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By J. E. Hilliard

AS is well-known, the length per unit volume, Lv, of any lineal feature (such as grain edges in a polycrys-talline specimen) can be estimated from a count of the number of point intersections with a random plane of polish. Specifically:' Lv = 2NA in which NA is the expected number of intersections per unit area of the plane. As with all other measurements in quantitative metallography, the estimation of Lv is subject to a sampling error, the magnitude of which will depend on the number of observations. The analysis is usually performed by counting the number of intersections falling within a closed test figure of known area applied to a succession of different areas on the plane of polish. The test figure can be drawn directly on the screen of a projection microscope or else superimposed on the image of the structure by means of a reticule in a focusing eyepiece of an ordinary microscope. The use of micrographs is very inefficient unless, as in the present study, these are also needed for some other purpose. Consider an analysis in which n applications are made of a test figure within which the expected number of intersections is N. The expected total number of intersections counted is then given by NT = nN If (N) is the standard deviation in N for one application of the figure and if the latter is applied to non-overlapping regions so that the N's are independent in the statistical sense, then the standard deviation in Nt is given by: a(NT) = a(N)vn Eliminating n from Eqs. [2] and [3] we obtain: Thus, k will be a constant for a given specimen and test figure. From Eqs. [ I] and [4] we find As is to be expected, therefore, the fractional error in the estimation of Lv is inversely proportional to the square root of the total number of intersections counted. It is very desirable to have at least a rough estimate of k before starting an analysis, since it will then be possible to decide in advance by use of Eq. [5J how many counts should be made in order to achieve the desired accuracy in Lv. Without such information the investigator, unless lucky, will either do needless (and tedious) work or else obtain a result with too large an error. It is very easy to calculate k for the limiting case of N — 0, i.e., when the test figure is vanishingly small. In this case there is a negligible probability of two or more intersections falling within the figure. There are therefore only two possible outcomes: a count of one with a probability of, say, p and a zero count with a probability of (I-p). Thus and Therefore: We might expect k to depend on N and therefore on the size of the test figure. Such a dependence was observed2 in the analogous case involving the estimation of grain-boundary area per unit volume by a count of the number of intersections of a test circle with traces of the boundaries on the plane of polish. In this case the theoretical value of k at the limit N — 0 was 1.41. It was also predicted that k would display an initial sharp decrease with increasing N. Experimentally, k was observed to decrease to a value of 0.62 at N - 6 and thereafter remain approximately constant. Furthermore, the value of k for N > 6 was found to be insensitive to the form of the structure provided no pronounced anisotropy or grain-size variation was present. In order to determinewhether k would exhibit a similar dependence on N in the estimation of grain-

Jan 1, 1967

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

VARIOUS organic compounds, such as borneol, carbon tetr a bromide, and hexachloroethane, solidify as transparent plastics with a fcc structure. Each of these substances undergoes a solid-state transformation from the plastic phase to a brittle phase at temperatures slightly above 20°C. Since it was known that these plastic crystals solidified like metals,1 it was decided to investigate the possibility that solid-state grain growth would occur in the same way as it does in metals. Two-dimensional grain growth in thin films of plastic organic compounds has been studied with the aid of cinemicrophotography. Samples varying in thickness between 250 and 1000 @ were prepared by subliming a thin layer of the compound onto a microscope slide plate which was then covered with a second slide plate.

Jan 1, 1968

By S. A. LoPilato, J. T. Smith

SEVERAL techniques have been evaluated for cooling the throat area of rocket-nozzle inserts to prevent erosion or fracture of the inserts during exposure to high operating temperatures and pressures. Self-cooled composites, such as infiltrated tungsten, have shown considerable promise for these applications. These composites can be fabricated by infiltrating the refractory matrix with a lower-melting metal or non-metal which is insoluable in tungsten. During firing, the lower-melting substance undergoes a series of continuous endothermic phase changes which absorb sufficient heat to maintain the nozzle matrix material at or below a safe operating temperature. At present, the state-of-the-art has reached a point where the refractory matrix density and microstruc-ture have been established as the critical parameters to be controlled for optimum self-cooled performance.'" Nondestructive testing has been utilized to ensure that porous tungsten billets were of uniform density and free from cracks or other defects prior to fabrication into rocket nozzle inserts. Ultrasonic-velocity techniques have been employed because of their reliability and reproducibility. The purpose of this note is to present and interpret the test data developed for porous tungsten matrices. For evaluation purposes, tungsten powders with Fisher subsieve sizes of approximately 4 and 18 p have been obtained for study from four commercial sources: the General Electric Co., Wah Chang Corp., Fansteel Metallurgical Corp., and Kennametal, Inc. Porous tungsten matrices were fabricated from the powders by hot pressing in induction-heated graphite die assemblies. Typical billets ranged from 3 in. diam, 2 in, high to 5 in. diam, 5 in. high. The ultrasonic-velocity measurement technique employed was through transmission, pulse echo at a frequency of 1.0 mc using matched barium titanate crystal transducers. The testing equipment included a pulsed ultrasonic generator, an amplifier, a specimen holder, and an oscilloscope, as shown in Fig. 1. The porous tungsten thickness was measured to i 0.0005 in, with precision micrometers while the oscilloscope achieved 0.02 psec time measurement accuracy. The time for a sound wave to pass through the billet, the bulk wave velocity, was calculated to 0.5 pct using Eq. [l]: V-} where V = bulk wave velocity, in. per psec, T = specimen thickness, in., and / = time, psec. To develop inspection standards, the bulk density of a porous tungsten billet was determined by the ASTM water-immersion technique.3 The ultrasonic-velocity measurements were completed at seventeen positions for each billet and averaged to develop a characteristic standard velocity for a particular tungsten powder at several density levels. A plot of ultrasonic velocity vs density is presented in Fig. 2 for six different tungsten powders. This graph has been established as

Jan 1, 1967

By H. C. Fiedler

THE development of the cube-on-edge secondary re-crystallization texture in Si-Fe strip depends upon the ability of inclusions to restrain normal grain growth. This ability is determined by the number and size of inclusions, which, for a given composition, is controlled by the thermal history of the material during the prior processing.' It has been shown2 that increasing the silicon content decreases the solubility of sulfur, and it is the purpose of this note to show the consequences of this decreased solubility for secondary recrystallization. Heats were made as previously described and cast into graphite molds.' The compositions are shown in Table I. Slabs 1 in. thick were cut from the ingots and either hot-rolled from 1000°C in the as-cast condition or after one of the heat treatments described later. The processing to the final gage of 12 mils followed the previous procedure.' To avoid cracking, the 5.2 pct Si alloy was cold-rolled at 150" to 200°C rather than at room temperature. The percent cube-on-edge texture developed by isothermal heat treatments was determined by dividing the maximum torque measured on disk sam-

Jan 1, 1968

By A. Hansson, G. E. Tardiff

WHILE it is generally known that cold-worked low-and medium-carbon steels exhibit substantial increases in tensile rupture ductility with increased deformation velocity172 (up to the von Karman limit), the observations for annealed or normalized steel do not permit simple generalization. Various investigators, for example, have reported both small increases1,3 and small decreases4,5' in rupture ductility with increased rates of deformation of normalized low-carbon steel. The purpose of the present note is to report on the dependence observed for strain-aged steel since preliminary work here indicates that strain aging results in the development of a consistent type of behavior that is understandable in the light of current knowledge of the lower yield dynamics for steels which deform inhomogeneously.6 This realization throws additional light on the influences responsible for the behavior of normalized steel. The results presented here were obtained for a 0.21 pct C, 0.012 pct N sheet (0.012 in. thick) steel which was received in a temper-rolled condition (approximately 3 pct reduction in thickness after process annealing); the as-received material had a spherodized structure with a ferritic grain size of ASTM 8. The material was selected for testing after 6 months room temperature aging, at which time the static lower yield and ultimate tensile strength measured 79 and 82 kpsi, respectively. ASTM 2-in. reduced section, 1/2-in.-wide specimens were used in smooth bar tests and 3/4-in.-wide specimens containing two 60-deg opposed edge notches (root radii = 0.002 in.) were used in notched bar tests. To facilitate strain measurement, the smooth bars were blued with ink and marked at 0.1-in. intervals along the gage length; the notched

Jan 1, 1968

By A. S. Argon, G. East

From their study of the anisotropy of grain boundary mobility in aluminum, the authors conclude that tilt boundaries have a higher mobility than twist boundaries because the atomic misfit at the pure-twist boundary is relatively small compared to the misfit at a tilt boundary for a given amount of misorientation. If this is true, then one would expect a twist boundary to have a lower grain boundary energy than the corresponding tilt boundary. Fig. 6, taken from the work of Gjostein and Rhines,10 shows that this is indeed the case for [001]-cu tilt and twist boundaries in the high-angle region, thus lending support to the authors' conclusion.

Jan 1, 1968

By P. H. Thornton

MaNY intermediate phases are solid solutions which have a solute-solubility range greater than 3 at. pct. These phases, which are generally very strong and often have simple crystal structures, are usually extremely brittle so that specimens of simple shape cannot be produced by the usual mechanical-deformation techniques. Furthermore, single crystals of reasonably uniform composition are difficult to grow by the Bridgman technique because the phases generally form by a peritectic reaction, which causes pronounced segregation. In this note, a technique is described for the preparation of thin-rod specimens of brittle intermediate phases, which may be used for physical-property studies such as resistivity changes' and for the conversion of such rods into single crystals. The method has been used for the preparation of rod single crystals of the phases and Ingots, of about 100 g weight and 11 mm diam, were made by melting together the appropriate amounts of high-purity materials (usually 99.999 pct) in sealed

Jan 1, 1967

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

THE use of galvanic cells for the determination of oxygen activities has spread rapidly since the suitability of calcia-stabilized zirconia as a solid electrolyte material was first demonstrated by Kiukkola and Wagner.' In many of these investigations:-7 including several at ARL, the free-energy changes for various oxidation-reduction reactions involving the oxides FexO, NiO, and Cu2O have been measured as a means of assuring that a cell apparatus is functioning properly. As a result, a large quantity of data pertinent to the calculation of the high-temperature standard free energy of formation (?GO) of these oxides has been accumulated. AGFexo has been carefully measured in many independent investigations, using a variety of techniques, and consequently is accurately known. chipmans has used this informa-

Jan 1, 1968

By Alexander Coucoulas

FABRICATION of thin-film circuits deposited on glass substrates requires the formation of permanent electrical contacts. Since thin films are in the order of a few thousand angstroms thick and are deposited on nonconductive surfaces such as glass, new methods of lead attachment are being pursued in the microelectronics industry. Ultrasonic welding is being considered in thin-film technology since joining can be accomplished between a wide variety of dissimilar materials.l,' Ultrasonic welding is accomplished by a transducer-coupling-tip system which converts high-frequency electrical energy into mechanical vibrations and delivers it into the weld region. During the process the tip oscillates in a direction parallel to the surface of the weldments, inducing shear stresses in the work pieces which are clamped between the tip and anvil. Though the basic bonding mechanism is not clearly understood, it has been described as closely akin to friction welding. In the course of an investigation concerned with ultrasonic we!ding of aluminum wires to tantalum thin films (1400A) deposited on glass, low weld strengths were related to glass failure. Upon investigating this condition, an improved method of bonding was developed where the aluminum was held at a temperature where a minimum amount of strain hardening occurred during the introduction of ultrasonic energy. Experimental Procedure. Aluminum wires (0.015 in,) were bonded to tantalum thin films with an optimized set of welding parameters (power, time, clamping force) employing a commercial 100-w 60-kc ultrasonic welder. Forty-five degree shear-peel tests, where the lead is pulled at a 45-deg angle with respect to the substrate at 0.2 in. per min, produced a large variation from zero to the strength of the wire, Table I. Inspection of the weld region generally revealed: glass cracking before and after testing; the removal of glass nuggets from the substrate by the lead during testing, Table I; thin-film penetration. In an effort to improve the shear-peel strength, the aluminum between the tip and substrate was heated above ambient temperature through an argon gas media prior to and during welding with the same parameters employed above. With the addition of heat: wire deformation was increased; shear-peel tests all failed at the weld-wire junction, leaving the bonded portion undisturbed; no evidence of glass cracking or film penetration prior to or after testing was observed. In order to prevent failure at the weld-wire junction due to excessive wire deformation, 0.035-in. aluminum wires were welded to tantalum thin films with an optimized set of welding and heating parameters. As

Jan 1, 1967

By Shrikant Lele

INTRINSIC and extrinsic stacking faults may be formed in fcc structures by similar processes with bounding S-and D-Shockley partial dislocations respectively.' The only difference between these two dislocations is that the side on which the fault lies is reversed. The number of nearest and next nearest neighbors of atoms is identical for the two faults, but that of next next nearest neighbors is different. Thus, the energies associated with intrinsic and extrinsic faults may be expected to be different but of the same order of magnitude. An extrinsic fault can be constructed from two intrinsic faults on adjacent close-packed planes. This suggests that the extrinsic fault energy is higher than the intrinsic fault energy. It is, therefore, surprising that extrinsic faults have not been detected in X-ray studies2 of deformed alloys of low stacking fault energy. These have, however, been observed in cerium3 by X-ray diffractometry and in Au-4.8 at. pct Sn4 and Cu-16.6 at. pct A15 alloys by transmission electron microscopy.

Jan 1, 1968

By P. L. Rittenhouse, M. L. Picklesimer

A rapid and seniquantitative method of determining prefered orientation on large numbers of. Zircaloy-2 specimens was desired. knoop microhardness measurerrzetzls were irvestigated as a solldtion to this pro6lem. The variation of Knoop microhardness measurerlerzts on selected planes as a function of 'irzdenle axis relutilje lo cryslallograplzic or fabrication divectals were used to corzstrrcl a polar coordinate hardness contour map. With use of an empirical relationslip between the single-crystal hardnesses and those of the polycrystalline material conentional pole figures could be constructed which compare favorably also obtained. To determine preferred oriention qualitatively from hardness data requires a minimum of twelve measurements per plane on three, preferattention to grain size, specimen prepartion, and in-rreinetzt, and analjlsis is of the order of- 45 to 60 rrin. THE design of structures from Zr alloys requires consideration of preferred orientation and the resulting anisotropy of mechanical properties. Rapid and semi-quantitative methods of evaluating anisotropy and of determining preferred orientation are needed for quality control and for examining the large number of test specimens required in development programs. The variation of Knoop microhardness with indenter orientation has been studied in single crystals of several hcp metals including titanium.' beryllium,' magneium, and zinc.4 The maximum hardness observed on any crystallographic plane other than the basal plane invariably occurred when the long axis of the Knoop indenter was either parallel or perpendicular to the projection of the [ OOOI.] direction on the plane of examination. When the major slip mode was (0001)(i2i0j the maximum hardness occurred at the parallel positio! but when the operating slip system was {10i0) (i210) the hardness was a maximum perpendicular to the [0001] projection. A minimum hardness was always observed at a rotation of 90 deg from the maximum. It follows that the orientation of the projection of the [0001] can be determined on any non-basal plane by making hardness measurements at a number of indenter orientations. The determination of the orientation of the [0001] projection on two non-parallel, preferably orthogonal, surfaces of the specimen will allow location of the [0001] direction in the specimen. It seems possible that such measurements could be used to examine, at least qualitatively, the preferred orientation existing in polycrystalline hcp materials. An investigation of the microhardness anisotropy in Zircaloy-2 was undertaken to ascertain whether these measurements could be used for this task. EXPERIMENTAL PROCEDURE Single crystals of Zircaloy-2 were grown by an a-8-a annealing sequence using electron-beam heating.= The orientation of the crystals was determined by a conventional back-reflection Laue technique. The crystals were then mounted on a goniometer head and the desired crystallographic faces were milled and chemically polished. Polycrystalline Zircaloy-2 specimens were prepared from fabricated sheets or plates. Inverse pole figures for these materials were obtained using the X-ray diffraction techniaue described by Jetter, McHargue, and illiams.' A Wolpert-Greis Micro-Reflex hardness-testing machine was used to make the Knoop microhardness measurements. The single-crystal and polycrystalline specimens were loaded to 0.5 and 2.0 kg, respectively. Determination of the scatter of hardness numbers as a function of applied load for several indenter orientations on several specimen surfaces showed that the loads selected were the lightest consistent with minimum scatter. Heavier loads did not appreciably decrease the scatter and produced hardness impressions too large to be conveniently measured with the equipment used. Seven crystallographic planes of the single crystals were examined, while six planes of examination were used in studying Zircaloy-2 polycrystals. The specimens were rotated 10 to 15 deg after each measurement and from four to eight impressions were made at each angle of rotation. RESULTS The two angles which were used to relate crystallographic directions and planes in the hcp cell to the planes of examination of the single crystals are shown in Fig. 1. 8 is the angle between the c axis. [0001]. and the normal, N, to the plane of examination. a is the angle between the long diagonal of the Knoop indenter and the projection of the c axis on the plane of examination. For exampIe, if P = 90 deg and a = 0 deg, the plane of examination is of the family

Jan 1, 1967

By Robert E. Green, T. Hinton

The velocities of the three possible modes of elastic-wave Propagation have been calculated for single-crystal aluminum at 1-deg intervals throughout the standard steveographic triangle. The results are presented as isospeed contours. The deviations between the direction of maximum energy propagation and specirzen axes are presented as arrows drawn within the standard triangle. The orientation factors associated with dislocation nzotion on the primary slip system only and also on all twelve slip systenzs have been calculated for all three elastic waves. The orientation factors associated with a longitudinal standing--7aue resonant specivnen hazle also been calculated. The relevance of these results to ultrasonic attenuation measurements is discussed. DUE to the widespread use of ultrasonics in the investigation of the properties of solids a number of authors15 have discussed in detail the theory of elastic-wave propagation in solids. In this paper the modes of wave propagation are evaluated according to the procedure suggested by reeen' for the case of single-crystal aluminum at 1-deg intervals throughout the standard stereographic triangle. The wave speeds are presented in the form of contour diagrams within the standard triangle. The deviations between the direction of maximum energy propagation and the normals to the wave fronts are presented as arrows drawn within the standard triangle. The orientation-de pendent factors (orientation factors) associated with dislocation damping as derived in the preceding paper6 have been calculated for the case of aluminum at 1-deg intervals throughout the standard triangle. The orientation factors for dislocation motion on the primary slip system only and on all twelve slip systems are presented in the form of contour diagrams, for both the traveling- and the standing-wave conditions. The relevance of these results to ultrasonic attenuation measurements is discussed. ELASTIC-WAVE PROPAGATION Three waves can be propagated in a linear elastic homogeneous anisotropic medium. The velocity of propagation v of each of these waves in a medium of density p can be obtained from the determination of the eigenvalues and eigenvectors of the matrix equa- The A's are a series of moduli which are functions of the elastic constants cij and the direction cosines 1, m, and n of the specimen axis. In the case of cubic single crystals where there are only three nonzero elastic constants cll, c12, and C, the A's are, The solution of Eq. [I] will give the wave speeds (eigenvalues) and the direction cosines a, 0, and y of the particle displacements (eigenvectors). To obtain the direction of maximum energy flux requires the calculation of the energy-flux vector ET with com- w is the angular frequency, A, the amplitude, and v the velocity of the wave. The direction cosines a, b, and c of the energy flux vector are then given by

Jan 1, 1967

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

The steady-state creep of TD Nickel NL + 2 001 pct TltOz) has been studied orer the telirperatve range 325&apos; to 1100O and the stress range 15,000 to 36,000 psi. At high temperatures (aboue 0.5 T& gran-boundary slzding is the )nost znportant )node of creep deformation, and the steady-state creep rate, is, can be related to stress and temperature by: where Q = 190 kcal pev mole and n has an unusually high value of 40. A creep mechanism based on cross slip of dislocations around The O2 particles can satisfactovily explain the low-temperature (T < 0.5 T,) cveep behavior, and the follo wing relation is applicable: Q, (a) is found to decrease from 57 to 46 kcal per mole as the stress is increased from 32,000 to 36,000 psi. THERE have been a variety of theories proposed to explain the influence of dispersed second-phase particles on the yield strength and flow stress of metals, and these have been reviewed recently by Kelly and icholson.&apos; However, only several attempts2"4 have been made to develop mechanistic treatments which characterize the creep behavior of dispersion-strengthened metals, and to date these have not been fully evaluated experimentally. weertman2 and Ansell and weertman3 proposed a quantitative creep theory for coarse-grairzed dispersion-strengthened metals, based on the concept that the rate-controlling process for steady-state creep was the climb of dislocations over second-phase particles, as suggested by choeck. The theory predicted that the steady-state creep rate, <,, was proportional to the applied stress, a, for low stresses and that is a4 o for high stresses. The activation energy for creep, Q,, was equivalent to that for self-diffusion, Qs.d., in the matrix. Some limited experimental evidence in support of this theory was obtained on a recrystallized Al-Alz03 S.A.P.-type alloy by Ansell and Lenel.6 Ansell and weertman3 also developed a semiquanti-tative theory for high-temperature creep of lineg-rained dispersion-strengthened metals in order to explain their results on an extruded S:A.P.-type alloy, which had a fine-grained fibrous structure. They suggested that the rate of dislocation generation from grain boundaries was the rate-controlling process, and fitted their results to the equation: where Q, was found to be 150 kcal per mole, i.e., QC- 4Q,.d. in aluminum. Similar high activation energies for creep7-&apos;&apos; and tensile deformation" of dispersion-strengthened alloys have been observed by other investigators for S.A.P.,&apos;" indium-glass bead omosites, and Ni + A1203 alls.&apos; There is no general agreement regarding the mechanisms involved in the creep of dispersion-strengthened metals, and this is due in part to the lack of detailed studies relating the structures of crept specimens to the mechanical behavior. The present investigation on thoriated nickel was undertaken with the aim of studying the structural changes which occur during creep of a dispersion-strengthened alloy and rationalizing the observed mechanical behavior in terms of the creep structures. EXPERIMENTAL METHODS The material used in this investigation was 1/2-in.-diam TD Nickel bar, which contained 2.3 vol pct Tho,. Obtained from E. I. duPont de Nemours & Co., Inc. The final fabrication treatment by DuPont consisted of -95 pct reduction by swaging followed by a 1-hr anneal at 1000°C. Transmission and replica electron microscopy revealed that the material had a fine-grained fibered structure with an average transverse grain size of -1 p and a longitudinal grain size of 10 to 15 p. Selected-area diffraction indicated that the fiber axis was parallel to (OOl), in agreement with the results of Inman eta1." All creep specimens were vacuum-annealed at 1300°C for 3 hr prior to testing. Transmission electron microscopy showed that the only structural change due to annealing was a slight decrease in dislocation density, confirming the reported high degree of structural stability.13 Furthermore, recrys-tallization or grain growth during creep was never observed. The structure typical of uncrept material (after the 1300 C, 3-hr anneal) is shown in Fig. 1. The grain boundaries are predominantly high angle and. although some areas show a tangled cell structure, the grain interiors are relatively dislocation-free. Individual dislocations are strongly pinned by the Tho2 particles; i.e., very rarely did dislocations move within a thin foil. The grey "halos" around some of the larger particles which protrude out of the foil surface arise from contamination in the electron microscoge. The Tho, particle size ranged from -100 to IOOOA, and the distribution is shown in Fig. 2. The technique used to obtain the data in Fig. 2 consisted of dissolving the nickel matrix in acid, collecting the Tho2 particles on cellulose acetate, and measuring about 1000 particle diameters in the electron microscope. Similar results were obtained by measuring about 600 particles in thin foils, an; the average particle size was found to be 2r, = 370A. Using the data in Fig. 2 (annealed structure), the mean planar center-to-center particle

Jan 1, 1967

By S. Shapiro, J. A. Ford

The crystallo graphy of several grains of the lamellar Ni-Ni3 B eutectic solidified under conditions appvoachirt equilibriun has been examined.. A preferred interlace relationship has been observed in this system which may be described as: A detailed study of this interface by means of an atomistic model reveals the interface Plane to be puckered and more accurately describable as: Analysis of the atomic configuration on these planes reveals that this interface conforms to the orientation criteria proposed for directionally solidified lanzellar eutectics. In addition, a model is proposed to help explain the growth of a "puckered" interface. DURING the past several years an increasing number of unidirectional solidification experiments on eutectic alloys have been reported in the literature. The primary emphasis, in most cases, has been the effect of growth variables on microstructure. Some authors have, however, studied the crystallographic orientations and interfacial relationships resulting from these experiments. Four crystallographic studies have been published;&apos;-4 in each of these there is a factor which tends to prohibit the extension of the observations beyond the particular system. In the Al-CuA12 system, the approximately equal volume fractions of the phases have resulted in sorrie controversy as to which phase constitutes the matrix. In the Mg-Mg,Sn eutectic the presence of several interconnecting lamellar systems2 complicates the analysis. The two remaining eutectics. 1nSb-b and Al-Ali, are both rodlike (the latter exhibits a plate morphology at low solidification rates): the matrix in each of these alloys is the simpler (fcc) phase. Studies of nucleation in eutectic alloys indicate that the more complex constituent is the nucleating -.phase.&apos; For the purpose of an analysis of interface crystallography it was deemed desirable to study a lamellar system in which the matrix was the more complex and, presumably. the nucleating phase. Recently it has been shown that there is a eutectic in the Ni-B system between Ni3B and i; preliminary investigation by the authors indicated that the matrix in this eutectic is the boride phase. The structure of Ni,B is reported to be orthorhombic, the compound being isostructural with cementite. This eutectic is therefore analogous to that between austenite and cementite. Furthermore, the Ni-B system is not susceptible to a competing eutectic reaction as occurs in the Fe-C alloys; nor does it exhibit a eutectoid decomposition. For these reasons the study of the interfacial relationship in the Ni-Ni3B eutectic was undertaken. PROCEDURE Ingots of nominal composition 3.5 and 3.6 wt pct B were induction-melted in boron nitride crucibles within a graphite susceptor under a boric oxide slag; a dynamic argon atmosphere was maintained over the melt to prevent rapid oxidation of the susceptor. The raw materials used were 99.97 pct Ni from Huntington Metals Division of International Nickel Co. and 99.8+ pct B chips supplied by the United Mineral and Chemical Co. The analyses of the starting materials are listed in Table I. The melt was held at 1500cC for 2 hr to insure complete reaction and allowed to cool to room temperature. The castings were chemically analyzed for boron and were metallographically examined for uniformity. The metallographic samples were mechanically polished through 0.1 p A1,0, and etched with Carapella&apos;s reagent. Each master casting was cut up to make several specimen blanks which were remelted, in boron nitride crucibles, to form ingots of 1/2 to 3/4 in. in diarn by 7 in. long. These ingots were unidirectionally solidified using a modified vertical Bridgman technique. The rate of solidification was assumed to be equal to the uniform rate at which the crucible-susceptor assembly was withdrawn from the induction coil. This rate was varied from 1.18 to 2.21 cm per hr. In order to perform these experiments it was found necessary to redetermine the eutectic composition. This was accomplished by the zone-melting technique described by Yue and lark.&apos; An ingot of 4.5 wt pct B was zone-melted in a horizontal boron nitride boat 7-1/2 in. long with a 112-in.-square cross section. A

Jan 1, 1967

By D. J. Schmatz, H. I. Aaronson, H. A. Domian

Diffusion kinetics in disordered hcp Cd-Mg alloys have been investigated by means of the Kirkendall effect and concentration-penetration curves determined with an electron-microprobe analyzer. Self-diffusion coefficients of both species were determined at the three marker compositions obtained, averaging 27.6, 46. 7, and 78.1 at. pct Mg, by means of the Darken analysis. These coefficients were then corrected for the unequal and concentration-dependent partial molar volumes of the two elements with the Balluffi analysis, and for the vacancy flux effect by the Manning analysis. The latter correction reduced the Balluffi correction produced larger changes in the self-diffusiv-ities; neither, however, produced statistically significant changes in the Do&apos;s or the H&apos;S. The most striking result of this investigation is that at all three compositions and at all temperatures studied both the uncorrected and corrected self-difjusivities of magnesium are higher than those of cadmium. The Cd-Mg system is the first one found in which the higher melting, lower vapor pressure element diffuses more rapidly. Both an empirical correlation due to Toth and Searcy and considerations of the atomic mechanism of diffusion indicate that this anomaly is probably due to a comparatively low value of the activation energy required for a magnesium atom and a vacancy to exchange sites, perhaps occasioned by the higher compressibility of magnesium atoms. KIRKENDALL effect studies have been previously reported for only two hcp solid solutions: the E phase of the Zn-Cu system1 and the a phase of the Cd-Hg system.&apos; In neither investigation were the marker-movement studies supplemented with the concentration-penetration curve determinations necessary to evaluate self-diffusivities by means of the atano and the Darken analyses. The present program was undertaken to obtain both types of data on a hexagonal solid solution in order to provide more detailed information relevant to the mechanism of diffusion in this type of lattice. The Cd-Mg system was chosen for this study because the disordered solid solution extends across the entire phase diagram at temperatures above 253"c5 and the substantial difference in the melting points of the component pure metals promised that marker movements would occur at reasonably rapid rates should the diffusivities of the two species be as unequal as might be anticipated. The experimental convenience of the relatively low melting points of cad-miun and magnesium and the availability of extensive and accurate activity data6 (required for application of the Darken analysis) were additional reasons for selecting this alloy system. Since the anisotropy of diffusion is not large in either pure cadmium7 or pure magnesium,&apos; the diffusion couples were prepared from polycrystalline components. The presence of a well-defined texture in the couples—the c axis of individual crystals tended to be normal to the diffusion direction— however, provides a fair degree of crystallographic definition to the data obtained. The principal (and entirely unexpected) finding of this investigation, that magnesium, the high-melting low-vapor pressure element, diffuses more rapidly than cadmium, in contradiction to a broad range of results in fcc and bcc alloys, as well as in the previously studied hcp alloys,172 makes the self-diffusivity determinations of immediate interest in understanding the origin of this anomalous result. EXPERIMENTAL PROCEDURE The cadmium (Belmont Smelting and Refining Co.) and magnesium (Dow Chemical Co.) used in this study were both of 99.99 pct purity. Alloys containing 51.0 and 65.6 at. pct Mg were prepared from these materials by melting under a MgC12-base flux in a high-purity graphite crucible. These alloys were subsequently hot-worked and then homogenized in a helium atmosphere at temperatures close to their solidus points. Sandwich-type diffusion couples of the type g/d/g were prepared from the pure metals by solid-state diffusion. Two-piece alloy couples of Mg/65.5 at. pct Mg (Mg/gCd) and Cd/51.0 at. pct Mg (Cd/CdMg) were welded by a liquation technique. The individual components of both types of couple were initially cylinders 1.27 cm in diam and in length; the ends of these cylinders were machined accurately flat and parallel. For both welding techniques, the pure cadmium cylinders and the alloys were chemically polished in a mixture of 40 pct ethyl alcohol, 40 pct hydrogen peroxide (30 pct conc), and 20 pct nitric acid,g while those of pure magnesium were polished in a solution of 10 pct nitric acid in ethyl alcohol.&apos; Immediately afterwards, both metals were rinsed in freshly distilled acetone, and then in similarly purified methanol.&apos; The Mg/Cd/g couples were assembled in a carefully cleaned stainless-steel welding fixture, in which a screw operating through a self-centering arrangement permitted a controlled pressure to be exerted upon a couple prior to welding.&apos;&apos; Tungsten marker wires 0.005 cm in diam were placed at the d:g interfaces of some of these couples, and imbedded in the couples during the application of pressure. As soon as a couple had been assembled, the welding fixture was inserted into a Pyrex capsule containing a packet of zirconium chips at each end. The capsule

Jan 1, 1967

By R. J. Wasilewski

Elastic constants have been determined on single crystals of maximum-melting-temperature NiAl compound (50.6 at. pct Al) at 25°C. Temperature variations of Young&apos;s modulus in the three principal crystal directions between -150°C and +800°C exhibit no anomalies similar to those repovted for the isomor-phous compounds brass and AuCd. It is concluded that the ordered CsCl structure is stable throughout the temperuture range investigated NICKEL aluminide is a congruently melting inter-metallic compound of CsCl (B2) structure, stable over a rather wide composition range (40 to 54 pct Al). It exhibits a lattice-parameter maximum of a. = 2.883A at 50.6 pct 1,&apos; at which composition the excess aluminum atoms are randomly distributed on the vacant nickel sites;&apos; at higher nickel compositions the excess nickel atoms replace substitutionally in aluminum sites, while at higher aluminum compositions vacancies are present in the nickel sublattice.&apos; For compositions close to NiAl no significant variation in order has been observed at temperatures up to 900°C.3 At high nickel (65 pct) compositions the existence of a martensitic structural transformation has been reported.4 NiAl is isomorphous with the ordered B-brass structure and with the high-temperature structures of AuCd and TiNi alloys close to equiatomic composition. All of these exhibit anomalous elastic behavior as the temperature of their diffusionless transformation to lower-symmetry structures is approached.&apos;-&apos; This behavior has been explained as indicative of low stability of the CsCl structure in these compounds.8 The present paper reports the experimental determination of the elastic compliances of single-crystal NiA1. EXPERIMENTAL METHOD 1) Specimens. Polycrystalline NiAl was prepared by induction melting of carbonyl nickel and high-purity aluminum and casting into solid copper molds in gettered helium atmosphere. The castings thus produced were canned in mild steel and impact-extruded at 1100 to 1200°C to 38-in.diam rod. After the steel sheath was pickled off, the rods were converted to single crystals by repeated high-frequency satisfactorily produced the desired orientations in the form of crystals 38 in. diam by 8-12 in. long. These were subsequently center less-ground to 7 to 8 mm diam by 12 cm long, electropolished (in 80 pct methanol, 20 pct HzSO, at 25°C and 15 v), and their axial orientation determined to 1 deg by the Laue back-reflection technique. The rod dimensions were determined to 0.01 mm and the densities determined from geometrical dimensions and the weight of every specimen. The average density was 5.905 0.005 g per cu cm. 2) Elastic Data Measurements. Room-temperature elastic compliances Sii were obtained by determining to 0.1 cps the fundameGtal resonance frequencies in the longitudinal and torsional vibration modes. At these frequencies the following relations hold: E =p(2lfif =pvl= Sn- 2r[Sll- S12- -£„«] g -P(2iftf = pvf = (s<« - fr(sii - sw - ±s»y where vl and vt are the velocities, and f andft the resonance frequencies of the longitudinal and torsional waves, respectively; 1 is the length of the specimen, and r is the direction cosine factor—{cos2 a • cos2 0 + cos2 a . cos2 y + cos2 0 ¦ cos2 Y}. Given three crystals of orientations (loo), (110), and (111)) i.e., F = 0, 14, and 13, we can obtain six equations for the three unknown compliances, thus providing adequate internal check. Mode mixing can readily occur in the relatively long wavelength resonance utilized here. This could cause a significant error in the torsion wave velocities calculated from the apparent resonance frequenies. Therefore, throughout the present work, a method, described previosl,&apos; was used to ensure that no significant mode mixing took place at resonance. The apparatus used was originally designed for the Elastomat, Magnaflux Corp.. Chicago, 111. determination of flexural vibration resonance frequencies. At room temperature torsional vibration mode could be established by suitable positioning of the thin wires from the input and pick-up transducers, and longitudinal mode by cementing thin magnetic foils at the ends of the specimen, and inducing the vibration by means of electromagnetic transducers. Only flex-ural resonance frequencies could, however, be obtained reproducibly over the temperature range of -150 to 800°C. These data are considerably less accurate, the error in the modulus being estimated at -0.6 pct from the specimen dimensions and the room-temperature Poisson&apos;s ratio. The reproducibility of the resonance frequencies in repeat runs was, however, to better than l in 15,000, hence the relative elastic modulus error less than 0.02 pct. Therefore, the temperature variation of the principal Young&apos;s moduli obtained by flexural resonance, relative to room-temperature values, is believed to be satisfactorily accurate.

Jan 1, 1967

By R. P. Abendroth

The hydrogen-water vapor ratio at which Fe-Cr alloy, chromium oxide, andiron chromite coexist in equilibrium was determined between 900" and 1200°C. A thermogravimetric method was used to determine equilibrium conditions. The results fit a straight-line relationship in the temperature region studied, and are given by Reduction experiments were also performed to confirm the results of the equilibrium investigation. ThE oxygen pressures at which Fe-Cr alloy, chromium oxide, and iron chromite coexist in equilibrium have been previously determined by Boericke and angert,&apos; Morozov and Novokharski,&apos; and Katsura and uan. Only one determination (at 1300°C) was made by Katsura and Muan, but it agrees with the results of orozov and Novokharski. The results of Boericke and Bangert, however, differ appreciably from the results of these investigators. Previous studies have assumed that the equilibrium metallic phase is pure iron, but Dahl and Van vlack have shown that the iron contains from about 1 wt pct Cr at 1000°C to over 2 wt pct above 1300°C. The chromium oxide also contains a small amount of iron in solid solution. In the present study, hydrogen-water vapor mixtures were equilibrated with the condensed phases, using a therrnogravimetric method to determine equilibrium conditions. The reaction can be written EXPERIMENTAL General Procedure. The starting material was a sintered pellet of Fe2O3-Cr2O3 solid solution with a hole in the center, and was placed on a fused silica hook. This assembly was raised into the preheated hot zone of the furnace in a helium atmosphere, hooked onto a fused silica hangdown suspended from one arm of an Ainsworth Model RV-AU-1 recording balance, and the starting weight determined. A flowing hydrogen-water vapor atmosphere was then exchanged for the helium by evacuation, and the sample reduced until the weight loss indicated the sample composition to be in the alloy-Cr2O3-chromite field. The tem- perature was adjusted incrementally until constant sample weight was achieved for several hours, to within 0.02 mg. A hydrogen-water vapor atmosphere of different composition was then admitted, and the same procedure carried out. At the end of a series of determinations, the sample was examined by X-ray diffraction to verify the presence of the desired phases. Microscopic examination of the silica hook showed no interaction with the sample, nor did it lose any weight. Several criteria were used to insure equilibrium besides constancy of weight. For a given hydrogen-water vapor composition, equilibrium was approached from both oxidizing and reducing sides by varying the furnace temperature slightly. The resulting slow weight loss or gain was observed for several hours. Constant weight could be re-established by returning to the original furnace temperature. The last criterion used was varying the relative amounts of the phases by further reduction or oxidation, and observing any changes in temperature required for constant weight for a given hydrogen-water vapor atmosphere. None were observed. This procedure was essentially the same as approaching the equilibrium from oxidizing and reducing sides, but larger weight excursions were carried out. Sample Preparation. Reagent-grade Fe2O3 and Cr83 powders were mixed in the desired proportions and heated in air at 1250°C for 2 hr. The mixture was re-ground and heated in air overnight at 1250°C. X-ray diffraction showed complete solid-solution formation as a result of this procedure. The solid solution was then pressed into l/2-in.-diam pellets using Carbowax 4000 as a binder. The hole was drilled in the center, and the pellets were sintered 24 hr at 1250°C in air on a bed of Fe2O3-Cr2O3 of the same composition, contained in an alundum boat. After cooling, the pellet surfaces were abraded with 310 paper to remove any surface compositional differences, such as loss of Cr2O3. Chemical analysis of the sintered pellets was 67.16 wt pct CrP3 and 33.02 wt pct Fe203. Atmosphere Generation and Control. The hydrogen-water vapor atmospheres were generated by passing Matheson ultrahigh-purity hydrogen, with no further purification, through two water bubblers contained in a constant-temperature water bath. Since the water-vapor dew points required in this study were below room temperature, the bath was insulated, and was cooled by thermoelectric-immersion devices. The bath temperature was controlled to 0.0l0C. Since rather high flow rates of about 900 ml per min were used through the furnace tube, an independent check of the dew point was made to insure saturation of the hydrogen by the water vapor. Although the dew point could only be determined to within 1/2"C, the determined dew points agreed with the water-bath temper-

Jan 1, 1967

By R. S. Wagner, C. E. Miller, H. Brown

A dc field was applied to liquid BI-Sx or Au-Ge alloys of eutectic composition. The liquid alloys were kept at a temperature slightly above the eutectic. The concentration changes due to electrodijfusion are large enough to cause nuclcation and growth of the primary phases at the respective electrodes. Nearly complete separation of Bi-Sn eutectic was obtained as well as substantial separation of Au-Ge eutectic. The effect of an electric field on the solute distrihn-tion was itluestignted itt tlirectiortally solidified rods of a dilute Bi-Sn (0.5 al. pc,t Bi) alloy. Field-freezing was carried out in small-diameter cupillay tubes to avoid cotuectice mixing -of the liquid. The relative sollcte corzcentratioi, Cs/Co , was rneusred by n radioac1il.e tracer netlod. Cs/Co can be made both largev than unity or srialler than the equilibiuwz distvibrrlion c.oejyicienl, k, , oiler a substattiul portion of the soliclifi&apos;erl rocls. A direct current, passed through a liquid-metal solution, can cause substantial concentration changes by electrodiffusion. The magnitude of the change depends on the difference in ionic mobilities of the atomic species in solution. Electrodiffusion has been studied in many binary and ternary liquid alloys.&apos;y2 It was found that the rate of material transport decreases with time for a constant applied field, as a concentration gradient is established in the solution. A steady-state concentration profile is achieved when electro-diffusion is compensated by chemical diffusion. This may seem to limit the use of electrodif fusion for metallurgical application. However, a way of utilizing the effect of electrodiffusion is to combine it with crystallization or controlled freezing. rakin was first to propose this as a new method of separating metal alloys of eutectic composition at temperatures slightly above the eutectic temperature. It was possible by this method to separate Bi-Sn and Bi-Cd eutectics into their component phases. Angus et al discussed the possibility that the effective distribution coefficient, keff, could be varied by proper application of an electric field during solidification. The combination of electrodiffusion and solidification, called field-freezing, was discussed in detail by Pfann and aner. It was shown that field-freezing can be used as a crystal-growth process, an efficient method for eutectic separation, and a new means of changing the effective distribution coefficient. k,ff, beyond the usual range of ko < k,ff < 1. The liquid layer adjacent to the solid-liquid interface can be either increased or depleted in solute due to

Jan 1, 1967

By G. G. Hancock, H. H. Johnson

Hydrogen gas at atmospheric pressure is shown to cause substantial embrittlement in a martettsitic high-stretzgth steel. Subcritical crack growth is observed at very lom stresses and with high growth rates. It is suggested that an adsorbed layer of hydrogen atoms at the crack-tip surface provides the damaging hydrogen. Oxygen in small quantity, as little as O.7 pct by volume, is shown to eliminate subcritical crack growth in gas environments caused by hydrogen or water vapor. However, dissolved oxygen in water has little or no influence upon crack-growth rates. Oxygen-stopped cracks may be restarted by water, or by hydvogen or water vapor if oxygen is removed from the environment. These observations are interpreted in terms of preferential adsorption of oxygen at the crack tip and the formation of an oxide barrier. RECENT investigations1-3 have demonstrated that environmental factors are frequently responsible for delayed failure in martensitic high-strength steels. The environment causes crack initiation from preexisting cracklike flaws at unexpectedly low stresses, often far below the uniaxial yield strength. The crack then propagates at a rate controlled by the environment and the crack-tip stress-field intensity; during this period crack propagation will cease if either the stress or the aggressive environment is removed, and this may be considered a definition of subcritical crack growth. Fracture occurs when the crack has grown to a critical length, such that the fracture toughness of the steel is exceeded. Several liquids are known to cause delayed failure, but water and water vapor are the most severely damaging of the environments investigated to date.&apos;-3 It has been suggested that hydrogen produced during corrosion reactions may be the actual embrittling agent2 The severe embrittlement caused by water vapor inevitably raises the question as to whether other gas environments are damaging. Previous work4&apos;5 has demonstrated that high-pressure hydrogen (2250 psi or greater) is an effective embrittling medium, as measured by such criteria as reduction in area, notch tensile strength, and time to failure. Moreover, the embrittlement was eliminated by the addition of small quantities of air or oxygen to the high-pressure hydrogen, but it was not influenced by additions of nitrogen or argon.4 In the present study attention is focused upon gas environments at atmospheric pressure, in particular hydrogen and oxygen. The influence of these constituents upon the initiation and growth of a crack from a pre-existing cracklike flaw in a high-strength steel was determined directly by the electric-potential method of monitoring crack growth. MATERIALS AND PROCEDURE The H-11 steel was supplied by the U.S. Naval Research Laboratory as 3 by 12 by 0.065 in. sheet specimens with 1-in. transverse center slots. The slot tips were finished by Elox machining to a radius of 0.001 in. or less. The yield strength was 230,000 psi; chemical composition and heat-treatment schedule are given in Table I. The experimental apparatus, precracking procedure, and incremental loading sequence have been described previously.3 In the only significant change, precracking was sometimes carried out by a hydrogen embrittlement and baking technique. All experiments were conducted at room temperature; the hydrogen gas environment was purified by a commercial palladium purifier. Crack initiation and propagation were followed by the electric-potential method,&apos;-3 using a calibration that has been recently dicussed. Stress-field intensities at the crack tip were computed by the conventional Irwin frmula; the plasticity correction was negligible and therefore not included. EXPERIMENTAL RESULTS A striking brittleness associated with molecular hydrogen at atmospheric pressure is demonstrated by the data in Table I1 and Fig. 1, which indicate that subcritical cracks in hydrogen initiate at lower stress-field intensities and propagate more rapidly than in fully humid argon. Ki and Kf are the crack-tip stress-field intensities at initiation and termination of subcritical crack growth, respectively. Termination, of course, corresponds to fracture. In both hydrogen and humid argon Ki is less than Kf

Jan 1, 1967

By R. F. Hehemann, Darrell W. Smith

The kinetics of alloying- in W-5 rot pct Re powder compacts were investigated at temperature about the upper limit for the formation of the x phase, such that a single intermediate phase was involved in the process. The rates and directions of motion of the a-o and o-b interface were assessed as functions of tinze at the sintering teri7peraticve by quantitative izetallog-ralhic techtziques. The iiotion 01 these interjuces could be specified approxitnate1.y by u Parabolic )-ate law and deviations from this ,rate law were attribuled to a complex interaction between surface dif&apos;fusion and volume diffusion during the initial stages of sintering. WHEN binary or more complex alloys are produced by sintering compacted blends of elemental powders, a complication is encountered which does not arise in the sintering of pure metals. In addition to concern for grain size and densification, the rate of inter diffusion of the component elements must be considered. The general problem of alloying during sintering has been treated by numerous investigators.&apos;-7 These investigations have been concerned only with systems that form continuous series of solid solutions and a concentric-sphere diffusion model4 provides a useful description of homogenization in these stems.&apos; Some controversy remains, however, over the contribution of surface and grain boundary diffusion to the homogenization process. Heckel% ePorts that homogenization can be described by volume diffusion at all temperatures, whereas other invetiators&apos;&apos; recognize the importance of surface and grain boundary diffusion, particularly at lower temperatures. Analysis of the homogenization process in partially miscible systems is complicated by the motion of the interfaces separating the individual phases. A simple analytical solution does not exist for such finite systems with spherical symmetry. It was the purpose of this work to examine the kinetics of the formation and dissolution of an intermediate phase in a binary system through an assessment of the motion of the interfaces separating this phase from the terminal solid solutions. PROCEDURE The W-Re system is an example of a partially miscible binary system and was selected for study because of its current importance in refractory-metal technology. The equilibrium phase diagram, Fig. 1, shows that the o phase will be formed by interdiffu-sion between tungsten and rhenium. At temperatures between approximately 2125" and 282O°C, the o phase will appear as the only intermediate phase in the diffusion system. In this work, a mixture of elemental powders containing 5 pct Re was employed. In such a mixture, the rhenium particles will be distributed randomly in a tungsten matrix. During sintering, a o-phase layer will form at the W-Re interface. The development and subsequent disappearance of the o phase are controlled by the relative rates and directions of motion of the 0-0 and a-p interfaces. The motion of these interfaces can be inferred from quantitative metallographic measurements of the average radii of the o shells surrounding rhenium particles. Elemental tungsten and rhenium powders of commercial purity were employed in these investigations. The rhenium powder was spheroidized from +200 mesh agglomerates by plasma-arc spraying and was then classified to yield a powder composed of essentially

Jan 1, 1967