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By R. D. Pehlke, J. V. Gluck

AS a portion of a general study of liquid-metal thermodynamics, high-temperature galvanic cells were used to study the effect of added dilute solutes on the activity of zinc in dilute solution with molten bismuth in the range 450° to 650°C. 1,2 The cells were of the type The experimental procedures have been described previously.1 In the course of studies conducted in the bismuth-rich corner of the systems Bi-Zn-Au and Bi-Zn-Cu, marked discontinuities were observed in the electromotive force-temperature relations for a number of the experimental compositions. Above the discontinuity temperatures, the relations, which were linear, exhibited slopes similar to the binary alloy of the same mole fraction zinc, as shown in Figs. I and 2. Below the discontinuity temperatures, the slopes were markedly different, but the relations remained linear. In general, as the amount of the third eletnent was increased, the slope of the lower portion of the relations tended to become less positive. The slopes of electromotive force-temperature relations reflect the entropy of mixing of zinc and, therefore, the occurrence of a discontinuity marks the transition between two different equilibrium situations involving the solution of zinc. A number of other investigators3-5 have used such observations to determine liquidus boundaries in binary alloys. Since the upper portions of the ternary electromotive force-temperature relations of this study had the same slopes as the binary alloys, the discontinuities are interpreted as marking the transition between the single-phase liquid region and the underlying two- and three-phase regions. Reference to the Zn-Bi equilibrium diagram6 confirms that the binary alloys were single-phase liquids at the experimental temperatures. Fig. I shows the electromotive force-temperature relations for the alloys containing Bi-Zn-Au and Fig. 2 shows similar relations for the Bi-Zn-Cu alloys. In the lower portion of each figure, the temperature of the discontinuity is plotted vs the mole fraction of the added solute at the various levels of zinc concentra- tion. Cross-plots from these curves at constant temperature permitted the construction of the partial liquidus surface isotherms shown in Figs. 3 and 4.

Jan 1, 1967

By R. D. Carnahan, G. A. Stone, R. J. Arsenault

An experimental technique has been developed for carrying out a dynamic tensile stress-strain test in which plastic strain is measured continuously throughout the microstrain region extending through the macroflow region to total deformations of 5 pet. The tests were carried out on niobium, samples having interstitial impurity levels of 160 and -800 ppm at temperatures ranging from room temperature down to 100°K. A band spectrum of activation energies was obtained from calculations based on the measured activation volumes and temperature dependence of flow stress. The inability of a single rate-controlling process to predict such a phenomenon has led to the proposal that several sequential rate-controlling dislocation mechanisms are operative in the preyield micro-strain region. These are thought to be: the motion of geometrical kinks, the formation of double kinks in edges, and finally in the macrostrain region the formation of double kinks in screws. In less pure niobium the effect of interstitial impurities is shown to be dominant in the microstrain region, suggesting that a fourth probable mechanism is overcoming interstitial barriers instead of geometrical kink motion and the formation of double kinks in edge dislocations. THE principal fundamental aim of most mechanical properties studies of crystalline solids is to determine the dislocation mechanisms responsible for the plastic behavior. The extension of such studies to the region of preyield microstrain behavior has received renewed attention in the past few years as the details of macroscopic flow behavior have become better understood. For the most part, microstrain studies have been carried out using one of two variations of a single experimental technique.1 The first method involves loading the sample at a constant extension rate to a predetermined stress level (less than the macroscopic yield stress), instantaneously unloading, and then determining the extent of plastic deformation to a sensitivity of 10"6. The microscopic stress-strain curve is then constructed from the results of a repeated series of such individual measurements, each of which involves loading to an incrementally higher stress level, by relating the accumulated plastic microstrain for each step to the maximum applied stress in that step. The second variation, also carried out by step-wise increases in stress, measures the total strain to a sensitivity of ~10"6 and relates the maximum stress to the area of closed hysteresis loops that are generated under certain conditions (namely, prestrained samples). The foregoing methods have yielded interesting information about the nature of preyield deformation and plastic response to stresses below the yield stress, but they offer certain disadvantages for studying the dynamic behavior of dislocations. In the first method it is physically impossible to specify a plastic strain rate inasmuch as the test sample is reexposed, as it is loaded to its maximum stress in a particular step, to lower stresses at which flow will take place. The strain corresponding to a given stress level on the stress-microstrain curve thus generated will then always be greater than that at the corresponding stress level of a truly dynamic test carried out at the same extension rate. The second method has been used to obtain correlations with dynamic macroscopic flow parameters by applying dislocation damping theory to the hysteresis loop areas.2 The approach has had some success but suffers in that only samples that have been prestrained a few percent can be studied. Although the stresses

Jan 1, 1968

By C. S. Yust, Lida K. Barrett

The change in shape of the void in a sirzterir~g copper mass has been investigated as a juntction of' density. A serial sectioning' technique was used to eoaltrate the irregular shape of the void at two levels qf density. A measure of the void size and configuration, the proximity number, is defined and used to describe the progress of void removal. The process of. void removal deduced front the observations of this study contrasts with current sintering models in that it takes into account the irregularity of structure of a sintering mass and demonstrates that isolated Porosity does not occur first as spherical pores, but as large, definitely nonspherical sections of the void void volume. The process of sintering, about which there is much practical and theoretical knowledge, has evaded a direct and thorough analysis despite the intensity with which it has been studied for 60 years or so. This is due, of course, to the complex structure of a sintering mass and the inability to observe directly the development of a fully dense solid from the initial particulate arrangement. Extensive theoretical analyses have been based on the adoption of one or another of several model systems, that is, by visualization and analysis of some sort of regular assembly or arrangement of geometric "particles" approximating the conditions of a sintering mass. It seems appropriate at this time to try to examine experimentally in some detail the extent to which a sintering mass of irregular particles dlffers from these models. Many models deal with neck growth and the initial stage of sintering and follow the direction established by ~ucz~nski' in 1949 for the sintering of spheres to flat plates. Recently Johnson and cutler2 have adapted these models to sintering of powder masses. coble3 has presented a mathematical model for sintering that applies to the middle and final stages of the process. These papers, without exception, assume a regular geometry, generally spheres in contact in a regular array. Rhines~ and coworkers, however, are studying the sintering process by applying a model based on the topological concept of genus which permits them to consider an irregular structure. whites has described the various models with the exception of that of Rhines et al., and the assumptions on which they are based and their shortcomings. The present paper examines the geometric changes that occur in the powder mass during sintering by examination of the void. The method is to analyze a series of partially sintered structures and to propose from this analysis the sequence of events which occur in the removal of the void space as a sintering mass progresses from a collection of individual particles to a solid body. The irregular nature of the stacking of particles and of the particles themselves will be taken into account. The significant points derived from this study are: first, accurate reconstructions of the irregular void shapes are presented; second, it is clearly established that closed porosity occurs first as widespread volumes of interconnected porosity, definitely nonspherical in shape; and third, a new factor, the proximity number, is defined, which serves in this paper as a tool for describing the void shape changes observed, and which will be used in a later paper as part of the basis of a mathematical model for sintering. While the specific material studied is copper, the observations are thought to be relatively general as indicated by comparison of the results with partially sintered structures in other materials presented in the literature, both metallic and nonmetallic. EXPERIMENTAL PROCEDURE Four series of specimens representing progressive stages of the sintering process were prepared by sintering high-purity copper powder for various time periods. A relatively large particle size was used so that the void-solid interface could be readily distinguished at low magnification. In three series of specimens a loose stacking of particles was obtained by pouring powder into an alumina mold and lightly tapping the mold. The green density of such compacts was approximately 40 pct of theoretical density. Two of these three series utilized irregularly shaped particles in the size range -230 +325 mesh, one series sintered in vacuum and one in hydrogen at 950°C. The third series of loosely stacked particles consisted of spherical particles in the size range -270 +325 mesh, sintered in hydrogen at 950°C. A fourth series was prepared from compacted irregular particles sintered in hydrogen at 950°C. The specimens for this series were formed by lightly pressing the irregularly shaped particles in a steel die; the green density of the pressed pellets was approximately 60 pct. The irregularly shaped particles used in this study are shown in Fig. 1. The density of these particles, measured by a toluene picnometer technique, is 98.2 pct of theoretical density. Each particle is highly convoluted, and in some instances appears in cross section to contain internal porosity. The density measurement, however, indicates that completely enclosed porosity is very small so that the individual particles have a highly irregular surface but are essentially fully dense copper. Therefore, most of the void space that appears in two dimensions to be isolated within the particle is actually at the particle surface and connected to the external void in the dimension not included in the plane of the cross section. The void space that appears as void surrounded by the par -ticle or within folds in the particle w~ll be r~fc\r?

Jan 1, 1968

By A. J. Stosick, J. R. Hoffman, E. Rudy, St. Windisch

The binary alloy system Mo-C zoas investigated by means of X-ray, metallog/aphic, thermoanalytical, and melting-point techniques on chemically analyzed specimens. The system, Fig. 39, is characterized by three congruently melting, intermediate phases, Mo2C, n MoCi-x, and aMoC1-,, of which only Mo,C is stable at temperatures below 1650°C. Substoichio-metrzc (~32.5 at. pct C) dimolybdenum carbide undergoes a homogeneous sublattice order-disorder transformation at temperatures of approximately 1400°C, whereas hyperstoichiorrletric compositions undergo a discontinuous Phase change. The order-disorder transitions in the Me, C phases are discussed in terms of the structural changes involved in the transformation processes and the absence of long-range sublattice coherency in stoichiometric or hyperstoiclziomet-ric compositions attributed to the impossibility of obtaining long-range order in a linear chain of alternating carbon atoms and vacancies. From the experimental phase relutionships and the known thermody-namic data for Mo2 C, limits for the free energies of formation for the high-temperature phases r) MoC1-, and aMoC1-, are deriued and found to be in good agreement with data previously obtained from phase equilibria in ternary metal-carbon systems. IN the course of studies of the high-temperature phase relationships in ternary systems of refractory transition metals with carbon,' a number of inconsistencies found in previous work necessitated a reex-amination of some of the related metal-carbon binaries. A reassessment of the binary system data also seemed

Jan 1, 1968

Jan 1, 1967

Jan 1, 1968

By Werner Engelmaier

Constant-strain rotating-bending fatigue tests were conducted on 2024-T3 aluminum alloy constant-strain McAdams-type specimens in ultrahigh vacuum, 10-lo Torr, and in atmospheric air. In the elastic strain range the ratio of vacuum-to-air fatigue life varied from about 10 at a maximum bending stress of 37 ksi to near unity at the endurance limit. After 10 pct of the fatigue life, intergvanular microcracks appeared on the surface which did not appreciably propagate further until the last 5 pct of the fatigue life, where trans-granular cracks propagating first in slip-plane cracking and then in the stress-dominated mode led to failure. No reduction in residual tensile strength resulted from the fatigue of the specimens short of fracture. The mechanism governing the fatigue life operates between the occurrence of the intergranular microcracks and the initiation of the trans granular cracks. MORE than forty years ago, Mc Adam' and Haigh2 published the first systematic studies showing that the fatigue properties of metals were greatly affected by environments. Gough and sopwith3 found in a later study that the fatigue life of metals subject to corrosion can be substantially increased by reducing the atmospheric pressure. This and their later work4'5 was, however, done in a vacuum of only 10~3 Torr. Subsequent studies6-' at a vacuum of 10- Torr showed that water vapor is the primary agent affecting the fatigue properties of aluminum alloys. Only recently was ultrahigh vacuum used for fatigue studied.l Various theories have been put forward to explain this phenomenon. Wadsworth and Hutchings12 postulated that cracks form very early in the test and that the chemical attack by the corrosive components of the atmosphere at the root of the cracks enhances the speed of the crack propagation. They also noted that chemisorbed layers of gas on the fresh crack surfaces prevent cold welding of the crack and make the separation irreversible. Ham and Reichenbach, on the other hand, reported that their specimens showed no cracks after a run in vacuum, even though the runs were long enough to have caused the specimen to fracture in atmospheric air. They also reported that in argon at 0.14 Torr the fatigue life was about 5 times longer than at 7 X lo-' Torr. Jacisinll reported that fatigue tests in dry nitrogen showed results close to those obtained in ultrahigh vacuum. The present experiment was designed to determine the extent to which cumulative fatigue damage, i.e., the accumulation of length of fatigue cracks, reduces the residual static tensile strength of an aluminum alloy in both ultrahigh vacuum and atmospheric air and to obtain fatigue-life data for this aluminum alloy at various strains. It was also hoped that information ex- tracted from these data might support one of the previously mentioned theories. 1) EXPERIMENT Test Specimens. The material tested was commer-cial 2024-T3 aluminum alloy. In addition to aluminum, this alloy contains approximately 4.4 pct Cu, 0.5 pct Fe, 0.5 pct Si, 0.6 pct Mn, 1.5 pct Mg, plus smaller amounts of other elements.13 Some typical mechanical properties of this aluminum alloy are listed in Table I.'~ The material was used in the as-received condition, i.e., solution-treated and cold-worked. Mc Adam-type1' constant-stress specimens and notched fatigue specimens were machined from 4 -in. -diam rods, Fig. 1. The critical section of the McAdam-type samples was polished with a 45-deg spiral motion to a No. 8 microfinish. The notch in the notched specimens was machined on a lathe with a forming

Jan 1, 1969

By R. H. Hopkins, R. W. Kraft

X-ray and metallographic analysis reveal that the preferred cryslallograPhic relationships in direc-tionally solid~fied Pb-Sn eutectic specimens can be stated: interface growth direction, Experiments in which tin single-crystal seeds were used to nucleate the eutectic demonstrate that the normal lamellar structure observed at steady state can be forced to break down initially to a semide-generate structure when the crystallograPhic direction of the tin seed does not lie within the preferred eutectic interface plane. A normal structure eventually develops by preferred grain growth. X-ray topo-graphs and rocking curves substantiate that the perfection of eutectic samples increases as growth proceeds until steady-state conditions prevail. RECENT years have seen substantial progress made in the understanding of eutectic solidification through both intensive theoretical1'' and experimental investigations (see Ref. 7 for a review and extensive bibliography of both aspects). Several important observations concerning the nucleation and growth aspects of binary eutectic solidification have been brought to light. Briefly some of these include the nonrecipro-cal nucleation of one phase upon another,'j9 the tendency for a specific low-index direction of one or both phases of the eutectic to be aligned in the growth direction during unidirectional solidification,'0711 and the production of lamellar microstructures having a preferred interface plane between "11-13 phases. Questions quite naturally arise as to the mechanism by which preferred grain growth evolves during eutectic solidification and what relationships (if any) connect the initial nucleation of one phase upon another with the preferred growth directions and interface planes observed after a few centimeters of growth in many systems. This study was initiated in an attempt to answer these questions. An experiment was devised in which both the nucleation and growth steps in the crystallization of a binary eutectic, Pb-Sn, could be correlated with subsequently developed eutectic morphology and crystallography. This was accomplished by nucleating the eutectic upon a tin single crystal seed and then causing the eutectic to grow from the seed by directional freezing. The morphology of the structures produced in this manner was then monitored metallographically and the orientation relationships and substructural perfection determined by X-ray analysis. The information thus ob- tained was correlated to the growth history of the samples. EXPERIMENTAL DETAILS The eutectic of composition 38.1 wt pct Pb and 61.9 wt pct sn14 was prepared by accurately weighing lead and tin of 99.999+ (from ASARCO and Lytess Metals and Chemicals, respectively), melting in a clean Pyrex beaker under an argon blanket, and casting into the proper crucible for resolidification as described below. Tin seeds were grown by the method of ~halmers," saw-cut, oriented by the Laue method, and soldered to the pull rod of the Czochralski puller. All seeds were given a final electropolishing (to assure the removal of any deformed material from the cutting operation) and acetone degreasing immediately prior to the nucleation experiment in which they were to be used. Eutectic samples were unidirectionally solidified in a horizontal graphite boat1' or by pulling from the melt16 with tin (or graphite) seeds. A flowing argon atmosphere was employed in all experiments and growth rates and temperature gradients, constant for a given run, varied from 2 to 4 cm per hr and 8" to 15°C per cm over the course of all the experi-

Jan 1, 1969

By J. W. Koger, R. E. Hurnrnel

QUENCHED, bcc p brass, P1, transforms to a mar-tensitic phase, when it is cooled below room temperature.' This transformation can be followed using resistance measurements since the resistivity of the martensitic phase is considerably larger than that of the parent phase, Fig. 1.' phillips3 first reported that, when Cu-Zn alloys containing between 37.0 and 39.0 wt pct Zn were quenched from the 0 region to room temperature, variable amounts of a phase could be observed depending on the mode of quenching. If the quench occurs very rapidly, the a phase forms by a "massive transformation". The resultant phase has the same composition as the high-temperature P phase from which it was formed. If the quench is less severe, the alloy is retained largely in the p form; however, some a is formed by precipitation. In this case, a contains more copper than the high-temperature 0 phase from which it has formed. The a phase most probably does not undergo a transformation in the temperature range where p transforms to low-temperature martensite. This can be deduced from the Eesistivity-temperature relation which is linear in this temperature range, Fig. 2. The stable a phase which is present along with R. E. HUMMEL is Assistant Professor, Department of Metallurgical and Materials Engineering, University of Florida, Gainesville, Fla. J. W. KOGER, Junior Member AIME, formerly with University of Florida, is now with Oak Ridge National Laboratory, Oak Ridge, Tenn. Manuscript submitted December 13, 1967. IMD.

Jan 1, 1969

By F. Weinberg, L. MacAulay

DAVIS,' in an investigation of solute redistribution along molten rods of dilute silver in tin, concluded that at horizontal temperature gradients below approximately 5°C per cm very little convective mixing takes place. Cole and winegard2 observed temperature oscillations in horizontal melts of tin, with temperature gradients of several deg per cm. They associated the temperature oscillations with the presence of convective flow in the melt. At temperature gradients less than 1°C per cm they did not detect convective flow. In the present work, direct measurements of con-vective flow in liquid tin have been made using a radioactive tracer technique. The results indicate that extensive convective flow occurs at temperature gradients below those previously reported. The apparatus used to determine the extent of con-vective flow is shown in Fig. 1. The graphite boat Fig. l(a), has two rectangular channels both of which contain molten tin. Radioactive Ag110 in the form of Sn-0.2 pct Ag alloy was introduced at the end of one channel, by rotating the cylinder shown. A series of fixed thermocouples were positioned along the center of the second channel to determine the temperature gradient. It was assumed that the two channels had identical temperature distributions. The graphite boat was inserted into a vycor tube which was surrounded by a multiple winding tube furnace as shown in Fig. l(b). The tin was melted in an argon atmosphere. The distribution of Ag110, as a function of position along the boat at a given time after introduction of the ~g"', was determined with the

Jan 1, 1970

By M. J. Mullikin, J. B. Conway

Several different equation forms were studied to determine the extent to which each particular equation type yielded an accurate representation of a given set of first-stage creep data. Specially developed least-squares computer programs were employed to obtain unique solutions for the creep-equation constants. In studies of creep data for lead at 14.5"C, nickel at 70OCC, and arc-cast tungsten at 2400°C consistently good representations were afforded by a third-degvee polynomial in t113. Other effective correlations were obtained with the Andrade, Cottrell-Aytekin, and de Lacombe equations along with a third-degree polynomial in t112. A newly proposed creep equation involving a hyperbolic-sine term in t1'3 was also found to yield very satisfactory results. This appears to be the first use of such a functional relationship in the analysis of transient creep behavior. In general, the deformation behavior of a material subjected to a tensile load is described in a strain-time plot. Experiments have shown that, following the instantaneous elongation which results on loading, the instantaneous slope (i.e., creep rate) of the strain-time curve decreases gradually with time and approaches what appears to be a constant value. Equations, therefore, which are proposed to provide an analytical representation of such first-stage or transient creep behavior must be consistent with these observations. In other words, at time zero, these equations must yield a finite deformation value corresponding to the elongation on loading. Furthermore, the first derivative of these equations must exhibit a fairly high although finite value at time zero, and then values which decrease with time. It is also preferable, in general, that the derivative eventually assume a constant value at high time values. Although many studies of first-stage creep behavior have been made and numerous equation forms have been proposed for expressing this type of deformation behavior, it is still not possible to state with any assurance which functional relationship will be adequate for a given set of measurements. Parabolic relationships have been employed most extensively although logarithmic expressions have been shown to be applicable in some instances. Combined forms1 have been studied in considerable detail and have on occasion been found to be very effective. One such expression is that of iXndradea and involves a modified parabolic expression: where 1 is the instantaneous length, lo is the length immediately following load application, t is the time, and p and k are constants. Another combined form has been proposed by weaver3 as follows: where E is the instantaneous strain, is is the linear creep rate, t is the time, and a and b are constants.

Jan 1, 1967

By C. G. Dunn

James, Jones, and Leak (JJL) conclude that growth-rate and orientation-distribution data obtained in a steep thermal gradient should be used with caution to account for isothermally produced recrystallization textures. I agree. However, it is not clear whether they conclude a) that the orientation dependence of rate of growth of secondaries in (commercial) silicon iron depends on both temperature and a temperature gradient or b) that, in applying rate data obtained in a steep thermal gradient, the isothermal annealing temperature must be close to the temperature for which the rate data apply. Also, it is not clear what tem-

Jan 1, 1967

By R. Ebeling, M. F. Ashby

The paper is in two parts. The first develops the formulae and method needed to calculate the size, nu)nber, spacing, and volume fraction of hard or inert particles in the interior of a specimen from measurernents made on an extraction replica; throughout, the spread of- particle sizes in a single specimen is taken into account, and the extraction efficiency of the replica is considered. A method for testing whether the particles are randotnly distributed in space is described, and the spacing of randomly distributed particles is discussed. The second Part describes the application of the method to copper containing spherical particles of silica; the description includes an estimate of the errors involved, and a comparison of this with alternative methods. All parameters except uolume fraction can be determined satisfactorily, and the method offers advantages over other electron-,rzicroscopic techniques when dealing with hard particles in a softer matrix, or inert particles in a chem-ically less inert matrix. 1 HE experimental measurement of sizes and numbers of discrete particles of a second phase embedded in a matrix material from opaque, plane sections has been considered by many authors, notably by Fullman.' It is assumed that, when the specimen is sectioned, the particles are also sectioned, so that the diameters of the circles of intersection of particles with the plane of the cross section ("surface diameters") are measured. It is difficult to derive the distribution of true particle diameters ("volume diameters") from measurements of the distribution of "surface diameters" on a plane section. The measurement of size and numbers of small second-phase particles by transmission electron microscopy through thin foils of matrix containing the particles has been described by Cahn and ~uttin~' and by ~illiard.~ Because of overlap and the fact that particles which intersect the foil surface may be sectioned whereas those in the bulk of the foil are not, it is again difficult to measure the true distribution of particle sizes. The use of replicas for this sort of measurement has not been analyzed in detail. A replica made from an opaque cross section, thus replicating the circles of intersection of particles with the plane of section, is analyzed by Fullman's method and suffers from the same difficulties. Under certain circumstances, however, extraction replicas can be used, and offer a special advantage in that they make the determination of the true distribution of particle diameters particularly simple. It is the purpose of this paper to describe this extraction replica method. Consider the example of an alloy consisting of SiOz particles, whose mean diameter is about 1000A, dispersed in a copper matrix. When the alloy is sectioned and mechanically polished, the particles are not sectioned, because they are much harder than the matrix, and so will be either left in the surface or pulled out whole, and because the particle size is smaller than the abrasive size of even the finest abrasive. The particles are chemically inert in solutions which chemically etch or electropolish the matrix, so that chemical treatments do not section the particles either. (Experimental measurements of particle shape in this alloy confirm this—truncated particles are never seen.) Small, hard or inert, particles are therefore not sectioned when the specimen is sectioned and polished. An extraction replica taken from this polished surface shows the true "volume" diameter of each extracted particle; the distribution of diameters seen on the replica is the surface distribution of true "volume" diameters, and the volume distribution of true "volume" diameters is easily derived from it. The extraction replica method is not subject to the difficulties associated with sectioning of particles, and avoids the problem of overlap from which the transmission method suffers. The method is well-suited for studying hard particles in a soft matrix. Examples are provided by internally oxidized alloys, oxide-dispersion strengthened metals like T.D. Nickel, and carbides, nitrides, and strong intermetallic compounds in metals. It should be possible to adapt polishing techniques in alloys containing softer but inert particles to avoid sectioning the particles (say by electropolishing or etching). The method is tested and illustrated in Sections 8 and 9 by applying it to a dispersion of spherical SiO2 particles in a copper matrix. I) SYMBOLS Symbols are defined where they first appear in the text. Volume fractions of particles are denoted by the symbol f, particle diameters by x, center-to-center particle spacings by D, and numbers of particles by N. Mean particle diameters and standard deviations about these means are denoted by x and a. Both arithmetic (subscript A) and geometric (subscript G) means are employed. In this paper we measure the distribution of true diameters of particles which touch or pass through a random-plane section of the specimen. We may want to know the distribution of particle diameters in the

Jan 1, 1967

Jan 1, 1967

Jan 1, 1968

By C. Altstetter, Y. Huang, E. de Lamotte

Nitrogen was introduced into pure niobium (colutn-bium) and dilute Nb- Zr alloy wires by equilibration with pure nitrogen gas at high temperatures. Room-temperature hardness was correlated with the alloy composition, heat treatment, and microstructure. Hardness was found to be most sensitive to the amount of nitrogen in solution; however, a significant hardening up to 500 Dph look place upon aging of quenched alloys. A coarse dispersion of nitride did not significantly increase the hardness of the material though the nitride was found to have a hardness of 1400 Khn. BY now the marked effect of nitrogen on the properties of bcc refractorv metals is we ll-documented. There are few studies, however, in which the state of the solute has been carefully controlled. Indeed, the composition-temperature-pressure relationships in nitrogen-refractory metal systems have been determined precisely for only niobium and tantalum.'-4 Most investigations on niobium have dealt with alloys High-nitrogen alloys cleaved on (100) planes and had negligible ductility. Precipitation was found to occur in either a discontinuous or a continuous fashion, depending on the composition and cooling rates. Upon cooling, the precipitation first proceeded discontinu-ously by the nucleation of nilride needles at subbound-aries and subsequent growth of a two-phase microcon-stituent. At lower temperatures continuous precipitation occurred in the subgrain interior ahead of the discontinuous precipitation interface. containing nitrogen, carbon, and oxygen in significant but uncontrolled and, in several instances, undetermined amounts. Thus, there has been some uncertainty regarding the presence and the distribution of precipitates. This paper presents results which relate the hardness and microstructure to the heat treatment and nitrogen content of niobium and Nb-Zr alloys. Niobium rod* produced by the Wah Chang Corp.

Jan 1, 1968

By A. J. Ardell, O. D. Sherby

The elevated-temperature steady-state creep behavior of polycrystalline a Zr was studied in vacuo under constant tensile stress. The experiments were conducted from 660° to 845°C over the stress range 870 to 5400 psi. The steady-state creep rate, is, of a Zr was found to be related to the applied stress, a, and temperature, T, by the equation where C is a constant. Two interpretations of the data are considered, each requiring different values of the parameters ß, Q, and . It is shown that this formula can be derived using Gilman's phenomeno logical equation relating dislocation velocity to the shear stress for the case where dislocation mobility is limited by the nucleation of kink motion. From the fundamental dependence of strain rate on dislocation velocity and the density of mobile dislocations, the factor exp(ßo) can be related to the stress dependence of the dislocation density, and Q to the energy of kink formation. The two interpretations considered are as follows: Case I—the parameters are adjusted so that the equation above describes the data over the entire range of stress and temperature, implying that creep is controlled exclusively by dislocation glide; Case IIthe parameters are adjusted to allow for the possibility that creep is diffusion-controlled at high stresses but glide-controlled at low stresses. For both cases the values of the parameters are within the spread permitted by the data. Factors favorable to the observation of the unusual stress -dependence of i, for a Zr are discussed and it is shown that the anomalously rapid rates of self-diffusion and the low modulus on the principal glide system are primarily responsible for the anomalous creep behavior. Metal-lograflhic observations are presented and discussed with reference to the overall creep behavior. PREVIOUS investigations of the creep behavior of a Zr have been conducted from room temperature to about 500C The results of these investigations are primarily of engineering significance because of the variety of conditions under which they were carried out, and the low testing temperatures employed. Little information is available concerning the fundamental nature of the elevated-temperature creep behavior of a Zr. This investigation of the creep behavior of a Zr above half the melting temperature (the melting temperature, T,, of a Zr is estimated to be about 1860"K was initiated because there are two significant anomalies of the physical properties of a Zr: a) the rate of self-diffusion in polycrystalline a Zr is anomalously rapid: b) both Young's modulus for polycrystalline a Zr and the shear modylus as-sociated with the prismatic slip system { 1010)( 1120) (the principal slip system in a Zr 7) have anomalously large temperature variations The importance of these quantities to the understanding of creep behavior has been demonstrated, and it was hoped that this investigation would provide a critical test of the predictions based upon the analysis of creep data for other pure metals. However, as the investigation progressed it became increasingly clear that the unusual creep behavior of a Zr could not be analyzed in a conventional manner. 1) EXPERIMENTAL EQUIPMENT AND PROCEDURES Two grades of zirconium, designated A and B, were used in this investigation. The analyses, as supplied by the vendors, are presented in Table I. Material A, with a nominal purity of 99.84 pct, was supplied by the Wah Chang Corp. in the form of cold-rolled sheet from which specimens were machined without further fabrication. Material B, with a nominal purity of 99.95 pct, was purchased from the Nuclear Materials and Equipment Corp. in the form of iodide crystal bar.

Jan 1, 1968

By R. E. Hummel, J. W. Koger

IT is generally accepted that the martensitic start temperature (Ms) can be determined by resistivity measurements and is that temperature where the resistivity vs temperature curve on cooling first deviates from a straight line.1-4 Both Titchener and ever' and pops5 have used resistivity measurements to follow the martensitic transformation in b1 Cu-Zn and ternary Cu-Zn-based b-phase alloys, respectively. Actually because of the nature of their measurements the temperature of minimum resistivity (M) was used by these authors to determine "Ms" . Also, due to experimental difficulties in detecting M, with resistivity measurements, Pops and Massalski 8 determined M, by optical microscopy. The present communication is concerned with high-precision, low-temperature resistivity measurements which reveal a definite M, temperature which differs from the temperature of minimum resistivity (M). It is also shown that M is merely the result of the geometry of the percent-transformation curve and the temperature coefficient of resistivity of the alloy. In other words, it will be demonstrated that M has no apparent significance (except that it denotes a temperature at which some percent of martensite can be detected in a given alloy). Alloy specimens were made by melting 99.999 pct Cu and 99.9999 pct Zn in sealed and evacuated quartz tubes and homogenizing them at 601PC for 300 hr. After the alloy was cold-rolled into foils suitable for resistivity measurements, it was quenched in ice water from 871PC. The chemical analysis showed a zinc content of 38.8 wt pct. The cooling rate during the martensite transformation was 1°C per min and was controlled with a thermistor. Electrical resistivity measurements were made using a K-3 type potentiometer; the reproducibility of the resistivity values was better than 0.03 pct. Temperatures were measured with a thermocouple to an accuracy of better than 0.2° C. Fig. 1 shows the resistivity vs temperature curves of the martensitic transformation in B1 Cu-Zn for both cooling and heating. The starting point of the martensitic transformation (M,) was taken as that

Jan 1, 1968

By Robert J. De Angelis, James H. Barker

An improved method for solving dynawzical dislocation problems using a digital computer is described in this paper. Interactions between two distinct types of dislocations were studied: attractive screw dislocations; and Lomer lock forming dislocations. One dislocation is positioned in the lattice and is initially at rest, while the other dislocation is moved through the lattice on an intersecting slip plane at a constant velocity in the range 0.5 to 0.999C. (C is the transverse velocity of sound.) The results obtained from these computations indicate that screw dislocations account for a small fraction of the total strain over a wide portion of the range of velocities studied. They further indicate that mixed dislocations mainly repel other dislocations in the neighborhood of the active glide plane. From this a possible explanation for cell formation is put forth. The density of Lomer locks expected to exist after a strain of 0.2 was found to be 1.4 x 106 cm-2 which is in good agreement with indirect experimental estimates. IN the past, predictions of favorable or nonfavorable dislocation reactions were based on the associated changes in elastic strain energy. Such considerations take no account of the probability of the two dislocations coming into contact to react. Venables1 was the first to approach these probabilities by considering the interactions between two moving screw dislocations on perpendicular glide planes. Because of the restrictive types of dislocations and glide plane geometry employed, his results have limited application to metallic crystals. The work to be presented here develops a general approach to solving dynamical dislocation problems; either dislocation-dislocation interactions, presented here in detail, or dislocation interactions with any other suitably defined stress field. Two types of dislocation-dislocation interactions common to face centered cubic (fee) materials are considered: those between pure screw dislocations of opposite sign on intersecting slip planes and those between mixed dislocations on intersecting slip planes, that can react to form a perfect dislocation. This latter reaction, referred to as the Lomer reaction, produces a locked product dislocation that finds it energitical favorable to disassociate into two Shockley partials and a stair-rod dislocation. This partial configuration known as a Lomer-Cottrell (L-C) lock plays a major role in work hardening of fee crystals. seeger2 names the L-C lock as the prime contributor to Stage II hardening while Kuhlmann-wilsdorf3 and Meakin and Wils- dorf4 also state that it is a significant contributor to work hardening. However, with a few notable exceptions,5-7 direct observations of the Lomer lock and the L-C lock by electron transmission microscopy are scanty, and even these are subject to other interpretations.5,6 In a study of partial dislocations present in austenitic stainless steel, whelan8 did not observe any L-C locks at the head of pile-up groups. This result contradicted existing work hardening theories and led him to postulate an alternate theory based on the stress required to break away dislocations intersecting a pile-up group, from their stacking fault nodes. Due to the importance of the Lomer reaction in producing L-C locks which are an essential feature in current work hardening theories and because there exist no data giving direct quantitative values for the density of locks, and because there has even been some doubt expressed as to whether this important reaction occurs at all, a study of the dynamic behavior of the mixed dislocations which form the Lomer lock was undertaken. Due to their ability to cross-slip with relative ease, screw dislocations play an important role in the deformation of fee crystals. For this reason, the second type of reaction considered here is between screw dislocations of opposite sign. In addition, computations in volving screw dislocation interactions are relatively simple, thus providing a convenient check on the cornputational scheme employed. DEFINITION OF PROBLEM The force exerted on a dislocation due to a generalized stress field is given by the Peach and Koehler9 equation: Here t2 and b2 are respectively the tangent and Burgers vectors of the dislocation, and T1 is the stress dyadic defining the local stress field. The stress field may be externally applied or generated internally by the presence of a lattice defect, such as a second dislocation, as is the case in this work. Frank10 has shown that an equivalent momentum, P, of a screw dislocation can be defined by: Here, EST is the total energy of a screw dislocation and ESo is its rest energy. The left side of Eq. [2] is the time derivative of momentum and the right side is the position derivative of the energy due to the dynamical nature of the dislocation. The total energy of a dislocation is the sum of the potential and kinetic energies. Weertman11 has developed the expressions which were used here; these give the potential and kinetic energies of uniformly moving edge and screw dislocations in an isotropic medium.

Jan 1, 1969

By A. Moskowitz, L. S. Redmerski

The corrosion resistance of stainless steels can be strongly affected by surface treatments. Changes in corrosion resistance can relate to surface composition, integrity and stability of the passive film, and to surface profile (roughness). Operations producing oxidation at the surface, such as annealing, heat treating, and welding, can result in a chromium-rich scale and a chromium-depleted metal surface. In order to restore full corrosion resistance, chemical or mechanical clean-up techniques must remove not only the oxide, but also a very thin layer of metal. Laboratory and field test studies show that these factors are particularly significant in less highly alloyed steels. Annealing stainless in a reducing atmosphere (bright annealing) avoids chromium depletion, but as-bright-annealed material does not display optimum corrosion resistance in certain environments. Electro passiva-tion can be applied to improve pitting resistance without significantly changing bright surface appearance. Potentiometric studies show that electropassivated material also displays significantly greater resistance to breakdown of passivity in acid solutions. The application of special surface finishes for appearance purposes can affect corrosion resistance. Roughness is a key factor. Samples of related appearance but with different surface profiles can show significant differences in corrosion resistance. Thus nonreflec-tive stainless with a relatively smooth surface produced by a special rolling process is much superior to material chemically etched to a similar low reflectivity. THE corrosion resistance of a stainless steel is affected by other factors in addition to its bulk composition and metallurgical structure. These other factors include those relating to the specific chemical and physical condition of the steel's surface. This paper will consider certain aspects of surface condition in relation to corrosion resistance. In particular, studies will be described on the effects of oxidation encountered in heat treating or welding operations, of passivation after bright annealing, and of different surface finishes. EFFECTS DUE TO OXIDATION When stainless steels are exposed to high temperature in an oxidizing environment, as in annealing or welding, the oxides formed are relatively rich in chromium. As a consequence of oxidation, the metallic layer directly beneath the scale may be low in chromium to some very thin but finite depth.1"8 Such a change in chromium content could lower the corrosion resistance at the surface, whether or not the oxide layer is removed. Studies were performed relating to the effect of oxidation and chromium depletion produced during annealing and welding on the corrosion resistance of stainless steels. The nominal compositions of steels used in this study and others are given in Table I. A) Annealing Studies on 17 pet Cr Steels. 1) Effects of Pickling Treatments. Studies were performed to investigate the corrosion resistance of air annealed type 430 stainless as a function of the amount of electrolytic pickling after annealing. The material used in this study had been air annealed and electrolytically pickled in the mill. All scale had been removed, and yet the material showed unusually poor corrosion resistance. Laboratory electrolytic pickling studies were performed to determine whether additional metal removal from the surface would improve corrosion resistance. Electrolytic pickling was performed in a sulfuric acid bath using various conditions of bath acidity, temperature, time, and current density. The samples were then rated for corrosion resistance in a ferric chloride spot test. For this spot test, a solution was prepared by dissolving 10 g of FeCl3 . 6H2O, 5 g of NaCl, and 2.5 ml of concentrated HC1 in 200 ml of water. An area on a specimen was cleaned and a drop of test solution was placed on the prepared area. After 5 min, the drop was rinsed off and the area wiped dry. The spot was then rated between 1 and 5 by visual comparison with standard spots. The numerical rating of the standard spots can be described as follows: 1—No clouding of surface; 2—very slight clouding of surface; 3—slight clouding of surface; 4—moderate clouding of surface; 5—strong clouding of surface. A rating of 1 or 2 was considered to have passed the test, a rating of 4 or 5 represented failure, and a rating of 3 was considered borderline. The severity of etching in this test has been related to the actual chromium content at the surface.4 Etching (clouding) occurs on type 430 stainless (rating of 4 to 5) when the surface chromium content is 14 pct or less. The effects of current density and retention time when electrolytically repickling this material in 6 pct sulfuric acid are shown in Fig. 1. Increasing the cur-rent density or retention time improved corrosion resistance as measured by the spot test. Similarly, increasing acid concentration of the bath or bath tem-perature was found to improve corrosion resistance. The conditions making for improved spot ratings resulted in increased metal removal, regardless of specific pickling conditions used, Fig. 2.

Jan 1, 1970