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By Richard W. Greene, Joel S. Hirschhorn

MATERIALS containing very large amounts of porosity, in the order of 50 to 90 vol pct, are extremely difficult to evaluate according to conventional mechanical behavior tests. This is usually a consequence of their low strength and brittleness, and the difficulty of preparing standard test specimens. A simple fatigue test has been developed and used successfully on porous nickel sheet materials requiring no specimen preparation; it could also be used for configurations other than sheet or plate. Samples of the sheet. 2 in. sq and about 0.025 in. thick, are placed in a vessel that is evacuated to about 50 f Hg by a mechanical pump. Distilled and deairated water is allowed to enter the vessel thereby filling the porosity (virtually all the porosity in these nickel ma-

Jan 1, 1970

By L. A. Tarshis, H. E. Cline

A stability criterion for a lamellar eutectic interface was derived previously1 assuming that the wavelength, A,. of the perturbation which grows most rapidly is much larger than the lamellar spacing. A. This assumption was required to permit averaging of both the interface temperature and composition over the complicated geometry of a lamellae. If this assumption is invalid, as has been suggested.2,3 then the problem becomes too complicated to solve completely. The first of these analyses1 did not calculate the wavelength. A,. of the initially unstable perturbation. whereas the more recent analysis.' which led to a contradiction of this assumption. did not include one of the key factors for determining this wavelength. To rigorously determine the wavelength, the effect of the curvature of the perturbed interface (not considered by either of the above treatments) must be included. By omitting this term, one would be led to an incorrect conclusion regarding the magnitude of A,. but to an accurate criterion for stability as evidenced by the excellent agreement with experimental observations.' In the case of single-phase alloys. the critical wavelength. A,. for instability can be calculated from the Mullins and Sekerka4 (M.S.) analysis which includes the effects of capillarity. In the following discussion, the M.S. analysis is applied to lamellar eutectics and the critical wavelengths calculated for reasonable growth conditions in Pb-Sn eutectic alloys. In order to apply the M.S. analysis to eutectics. one may substitute i) the effective liquidus slope.1 m*. for the single-phase liquidus slope and ii) the ratio of the bulk alloy composition. C,. to the average interface composition in the liquid (Ci = CE where CE is the equilibrium eutectic composition) for the distribution coefficient to give:

Jan 1, 1970

By E. A. Metzbower

STEREOGRAPHIC projections of hcp metals depend upon the c/a ratio. Hu1 has recently published standard projections for titanium (c/a = 1.5873) of the (000l), the basal plane, the (1010), the most prominent slip plane, and the (1012), the most prominent twinning plane. Caplan et a1.2 and Hul have also published tables of angles between poles of planes, between directions, and between directions and poles of planes. From these tables standard projections and double stereograms can be constructed. However, by using the on-line CALCOMP plotter with a CDC 3800 computer, direct plots of standard stereographic projections of titanium (c/a = 1.587) have been made.

Jan 1, 1970

By Leonard B. Griffiths

In a recent communication, Smith and Wood described some results of 800°C compression/creep tests on WC-12 wt pct Co alloys in which plastic flow in the WC particles was believed to have occurred. The deformation observed in the WC particles was found to be a function of the rate of loading. The authors suggested that their data constituted support for the Ansell6-Lenel theory of yielding in dispersion-strengthened alloys. I do not agree with this interpretation since the Ansell-Lenel theory does not apply to the type of alloy in question. In this alloy, the dispersoid is present to the extent of about 80 vol pct. Even where there is no continuous skeleton, which apparently is the case in this instance, the simple fact is that nearly all of the load is carried elastically by the stronger material (wc).7 The constraint imposed upon the matrix, by virtue of the differences in Young's modulii and Poissons ratios, severely limits the stress level to which it may be subjected (assuming that the interfaces remain intact). If one allows for the constraint and then performs the same computation as in Smith and Wood, one finds that the stress on a WC particle is about 4 x 105 psi. This is about 21/2 times lower than the predicted fracture stress for WC. I would completely agree with the final paragraph of Smith and Wood, namely, that loading rate is of considerable significance. However. a more likely interpretation of their data is, I submit, that in the absence of stress relaxation (by secondary slip or climb) those WC-Co interfaces subjected to a normal tensile stress begin to fail. Once this occurs, the stress distribution will change rapidly and "premature" fracture of the WC then becomes quite probable. Tne serrated edges shown in Fig. 1 may very well be fine, interface fissures.

Jan 1, 1970

By E. Ryba, D. J. Michel

SAMPLES of REZn2 (RE = rare earth) intermetallic compounds prepared by a variety of techniques have been shown to exhibit an extensively twinned micro-structure.1-4 We have recently conducted compression tests at room temperature on specimens of HoZn2 prepared by a powder metallurgy technique.' The microstructures of specimens before and after testing are shown in Fig. 1. The "before" specimen, Fig. l(a), shows the basic twin structure of this material. Fig. l(b) shows the microstructure of the "after" specimen just below the fracture surface and reveals considerable cross-twinning as well as additional

Jan 1, 1970

By C. S. Barrett

WhEN a collimated beam of protons or other energetic particles is scattered by a single crystal, the emerging particles produce patterns that contain much crystallographic information. Calculations of the trajectories of individual particles can predict with reasonable accuracy the complete pattern (which is related reciprocally to channeling, now studied in detail6) but the task is a lengthy one which has been completed for very few cases. A many-beam dynamic diffraction calculation of the patterns would be even more difficult and in some cases may be invalid. Because of these complexities, simple methods that will predict to a rough approximation the relative intensities of the lines in films of the back-scattering patterns of a given crystal are wanted. I have found a method which, although it is not a valid computation of intensities or of film darkening by either dynamic or kinematic diffraction principles or by trajectory calculations, nevertheless is found to be useful in practice. It has been tested on several crystal types,7 and is here tested on additional ones. The method consists in first calculating the structure factor F(hk1) for the (hkl) plane, of spacing d, by the familiar equation: where the summation extends over the atoms in the unit cell and fj is the atom scattering factor of the jth atom (using tables computed for electron diffraction, preferably those computed without exchange). Then the F values are squared and summed over all the orders, n, for which F2 has an appreciable value, giving a quantity: Finally, I, is expressed as a percentage of Ic for the

Jan 1, 1970

By A. U. Seybolt, R. E. Honnemon

THE purpose of this communication is to present activity data of nickel in the Ni-A1 binary system that was obtained for oxidation studies in this system. This data has been calculated from previous aluminum activity data at 1000°C1,2 by two types of Gibbs-Duhem integrations. These results should be of particular current interest to oxidation studies of aluminide coated nickel-base superalloys3 as well as other problems. The aluminum activity of Steiner and Komarek1 is plotted in Fig. 1 as a function of composition in Ni-A1 alloys at 1000°C. The dashed parts of the aluminum curves represent our approximate extrapolations from the directly measured regions. In the terminal solution regions (a and L phases) standard parabolic solution functions of the following form are assumed: where i is the component subscript, Ki is a constant at a fixed temperature, and xi is the atom fraction. The resultant nickel activity curve at 1000° C from the Gibbs-Duhem integration4 of the aluminum data is shown in Fig. 1. The solubility ranges of the phases present in the Ni-A1 binary at 1000°C are also denoted at the bottom of Fig. 1. Corresponding values of the nickel activity, aNi and yNi, are listed in Table I at useful compositional intervals. including phase boundary values. The aNi and yNi data listed in Table I are subject to the uncertainties present in the experimental aluminum activity data1 and to deviations from parabolic solution behavior in the terminal solutions. The errors introduced into aNi and yNi due to the parabolic solution assumption are expected to be relatively small (<20 pct of the values given) in all the phases except the liquid phase. Some deviation from parabolic solution behavior in the liquid phase is indicated

Jan 1, 1970

By W. White, C. S. Barrett, R. M. Mueller

THIS communication reports film-recorded low-energy (-100 kev) proton blocking patterns&apos;-3 for hcp and wurtzite crystals. In particular the sequence of relative line intensities* (corresponding to planar blocking) of common hcp metals is compared with those of the wurtzite semiconductors CdS and CdSe. The results show that the sequence is characteristic of structure. For closely similar structures such as those of CdS and CdSe, differences of line intensity attributable to the difference in atomic number, 2, of the scattering centers may also be seen. The apparatus and techniques used in this work were identical with those reported previously in a study of cubic systems.3 All metals were given standard metal-lographic etches, and the semiconductors cleaved, immediately prior to introduction to the vacuum system. Fig. 1 shows the unit cell of the wurtzite structure, and the geometry used to obtain the [1120] and [0001] patterns of Fig. 2. The axial ratio, c/a, for all ma- terials of Fig. 2 is close to 1.63. The patterns are then directly comparable in linear dimensions inasmuch as they have been reproduced at the same overall magnification of the patterns. (Overall magnification is proportional to the product of film-to-target distance and printing magnification. Thus the 1/6-in.-diam beam passage hole in the center of the film need not appear of uniform size in the prints.) The patterns for a given orientation, though similar

Jan 1, 1970

By R. L. Skaggs, R. A. Molsberger

DARKEN1 has pointed out that in most binary liquid metal systems the thermodynamic behavior is relatively simple in the terminal regions. Between the terminal regions. the thermodynamic behavior is more complex. To describe this behavior. he has defined the stability and the excess stability as shown: Qualitatively, an inflection in the free energy of mixing curve results in a change in sign, from positive to negative, of the stability function and is associated with a phase separation. Conversely, a large, positive stability over a narrow composition range is indicative of compound formation. Darken has shown a number of binary systems where the excess stability is constant in the terminal regions and varies sharply in between. The work described in this communication was undertaken to study the variation of stability and excess stability in a binary system as a function of temperature. In addition, this work provides means for the direct comparison of previously existing equilibrium (activity) and calorimetric (molar heat of mixing) data on the Hg-Sn system. Hildebrand2 measured the vapor pressure of mercury over Hg-Sn alloys at 595°K. Calorimetric studies were made by Kawakami3 at 523°K and by Kleppa4 at 423°K. In this work, the equilibrium vapor pressure of mercury was measured over a series of Hg-Sn alloys at 453" and 503°K by use of fused salt manometer with one arm exposed to mercury vapor. Deflections of the fused salt manometer were balanced by argon pressure on the other arm. Argon pressure was subsequently measured with a dibutyl phthalate manometer. Tin activities were determined by graphical integration of the Gibbs-Duhem equation making use of the familiar Darken5 a function. The activities of mercury and tin showed positive deviation from Raoult&apos;s law at 453 and 503°K as Hildebrand observed at 595 K. In Fig. 1 are plotted log activity of mercury and tin vs reciprocal temperature. The plot contains activities obtained from calorimetric studies. Hult-gren6 has calculated activities from Kleppa&apos;s4 data, and Kubaschewski7 has similarly treated Kawakami&apos;s7 data. Presumably. in each case a regular solution was assumed. For regions where a two-phase field

Jan 1, 1970

By d&apos, C. McCoul, C. Antonio, R. Krohn

MOST of the commercial colored gold alloys for jewelry applications are based on the Au-Ag-Cu-Zn system. Although work has been done on the constitution of the Au-Ag-Cu system.&apos;-4 there are no reports in the literature on the effects of zinc additions in these alloys. We have metallographically determined the a =al + a2 transformation temperatures in 91/2- and 131/2-karat alloys in which varying amounts of zinc have been substituted for copper and silver. Samples were cast in the form of 1/2-in. round bars

Jan 1, 1970

By W. C. Winegard, C. J. Simpson

BNINGESSNER et al.1 have shown that the solidification substructure in dilute cadmium alloys persisted after repeated deformation, recrystallization, and annealing treatments. On the basis of this and similar evidence, Whelan has suggested in a recent publication&apos; that the solidification structure might affect the mobility of grain boundaries even after primary re-crystallization. This suggestion is important, since the technique used by previous investigators3-5 to fabricate grain growth specimens consisted only of casting, deforming, and recrystallizing prior to the grain growth anneal. Usually no attempt was made to homogenize samples with prolonged annealing. Experiments. To test the Whelan hypothesis, grain growth experiments were performed with samples in which the degree of solute segregation was altered by controlling the solidification rate of the alloys. The initial experiments were performed on the Pb-Ag system. Alloys containing 0.01 at. pct Ag were produced from 99.9999 pct Pb and 99.999 pct Ag. Cylindrical samples, 40 cm long and 12 mm in diam, were solidified in graphite-coated Vycor tubes by lowering them through a vertical furnace at varying rates with the furnace power settings constant. Six-centimeter sections were discarded from each end, and the 28-cm section from the center was cut into sections 25 mm long for grain growth experiments. These samples were deformed with the aid of a drophammer to a uniform thickness of 5.7 mm. After almost instantaneous recrystallization, the samples were given a grain growth anneal for various times at 260°C in a salt bath. Experimental results are shown

Jan 1, 1970

By H. R. Thresh, A. F. Crawley

THIS paper reports the results of viscosity measurements on cadmium and indium undertaken as part of a continuing program of liquid metals research at the Mines Branch, Department of Energy, Mines and Resources, Ottawa, Canada. For several years this work has continued with support from the Canadian Zinc and Lead Research Committee and the International Lead and Zinc Research Organization. In the literature, existing viscosity data for cadmium are conflicting and for indium are scarce. To achieve reliable viscosity values, further work was deemed desirable. Viscosities were measured using an absolute technique applied to an oscillating closed right cylinder of liquid metal. The apparatus, constructed in this laboratory, and the techniques involved in its use have been described in an earlier paper.&apos; In calculating viscosity coefficients from the experimental data. Roscoe&apos;s2 mathematical analysis was used. Because accurate viscosity determinations are dependent on accurate density data, and since the available data in the literature are conflicting, the densities of liquid cadmium and indium were also determined in this laboratory by a pycnometric technique. This increased the control exercised over all the variables contributing to the accuracy of viscosity measurements. For both density and viscosity determinations, cadmium and indium of 99.999 pct purity were used. These materials were obtained from Cominco Ltd. In order to suppress excessive evaporation losses and help prevent oxidation, a technique developed in measuring the viscosity of zinc&apos; was used for cadmium. This involved maintaining an atmosphere of purified hydrogen in the viscosimeter during the rela- tively long periods while the experimental temperature was changed and stabilized between individual determinations of the logarithmic decrement. Then, immediately prior to a decrement measurement. the viscosimeter was rapidly evacuated to a pressure of about 2 X 10-6 torr. On the other hand. with indium. no difficulties arise from vaporization or oxidation. In this case. therefore. the apparatus was held under a constant vacuum of about 2 x 10-6 torr. When all sources of random and systematic error have been evaluated, the technique is considered to yield data accurate within 10.5 pct. The viscosity of cadmium was measured to a maximum temperature of 451.8°C and that of indium to 346.5°C. These temperatures are. respectively. 130° and 190°C above the melting points. Two separate runs were made on indium. The results are given in Table I and, when plotted. yield the smooth curves evident in Figs. 1 and 2. Values of A and C to fit the well-known Andrade1 equation were determined by a regression analysis. The equation is: where n = coefficient of viscosity. i = specific volume. T = temperature in °K Despite its empirical nature. Andrade&apos;s equation has been shown by many workers to describe accurately the temperature dependence of viscosity. During the current research program, this equation has been found to fit the data precisely for all the metals and alloys that have been studied.5,6 The A and C&apos; values for cadmium and indium are given in Table 11. Comparing the magnitude of the present data with those of previous workers,7-10 as has been done in Fig. 1, it is evident that the results of Fisher and Phillips10 deviate markedly from the rest. With the exception of one point from Gering and Sauerwald,7 all other data agree within ±2.5 pct. However, the agreement between the present results and the work of Menz and sauerwald9 is especially good over the entire experimental temperature range. Such agreement may be expected since Menz and Sauerwald&apos;s

Jan 1, 1970

By C. R. Watts

The feasibility of producing composites containing nickel or molybdenum fibers in a beryllium matrix was inrestigated. The composties studied were jabricaled by powder mallurgical techniques. The 1-mil-diarr nickel fibers reacled completely below 900°C, converling the fibers .from nickel to Ni5Be2,. As the /LO/-pressing temperalure as raised above 1110oC, tlie nickel diffused outward from the beryllide fibers. The solid solubility of nickel in beryllium was clboul 20 wt pet at the 1100°C pressing temperature a1 the zone-fiber interface. The 1.5-mil-diam molybdenum fibers slzolred no evidence of reaction and little evidence of diffitsion after pressing at 900°C. Between 1000° and 1050°C pressing conditions, the fibers began lo react , producing 1ayers of MoBe2 and MoBe12, respectively surrounding the molybdenurn core. The struture remained the same at 1100°C with no evidenre of solid solubility of the molybdenum in the berylium or vice versa. In recent years a considerable amount of attention has been devoted to the determination of methods for improving the mechanical properties of materials through the use of fiber or whisker reinforcement. Previous work with metal matrix composites indicates that the study of the chemical compatibility of the fiber and matrix is an area requiring greater understanding. The metal-metal or ceramic-metal interface is frequently subject to chemical reactions that may result in the formation of hard brittle intermetal-lic compounds and/or low melting point eutectic compositions. The reaction products may reduce both the low-temperature and elevated-temperature strength of the composite by weakening the fiber-matrix bond, producing premature failure at the interface. It is well-known that most metal-metal systems and many metal-ceramic systems of interest for structural composites are thermodynamically unstable,&apos;-" particularly at elevated temperatures. If, however, the rate of reaction under the conditions of fabrication is sufficiently low. composites can be fabricated that can be used efficiently for indefinite periods at low temperatures and for short periods at elevated temperatures. This paper presents the results of a series of tests to determine the compatibility of nickel and molybdenum fibers with beryllium at various hot-pressing temperatures. Nickel was selected as a candidate fiber material primarily because the relatively ductile fibers might be useful as crack arresters in applications such as ballistic impact where crack growth can result in catastrophic failure. The high density and the reactivity of nickel were primary factors detracting from its selection as a possible reinforcement. Molybdenum with a modulus of elasticity of 52 Xlo6 psi is one of the few metallic materials having a modulus higher than beryllium (42 X lo6). Its high modulus, coupled with its refractory characteristics, made molybdenum an attractive candidate for a relatively stable fiber reinforcement for beryllium. Its density, being higher than that of nickel and over five times that of beryllium: detracted from its other characteristics. EXPERIMENTAL PROCEDURE The specimens were prepared from beryllium powder with a dispersed phase of fibers by powder metallurgical techniques. P-20 grade powder, Table I, from Berylco was used as the matrix material. Short lengths of 0.001-in.-nominal-diam nickel fibers supplied by the Sigmund Cohn Corp. and 0.0015-in.-nominal-diam molvbdenum fibers obtained from the General Electric Co. were used as the dispersed phase. The composite constituents were combined under an argon atmosphere by mechanically mixing the powders and fibers. The compositions used were nominally 1 vol pct fibers. After mixing. the composites were hot-pressed into a-in.-diam pellets under an argon atmosphere at 900°, 1000". 1050". and 1100°C at a pressure of 6000 psi with no hold time at these temperatures so that a comparison could be made between the resultant microstructure and hot-pressing temperature. The billet was heated at a rate on the order of 30°C per min to the desired temperature and then cooled at a somewhat slower rate. The microstructure obtained should be considered as characteristic of the integrated time-temperature history of the sample, as well as the maximum temperature attained. Upon removal from the hot-pressing dies. the specimens were cut. mounted. and polished by standard procedures. No etchant was used in specimen preparation. Photomicrographs, electron microprobe scans, and electron back-scatter pictures were made. X-ray dif-fractometer patterns were made of several of the specimens. but only the lines for beryllium could be resolved. Specimens for optical and electron microprobe examination were selected partially for the roundness of the cross section. A round cross section was taken to indicate that the body of the fiber was approximately normal to the surface and that therefore effects due to fiber material immediately below the surface could be neglected. RESULTS AND DISCUSSION The microprobe scans indicated that nickel reacted as low as 900°C, converting the entire fiber cross section to NisBe21. Fig. l(a). There was no evidence of further reaction from the optical or the back-scatter pictures, Figs. 2(n) and 3(a).

Jan 1, 1970

By Ashok K. Sinha

During the course of an in~*estigation into the occurrence of ordered AB3 structures, the following new phases have been found —CrRh3 (AuCu3 type), CrCo3 (MgCd3 type), HfCo4 (Ths Mn23 type), and WPt, MoPh type). The composition of the TiPt3-x phase (TiNi, type) is close to Ti23Pl77. The alloy chenzistry of transition rnetal AB3 structures is rezliewed in the light of electron concentration correlations of hex-agonality recently obtained for quasi-binary alloys. The relatizte colurne contraction in the AB3 structures increases with increasing difference in volume of the conzponents. A family of ordered close-packed layered structures is formed by stacking identical layers of composition AB, in various sequences, such that the coordination is twelvefold throughout and there are no A-A contacts. Previous work&apos; on quasi-binary AB3 alloys has led to the conclusion that the stacking sequence of the AB, structures changes with increasing radius ratio RA/RB from a purely cubic, through different mixtures of hexagonal and cubic stacking to a purely hexagonal stacking. However. for binary AB3 alloys, a correlation between the type of the crystal structure and the position of the components in the various volumns of the periodic table has been noted.2-5 It has been noted6 that this correlation appears to hold even though the radius ratio RA/RB may vary over a considerable range with the location of the components in the three long periods. Another study7" of several quasi-binary systems led to the conclusion that an increase in hexagonality of the stacking is associated with increase in the electron concentration e/a. as defined by the average per atom of the total number of electrons outside the inert gas shells. In apparent conflict with this conclusion, it is known that seven binary alloy structures isotypic with TiNi3 which is 50 pct hexagonal occur at a higher electron concentration (e/n = 8.5) than that (e/a = 8.25) for the 100 pct hexagonal MgCd3 type structure present in seven binary AB3 alloys. Table 111. In the present work, an investigation into the occurrence of binary AB3 structures in transition metal alloys was made, and a survey of binary AB3 structures is presented. EXPERIMENTAL The starting materials were pure metals of 99.9 wt pct purity. The alloys were arc-melted under partial pressure of argon and annealed in sealed silica capsules lined with molybdenum foil under argon at- mosphere. The total weight loss upon melting and subsequent annealing was always less than 1 pct and hence the alloys will be referred to by their intended (unanalyzed) compositions. Wherever the constitution permitted. the alloys were given a homogenizing treatment at 1200°C (3 days) prior to annealing. Unless otherwise stated all alloys were annealed at 900°C for 1 week and water-quenched. Sometimes the final annealing treatment was carried out on powders to accelerate the attainment of equilibrium. X-ray powder patterns were taken using a Guinier-de Wolff focusing camera (CuK, radiation) or an asymmetrical focusing camera (Co or CrK, radiation). For lattice parameter determination. internal silicon standards were employed. The intensity calculations were made using a Fortran IV program written by Jeitschko and parthe.9 RESULTS Twenty AB3 and three AB4 alloys were investigated. Table I lists the crystallographic data on some of the intermediate phases encountered in the present work. Table II contains the X-ray data for HfCo, (Th,,Mn,, type). The positional parameter, x. was assumed to be 0.378. the value for Th6Mnn2310 The X-ray pattern of ZrCo, was very similar to that of HfCo, and the previous structure determination of ZrCo, by Kuzma el al." was confirmed. Ordering in the alloy CrCo could be ascertained by the presence of only one weak super lattice line (101). the others being too weak presumably owing to the small difference in the scattering powers of chromium and cobalt. This line was observed in the X-ray pattern of powder from the massive sample annealed at 830°C (7 days) after the powder had been reannealed at 600°C (24 hr). The diffraction pattern of the powder similarly reannealed at 830°C (24 hr) contained only the lines due to a mixture of hcp and fcc Co(Crj solid solutions. Therefore, it appears reasonable to assume that O2 and/or N2 contamination which would be less likely to occur during the 600°C anneal was not responsible for the observed weak reflection. Also. this reflection cannot be identified with any of the strong lines of the neighboring s phase which is present in the Co-Cr system at higher chromium contents. The composition corresponding to the TiNi3 structure observed by Raman et al.12 in the two-phase alloy Ti,zt,, has been established in the present work as being between There was satisfactory agreement for the low-angle lines (up to d = 1.997A) between the observed diffraction pattern of TiCua and that calculated assuming the ZrAu, structure. as recently proposed by Pfeifer-et a1.I3 However. some of the superlattice lines. e.g., at d = 1.937 and 1.919A. predicted by the ZrAu, structure were not actually observed eve? though neighboring lines. at d = 1.947 and 1.986A. of comparable calculated intensity were present. The ZrAu

Jan 1, 1970

By D. T. Peterson, T. Carnahan

The diffusion coejTicients of carbon, nitrogen, and oxyget were determined in $ thorium over the tempernilcre range 1440" io 1715°C. The diffusion coyfiicir?zls are given by: D = 0.022 exp (-27,000/RT) jor carbo)~, D = 0,0032 exp(-l7,00Q/RTj for nitrogen, and D = u.0013 expt(-11,UOU/RT) for oxygen. Cavl~orz was found to increase the hardness of thoriunz nearly linearly with concentration over the range 100 to 1000Ppm carbon. ThORIUM has a fcc structure up to 1365°C and a bcc structure from this temperature to its melting point at 1740°C. Diffusion of carbon, oxygen, and nitrogen in bcc thorium was of interest in connection with the purification of thorium by electrotransport.&apos; In addition, it was possible to measure the diffusion of all three of these interstitial solutes in the same bcc metal. Only in niobium, tantalum, vanadium, and a iron have all three interstitial diffusion coefficients been measured in a given bcc metal. Diffusion coefficients have been measured for carbon and oxygen in a thorium by Peterson2, 3 and for nitrogen by Gerds and Mallett.4 Activation energies for diffusion are reported by the above authors to be 38 kcal per mole for carbon, 22.5 kcal per mole for nitrogen, and 49 kcal per mole for oxygen. Values of the diffusion coefficients of carbon and nitrogen in 3 thorium have been reported by Peterson et al.&apos; However, these were secondary results of their investigation of electrotransport phenomena in thorium and it was hoped that the present study could provide more precise data. EXPERIMENTAL PROCEDURE The specimens used in this study were the well-known pair of semi-infinite bar type. The couple was formed by resistance butt welding two 0.54-cm-diam by 3.0-cm-long bars of thorium together under pure helium, the concentration of the solute being greater in one cylinder than that in the other. The finished couple then contained a concentration step at the weld interface and diffusion proceeded only along the axis of the rod. The thorium used in this study was prepared by the magnesium intermediate alloy method.5 The total impurity content was less than 400 ppm. The major impurities were: carbon, 100 ppm: nitrogen, 50 ppm; and oxygen. 85 ppm. The total metallic impurity content was less than 150 ppm. The high solute concentration portions of the diffusion couples were prepared by adding the solute to the high-purity thorium in a non-consumable electrode arc melting procedure. Carbon and nitrogen were added in the form of spectroscopic graphite and nitrogen gas while a Tho2 layer was dissolved by arc melting to add oxygen. High-purity thorium formed the low concentration portions in the carbon and nitrogen couples. The low oxygen portions were obtained by deoxidizing high-purity thorium with calcium for 3 weeks at 1000°C according to a method reported by Peterson.3 The high C-Th contained 400 ppm C, the high N-Th contained 400 ppm N, the high 0-Th contained 220 ppm 0, and the low 0-Th contained 25 ppm O. The high O-Th was brine-quenched from 1500°C to retain most of the oxygen in solution at room temperature. These concentration levels were all below the solubility limits in 0 thorium at 1400°C. A resistance-heated high-vacuum furnace was used to heat the couples. The samples were mounted horizontally on a tantalum support which had small grooves near each end. Spacer rods of thorium, 0.4 cm in diam, were placed in these grooves to prevent contact between the sample and the tantalum support. This arrangement should have prevented contamination of the sample by contact with the support. In further effort to reduce contamination, the oxygen diffusion couples were sealed inside evacuated outgassed tantalum cylinders lined with thorium foil. Thorium rings around each end of the samples acted as spacers in this case. Pressure during diffusion runs was about 10-6 torr after an initial outgassing stage. Temperature measurements were made by sighting on black body holes in the sample support adjacent to the samples with a Leeds and Northrup disappearing-filament optical pyrometer. Temperatures were constant during a diffusion anneal to ±5C. The observed temperatures were corrected for sight glass absorption after each diffusion run. The pyrometer was checked against a calibrated electronic optical pyrometer and a calibrated tungsten strip lamp with the electronic pyrometer being taken as the standard. All temperature readings agreed to within ±3C over the temperature range 1450" to 1690°C. Time corrections due to diffusion during heating and cooling were necessary because of the short diffusion times. The diffusion times ranged from 6 min for the oxygen sample run at 1690°C to 90 min for the carbon sample run at 1500°C. A series of temperature vs time plots were made for heating and cooling of the samples to the various diffusion temperatures. This data was then used in a method according to shewmon6 to determine the time corrections. The corrections amounted to

Jan 1, 1970

By H. J. Levinstein, H. J. Guggenheim

RbFeF3 is a transparent ferromagnet with a large faraday rotation which permits the direct observation of magnetic domain structures in bulk crystals. If the position of dislocations within the crystal were known a study of domain wall dislocation interactions would be possible. In this paper an etch pitting solution is described which gives a one-one correspondent between the etch pits and the dislocations intersecting the (100) surfaces of RbFeF3 crystals. In addition, RbFeF3 is shown to have sufficient plasticity so that known arrays of dislocaticms can be put into the crystal. It is concluded that RbFeF, is an ideal material for the investigation of domain wall dislocation interactions. THE influence of lattice defects on the motion of domain walls in ferromagnetic materials has been studied extensively both theoretically and experimentally.4 The experimental data obtained has been qualitative in nature due to the lack either of a quantitative knowledge of the magnetic domain array in the material or of the nature of the dislocation configuration in the material. At room temperature RbFeFJ has the cubic perovskite structure. It is ferromagnetic below 86°K.5,6 It is also transparent and has a large faraday rotation in the magnetic state.7 The domain structure of this material is observable in three dimensions in crystals which are millimeters in thickness.&apos; Since RbFeF3 satisfies the requirements of having an easily visible three-dimensional magnetic domain structure, it was of interest to determine if the dislocation structure of the material could be determined and if the material was sufficiently plastic so that dislocations could be introduced into the as grown crystals. This is a report of the results of that investigation. EXPERIMENTAL PROCEDURE The crystals of RbFeFs used in this experiment were grown by a technique described elsewhere.5 In order to obtain flat strain-free surfaces, the samples were first cut to the crystal orientation desired and the surfaces were polished by employing standard metallographic techniques. The samples were then immersed in a solution of 1 to 3 g of KOH in 100 ml of water. This solution removes the damaged surface layers uniformly leaving a film on the surface of the sample. Etch pits are obtained by immersing the sample in an approximately 50-50 solution of 30 pct peroxide and concentrated acetic acid. The film formed during the KOH treatment turns deep red in color in the etching solution and flakes off the sample. The etching time required depends upon the pit size desired and

Jan 1, 1970

By Pradeep K. Rohatgi, David N. French, Surendar M. Jain, Clyde M. Adams

The effect of solute concentration and diffussivity on dendritic solidification of dilute binary aqueous solutions has been investigated; chlorides of sodium, potassium, lithiurn, and hydrogen were used as solutes. Dendrite spacings were measured in spherical droplets and in unidirectionally solidified specimens. In the droplets, the freezing rate is uniform over the entire specimen and remains constant from the beginning to the end of solidification. In the unidirec-tionally frozen specimens the freezing rate varies within a given volume of liquid during the solidification cycle; in addition, it varies with location uithin the specimen. Mass transport analysis has been used to calculate the supersaturation, AC, supercooling, AT, and transcerse growth velocity, V , of ice dendrites during solidijication from the dendrite spacings measured in the droplels. The ice dendrite spacing in a given solute increases lineary with the solule concentralion at a fixed freezing rate. The ualues of AC, AT, and V increase with an increase in solule concentration. The value of AT in the aqueous solution is of the same order of magnitude as in Al-Cu alloys of the same concentration; the dendrite spacings in Al-Cu alloys also increase with an increase in solute concentralion. For the jamily of aqueozrs solulions incestigaled, the dendrite spacing increases linearly with solute diffusivity at fixed values of concertralion and freezing ,rate. The values of ?C and ?T decrease, whereas the value of V increases with an increase in solule diffusicity. The measured dendrite spacings , L, can be expressed by the relatiun: L = K;(dfa/db) 4 K2C +K3D - K4 where dfs/d? is-change in fraction solid with time (freezing rate), C is solute concentration, D is solute diffusivit K1 = (14 * 4)pmin1&apos;2, K2 = (70 ± 10) pl (moles)- K3 = (24 r 3) . l05 psec (cm)-~. K. = -132 ± 10) 1. FREEZING of solutions is almost always an ehunmix-ing" process because the composition of crystallizing solid generally differs from that of the parent liquid. " Solute concentration and transport are therefore in]portant considerations in solidification of solutions. The influence of these factors on the dendritic solutions produced from metallic solutions is of practical significance since the properties of the solid aggre-gate are often strongly influenced by dendrite spacing.&apos;&apos;&apos; Alexander and Fthines3 found that dendrite spac- ings generally increase with solute concentration in several metallic systems. Michael and Bever1 have observed an increase in a aluminum dendrite spacings in dilute A1-Cu alloys. Rohatgi and AdamsJ have reported a linear increase in a aluminum dendrite spacings with increasing copper contents up to 28 pct in A1-Cu alloys. Bolling and Tiller"&apos; have theoretically examined the effects of solute concentration and diffusivity on the growth of cells and dendrites. Their analysis of dendritic growth assumes a steady-state growth and the maximum possible velocity for dendrite propagation. In addition, the quantitative analysis is restricted to dendrites of rotational symmetry and is therefore not directly applicable to the plate-shaped dendrites of ice obtained in the present study. There are practically no experimental observations of the effect of solute diffusivity on dendrite spacings in metallic systems. The reason appears to be the lack of experimental data on solute diffusion coefficients in liquid metallic solutions. The present work is concerned with the effect of solute concentration and diffusivity on dendritic solidification of dilute aqueous solutions: the solutes examined are potassium chloride. sodium chloride, lithium chloride. and hydrogen chloride. There were several reasons for selecting these solutes. The variation of dendrite spacing with freezing rate in these solutiolls is similar to that observed in A1-Cu alloys.8 These aqueous solutions have almost identical phase diagrams at dilute concentrations. Fig. 1. and the diffusion coefficients show very little variation with solute Concentration.9,10 Dendrite spacings were measured as a function of freezing rate. solute concentration. and solute diffusivity. Dendrite spacings were measured in two different types of freezing systems. droplet and unidirectional, respectively. In the droplet freezing system

Jan 1, 1970

By T. S. Lundy, R. E. Pawel

Effects of short-circuiting paths on observed diffusion behavior in real crystalline systems are considered. It is concluded that experimentally measured diffusion coefficients may vary widely from values associated with true lattice diffusion to those appropriate for short-circuiting paths alone depending upon the conditions of the experiment and the sensitivity and completeness of the data. IN 1961 Harrison1 classified experimentally observed diffusion behavior in systems involving both lattice and dislocation-enhanced atomic transport into three categories. His types A and C were limiting cases where the measured diffusion coefficients using the usual serial sectioning techniques were representative of lattice diffusion (with only slight effects of dislocations) and dislocation-network diffusion (with only slight effects from lattice diffusion), respectively. In both cases A and C for a sectioning experiment in which the diffusion couple has the semi-infinite geometry and unidirectional diffusion takes place from a plane source located at the origin of the coordinate system, he pointed out that Gaussian penetration behavior should be observed. For case A the lattice coefficient should be slightly enhanced by dislocation contributions, and the model of Hart2 can be used to predict the amount of this enhancement. For case C the observed coefficient should be that for the dislocation network and have little or nothing to do with lattice diffusion. Hart&apos;s model in its general form is still applicable, but the apparent diffusion coefficient for this case is virtually independent of dislocation density. Harrison&apos;s case B is that for which non-negligible contributions exist for transport by both mechanisms and "the concentration distribution does not approximate to any simple form." With the possible exception of very low temperatures where diffusion distances approach atomic dimensions, any real diffusion specimen will in general show non-Gaussian behavior provided the data are complete enough to uncover it. Thus, a "complete" set of data for any real system cannot be expected to be totally amenable to treatment by a simple mathematical model which does not take into account the relative distribution of transport by the various modes or submodes. For a particular sensitivity of specimen analysis and at a given temperature of annealing if the concentration profile could be observed as a function of time, "the behavior will initially be type C, and will develop into type B. and ultimately type A".1 Thus, it appears that the type of diffusion behavior which is experimentally observed in a given system depends very much upon the particular experimental conditions and the particular tools available to obtain the data. Interpreted in this fashion, Harrison&apos;s classification refers not to the diffusion behavior as a whole but to the relative sensitivity of the method of examination and completeness of the data. In the present paper we will: 1) assume that the measured penetration behavior follows the same general classification as that proposed by Harrison; 2) give, for diffusion in tungsten, examples of the range of diffusion coefficients that it is possible to obtain in a single experiment; and 3) speculate that some arguments which consider the possibility of short-circuiting effects being responsible for "anomalous" diffusion in several bcc metals may have been discarded prematurely.3 Both monocrystalline and polycrystalline tungsten were used in this work. The former was obtained as triple-pass, electron-beam zone-refined 6.0-mm-diam rod from Materials Research Corp.. Orange-burg. N.Y. The latter was swaged, high-purity bar stock which was annealed for 2 hr at 2200°C and 10-9 torr to yield an average grain diameter of about 25 /i. The tracer Nb95 was received in oxalate solution from the Isotopes Division, Oak Ridge National Laboratory. Experimental procedures of specimen preparation, isothermal diffusion annealing, serial sectioning by anodizing-and-stripping, and y counting of the individual sections to determine the tracer penetration profile after a given diffusion anneal have been described elsewhere.4 However, it should be noted that the anodizing-stripping sectioning technique has the particular advantage for this research of permitting sectioning to be accomplished over a wide range of

Jan 1, 1970

By Rex O. McLellan

The formation of a monovacancy in a metal is simulated in an elastic model by the displacement of the surface of a small spherical cavity in a large elastic continuum. The application of linear elasticity to this distortion results in a well- known formula for the energy and an expression for the concomitant entropy change due both to the shear strain in the continuum and also to the dilation of the solid resulting from the boundary conditions at the surface of the solid. Elastic data (the sliear modulus and its temperature coelficient) are used to calculate the entropy and energy of formation for many metals. Despite the simplicity of the assumptions involved, the agreement between the calculated entropies and energies and experimental values is remarkably good. In recent years there has been a large increase in measurements of the absolute concentration of mono-vacancies in metals as a function of temperature. Hence new data for both the energy and the noncon-figurational entropy of formation of monovacancies has become available. Recent measurements&apos; of the anomalous (non-Arrhenius) self-diffusion in many bcc metals has also focused interest on the prediction of the thermodynamic parameters of mono- and multi-vacancies in those metals for which no data are available. Damask and Dienes&apos; have discussed the various theoretical calculations of the energy of formation EL, of a monovacancy. These include simple models involving the breaking of atomic bonds on moving atoms from the interior of a crystal to the surface, models combining elastic calculations with surface-energy terms and detailed quantum mechanical calculations. The simler models give the correct order of magnitude of &, but tend to overestimate it by a factor of about two. The quantum mechanical calculations4"7 have been carried out for the noble and alkali metals with generally reasonably good agreement with the available Ef data. The calculation of entropy of formation Sfv14 lnvolves a fundamental calculation of the perturbation of the phonon spectrum caused by the creation of a vacancy. Huntington, Shirn. and wajda8 have given an approximate evaluation of sJV by considering an Einstein model for the localized vibrations in the immediate neighborhood of the defect and then using elastic theory to calculate the entropy associated with the shear stress field in the distorted crystal (as originally proposed by Zenerg). They also included a term due to the dilation of the crystal. They obtained a value of 1.47k for copper, in good agreement with the experimental value (1.50k). However, Nardelli and Tetta- manzi1° have recently shown that neglecting the coupling between atoms (Einstein Model) may lead to a serious error so the agreement may be somewhat fortuitous. In this work simple linear elastic theory is used to calculate the entropy and energy of formation of mono-vacancies. Despite the simplicity of some of the assumptions involved, the agreement with the available experimental data is remarkable. However. the reasonable degree of success in the application of linear elastic calculations to the excess entropy of a solute atom in a dilute solid solution1&apos; indicates that the application of elastic theory to vacancies. where the interaction of different atomic species is not involved, may not be inappropriate. THE ELASTIC MODEL The metal is assumed to be a spherical elastic continuum. A small spherical cavity of volume V = 4i;v:&apos;/3 is cut from the center. removed. and dissolved rever-sibly in the bulk of the material. TO a good approximation no net atomic bonds are broken and the material does not undergo a volume change although the externally measured volume of the body would increase by V. The radius of the sphere of metal is much larger than r Next a negative pressure is applied to the cavity causing its surface to be displaced inward by an amount simulating the relaxation of the lattice around a monovacancy. In this model the energy and entropy accompanying the distortion are taken as 4, and <. As a first approximation the equation of state for the solid is taken as: r = ro(i + *~D LiJ where K is the bulk modulus. P the hydrostatic pressure. Vo the volume of the material at 0°K and zero pressure. and d+/dT = 30. where 0 is the linear thermal expansion coefficient. The variation of entropy with hydrostatic pressure is given by the Maxwell equation: These equations give the entropy change resulting from increasing the hydrostatic pressure from 0 to P as: and since • we have: This is the entropy arising from the dilation resulting

Jan 1, 1970

By D. G. Westlake

Resistance was measured as a function of temperature, 77° to 350°K,for niobium with hydrogen concentrations up to 3.76 at. pct. Cooling curves exhibited a discontinuity in slope that was attributed to the initiation of hydride formation. A thermal hysteresis was explained in terms of diffusion and the effects of mechanical constraint on nucleation and growth. The heat of solution of hydrogen in saturated Nb-H solid solution was 2. 737 * 0.045 kcal per g-atom, including an unknown stress contribution. The critical ternperatures for hydride formation during cooling and for embrittlement are correlated but not coincident. This, too, has been explained in terms of mechanical constraint and stress-itlduced tratzsfomtation. Nb-H alloys undergo a ductile-brittle transition with decreasing temperature.&apos;-3 Similar behavior has been noted for v-H.1,5 For the latter system, there is evi-dence6 suggesting coincidence of the temperature of minimum ductility and the critical temperature T, for initiation of metal hydride precipitation during cooling. A decrease in ductility due to the presence of brittle hydride particles is readily explainable. The fact that ductility begins to decrease at some temperature higher than T,4,5 has led us6 to suggest that precipitation may be strain-induced locally during tensile testing. Wood and Daniels&apos; have reported that a plot of temperatures for 10 pct reduction in ductility vs hydrogen concentration in niobium is not coincident with, but parallels, the solvus.7,8 They believe this indicates a correlation of precipitation and embrittlement. Unfortunately, the two reported solvuses 7,8 to which Wood and Daniels refer are not in agreement with each other. Furthermore, neither solvus was determined experimentally: each was a plot of calculated solubilities. Thus. neither is highly dependable for determining whether embrittlement coincides with initiation of hydride precipitation. Longson 9 studied phase relations in the Nb-H system between 77° and 473°K by dilatometry. Comparison with metallographic observations convinced him that discontinuities in the slopes of his dilatometric plots were coincident with the initiation of hydride precipitation. Plotting the logarithm of the hydrogen concentration vs the reciprocal of the temperature at which precipitation was initiated during cooling, he obtained a straight line shown in Fig. 1. Walter and chandler,&apos;&apos; using X-ray techniques to detect the for mation of a second phase? have obtained three experimental points in the temperature range 295° to 338°K which fall within Longson&apos;s experimental error for this plot. A similar plotg of temperatures at which dissolution was completed during heating was a parallel line shifted toward higher temperatures. A straight-line plot was obtained, also, for the temperatures of the ductile-brittle transitions,9 but it was shifted toward still higher temperatures. Longson calculated an activation energy of 2.980 * 0.300 kcal per mole for the hydrogen embrittlement mechanism, compared with 3.180 * 0.400 kcal per mole for hydride formation. Despite this agreement, he concluded, "It seems unlikely that embrittlement results from hydride formation..." because hydrogen embrittlement was observed at temperatures above the solvus. It is our contention that embrittlement is correlated with precipitation of the hydride.6 Because only Longson has investigated Nb-H phase relations at sub-ambient temperatures, we deemed it advisable to re-determine the temperature dependence of the solubility using the resistometric technique already proven successful for the V-H system.6 Coincidence of our solvus with temperatures for embrittlement would

Jan 1, 1970