. 2, contains both line markings and some spheroidal retained-ß phase. The ß phase seen in this micrograph should not be confused with the line marking, since it originates from the iron present as an impurity in the sponge metal. It will be noted that the line markings seem to have a definite orientation pattern with respect to the grains and in titanium noticeably resemble the precipitation occurring in artificially aged high purity Al-Cu alloys. This similarity led to the hypothesis that the line markings observed in titanium and a titanium alloys resulted from precipitation of some unknown phase. With the work of Hägg1 and McQuillan2 as background, there was little reason to suspect hydrogen of being responsible for the line markings. Hagg reported that up to 33 atomic pct H was soluble in a titanium, and McQuillan reported an a solubility of up to 8 atomic pct. Furthermore, McQuillan examined metallographically a 5.1 atomic pct H alloy quenched from 300°C and stated that the structure appeared to be a single-phase a solid solution. Line markings have been observed frequently and were first noted by Jaffee and Campbell3 in 1949. They did not observe them in vacuum-annealed titanium and a Ti-O and Ti-N alloys, but did observe them in Ti-H alloys containing 0.25, 0.5, and 1 atomic pct H. They stated that it was doubtful that the markings were a second phase based on hydrogen, because 1 atomic pct was far from the accepted solid solubility of hydrogen in titanium. Finlay, Resketo, and Vordahl,4 in 1950, concluded that the markings were a true second phase as a result of observations on their etching characteristics. Anderson5 Commenting on these markings in titanium was inclined to associate them with hydrogen, but was loath to call them titanium hydride, because of the reported high solubility of hydrogen. Work at Battelle Memorial Institute for the Navy Bureau of Aeronautics," done concurrently with the work described in this paper, provided information on the experiment converse to that described by Jaffee and Campbell in 1949. This work showed that the amount of line markings in unalloyed titanium could be decreased by vacuum annealing at elevated temperature. It was suggested that this was the result of removal of hydrogen; previously, the data of Jaffee and Campbell9 howed that the markings appeared when hydrogen was added. Recent work at Battelle for the Ordnance Corps, Department of the Army, which is described here, now establishes the identity of the markings as a titanium hydride phase. A sample of high-purity titanium rod 1/4 in. diam, 0.009±0.001 wt pct H (0.43 atomic pct), Fig. 1, was resistance heated in a 0.05 micron vacuum for 41/2 hr at 1500°C. During the early states of heating, the pressure increased to 150 microns, indicating that gases were being evolved. After cooling in vacuum, the iodide titanium rod was analyzed for hydrogen. Vacuum-fusion analysis showed 0.0006 ±0.0003 wt pct H (0.03 atomic pct) to be present.* Metallographic examination of the vacuum-annealed rod showed only a transformed ß structure. There was no evidence of fine line markings, Fig. 4. A section of this vacuum-annealed rod was cold rolled to 0.040 in. thick sheet and annealed for 1 hr

Jan 1, 1953

By C. G. Dunn, J. L. Walter

The c/laracterzstics of cube-oriented nuclei ard other matrix grains that are associated with secondary, recrystallization to the cube texture in high-purity silicon iron were investigated by me-tallographic and X-ray methods. The results show that the structure consists of relatively perfect grains of average diameter between one and two times the sheet thickness ad that the texture has a moderately strong (110) [001] component and a weak (100) [001] component. The results also indicate that matrix stability results from the two-dimensional nuture of the graitzs and that cube-orzented nuclei are neither more Perfect nor larger grains than other matrix grains but have a preferred [001] direction in the rolling direction and have a more effective driving force for growth than other grains because of a low (100) surface energy. THE structures and textures of fine-grained rnatrices determine to a large extent the kinds of secondary recrystallization textures that form on annealing. The understanding of secondary recrystallization processes therefore depends on adequate information about the initial matrices. Matrices usually have three characteristics: 1) they consist of fine-grained primary recrystallization structures, 2) the fine-grained structures are stable toward normal grain growth, and 3) they contain secondary recrystallization nuclei. Stability toward normal grain growth may be due to either a strong single orientation texture (texture inhibition)&apos; or a dispersed second phase (dispersed phase inhibition).2"4 If normal grain growth is not inhibited by either of these two factors, it nevertheless stops when the average grain size is between one and two times the sheet thick- ness.5 This thickness effect satisfies one of the characteristics of a matrix for secondary recrystallization. Its importance in the development of the cube texture in high-purity silicon iron by secondary recrystallization was pointed out by the authors in a recent paper on tertiary recrystallization7 and will be discussed further in the present paper. Assmus, Detert, and he8 have provided some information on a matrix for secondary recrystallization to the cube texture in silicon iron. They found a (110)[001] or Goss texture with enough spread about the rolling direction to include a small amount of the (100)[00l] orientation. The distribution of the [00l] directions was strongest parallel to the rolling direction for both (100) primaries and cube secondaries. These authors found no correlation between size of a matrix grain and orientation and concluded that some property other than size must be the distinguishing characteristic of the cube-oriented nucleus. No consideration was given, it

Jan 1, 1961

By Robin O. Williams

AN investigation has been made of the Ni-Cr system for the purpose of elucidating certain points, namely the nature of aging in both terminal solid solutions and the nature of the phase diagram. Information pertaining to solubilities and precipitation has been obtained. Experimentation Five alloys, Table I, were arc melted in a cold copper crucible using electrolytic chromium and car-bony1 nickel, both dry hydrogen treated. These 100 g buttons were homogenized 24 hr at 1300°C in dry hydrogen and air cooled. Powders were prepared by filing or pulverizing and subsequent heat treatment was done in vacuum or helium using titanium chips as a getter. Powder of —80 mesh was filed from the 60 pct Ni alloy quenched from 1000°C and was sealed in silica under vacuum using a 250 °C outgassing. After aging as indicated in Table I1 the lattice parameters were measured on the quenched samples using the standard cos" 6 extrapolation. These parameters are considered accurate to roughly 0.0001A. In all cases chromium lines of 2.8812 ± 0.0005Å at 30°C were found. Drastic quenching from sufficiently high temperatures produced very sharp body-centered-cubic lines in the first four alloys without indications of transformations. Temperatures to 1250°C were used. Solid samples less than 1/16 in. thick were quenched in water without transformation and the powders could be adequately quenched in small helium filled thin wall silica tubing using a water quench. For those powder samples which were quenched from the two phase field the relative intensity of the body-centered-cubic lines and the face-centered-cubic lines were estimated and extrapolated to give the indicated solubility data in Fig. 1. The data for the two higher alloys were somewhat limited, the plotted points being the lowest temperature where no nickel phase was found. Neither filing, abrading, pulverizing, nor cooling to —190°C produced any new diffraction lines for solid samples quenched from the single phase region, nor did the character of the body-centered-cubic lines change Single phase body-centered-cubic powders likewise did not change on cooling to —190°C. Also, samples which had some precipitation due to inadequate quenching showed no additional changes under these conditions. The first change apparent by X-ray diffraction form samples quenched almost fast enough to prevent precipitation was the diffuseness of the body-centered-cubic lines, particularly on the low angle side, For slower cooling rates the diffuse face-centered-cubic lines appeared. Work on the large grained castings showed profuse streaking through some of the Laue spots while oscillating patterns showed broad body-centered-cubic and face-cen-tered-cubic lines as well as some new lines. For the 23.6 pct Ni alloy the new lines corresponded to 2.16, 1.96, and 1.86A and were more similar in character to the face-centered-cubic lines than the body-centered-cubic lines. Samples which were air cooled gave only face-centered-cubic and body-centered-cubic lines which were still broad. One pattern indicated that face-centered-cubic (111) plane was parallel to a body-centered-cubic (110) plane. For those samples which were examined by light microscopy there were details which were not resolved. However, varied and beautiful structures were obtained. Fig. 2 is of an alloy quenched in a helium filled silica tube from the single phase region and shows particles associated apparently with dislocations which are arranged in low angle boundaries. Finer, general precipitation has also taken place within the grains. Figs. 3 to 5 show the variety of structures produced in these alloys on continuous cooling. It appears that there are four distinct modes of precipitation as evidenced by these, figures. Annealing these structures at higher tem-peratures in the two phase field gives structures as shown in Fig. 6, which shows nickel plates in the chromium matrix which reprecipitated nickel on a much finer scale of the final quench. Lower annealing temperatures and shorter times naturally give finer plates of the nickel-rich phase. Samples of the first four alloys were annealed for appreciable times between 900º and 1250°C and gave structures like Fig. 6. The relative amounts of the two phases were measured and extrapolated to give solubility data as indicated in Fig. 1. The point at 1250°C was deduced from data of Oxx.1 These and most of the other samples were checked for ferromagnetism but none was apparent. In fact, it appeared that the magnetic susceptibilities were not more than three times that for paramagnetic chromium. Discussion In Fig. 1 it is seen that the solubility of nickel in chromium can be represented by a slightly curved line on the usual log X vs 1/T plot, These data are believed to be accurate to roughly 5 to 10º. There is only fair agreement with the data of Taylor and

Jan 1, 1958

By O. J. C. Runnals

The intermetallic compounds NpAl2, NpAl3, and NpAl have been prepared, and examined by X-ray diffraction methods. The compounds are isostructural with the corresponding U-Al compounds. NpAl3 is face-centered cubic with a = 7.785A and has the MgCu2 structure. NpAl is simple cubic with a = 4.2624 and has the AuCU3 structure. NpAl4 is body-centered orthorhombic with a = 4.428, b = 6.268, and c = 13.71A. The published description for the atomic positions in UAl, applies also to NpAl4 THE U-Al system has been examined by Gordon and Kaufmann.1 They identified the following intermetallic compounds: UAI2, UAl3, and a third, tentatively identified as UAl5. A structure analysis of the latter compound by Borie2 proved that the formula UAl4 was more consistent with the X-ray data. The crystal structures of UAl2 and UA have been reported by Rundle and Wilson.3 UAl2 was found to be isostructural with MgCu. The atomic positions in the simple cubic UA1, cell were found similar to those in the AuCu3 structure. Three analogous compounds exist in the binary system Np-Al. X-ray data for the compounds NpAl2, NpAl3, and NpAl4 are reported below. The neptunium used in the investigation was supplied through the courtesy of the Argonne National Laboratory as neptunium (V) nitrate. It was stated to have a radioactive content of 99.25 pct Np237. The impurity limits had been established by a spectrographic analysis given in Table I. Any titanium, boron, or bismuth impurity should be effectively removed during the fluorination of NpO2 to NpF4, and sodium, lithium, magnesium or strontium during the alloying procedure. The oxalate ignition technique, described by Westrum for the preparation of finely-divided reactive PuO2, was used.The neptunium (V) nitrate solution, containing 100 mg Np, was evaporated to dryness on oxalic acid crystals. The resulting oxalate was calcined to NpO, by heating in platinum at 650°C for 2 hr. An equimolar mixture of anhydrous hydrogen fluoride and purified hydrogen was passed over the NpO2 for 2 hr at 500°C. According to Fried and Davidson" the above fluorination conditions should produce the purple-black fluoride, NpF3 However, the light-green product showed only NpF4 lines on an X-ray diffraction pattern and contained only an estimated 5 pct of finely dispersed black NpF3 particles on microscopic examination. NpAl3: An intimate mixture of 50 mg of neptunium fluoride and aluminum powder (99.99 pct pure, —28 to $60 mesh) was heated to 900°C in a BeO crucible in vacuum by a tungsten coil for 2 hr, to allow the following reaction to proceed: NPF4 + 7Al + NpAl, + 4AlF. [1] The formation and sublimation of aluminum mono-fluoride in this system was verified from an X-ray diffraction analysis of the sublimate. The diffraction pattern was similar to one obtained in the aluminum reduction of UF4 to UF3,6 showing both Al and AlF3 lines. The resulting alloy was sintered at 1100°C for 1 hr. A powdered specimen of the crystalline product was sealed in a thin-walled quartz capillary for X-ray examination. The photograph was taken on a 14.32 cm General Electric powder diffraction camera, using filtered copper radiation. The films were calibrated in terms of a NaCl standard pattern. The wavelengths used in the calculations were 1.5418A for Cu K and 1.5405A for Cu K The powder diffraction pattern showed that NpAl is simple cubic with a = 4.262 % 0.005A, and is isostructural with UA13 where a = 4.27A1 or a =

Jan 1, 1954

By R. A. Swalin, A. H. Geisler

THIS study represents an investigation of the effect of annealing temperature on the texture of drawn molybdenum, iron, and an iron alloy containing 14 pct Al. The effect of temperature on annealing textures has not been widely investigated in the past. One of the obstacles in making such a study using usual X-ray diffraction techniques results from the

Jan 1, 1957

By A. U. Seybolt

DURING the course of experiments involving oxygen equilibrations with a high-purity Pd-5 at. pct Rh alloy, the appearance of a subscale was noted. Most of the heat treatments in a pure oxygen atmosphere were performed at 900°C. The presence of the subscale was noted when the oxygen partial pressure was in excess of approximately 95 mm, up to 1 atm, the highest pressure used. According to available thermodynamic information&apos; on the free energy of formation of Rh2O3 (the only reliably reported solid oxide of rhodium), this oxide should not be stable under these conditions, nor, of course, any oxide of palladium. Extraction of the subscale from the matrix was affected by treatment with aqua regia, and the resulting X-ray diffraction powder pattern is shown in Table I. This pattern is not that of Rh2O3, nor that of any known rhodium or palladium oxide. It can be indexed on a hexagonal lattice with a. = 5.22Å and co = 6.0Å. In addition to this unknown material, there was a weak Rh2O3 pattern. An X-ray fluorescence analysis of the powder gave 3214 palladium counts per sec and 5381 rhodium counts per sec, thus indicating the likelihood of a double oxide of palladium and rhodium. In view of the fact that the above result was obtained on a single sample, it is perhaps best not to insist upon the above ratio of about 0.6, but possibly to tentatively assume 0.5 or 1/1. The small amount of Rh2O3 in the X-ray pattern might have occurred on cooling, and it seems possible that the double oxide, below some temperature level, is not as stable as Rh2O3. To examine this point, some of the extracted double oxide was heated on a sheet of pure palladium in air at 900°C, and allowed to furnace-cool over a period of several hours. The X-ray diffraction pattern of the powder showed approximately the same intensity of Rh2O3 and the "hexagonal" oxide as before, but, in addition, a rather faint pattern of another crystalline species made its appearance. This finding again suggests partial transformation of the major (double) oxide to other oxides on cooling from 900°C. Application of the phase rule shows that only one equilibrium oxide (subscale) could have been present at temperature. Vacuum-fusion, oxygen analysis of the extracted subscale showed 7.7 ± 0.7 pct O. Combining this information with that of the X-ray fluorescence analysis suggests the formula PdRhO. This compound should have an oxygen content of 7.07 pct, which is within the range of error of the oxygen analysis. However, until a more careful stoichiometric study is made, it is suggested that the formula be written

Jan 1, 1965