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By R. K. Datta, T. S. Davis

YVO4:EU, excited under 3650A radiation, shows a marked increase in total brightness with in~rease in temperature. At 25°C the response to 3650A radiation is about 48 pct of its maximum response which occurs at about 350°C, Fig. 1. In an attempt to explain the phenomenon, one of the present authors' (R.K.D.) investigated the diffuse reflectance spectra of the phosphor at different temperatures (up to -150°C) and was unable to observe any significant change to which the increased brightness could be reasonably ascribed. Since then diffuse reflectance spectra at elevated temperatures have been obtained in this laboratory using an improved device. A significant decrease in the diffuse reflectance of a phosphor in the ultraviolet region—especially in the longer wavelength region—at -300°C has been observed. The purpose of this note is to describe the device used for high-temperature reflectance measurements and to explain the increased brightness of YVO4:Eu phosphor at elevated temperatures under 3650A excitation. Experimental. YVO4 and YVO4:Eu samples were prepared as previously described.' The elevated-temperature reflectance spectra were obtained with a Cary 14 spectrophotometer equipped with a diffuse reflectance accessory and a ring collector. CaF2 was used as the standard. The cell used

Jan 1, 1969

By Fritz Wald, Richard W. Stormont

lHE general constitution of a number of metal-lead telluride and metal-tin telluride systems has recently been studied in an effort designed to furnish background information for the study of degradation mechanisms on junctions between thermoelectric power generation materials and metals.1"4 This paper reports further results of that effort. It was found that cobalt-lead telluride constitutes a stable pseudobinary section through the ternary Co-Pb-Te system. Materials used in the study were lead and tellurium of semiconductor-grade purity (American Smelting and Refining Corp., 99.999+ pet). Cobalt (Johnson Matthey & Co., 99.999 pet purity) was used in the form of slices cut from rods of 5 mm diam. Twenty- gram charges of the alloys were melted in evacuated quartz ampoules. Thermal analysis, as described previously,2'3 and metallographic and X-ray diffraction methods (Debye-Scherrer photographs) were used as investigative tools. Substantial difficulties were encountered in polishing, as reported previously for the lead telluride-iron system.3 A number of different etches were used, including dilute aqua regia, Murakami solution, an etch containing copper nitrate,3 and HC1-HNO3-acetic acid-water mixtures. None of these etches gave consistent results over the complete range of cobalt concentrations. On the alloys containing bulk cobalt in the form of primary

Jan 1, 1969

By J. H. Swisher

HIGH-temperature anneals in wet hydrogen are widely used in research as a technique for decarburiz-ing Fe-C alloys. This technique is also used commercially in processing low-carbon steels for magnetic applications. The results of some calculations to be presented show that for temperatures up to 1100°C there is a critical temperature for maximizing the decarburization rate of alloys containing about 0.1 pct C. The low-temperature portion of the iron side of the Fe-C phase diagram1 is reproduced in Fig. 1. Preliminary calculations show that the critical temperature is between 727" and 905°C. In this range, the alloy contains two phases during heat treatment, ferrite and austenite. Decarburization therefore occurs by a process termed "diffusion accompanied by a phase change".' For intermediate stages of decarburization, the carbon concentration profile in a flat plate is shown in Fig. 2. The carbon content increases linearly from zero at the surface to a value, cB , at the two-phase boundary. cB is known from the phase diagram, see Fig. 1. At the interface where x = 5, the carbon content increases to ci, the initial concentration in the alloy. smith3 has derived an equation which describes the rate of movement of the boundary. With a rearrange-

Jan 1, 1969

By L. S. Castleman, R. K. Hotzler

We are currently studying the effects on recrys-tallization of impurities diffused into dispersion-hardened alloys. Our interest in this phenomenon was originally aroused by the observation that the recrystallization temperature range of tungsten "doped" with alumina and silica, or with thoria, is lowered drastically if nickel is plated onto the tungsten prior to heat treatment.' In this note, we report a similar effect that sulfur has on the recrystallization behavior of thoriated nickel. The experimental procedure for this exploratory phase of the investigation has consisted simply in heating commercially obtained stress-relieved samples of thoriated nickel for varying temperatures and times in sealed capsules containing air and small quantities of sulfur. The samples contain 2.4 vol pct thoria and initially less than 18 ppm S by weight; they are prepared either from 0.5-in.-ciiam rod stock or from 0.092-in. sheet and are in the "as-received" (stress-relieved) condition prior to exposure. In an atmosphere free of sulfur, such samples do not show evidence of recrystallization after being annealed for 1 hr at a temperature of 2500°F (1372C).2 The photomicrograph in Fig. 1 shows the microstructure of one of our samples annealed for 75 hr at 1000° C (1832°F) in a sulfur-free capsule. The grain structure is hardly evident (if at all) at 465 times magnification. In contrast, the photomicrograph of Fig. 2 shows the recrystallization that has taken place in a sample exposed to sulfur for 5 hr at 1000°C (1832°F). A nickel sulfide phase is visible at the grain boundaries of the light-appearing grains. We have also observed recrystallization to occur in a sample annealed at 600°C (1112°F) for 25 hr. This temperature is below the 637°C (1178°F) eutectic in the Ni-S system. In the latter case, no nickel sulfide phase is evident in the microstructure. Moreover, we have noticed the occur-

Jan 1, 1969

By H. J. Engell, W. Frank, A. Seeger

SWISHER and ~urkdogan' have determined the solubility of oxygen in a iron. They found it to lie between 7 and 10.5 at.-ppm at 881°C. Using earlier work on the permeability of oxygen in bcc iron,' they arrived at the following expression for the diffusion coefficient of oxygen in bcc iron (k = Boltzmann's constant, T = absolute temperature): where The present authors3 have estimated the activation energy QD for the diffusion of oxygen in bcc iron in two different ways from various experimental data.2'4"6 In the first method QD + QS (QS = heat of solution for oxygen in bcc iron in thermodynamic equilibrium with solid FeO) was determined either from data on the reduction of FeO with hydrogen4 or from measurements of the internal oxidation of silicon in a iron.5 Using an estimate of QS from investigations of the oxygen solubility in 6 iron2 (in thermodynamic equilibrium with molten FeO) Q = 0.97 ev or Q~ = 1.06 ev were obtained. From the magnitude of these values it was concluded that oxygen migrates interstitially in bcc iron and that consequently the activation energy QD for diffusion of oxygen has to be identified with the migration energy E~ of the oxygen atoms. Therefore, for a second estimate of QD from the diffusion coefficient of oxygen in 6 iron at 1450" ~,~ we used the theoretical expression:3 (a = length of elementary cube edge, m = mass of interstitially diffusing atom, sM = migration entropy), applicable to diffusion via the octahedral interstices in bcc lattices. Taking sM = 3.8 k (migration entropy of carbon in a iron), one gets Q = 0.90 ev. Hence, in Ref. 3 Q = (0.98 *0.1) ev was proposed as a plausible value for the diffusion energy of oxygen in bcc iron. sM + 9 (9 = solution entropy for oxygen in bcc iron) can be determined from permeability measurements.4 Using the above-mentioned estimate for QS , the following expression for the solubility c (atomic concentration) of oxygen (in thermodynamic equilibrium with solid FeO) in bcc iron was derived: From [4] the solubility of oxygen at 881°C in a iron is calculated to lie between 0.6 and 12 at.-ppm. We see that the solubility determined by Swisher and

Jan 1, 1969

By J. H. Bechtold, R. Kossowsky

1 HE superplastic behavior of the eutectoid A1-78 wt pct Zn alloy has been thoroughly investigated by Back-ofen et al.' The superplastic elongations and the marked resistance to necking were rationalized in terms of high strain rate sensitivity. In a subsequent paper2 superplastic behavior was formulated to show Nabarro-Herring diffusional creep as rate controlling at low strain rates, giving way to a dislocation climb process at higher strain rates. In a paper devoted to an interpretation of superplasticity in two-phase alloys, Packer and sherby3 have included the results of an examination of the structure of an Al-Zn eutectoid specimen before and after superplastic deformation. No significant change in grain size or directionality was observed in the deformed microstructures. This one observation led the authors3 to suggest that con- tinuous recrystallization or grain boundary migration was responsible for superplasticity. The purpose of this note is to report our observations on the superplastic behavior of the Al-Zn eutectoid alloy which differ in certain respects from works previously reported. Following Hayden et al., the results are discussed in terms of dislocation climb as the important factor during superplastic deformation. A heat of nominally high (99.995) purity 22 wt pct A1-78 wt pct Zn was induction-melted and cast into a 0.5 by 6 by 12 in. slab. The slab was heated to 350°C and rolled to 1/8-in.-thick plate. The plate was then cold-rolled to 0.040-in. thickness, annealed at 35OaC, and rolled to the final thickness of 0.020 in.* Speci-

Jan 1, 1969

By A. U. Seybolt

DURING the course of an investigation of hot corrosion of nickel-base superalloys (combination oxidation-sulfidation attack at high temperature), it was considered possible that sulfur might gain entrance to the alloy in part, at least, by diffusion through the scale. Cr203 is nearly always observed as a prominent component of the oxide scale, and hence some experiments were carried out to examine the tracer diffusion of sulfur through Cr203 at 1000° C in the upper temperature range experienced by jet engine blades and vanes. Some hot-pressed Cr203 discs of quite high density were available from an earlier investigation1 on the rate of crf3 migration through Cr203. The Cr203 was 99.3 pct pure and contained -0.06 pct Fe as the largest metallic impurity. Additional data is given in Ref. 1. In this earlier work it was found that the rate of cation diffusion was independent of the atmosphere of thermal equilibration when using nitrogen, argon, or air, and also that the electrical conductivity of the hot-pressed Cr203 compacts was likewise independent of atmosphere in this range, thus indicating that the de-

Jan 1, 1969

By J. Pinto, F. Galasso

THE current emphasis in preparing boron fibers by reduction of gaseous boron compounds on a resistively heated metal wire substrate has renewed interest in the borides of those metals which have relatively high melting points and are available as fine wires. A knowledge of the structures and properties of the borides, which are formed when boron diffuses into the metal core during boron deposition, can be of assistance in the understanding of the boron fiber formation process and the fiber properties. Many of these borides are well-known and their properties have been measured. However, when an unidentified boride is found in the core, it may be difficult to establish its composition because of the small amount of material available, the preferred orientation effects on the reflections in its X-ray pattern, and the possible overlap of X-ray reflections if several borides are present in the core. For example. the proper indexing of the X-ray pattern of WB4, which was formed in the tungsten substrate core during boron fiber formation, was accomplished only after small single crystals of this boride were grown and X-ray precession investigations were conducted.' This note presents the results of a study of the phases formed in the core when tungsten, tantalum, and molybdenum metal wires were used as substrates in the boron fiber preparation process with particular emphasis on the identification and characterization of a higher boride of molybdenum analogous to WB,. Boron was deposited on resistively heated stationary 0.0012-in.-diam tantalum, tungsten, and molybdenum wires at 1050°C for various times up to 60 sec using boron trichloride and hydrogen as the reactant gases. After 60 sec of boron deposition the fibers were approximately 0.006 in. in diam. Examination of photomicrographs of fiber cross sections showed that the boron had diffused nearly to the center of the tungsten and molybdenum cores in 15 and 30 sec, respectively, and only halfway to the center of the tantalum core in 60 sec. X-ray diffraction photographs of the fibers indicated that it was also after 15 and 30 sec deposition times that the tungsten and molybdenum metal reflections, respectively, had disappeared from the X-ray patterns of the fibers. The patterns of the boron fibers produced using tantalum wire as a substrate showed that amorphous boron, TaB2, and tantalum metal were present after a few seconds deposition time and remained even after deposition times of 60 sec. Until a deposition time of 15 sec was reached, the tungsten substrate fibers contained amorphous boron,273 6WB, W2B5, and WB4 as well as tungsten metal, while the molybdenum substrate fibers contained amorphous boron, MoBa, Mo2B5, and molybdenum metal for deposition times up to 30 sec. Just before the molybdenum metal pattern disappeared, a pattern similar to that of WB, appeared, suggesting that a phase, MOB,, isomorphous with WB,, was present in the fiber. This same pattern was obtained from the product formed by heating a mixture of molybdenum metal and excess boron powder in a boron nitride crucible at 1960°C in an argon atmosphere. As was the case with the WBn pattern, this pattern could best be indexed on the basis of a hexagonal unit cell rather than the tetragonal unit cell Chrktien and Helgorsky reported for ~0~4,~ see Table I. The unit cell parameters for MoB4 were calculated to be a, = 5.214A, co = 6.358A. Assuming the space group P63/mmc and positions5 2M01 in 2b and 2MoII in 2c found for tungsten in WB~,' a logical structure for MOB, was determined using geometrical considerations to place the boron

Jan 1, 1969

By R. T. DeHoff

A theoretical development is presented which reformulates Fick's first law for diffusion in the solid state. The diffusion flux of component i in a multi-component system, Ji, is related to its local concentration, ci, and local jump frequency, ri : where a is a geometric factor and d is the jump distance. The product, ciri , is defined as the local concentration of atomic jumps for component i. The analog to Fick's second law is also derived. A solution to this equation is presented, which permits the experimental determination of the variation of atom jump frequency with composition in multicomponent systems. HISTORICALLY, the description of diffusion in the solid state has been presumed to be best approached as an application of more general diffusion laws, known as the phenomenological equations. These equations relate the flux, Ji, of the various components, expressed in atoms, grams, or volume, to the driving force involved, expressed as either a compositional or chemical potential gradient, sumption that the flux is simply proportional to the driving force is the foundation of this approach. The phenomenological equations take the form: where the concentration gradients are assumed to be the driving force, and: if the chemical potential gradient is taken as the driving force. The coefficients Dij in Eq. [1.] are the "diffusion coefficients"; the elements of the corresponding matrix in Eq. [2], the Mij, are called the "mobilities". Eqs. [I] and [2] may be considered to be definitions of these phenomenological coefficients. A formidable body of literature has been generated about these equations; this literature dates back to their original formulation for the simplest case of binary diffusion in a fluid, by Adolf Fick, in 1855.' This description has been shown to be self-consistent. However, the "constants of proportionality", the Dij or ,Mij, are not constant: they vary with composition in all but the simplest systems. Even in the case of tracer diffusion, wherein it can be shown that the diffusion coefficient is constant, the mobility, which is considered in irreversible thermodynamics to be the more physically meaningful quantity, varies with the concentration of the tracer involved.' In more complex systems, it is necessary to evaluate the entire matrix of phenomenological coefficients, as a function of composition, in order to describe diffusion locally. Further, in order to determine this matrix experimentally, it is necessary to produce diffusion couples that have different sequences of compositions; the matrix may be evaluated only at points where these "composition paths" cross.* Finally, and perhaps most

Jan 1, 1969

By Klaus Schwerdtfeger, Leo Zwell

The equilibrium between Ir-Fe or Rh-Fe alloys, iron oxide (wüstite or magnetite), and CO2-CO atmospheres has been determined at 1200°C. The data are used to derive the activities in these binary solid solutions. Both systems show negative deviations from Raoult's law. The lattice parameters are given for the investigated Ir-Fe and Rh-Fe alloys. IRIDIUM and iron form a continuous series of fcc solid solutions at elevated temperatures.' Rhodium-rich Rh- Fe alloys have fcc structure.' In the medium concentration range an ordered bcc phase is stable at temperatures up to about 1300°C. Phase relations in iron-rich alloys are not well-known. No thermody-namic data are available for these alloys. EXPERIMENTAL METHOD The experimental method used was to measure the equilibria between a gas phase of known CO2/C0 ratio, the alloy, and iron oxide (wüstite or magnetite). In one series of experiments the alloys of known composition were heated in CO 2-CO gas mixtures. After treatment (usually 1 day) the sample was quenched to room temperature and its surface examined visually to determine whether an oxide tarnish had formed. The procedure was repeated at slightly higher CO 2/CO ratios until the CO 2/CO ratio of incipient oxidation was found. Subsequently, the CO 2/C0 ratio was lowered again in small increments until the tarnish was reduced. In other experiments mixtures of alloy and iron oxide powders were pressed into pellets and equilibrated with the CO2-CO gas phase. In order to ensure that equilibrium was attained, two specimens with different starting iron content were heated side by side; in most cases, equilibrium was approached in one pellet by reduction of iron oxide and in the other pellet by oxidation of metallic iron. The sample was quenched to room temperature, and the composition of the equilibrated alloy was determined by X-ray measurements of lattice parameters and comparison of these values with calibration curves obtained from alloys of known composition. The oxides present in the specimens were identified by comparison of their diffraction patterns with those in the ASTM Card File. It may be expected from the noble character of iridium and rhodium that no appreciable amount of iridium or rhodium is dissolved in wiistite and magnetite under the present experimental conditions. The activity of iron in the alloy is then equal to that established in the iron oxide by the COrCO atmosphere. The activities of iron in wüstite and magnetite, as a function of oxygen pressure, were taken from the work of Darken and Gurry,

Jan 1, 1969

By David R. Poirier

Activity data of carbon as a function of both temperature and composition throughout the stable austenite range is correlated by mearts of an equation derived from a quasi-chemical model. The carbon activity data of austmite for temperatures between 800° and 1200°C are utilized in conjunction with the activity of carbon calculated for the y solidus using the activity of carbon in liquid iron and published austenite-liquid equilibria. The results agree very well with Chip-man's correlation; however, a small difference in the activity of carbon in the high-temperature range of the austenite field is evident. Excellent agreement is found for the heat of solution of graphite in infinitely dilute austenite; from this study the value is 10,550 cal as compared with Chipman's value of 10,680 cal. AS part of a program to study microsegregation in dendritic solidification of ternary Fe-C-Cr alloys, it was desirable to be able to describe the equilibria between austenite and liquid iron in Fe-C-Cr alloys. In this regard, it was necessary to correlate existing data on the activity of carbon in Fe-C austenite as a function of both temperature and composition. At that time, Chipman's analysis1 of the thermodynamics of binary Fe-C austenite was not available. It will be shown that this study and Chipman's study agree rather well throughout the stable austenite range of temperature and composition; however, some small differences appear at temperatures greater than the eutectic temperature. Benz and Elliott 2 presented isoactivity lines for austenite superimposed on their revised Fe-C phase diagram. Using an expression from Darken and Gury 3 representing Smith's4 activity data between 800" and 1000°C, they found that the activities extrapolated above 1000°C to the solidus did not agree with the activities determined from the corresponding liquidus compositions. It is the purpose of the following argument to reconcile carbon activity data of austenite with the activity in liquid Fe-C alloys as determined by Rist and Chipman. 5 In addition, a simple analytical expression is sought for computational convenience. ACTIVITY DATA OF CARBON IN ZRON Fig. 1 shows the activity of carbon in Fe-C austenite as determined by Smith, 4 Schenck and Kaiser, 6 Scheil et a1.,7 and Bungardt et al.' The lines are merely drawn to separate the data into the respective isotherms. These data are inadequate to determine the activity of carbon at temperatures greater than 1200°C. The activity coefficient in Fe-C liquid alloys was assumed by Rist and chipmans to obey the following

Jan 1, 1969

By R. A. Corley, W. R. Wilcox, J. R. Teviotdale

Chemical vapor deposition of hafnium carbide yielded whiskers, needles, dendrites, faceted crystals, and adherent coatings. The gas stream compositiom and the mass transfer conditions determined the habit of the deposit. The deposits were obtained at temperatures ranging from 1100" to 1800°C. HAFNIUM carbide has the highest melting point of any binary compound; therefore, its various potential applications are a subject of vital interest to the aerospace industry. The experiments described herein were performed to investigate the chemical vapor deposition of hafnium carbide with particular interest being placed upon the possible production of high-strength single-crystal whiskers for composite materials. In 1931 Moers 1 used a gaseous mixture of HfC14, Hz, and toluene to vapor deposit crystalline hafnium carbide on a tungsten filament heated to 2400°to 2800°C. More recently Lepie 2 deposited hafnium carbide on graphite using HfC14 and methane in a helium gas carrier. The pyrolytic depositions described here were accomplished in graphite tubes by using various gas mixtures and dopants. The resulting crystal habits included whiskers, needles, needle dendrites, bulbous dendrites, faceted crystals, and smooth, adherent poly-crystalline layers. EXPERIMENTAL The depositions were carried out in an induction-heated graphite tube, 1.2 cm ID, which was contained in a vertical 9-cm-ID quartz tube. (A more detailed account of the experimental procedures and results is given in Ref. 3.) Refractory oxide fiber and tubes and graphite felt were utilized jointly and singly for therma1 insulation. A typical temperature distribution is shown in Fig. 1. The reactant gases were introduced at the top and removed at the bottom of the tube. Table I summarizes the experimental conditions and results. Many deposition habits were obtained. X-ray analyses showed that they possessed the hafnium carbide structure. Almost invariably these formed well above the point of maximum temperature in the graphite tube. The habit depended strongly on the gas composition. In a series of runs (e.g., run A) using HfC14 and toluene in H 2, hafnium carbide coatings, Fig. 2, were reproducibly obtained at the position where the tube wall was 1400°C, and bulbous dendrites, Fig. 3, were

Jan 1, 1969

By F. A. Veer, W. G. Burgers, B. H. Kolster

Starting-- from Cu-Si diffusion couples a study of diffusion in the intermetallic compound Cu3Si of the Cu-Si system has been made. Mmker experiments showed copper to be the diffusing element. From the rate of growth of the Cu3Si phase diffusion coefficients were derived. The activation energy for diffusion is 18.6 kcal per mole. The couples show some interesting microscopic features, for which a tentative explanation is given. THE synthesis of dimethyldichlorosilane, (CH3)2SiC12, an important compound in the manufacture of methyl-silicones, takes place at the surface of a thin Cu3Si layer deposited on a mass of silicon particles."' By passing CH3C1 vapor at about 350°C, silicon atoms are consumed from Cu3Si in forming the volatile silane molecules, thus leaving copper atoms at the surface. It is well-known that copper acts as a poison for the above-mentioned reaction by catalyzing the dissociation of methylchloride.' However, no poisonous effect is observed, at least not before most of the silicon from the particles is converted into silane.3 This would be understandable, if either the copper atoms diffuse through the Cu3Si deposit to the underlying silicon or silicon atoms diffuse in the reverse direction to the copper, both processes resulting in the formation of new Cu3Si and so ensuring the proceeding of the reaction. In this paper experiments are described, demonstrating copper to be the diffusing element. Also a very low activation energy for the diffusion is observed. EXPERIMENTAL The silicon used contained 1 ppm Mg and 1 ppm Cu; the copper was spectroscopically pure (Fe: 2 ppm; Ag, Mg, Si: 1 ppm). The copper and silicon samples were prepared in the form of blocks of approximately 10 by 10 by 5 mm with two parallel sides by spark-machining. The blocks were ground on emery paper (grit 600), etched (copper with nitric acid, silicon with a 4:l nitric acid:hydrofluoric acid mixture), and cleaned with alcohol. As the brittleness of the silicon did not allow a welding procedure to prepare the diffusion couples, the copper and silicon blocks were pressed together in a steel clamp. The pressure exerted by the clamp brought about contact between the parts of the couple and so ensured proceeding of the diffusion. The couples were heated in a vacuum furnace (about 10"5 Torr). The temperature was stabilized within 1 pct. After a heat treatment a section parallel to the direction of diffusion was examined in the microscope and in the X-ray scanning microanalyzer. To determine whether copper or silicon is the diffusing element marker experiments were carried out using tungsten wires with a 20-p diam. EXPERIMENTAL RESULTS Figs. 1, 2, 3, and 4 give micrographs of diffusion zones of Cu/Si couples. Analysis by the electron mi-croprobe of the Cu/Si samples after a definite heat treatment revealed the existence of only one intermetallic phase as can be seen from the line scan shown in Fig. 5. From the X-ray diffraction pattern it could be deduced that this phase was CU 3 Si.4 Even when diffusion zones of considerable width (up to 600 p) were obtained, no other phases occurring in the Cu-Si system could be detected, neither by the electron microprobe nor by X-ray diffraction analysis. The optical anisotropy of the Cu3Si phase made it possible to observe the columnar shape of the crystal-

Jan 1, 1969

By P. R. Sahm, T. V. Pruss, D. A. Gandolfo

Cb 3 Sn powders were hot-pressed to estahlish densi-fication conditions and assess the possible use of such compacts in multiphase structures with ceramic or magnetic inclusions. Superconducting transition temperatures, Tc, were measured as a function of powder particle size, pressing temperature, and second-phase admixtures. The highest transition temperatures were found in coarse powder (5 to 500 u) compacts and were only weakly depended on pressing temperatures up to 1200°C. Fine powders (below 5 p), however, both single-phase CbsSn and Cb3 Sn-composites, showed a stronger dependence on hot-pressing temperatures. While Al2 O3 phase admixtures did not affect T, much more, a Pronounced T, degradation was observed upon the addition of ferrimagnetic Fe2 Mno. 5 Zno.5 O4 powders. Likewise, critical current densities, Jc, at 4.2° K were lowered appreciably in the ferrite doped samples, whereas the neutral A1203 inclusiow gave slightly improved Jc values. MULTIPHASE structures in electronically active materials have recently gained in interest as pointed out by Galasso in a review article.' In superconductors the most widely reported group are eutectic alloys which have been mostly investigated with respect to the proximity effect.2"4 In addition, "artificial eu-tectics", for example in the form of mercury-vycor glass sponge5 or fine niobium wires imbedded in a copper matrix,= have been prepared to attain higher critical fields and critical current densities. The idea was to enhance flux pinning phenomena by second-phase inclusions or ho1es. 7 Flux pinning should also be possible by the introduction of insulator inclusions into a superconducting matrix. Ceramic-metal combinations are most easily produced by hot pressing (= pressure sintering), as it permits an almost unlimited selection of material combinations. Cb 3 Sn has been prepared by vapor phase growths or in the form of thin films. Large compacts must be sintered,1° however, and normally present difficulties. At temperatures below 1350°C insufficient densities are obtained and at higher temperatures the loss of tin due to dissociation upsets the stoichiometry. Hot pressing is a natural approach to circumvent the problems, since one can obtain satisfactory densities despite low sintering temperatures. This work was mostly concerned with establishing conditions to hot press Cb3 Sn and Cb3 Sn multiphase structures (= composites), because no data are presently available, and to evaluate these with respect to their transition temperatures. However, a few measurements on critical current densities were also carried out, in particular to assess the value of ferrimagnetic inclusions. I) EXPERIMENTAL PROCEDURE The experimental procedure involved the preparation of feed material and powders, hot pressing, and evaluation of the resulting ingots. As no attempts were made to synthesize Cb3Sn from the elements during hot pressing, feed material had to be produced. For this purpose, a stoichiometric Cb-Sn powder mixture was compacted into a 3-cm-diam ingot (80,000 psi) and then inserted into a quartz tube and evacuated. Rf heating was employed. Above the tin melting point (230°C) liquid tin was forced out of the ingot, but was pulled back by capillary action after approximately 0.5 hr of continuous pumping at 700°C. Thus, it appears that evacuation at this temperature caused desorption of impurity gas creating wetting surfaces which, later on, favored alloying at relatively low temperatures. After a presintering period of 17 hr at 800°C, the quartz tube was tipped off and sealed into another such larger-diameter tube which, in turn, was connected to a pump system. This configuration permitted a temperature treatment at 1400°C, carried out for 65 hr, without collapsing of the glass walls or unfavorable chemical interaction of Cb3Sn with the quartz. The resulting material was

Jan 1, 1969

By Robert D. Pehlke, Weldon L. Daines

The reduction of manganese oxide from a basic slag by silicon dissolved in liquid iron at steelmaking temperatures was studied to determine the rate-controlling step for the process. The experiments were carried out under an argon atmosphere in a resistance-heated vertical-tube furnace. The two liquid phases, slag and metal, were held in zirconia crucibles. Sampling and chemical analysis of the slag phase led to time-concentration curves for the system. Results obtained by varying parameters such as temperature, stirring rate, concentration, and melt geometry defined the limiting reaction mechanism. The reduction of manganese oxide by silicon is a fast reaction and reached equilibrium within 90 min. The rate of stirring has a marked effect on the reaction rate, while, on the other hand, the effect of temperature is very small. This identifies the rate-controlling step as diffusion rather than interfaciul chemical reaction. The variation of other parameters revealed that a) diffusion of manganese in the iron phase is the slow step, b) the value of D/6 for manganese in iron at 1550°C is 7x 10-4 cm per sec, c) the energy of activation for the apparent rate constant is 7 kcal per mole, and d) increasing the amount of silicon in the iron decreases the diffusion coefficient of manganese. THE equilibrium relations pertinent to the reduction of manganese oxide from a steelmaking slag by silicon dissolved in liquid iron have been studied, but little is known about the mechanisms that control the rate of the process. The purpose of the present investigation was to study the rate of reduction by silicon and to determine the rate-limiting step. The effects of stirring rate, temperature, composition, and melt geometry were investigated as a means of identifying the controlling step. On the laboratory scale, relatively little work has been done in the area of slag-metal kinetics, primarily because of the problems confronted in attempting to contain liquid slags and metals in laboratory crucibles at steelmaking temperatures. Since graphite is an ideal material for a crucible, several investigations have been carried out on the reduction of various oxides from a slag by carbon in graphite-saturated iron and on the transfer of sulfur between a slag and graphite-saturated iron. Most of this work has been performed in induction furnaces. Studies where the container was not graphite are extremely limited. A single kinetic study of manganese transfer between molten iron and basic slags was carried out by Sano, Shiomi, and Matsushita.' These investigators prepared calcium oxide and titanium oxide crucibles to contain the two-phase system. Only a few experiments were carried out and the results had to be treated qualitatively. Despite the paucity of kinetic data, a large quantity of information is available in the literature concerning the thermodynamics2-12 and physical properties'3-21 of the slags containing manganese oxide and the dilute liquid iron alloys containing manganese and silicon which were involved in this research program. EXPERIMENTAL METHOD A vertical-tube resistance-heated furnace was used in this investigation to study the slag-metal reaction Although most previous slag-metal studies were carried out in induction furnaces, a resistance furnace has several advantages including better control of temperature and stirring rate. Hence, a resistance furnace was selected for this study, and its design is shown schematically in Fig. 1. Slip-cast, fine-grained, low-porosity, lime-stabilized cubic zirconia crucibles were used for the kinetic experiments. The crucibles were 4 1/2 in. high and 2 1/8 in. OD with a 1/16-in. wall. The crucibles were only slightly

Jan 1, 1969

By N. J. Grant, B. C. Giessen, U. Wolff

With the aid of the splat-cooling technique of rapid quenching, metastable alloy phases based on antimony ad bismuth have been prepared. At room temperature, simple cubic phases were found in the Sb + Au, 56 + Yd, and Sb + Ni systems. Another phase was retained in the Au-Bi system at -190°C; in this systent, a microcrystalline phase and a rhombohedrally distorted phase were also observed. The crystal chemistry of these phases is discussed in terms of their valence electron concentration range. A remarkable five-step Phase sequence was found upon heating and equilibration of certain metastable Au-Bi alloys. USING the splat- cooling technique of rapid quenching from the liquid,' a large number of metastable intermediate alloy phases have been prepared in recent years. Thus, Hume-Rothery phases of the hexagonal type based on the valence electron concentration have been produced in systems where they are missing in equilibrium, e.g., Ag-Ge 1 or AU-Sb. 3 In a comprehensive study of metastable alloys based on tin, simple hexagonal metastable y phases were found, raising the total of stable and metastable y phases from 3 to 13. 4 In the In-Bi system, five new metastable intermediate phases were retained.' In most cases, the new metastable phases have some crystal chemical characteristics in common: a) They have rather simple, elementlike structures with few atoms per unit cell, e.g., y phase,4'5 or the metastable primitive cubic phases in the Ag-Te and and Au-Te systems.= b) Their structures are often related to those of the terminal phases, or to elements that are straddled in their position in the periodic table by the constituent elements; this is the case for metastable ß (In-Bi) with the structure of white ß Sn,' or metastable a (Cd-sn). 4 c) They seem to represent the crystal structures appropriate to certain average group number (AGN) ranges in which no or few single-phase structures exist in equilibrium. These average group number ranges can probably be equated in the case of many elements of the Ba(Zn)-Bs(As) groups with the averaged valence electron concentration. In the present work, the splat-cooling technique has been applied to the alloys of antimony and bismuth. In equilibrium, neither element forms intermediate alloy phases with other B elements from groups Bl(Cu) to B4(Si) that contain more than 66.7 at. pct of Sb or Bi, respectively, e.g., AUSb 2. 7 Thus, antimony- or bismuth-rich phases, which might be closely related to antimony or bismuth, and which would reflect struc- tural changes occurring on alloying with small amounts of addition elements, do not exist. Also, the terminal solubility of antimony and bismuth for all B metals is very small. It was therefore of interest to investigate the influence of enforced, nonequilibrium solid solution of addition elements in antimony and bismuth on their crystal structures. It was found that additions of group B 2-B4 metals act distinctly differently than additions of group T 10 and B1 metals. The latter set of additives will be treated here. EXPERIMENTAL TECHNIQUES Alloy preparation and splat-quenching followed closely the procedures described in Refs. 1, 4, and 5; they consisted of the preparation of master alloys from high-purity starting materials (99.99+ pct) and blast-atomizing of 20-mg quantities onto copper sheets. The resulting approximately 1 to 5 u thick foils were investigated by X-ray diffraction. The cooling rates obtained are of the order of 107 to 10 8 C per set,'" causing solidification to proceed at a rat; of approximately 100 cm per sec.' Powder patterns of the resulting fine-crystalline materials were taken with filtered CuK, radiation. For antimony alloys the substrates were held at room temperature and for bismuth alloys at -190°C both during splat foil deposition and X-ray investigation. Annealing treatments at several

Jan 1, 1969

By R. E. Fryxell, E. C. Duderstadt, P. K. Conn

Permeation rates for nitrogen through are-cast tungsten were measured in the temperature range 1800° to 2600°C at nitrogen pressure differentials of 1.0 and 0.1 atm. Gas chromatography was used to measure the quantities of nitrogen which permeated through 0.26-and 0.53-mm-thick membranes. Permeation rates were proportional to the difference between the square roots of the nitrogen pressure on each side of the membrane and inversely proportional to membrane thickness, indicating that atomic nitrogen was the difjusing species and that diffusion was the rate-limiting step of the process. Permeation coefficients calculated from the rates may be represented by the equation: where P is expressed in the units cu cm (stP)-mm per 1/2 sq cm-min-atm"' and 70.0 * 0.8 is the activation energy in kcal per mole of permeating species. In a previous paper' permeation rates were reported for hydrogen and for oxygen through tungsten. The permeation cells used for the hydrogen measurements were suitable for measuring nitrogen permeation under similar conditions, so the study was extended to include nitrogen. Permeation rates of nitrogen through the polycrys-talline arc-cast tungsten membranes were measured in the temperature range 1800" to 2600°C using two membrane thicknesses and two nitrogen pressure differentials. Permeation coefficients were calculated and the activation energy of the process determined. THEORY For diatomic gases which dissociate prior to diffusion, the quantity of gas which permeates through a membrane or wall at an elevated temperature where bulk diffusion is the rate-limiting step of the process is given by the equation: where: q = total amount of gas permeating a membrane, P = temperature-dependent permeation coefficient, A = area of membrane, t = time, p1 = gas pressure of high-pressure side, p2 = gas pressure of low-pressure side, and d = thickness of membrane. When bulk diffusion is the rate-controlling step, and the solubility of the gas obeys Henry's law, a further relationship is that, for any given temperature and pressure, the permeation is the product of diffusivity and the amount in solution. The permeation coefficient, P, is temperature-dependent according to the equation: where: Po = permeation constant, Q = activation energy, R = gas constant, and T = absolute temperature. EXPERIMENTAL PROCEDURES Cell Design and Experimental Apparatus. Two of the permeation cells used for the previous measurements of hydrogen permeation are shown in Fig. 1. Each consisted of a cylindrical chamber divided into two parts by a permeation membrane fabricated from high-purity (>99.9 pct W) wrought tungsten sheet made from vacuum arc-cast tungsten. The membrane in one cell was 0.26 mm thick and the other was 0.53 mm. The fabrication of these cells was described previously.' The permeation cells were mounted vertically in a high-temperature tungsten resistance furnace and the membranes and the center portions heated to test temperatures. Temperatures were measured by sighting an optical pyrometer on the edge of the membrane through a small hole in a tungsten plate which was fastened to the side of the cell. This arrangement provided an approximate black-body condition and eliminated the need for emittance corrections. Appropriate corrections were made for the quartz window through which the temperatures were measured. Argon gas flowed through the 10-liter volume of the furnace at the rate of 4.7 liters per min. An impurity

Jan 1, 1969

By A. Totani, S. Nakajima, H. Okazaki

The phase diagram for the SnTe-SnSe system has been studied in the temperature range from 300° to 900°C by differential thermal and quenching techniques. The X-ray measurements were made on quenched specimens. High-temperature diffraction was also made to study the phase transition in SnSe. The system is proved to be of a eutectic type in which no intermetallic compound exists. The eutectic point is at the composition SnTeo.55 Seo.45. the eutectic temperature being 755°C. Solid solubility limits are SnTeo.6Seo.r and SnT eo. 3s Seo.6s at the eutectic temperature, and change almost linearly to SnTeo.aaSeo.lz and SnTeo.18 Seo.az as temperature decreases to 300°C. It was shown that the SnSe phase has a phase transition of the second order at about 540°C and that the transition temperature decreases with increase of the SnTe content. THERMOELECTRIC properties of tin telluride (SnTe) and tin selenide (SnSe) have been studied extensively in recent years. The variation of physical properties with composition could be of interest if these compounds form an appreciable crystalline solution. The purpose of present investigation is to confirm the formation of crystalline solution or intermetallic compound, if any, and to establish the phase diagram for this system. The crystal structure of SnTe is NaCl type with a cubic unit cell1 (a = 6.313A). The crystal of SnSe having an orthorh2mbic unit cellz (a = 11.496, b = 4.1510, and c = 4.4437A) is isomorphous with tin sulfide (SnS) which has a distorted sodium chloride structure. It has been known that SnSe has a phase at at 540°C; the transition has been assumed to be of the second order. As far as we know, only two studies on the SnTe-SnSe pseudobinary system have been reported. The conclusion obtained in these papers is that, in the composition regions near SnTe and SnSe, the system forms a crystalline solution of the SnTe structure and the SnSe structure, respectively, and that, in the intermediate region, both phases coexist. However, neither the variation of the solid solubility vs the temperature nor the liquidus and solidus were investigated. Hence present writers have attempted to determine the phase diagram of the system by differential thermal analysis (D.T.A.) and X-ray diffraction. EXPERIMENTAL Sample Preparation. Starting materials, SnTe and SnSe, were prepared by the direct fusion of commercially available high-purity (99.999 pct) elements. Stoichiometric amounts of each couple Sn-Te or Sn-Se were weighed into a clear fused silica ampule. After evacuation to a pressure below 10-3 mm Hg, the am- pule was sealed, and annealed at 900°C for 5 hr. The melt was quenched in water. X-ray analysis confirmed the formation of a single phase of SnTe or SnSe. The other samples, SnTel-,Sex were synthesized from these SnTe and SnSe by mixing them in the required ratio, followed by annealing at 900°C and quenching. These samples were used directly for D.T.A. For X-ray measurements, samples were annealed at 700°, 600°, or 500°C for 100 hr or at 300°C for 150 hr, and then quenched in water. It was found that the lattice constants of the SnTe phase annealed for 150 hr at temperatures above 500°C did not differ from those annealed for 100 hr at the same temperatures. However the X-ray phase analysis showed that at 300°C the annealing for 150 hr was necessary to attain a true equilibrium state. D.T.A. The solid-liquid equilibrium temperature was determined from D.T.A. measurements. The sample was sealed in an evacuated silica tube and molybdenum powders sealed in an another tube were used as a reference material. The sample and the reference tube were placed in a nickel block and were heated from room temperature to 900°C at a rate of 3°C per min and then cooled down at the same rate to 600°C. Thermocouples for these measurements were Pt-Pt. Rh (10 pct) and the error of temperature measurements was within + l0C. D.T.A. curves were obtained on a two-pen recorder and an automatic controller (PID type) was used for the program of heating and cooling. When temperature reaches the solidus from the low-temperature side, there appears an endothermic peak. The solidus temperature was determined by extrapolation of the straight portion of the starting flank of this peak to the base line. In a similar way, the liquidus temperature was determined from an exothermic peak on D.T.A. cooling curve. In the case of supercooling, if any, its degree can be estimated from the magnitude of the abrupt temperature rise. X-Ray . X-ray powder patterns were taken by a diffractometer using CuK, radiation. Since the SnSe crystal is cleaved easily, the powders become flaky when SnSe-rich samples are ground in an agate

Jan 1, 1969

By D. H. Baldwin, R. E. Reed-Hill

Six compositions of polycrystalline ZY-0 alloys, containing up to 4.2 at. pct 0, were tested in tension between 77° and 600° K. The data obtained from each of the compositions corresponded closely to a rela-ion between yield stress and absolute temperature of the form In s/so = BT, where oo is the yield stress extrapolated to zero degrees and B is a constant. In agreement with others who have observed this relationship, it is shown that the activation energy may be expressed as Ho In so/s. In the present specimens Ho is approximately 18,000 cal per mole and is apparently independent of temperature and composition inside the limits of the investigation. It is also demonstrated that this form of activation energy cowesponds to a strain rate sensitivity parameter RT/Ho. Oxygen was also noted to have an effect upon the operative deformation mechanisms. With increasing oxygen concentration there was an increased tendency to observe both nonbasal slip and cross-slip phenomena. Oxygen does not seriously inhibit twinning more than it does slip. Twins were observed in all specimens tested. It is becoming increasingly evident that interstitial atoms in solid solution are able to interact strongly with mobile dislocations. Stein, Low, and seybolt,&apos; have shown that, if the carbon concentration in bcc iron is lowered below the solubility limit, its flow stress temperature dependence is markedly reduced. This suggests that carbon atoms in interstitial solid solution may be responsible for the pronounced temperature dependence of the flow stress normally observed in iron. This view has recently been challenged by Leslie and sober2 who observed a strong flow stress temperature dependence in iron to which a trace of titanium had been added in order to remove carbon atoms from solution. Since the interstitial concentration must be reduced below approximately 1 ppm in order to produce a pronounced effect on the flow stress temperature dependence,&apos; studies of the effect of interstitials on the flow stress in iron necessarily involve serious experimental difficulties in alloy preparation. There are other metals, however, in which strong effects of interstitial solutes upon both the flow stress and its temperature dependence are observed. Of particular significance is zirconium which, according to Domagala and Mcpherson, 3 is capable of dissolving 28.6 at. pct O. The O-Zr alloy system is an almost ideal system for studying the interaction of interstitial atoms with deformation modes since it is possible to form alloys capable of study over an extensive range of compositions. Mills has made such a study using single crystals oriented primarily for single prismatic slip4 and has found an effect of oxygen concentration on the flow stress temperature dependence analogous to that observed in iron due to carbon by Stein, Low, and Seybolt. The present paper is specifically concerned with the effect of oxygen on deformation in polycrystalline zirconium. Although plastic flow in this type of specimen is much more complex than that reported for the single-crystal work, and involves both slip (on several different types of planes) and mechanical twinning, the results of this investigation are in general agreement with the single-crystal observations concerning the effect of oxygen on the temperature dependence of the flow stress. In addition, they also demonstrate that oxygen affects the acting deformation systems. This is in contrast to single-crystal results4 that showed only single slip on a prism plane. EXPERIMENTAL PROCEDURE Material. High-purity hot-rolled zirconium strip, 0.2 in. thick by 4 in. wide, of 0.10-mm average grain diameter, was used for forming alloys. It was obtained from the Carborundum Metals Co., Akron, N.Y., whose analysis indicated the major impurities were, in wt ppm: Hf, 540, C, 145; Fe, 100; and 0, <80. The plate texture was similar to a wire texture, with basal planes generally parallel to the rolling direction and basal poles randomly distributed about the rolling direction. The heat treatments described below did not appreciably alter the basic texture. specimen Preparation. Small threaded-end tensile specimens were machined from the plate with axes perpendicular to the rolling direction. These transverse specimens had gage sections 1 in. long by 0.060 in. in diam. The small gage section diameter was dictated by the fact that the alloys were formed by dif-

Jan 1, 1969

By M. J. Marcinkowski, E. N. Hopkins

An investigation has been made of the ß(fcc) — a(hexagonal) transformation which occurs in lanthanum using both electrical resistivity and transmission electron microscopy techniques. It has been shown that the ß phase can be retained below the transformation temperature by rapid quenching but that the sample immediately begins to transform to the a phase. The transformation is observed to nucleate in the vicinity of inclusions. Based on the above observations, a detailed model of the transformation has been advanced which involves the nucleation of an extrinsic stacking fault bounded by a pair of Shockley partial dislocations in the vicinity of some heterogeneity, i.e., an inclusion. The stress field of the resultant dislocation pair acts to nucleate extrinsic faults in adjacent planes and leads quite naturally to the B-a conversion with a minimum of strain energy induced in the crystal. LANTHANUM possesses an fcc structure ß) (8) upon cooling transforms to a hexagonal modification (a) in much the same way as cobalt. The one exception, however, is that the stacking sequence of the closest packed planes in a La is ABAC ABAC, and so forth,1 whereas in cobalt it is ABAB, and so forth, i.e., hep. Mainly on the basis of transmission electron microscopy techniques, there seems to be little doubt that the 0 — a transformation in cobalt involves a dislocation mechanism2 although its exact nature still remains obscure. Although the ß - a transformation in lanthanum is somewhat more complex than that occurring in cobalt, it was thought that its very uniqueness would be helpful in understanding fcc — hexagonal transformations in general. Such a general understanding of these transformations is important since they represent what are perhaps the simplest of the martensitic class of transformations. The experimental techniques used were those of electrical resistivity and transmission electron microscopy. EXPERIMENTAL PROCEDURE The lanthanum used in this investigation was prepared by the calcium reduction of lanthanum fluoride in a tantalum crucible under an argon atmosphere as described by Spedding et al. The residual calcium was removed by vacuum remelting in a tantalum container. Portions of the metal were then analyzed by emission spectroscopy as well as vacuum fusion. The amounts of the various impurities that were found are listed in Table I. A portion of the lanthanum ingot was swaged at room temperature into 0.030-in.-diam rod for the resistivity samples while the remainder was rolled into 0.010-in.-thick sheet for the transmission electron microscopy phase of this investigation. In order to eliminate the plastic deformation induced in the samples during fabrication, they were sealed in evacuated tantalum lined quartz capsules and annealed for 1 hr at 700° C. Specimen resistances were measured using the conventional "four-wire" technique described by MacDonald, 4 employing a type K-3 Universal Potentiometer and a standard 0.001-ohm resistor, both manufactured by Leeds and Northrup Co. By taking into account all of the possible errors in the apparatus, it was felt that the absolute resistivities of the approximately 0.87-in.-long specimens measured are reliable to 3 pct. Resistances from room temperature to 700°C were measured using a vacuum furnace. In order to avoid sample contamination by the thermocouple, chromel-alumel leads were spot-welded into a tantalum shield which in turn was welded to the lanthanum specimen. Resistances below room temperature were obtained by transferring the sample to a helium gas-filled quench tube and slowly dripping liquid nitrogen into a surrounding dewar flask. A steady reduction of temperature to about —190°C was completed in about 23 hr, and the resistances were measured at various temperature intervals. As will be shown shortly, rapid quenching from above about 350°C was sufficient to suppress the B -a transformation initially but subsequent annealing at lower temperatures leads to a partial ß --a conversion. To investigate this aspect of the transformation, the samples were suspended in the hot zone of a helium-filled furnace from which they could be rapidly dropped into the quench tube mentioned previously which was now

Jan 1, 1969