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By R. E. Carter, F. D. Richardson

Self-diffusion coefficients have been measured for iron in wustite (700° to 1000°C) and for cobalt in cobaltous oxide (800&apos; to 1350°C) by means of radio-isotopes. Both sectioning and decrease of surface-activity methods have been used and a particular shortcoming of the latter method has been disclosed for wustite. The effects of oxygen pressure on the composition of cobaltous oxide and on the diffusion coefficient of cobalt in the oxide have been established. The effect of the preparation conditions of the cobalt-oxide specimens on the diffusion measurements has been determined. It has been concluded that diffusion of cobalt occurs via vacant cation sites and that a cobaltous-oxide disk reaches equilibrium with its environment in a time which is very short compared with that needed for diffusion of the radio-isotope. THE availability of radioactive isotopes in recent years has permitted the measurement of many self-diffusion coefficients which were hitherto impossible to determine. With the advent of radioactivity, the method of measuring diffusion coefficients has also changed. The earlier sectioning method by which the concentration profile of the diffusing species was determined in the diffusion specimen has often been rejected in favor of the decrease of surface-activity method first developed by Von Hevesy,&apos; and extended by Steigman, Shockley, and Nix,&apos; and Raynor, Thomassen, and Rouse." With the experimental arrangement where an infinitely thin deposit of tracer is diffused into a semi-infinite cylinder, the decrease in activity of the active face due to diffusion of the tracer into the specimen is measured by counting the active face before and after diffusion. Under these conditions, the appropriate solution of the diffusion equation is R = e*(l-<K/Z) [1] where R is the ratio of the counting rates after-to-before diffusion, $& is the Gaussian error integral of \/Z, and Z is defined as Z = p2Dt, p being the linear-absorption coefficient of the detected radiation in the diffusion specimen, D the self-diffusion coefficient, and t the diffusion time. In the older sectioning method the concentration distribution of the tracer is found after diffusion by analysing thin parallel sections cut from the active face of the diffusion specimen. As seen from the solution of Fick&apos;s second law for the distribution of an infinitely thin source after diffusion into a semi-infinite cylinder the log of the concentration plotted against x&apos; will be a straight line of slope log e/4 Dt. The diffusion coefficient thus can be calculated directly. The units of the tracer concentration are completely arbitrary, since any change in units does not change the slope of the log c vs x2 lot. Although both of the above methods have been widely used, a thorough experimental comparison does not appear to have been made. Birchenall and Mehl,&apos; during an investigation of the self-diffusion rate of a and r iron by the surface method using Fe" tracer, diffused and sectioned one welded couple. The diffusion coefficient from this run agreed with those by the surface method. Buffington, Bakalar, and Cohen," during an investigation on a and y iron

Jan 1, 1955

By L. G. Schulz, P. Spiegler

The electrical resistivity and the temperature coefficient of resistivity were measured with a potentiometric method using pure mercury as a reference material. Measurements were made nea,v roorn temperature. A detailed study was made of Hg,TI, near its melting temperature. THE work to be described was originally undertaken to provide the necessary data for interpreting the results of some optical experiments,&apos; but because of the growing importance of liquid metals,273 it appeared that the results of the resistivity measurements should be published separately. For convenience the alloys selected were those which are liquid at room temperature. Special consideration was given to the Hg-T1 alloy closely corresponding to Hg,Tl, because recent X-ray diffraction results of Smallman and Frost seemed to show that the solid structure may persist to some extent into the 1iquid. EXPERIMENTAL PROCEDURE A potentiometric method was employed in which the resistivity of mercury was used as a reference. The essential features of the samples are shown in Fig. 1. A capillary tube CT with a bore of approximately 1.5 mm was fitted into two end cups, T, which were made of Teflon. A pair of current electrodes CE were immersed into the excess liquid metal which partly filled the end cups. The potential electrodes PE were inserted into CT through short pieces N of a no. 18 hypodermic needle held in place with Saureisen cement SC. As shown, the lower ends of the PE7s were reduced in diameter to 0.25 mm to minimize the distortion of the liquid metal cross section. Several methods were used to insert an alloy into the sample, but the usual one with mercury alloys was to fill the sample container with a weighed quantity of pure mercury* and then add weighed the sample tube in a vacuum. Because of rapid corrosion, samples containing gallium were of necessity prepared in a vacuum. To obtain the specific resistivity of an alloy the resistance of the sample containing the alloy was measured and compared with the resistance when the container was filled with mercury. Resistances were measured in the temperature range of 20" to 60°C to obtain the temperature coefficient of resistance. The electrical measurements were made by connecting the sample in series with the standard one-ohm resistance, and the potential drop measured alternately over the sample and the standard resistance. To correct for stray thermoelectric effects provision was made for reversing the direction of the current, and the true potential drop was taken to be the average of that obtained for the two directions of current flow. Various materials were used for the electrodes, the most uniform results being obtained with nickel. EXPERIMENTAL RESULTS The numerical results are presented graphically in Figs. 2 and 3 and in tabular form in Tables I and 11. Following are remarks on results of individual alloys. 1) Hg-In—This was the first alloy studied, and

Jan 1, 1960

By D. C. Jillson

WORK in recent years1-&apos; has indicated a complexity of the processes of deformation of metal crystals not previously appreciated and not fully accounted for by any hypothesis so far advanced. Furthermore, the nature and mechanism of formation of nuclei of recrystallization have not been determined precisely. The deformation of single crystals of zinc has been studied frequently, but the purity of the zinc and the perfection of the specimens sometimes have been given little consideration. Methods have been developed recently that readily yield zinc single-crystal specimens of high quality.5 In the present work, such specimens were deformed in various ways under various conditions, and deformed specimens were annealed to obtain information regarding recovery, recrystallization, and grain growth. The paper attempts to correlate and evaluate previous data, as well as to present new data, in order to determine areas in which more detailed work might be done most profitably. Tests at temperatures from the freezing point (419.46°C) to room temperature revealed glide only on basal planes in a close-packed direction (100)*, as reported by Mark, Polanyi, and Schmid6 and others. Markings probably similar to those observed by Kolesnikov7 and Boas and Schmid8 were noted in specimens stretched at elevated temperatures, but it seemed clear that these were not caused by prismatic or pyramidal slip (see second paragraph of section on Phenomena Involving Bending of the Basal Plane). Twinning Twinning on the octahedral plane of a face-centered cubic metal has been pictured as a process of simple homogeneous shearing along that plane in a [112] direction. It was recognized by Mathewson and Phillipsv and others""" that the (102) twinning of zinc required a somewhat more complex mechanism and might be considered as a homogeneous shearing of (102) planes in a [211] direction plus slight adjustments of atoms to positions of greater stability or lower energy, or as a single movement of each of the atoms in the same sense into the final positions. Gough and Cox" modified Mathewson&apos;s mechanism to obtain a more stable lattice configuration, but it is not clear that they succeeded, and their mechanism requires movement of some of the atoms in a sense opposite to that of the overall twinning movement. They also suggested that twinning may occur as a result of previous basal slip. This conclusion was based on the observation that twinning caused by alternating torsion was clearest and most profuse at positions for maximum basal slip rather than for maximum stress on (102) planes in the close-packed direction (not the twinning direction), and no mechanism was described. It might be wondered whether resolution of stresses on the twinning plane in the twinning direction would have afforded a simpler explanation. If twinning is essentially a simple homogeneous shearing along the twinning plane, it would seem that twins should grow by a smooth, continuous mechanism, and, indeed, that a simple reversal of stresses should reverse the shearing and de-twin the crystal. Cylindrical tablets 1/8 to 1/4 in. thick were cleaved from singlle-crystal specimens and were squeezed, perpendicular to a second-order prism plane, to give a tensile stress perpendicular to a first-order prism plane. A "click" was heard and a thin, needle-like twin appeared on the basal cleavage face. If squeezing was continued smoothly, the twin, viewed at magnifications up to X500, grew smoothly and quietly (fig. 1). X-ray examination verified that the twinning was of the (102) type. Rotating the compression axis 90" to reverse the stress then caused a smooth, continuous shrinkage and ultimate disappearance of the twin (fig. 2). The squeezing also caused a rumpling of the basal

Jan 1, 1951

By P. G. Winchell, J. K. Jackson

The strtcture of body-centered Fe-Ni-C alloys (0 to 16.5 wt pct Ni) containing less than 0.015 wt pct C was investigated by measuring the carbon-diffusion peak at low frequencies with a torsion pendulurrr. By determining the Snoek damping in ferrite and in quenched alloys of identical composition, the effects of nickel content and heat treatment were separated, and the existence of a structure in which Snoek damping is greatly reduced was revealed in the quenched ternary alloys. The relative amount of this structure increases with increased nickel content and cooling rate. It is proposed that this structure may be highly imperfect or tetragonal. In Fe-Ni-C alloys containing only ferrite the addition of nickel (0 to 5.1 wt pet) decreases tke area of the carbon-diffusion peak and shifts its position to lower temperatures but broadens the peak only slightljl. The decrease in peak area with increasing nickel implies that short-range interactions with the nickel atoms prevent some of the carbon atoms from participating in the relaxation process. The shift in the peak position indicates a long-range effect of nickel on the movement of carbon atoms so that at 300°K the diffisivity of carbon in -ferrite is increased by about 35 pct by the addition of 5.1 tut pct Ni. The results are presented as distributions of relaxation strength 072 the activation energy under the assumption that the frequency factor is invariant. BODY-CENTERED iron-base solid solutions dissolve carbon interstitially in the octahedral sites. The occupation of an octahedral site produces a tetragonal distortion of the surrounding lattice. These sites fall into three sets according to the orientation of the tegragonal distortion associated with each and may be identified by their lattice coordinates as: type 1/2 0 0, type 0 1/2 0, type 0 0 1/2. At low carbon levels in cubic ferrite the carbon atoms are distributed at random1 among these sites. In high-carbon body-centered iron-base solid solutions, which are unstable with respect to several two-phase mixtures, a tetragonal structure occurs as the product of the diffusionless transformation of austenite. This transformation is commonly accompanied by appreciable microstrain and its product is called martensite. The tetragonality of martensite, a supersaturated solution of carbon in a iron, is maintained prior to decomposition even though local diffusion of carbon occurs as evidenced by carbide precipitation. The tetragonality is taken as evidence that one set of octahedral sites is preferentially occupied by carbon. (This preferential occupation is called ordering below.) Support for this view is presented by the absence of strain-induced carbon-atom diffusion in high-carbon solid solutions (martensite). Such diffusion occurs in ferrite and produces the 40°C internal-friction peak observed at 1 cps frequencies.&apos; Thus, there appears to be qualitative evidence favoring the view that at sufficiently high carbon levels tetragonality arises spontaneously as a result of the ordering of the carbon atoms; however, no experimental evidence exists concerning an equilibrium between cubic and tetragonal body-centered solid solutions. Moreover, attempts to estimate the energy of ordering7-&apos; predict a value too low to maintain the tetragonality observed at medium carbon levels, 0.3 to 0.6 wt pct C. In the present work an attempt using internal-friction measurements is made to establish the presence or absence of tetragonality in low-carbon body-centered solid solutions formed by quenching austenite. Fe-Ni alloys containing about 0.01 wt pct and 0 to 15 wt pct Ni were selected for the study. While the work was in progress Gilbert and Owen10 reported that the transformation which occurs in these alloys during quenching at rates up to 5000°C per sec is not martensitic but is more properly categorized as massive. Thus, the solid solution

Jan 1, 1964

By B. L. Averbach, M. F. Comerford, M. B. Rough

The volume fraction of ß phase was determined in a Ti-6Al-4V alloy by measurements of integrated diffraction intensities. The (0002), and (100)ß diffraction lines were chosen because this combination minimizes the errors resulting from preferred orientation. The difficulties arising from fluorescence radiation were eliminated by use of a diffracted beam monochromator. A specimen quenched from 1475OF (800°C) contained approximately 5 pct ß, but in specimens quenched from higher temperatures no ß was found. The ß phase formed during aging, and in specimens solution treated at 1570oF (855oC) approximately 10 pct ß was present after aging at 1000°F (540°C) for 24 hr. This ß appears to form by decomposition of martensitic a&apos;. ThE kinetics of the reactions which occur during the heat treatment of titanium alloys are complex &apos; and not completely understood. It has been proposed that hardening occurs in some alloys&apos; on aging by the precipitation of a transition phase w followed by the formation of the stable a and ß phases. It has been proposed for other alloys2 that the a&apos; marten-site decomposes by precipitating finely dispersed a particles. Most investigations have been hampered by the difficulties of determining quantitatively the amounts of the various phases present. This paper is concerned with the measurement of the amount of ß phase by an X-ray method, similar to one developed for the determination of retained austenite. The principal new feature was the use of a mono-chromator in the diffracted beam in order to reduce the fluorescence arising from the sample. EXPERIMENTAL PROCEDURE The experiments were carried out on an alloy of nominal composition Ti-6Al-4V (actual weight percentages: 6.2 Al, 4.1 V, 0.02 Mn, 0.17 Fe, 0.005 H, 0.03 C, and 0.02 N). The material was received as 5/8-in.-diam centerless ground rods in the annealed condition. The heat treatments were carried out in a vacuum of approximately 0.03µHg. The X-ray intensity measurements were made on 3/8-in. thick discs. The surface was prepared by grinding off about 0.060 in. and electropolishing in a solution af 60 ml (70 to 72 pct) perchloric acid in 1000 ml glacial acetic acid with a current density of 0.5 amp per sq cm.q The X-ray determination is based on the proportionality of the diffracted intensity of each line to the volume fraction of the corresponding phase. In calculating the intensities for a powder sample it is assumed that a large number of grains con- tributes to the diffracted intensity and that the grains are oriented at random. The presence of preferred orientation introduces serious errors in the relative intensities. The material used in this investigation exhibited a strong preferred orientation, which could not be removed by heat treatment. Other investigators have also found that preferred orientation may be retained after phase transformations. Glen and pugh5 performed a detailed analysis of the randomness expected after several allotropic transformations, but stated that this is not observed. Burgers,6 and Burgers and Ploos van Amstel,7 found that, in zirconium, the original orientation is retained after two phase transformations. Newkirk and Geisler8 observed similar behavior in titanium. On the basis of this evidence, it appears that, in the absence of plastic deformation, textures present in annealed titanium alloys are retained. Heating an a-ß alloy to the all-ß region and subsequent cooling to room temperature do not make the orientation of the mar-tensite different from that of the original a phase. In the present investigation it was possible to take advantage of the crystallographic relationships involved in the martensitic transformation to minimize the errors associated with preferred orientation. The relative orientation for titaniu-m marten-site9 takes the form (0001), 11 (110)ß; [1120], 11 [lll]ß. The same relationship has been proposed for zirconium&apos; and certain titanium-base alloys.10-12 Additional sets of approximately parallel planes have been determined for titanium-nickel alloys." The influence of preferred orientation can be minimized by comparing intensities from parallel planes in the two related phases. If it is assumed that each family of planes in a given phase is equally well populated, the effect of preferred orientation can be eliminated by using the normal multiplicity for the family of planes since each set of parallel planes is equally preferred for any orientation of the sample relative to the X-ray beam. The most suitable combination of reflections in the Ti-6A1-4V alloy appeared to be (0002), and (110)ß It must be recognized that the ß formed during aging of the Ti-6A1-4V alloy is a precipitate rather

Jan 1, 1960

By Nichols J. Grant, Bill C. Geissen

In low temperature phase diagrams, liquidus curves below about 1500°C are relatively easily established, e.g., by thermal analysis or separation of coexisting solid and liquid phases, followed by chemical analysis. Experimental difficulties increase considerably at higher temperatures and in systems involving more reactive metals. Although there are now thermocouples available for use from 1600" to 2400°c, as summarized by Caldwell,&apos; the need for frequent calibration, aging, and contamination problems, and unavailability of suitable protection tubes has sharply limited their use at higher temperatures. Many of the high melt- ing metals are found to react with refractory oxides. TO avoid such problems, a frequently used procedure is the diffusion and saturation method, as described by Spedding et a1.&apos; for the system La-C. This technique involves the annealing of one metal or a suitable alloy in a crucible of the other element at a temperature above the melting point, followed by chemical analysis of the center of the melt, after equilibrium is established. Further, if an alloy system is to be investigated employing the electron microbeam probe, and calibration charts have been established, it may be possible to measure the alloy concentration at the center of a cored as-cast structure, and to conclude from this points on the liquidus curve in a manner similar to the one to be described. It is known that in phases with a broad homogeneity range the rapidly cooled, cored, as-cast structure of an alloy presents concentrations having different lattice constants; this spread of lattice constant values contributes to the broadened lines of a powder pattern for the as-cast condition. The region of the crystal which is first to solidify will then correspond to the edge of the lines if the change of the lattice parameters with concentration is monotonous. In the course of the determination of the Ta-Tr phase diagram,3 it became evident that such behavior made it possible to construct the

Jan 1, 1963

By W. N. Carr, J. R. Biard, B. S. Reed

An analysis of the semiconductor injection laser is presented which is based on a phenomenological model using device and material parameters. The intent of the laser threshold analysis is not to predict from theory the actual threshold current density but rather to provide a logical means of interpreting experimental results. The device and material parameters have been selected such that they describe both the threshold conditions and quantum efficiency of the lasev. A technique is proposed whereby the current required to obtain a population inversion is predicted from device 1-V characteristics. Experimental data are presented which support the analysis. THIS investigation is concerned with the characteristics of GaAs lasers fabricated in this laboratory. However, the assumptions used in these calculations should not limit their application to GaAs alone. It is felt that the analysis is sufficiently general to be useful in describing the operation of other semiconductor-laser materials. ANALYSIS heavily doped semiconductors to be considered. The absorption and/or generation of optical radiation may be completely specified in terms of q(E) and the probability functions f,,(E) and f,(E) which define the occupancy of the valence-band and conduction-band levels, respectively. The symbols used in this analysis are listed at the end. Following the approach of all&apos; it can be shown that the effective gain coefficient, g, in the plane of a forward-biased P -N junction is g(E)=-ai@)[1-fv(E)-fc(E)] [1I In particular Eq. [I] holds for the photon energy at which lasing occurs, Ep. Throughout the following discussion Eq. [I] is considered only for the lasing transition E = Ep. For simplicity the functional energy dependence of the various factors is omitted in subsequent equations. Unless otherwise stated the symbols used represent the values at Ep. If the analysis is limited to the P-type side of the laser junction, the function q(l -f,,) is recognized as the band-to-band absorption in the P-type material at thermal equilibrium. Under forward-bias conditions the function f, is determined by the electron quasi Fermi level in P-type material. For sufficiently large forward bias the second term in Eq. [3] will become dominant and net gain will result; i.e., g will become positive. In order to simplify the subsequent analysis several assumptions are in order at this point. a) No conductivity modulation occurs. /„ is independent of f, and therefore go is a constant. b) The P-type material is heavily doped such that the degeneracy of the valence band permits popu-

Jan 1, 1964

By P. W. Bakarian, John C. McDonald

Three magnesium alloys were processed in various ways to exhibit a wide variation in the ratios of yield strength and tensile strength in the rolling direction compared to the cross-rolling direction. Basal-plane pole figures were prepared from several specimens. A fair correlation was observed between the property ratios and the ratio of percent of poles oriented in the cross-direction quadrants compared to the percent oriented in the rolling-direction quadrants of the pole figures. THE modes by which magnesium crystals deform are such as to lead to marked preferred orientations in all forms of wrought products. The effect of the active modes at room temperature, coupled with these orientations, is often to produce a lower compressive yield stress compared to the tensile yield stress. The phenomenon is due to easy twinning in compression, and has been well-related to the preferred orientations as described by basal-plane pole figures of the hcp magnesium single crystal. The literature contains some information on the variation with test direction of the tensile properties of sheet, but no quantitative relationship to the observed pole figures has been established. These effects have been reviewed in the few com- prehensive treatises in English which have been written on magnesium technology and metallurgy.1°3 Roberts presents several pole figures, but no tensile-property data in the plane of the sheet. Raynor has no pole figures, but quotes Frommer&apos;s4 results. The information in Beck&apos;s compendium more or less parallels the results of Jones and powell.5 In both a Mg + 1.5 Mn alloy and a Mg + 4.6 A1 alloy, cold rolling was found not to change the general situation of higher properties in the cross-rolling direction,* than in the rolling direction. Thomas&apos;6 X-ray studies of Jones and Powell&apos;s specimens did not permit correlation of properties and preferred orientation. Ansel and Betterton7 report tensile and compressive properties on three other alloys as a function of degree of cold rolling, plus a recrystallizing anneal. As rolled, there was a change in anisotropy with degree of reduction, but all alloys were reasonably isotropic in tension when annealed. X-ray diffraction photograms illustrated the kinds of orientations present, but were not correlated with the properties. Bakarian8 has described a method of determining quantitatively a preferred orientation, and illustrated the method by applying it to pure magnesium and two of its alloys. This method was used in the present work as a basis for correlating the strength properties with the texture.

Jan 1, 1965

By Jei Y. Choi, P. G. Shewmon

Using a scratch smoothing technique, the magnitude and the ratio of the surface diffusion coefficients (D,) in two orthogonal directions have been measured on copper for over 100 different surface orientations. Anisotropy was found for all surface orientations except those lying near the (100) and (111); however, these anisotropies were rarely greater than 2.0. The direction of maximum D, appears to coincide with the direction of step edges on any given surface, and if no such steps exist, no anisotropy is found. Thus the jump frequency along a step edge is shown to be faster than the frequency of a jump over the step. The values of Ds and AH for the (100) and the (111) orientations agree quite well with those obtained earlier by the grain boundary grooving technique. It is proven that the directions of maximum and minimum D, (the principal axes) for any surface orientation are known if the perfectly ordered plane corresponding to the given surface orientation possesses a plane of mirror symmetry. Thus the principal axes of D, for orientations lying along the sides of the unit stereo-graphic triangle are always known independent of the extent of thermal disorder or impurity adsorption. The merits and shortcomings of King and Mullins&apos; recently published equations relating Ds to the rate of scratch smoothing are discussed. 1N an earlier paper the authors have reported the variation of the surface diffusion coefficient (Ds) with surface orientation on copper.&apos; In that study Ds was determined from the rate of growth of grain boundary grooves on symmetric bicrystals. This gave values of Ds from 850° to 1070°C in a given direction on each of the six surfaces. It was found that the activation energy for surface diffusion was essentially the same for all six surfaces. The theory developed to explain these data assumed that the free energy of any given type of surface site depends only on the number of nearest neighbors the atom has. This same theory predicted that on any given surface Ds should be independent of direction. The primary aim of this study was to check the validity of this prediction for a wide range of surface orientations on copper. The growth of grain boundary grooves is ideal for studying Ds in a given direction on a given surface over a range of temperatures, because the same specimen can be repolished and used again. However, there is considerable work involved in growing a symmetric bicrystal, and for a survey of Ds in two or more directions on many surface orientations, the technique would be arduous. A better technique appeared to be the scratch method used primarily by Mykura. 2 If a scratch is placed in a surface whose surface tension is independent of orientation, the surface will smooth out in time under the influence of surface tension. To determine D, from this flattening, Blakely and Mykura2 used an approximate solution which was assumed to describe the rate of flattening. Recently King and Mullins3 (hereinafter K and M) have given a more exact analysis of the flattening of an isolated scratch. A second aim of this paper was to check the validity of this newer analysis and compare the values of Ds determined thereby with the values obtained from grain boundary grooving techniques. EXPERIMENTAL PROCEDURE In an effort to work with a particular predetermined surface orientation, light orthogonal scratches

Jan 1, 1963

By R. L. Grunes, F. K. Kies, C. D&apos, Antonio

THE several studies concerned with the annealing of thin nickel films have largely been restricted to films of a single thickness.1-4 It is well-known, however, that both physical and mechanical properties depend upon film thickness.5, 6 The strength-thickness relations found in vapor-deposited nickel films in the annealed and as-deposited states, as an example, are at least partially due to the density and arrangement of imperfections within the films.7, 8 For these reasons, the annealing characteristics of thin nickel films as a function of thickness were investigated. Electrical resistance was chosen to monitor annealing behavior since resistance changes are partially dependent upon defect structure. In addition, the equations predicting film resistivity as a function of thickness are already available.9, 10 Further advantages afforded by electrical-resistance measurements are its adaption to continuous readings during annealing and its relative simplicity. Nickel films were vapor-deposited, at average rates of 60Å per sec, on Vycor substrates held at room temperature in vacuums of about 10-5 torr. Afterwards, deposition-thickness measurements were made using a multiple-beam interferometric technique. A more detailed description of deposition procedures and the interferometer appear elsewhere.7, 8 The four-probe method was employed in measuring electrical resistance since this technique measures film resistance without contributions from lead wires and contacts. Resistance measurements were made before, during, and after annealing to temperatures of 700°C under vacuums of approximately 10-4 torr. Measurements were made every 25°C or more often when necessitated by unusual resistance changes. Cooling and heating rates were maintained at approximately 5°C per min. Typical resistivity vs temperature curves are shown in Figs. 1 through 4. It is apparent from these

Jan 1, 1965

By D. T. Novick, M. B. Bever, B. Roessler

Ordered and disordered specimens of the alloy CusAu were cold worked and then annealed at 2880, 310°, and 340°C, together with disordered unworked specimens. me resistivity decreased during annealing mainly as a result of ordering; the resistivity measurements suggest that in cold-worked specimens the growth of antiphase domains is impeded. The strength properties increased during annealing at 288 "C; in cold-worked specimens this increase was lo a level above that for cold-worked specimens which had not been annealed. X-ray diffraction showed that after annealing for a few hours at 288ºC, the long-range order increased to a constant value; additional annealing at 288ºC resulted in the growth of antiphase domains in which the degree of order was constant. Changes in peak breadth and particle size confirmed that in cold-worked specimens the major effects of cold work were not eliminated during annealing at 288 "C, although a slight recovery process occurred. When a specimen of the alloy Cu3Au is heated to a temperature below the critical temperature (388ºC), long-range ordering tends to occur in a specimen containing less than the equilibrium amount of order characteristic of that temperature Ideally, a specimen of Cu3Au contains no long-range order if it has been quenched from above the critical temperature. Long-range order is reduced by cold work. If cold-worked specimens are heated, restoration processes such as recovery and recrystallization may occur,

Jan 1, 1963

By S. R. Goodman, Hsun Hu

A study has hem made of the formation of annealing textures in an 18-8 austenitic stainless steel (Type 304L) from various deformation textures obtained by rolling at different temperatures. When the deformation texture is a mixture of the ferritic type and the brass type owing to the pres -ence of both martensitic ferrite and retained aus-tenite in the specimen, recrystallization takes place by the growth of the existing austenite phase. In a previous report,&apos; it was shown that the rolling texture of austenitic stainless steel (Type 304L) changed gradually from the brass type to the copper type with increasing temperature of deformation above 200°C. These changes are similar to those in high-purity silver2,3 and electrolytic copper;4 a brass-type texture is favored at low rolling temperatures, whereas a copper-type texture is favored During the course of rolling -texture transition from the brass type to the copper type, the subsequent recrystallization textures change accordingly. The orientation relationship between the annealing textures and the various rolling textures, being consistent with previous observations on various fcc metals, can be described as [Ill] rotations of approximately 25 to 40 deg. Carhide precipitation may influence the annealing textures. at high rolling temperatures. Furthermore, the annealing textures in high-purity silver5 and electrolytic copper4 were found to depend entirely on the prior deformation texture. From a copper-type rolling texture a strong cube texture will form upon recrystallization, whereas from a brass-type rolling texture the annealing texture will be quite different from the cube orientation. In an earlier comm~nication,6 the formation of a strong cube texture in 18-8 austenite stainless steels (Types 304 and 304L) was reported briefly by the authors. The present paper constitutes the results of a complete study of the annealing textures obtained from a

Jan 1, 1965

By J. W. Rutter, K. T. Aust

Observations are presented of the formation of annealing twins during the growth of a recrystallized grain into a striated, melt-grown crystal of high-purity lead. The formation of an annealing twin resulted in replacement of the original migrating boundary by a large-angle grain boundary of the caincidence-site type or by a near-twin boundary. The results support the Fullman-Fisher theory of annealing twins and demonstrate the usefulness of the coincidence-site model. FULLMAN and Fisher1 have advanced the following theory to account for the formation of annealing twins during grain growth. Whenever a grain A grows into a matrix of grains S1 and S2, a twin A&apos; of grain A may form, as shown in Fig. 1, if the following energetic condition is satisfied: where "E" and "a" refer to the specific interfacial free energy and the area, respectively, of the boundaries indicated by the subscripts. In effect, the twinned grain will persist when the energy of the boundary between the twin(A&apos;) and the matrix grain (S, or S,) is less than that of the boundary between the original growing grain (A) and the matrix grain by an amount which exceeds the energy of the coherent twin boundary between A and A&apos;. Experimental observations on the changes in grain boundary free energy accompanying the formation of twins1 are in agreement with the theory outlined in Eq.[l]. Direct observations of the formation of annealing twins at moving grain corners1"3 and the depend-

Jan 1, 1961

By K. T. Aust

The occurrence of annealing twins in high-purity aluminum resulted in the formation of grain boundaries having orientation relationships which correspond to a high density of coincidence sites. The results provide support for the coincidence site model and indicate that large-angle coincidence boundaries have lower free energies than large-angle noncoincidence boundaries. Observations are presented concerning the coherent structure of twin interfaces in aluminum and the importance of inter-facial energy in preferred orientation. RECENT experiments1 have shown that when an annealing twin is formed during grain boundary migration in zone-refined lead, a large-angle random boundary is replaced at the growth front by a large-angle coincidence site boundary. The coincidence site orientation relationships obtained by twinning were of the type considered by Kronberg and Wilson,2 Frank,3 and Dunn.4 On the basis of the theory of annealing twins advanced by Fullman and Fisher,5 these observations indicate that the energy of a coincidence site boundary is less than the energy of a random boundary by an amount which exceeds the energy of the coherent twin boundary. This energy difference between the coincidence and random boundaries must be at least about 5 pct since the ratio of twin boundary energy to grain boundary energy in zone-refined lead is 0.05 * .014.6 Fullman7 has found that the twin boundary energy in aluminum is about 21 i 5 pct that of a large-angle grain boundary. A twin boundary energy as large as this would be expected to exclude the formation of many coincidence site grain boundaries, especially those which have a relatively low density of coin- cidence sites. Therefore, if the coincidence site model is a useful interpretation of certain large-angle boundaries, then it would be predicted that only coincidence boundaries which separate adjacent crystals with a relatively high density of coincidence sites may be obtained as a result of twinning in aluminum. The present experiments provided a means of testing this prediction since annealing twins occurred during the growth of recrystallized grains into striated, melt-grown single crystals of zone-refined aluminum. EXPERJMENTAL PROCEDURE A striated single crystal of zone-refined aluminum, about 1 cm sq and 37 cm in length, was obtained during zone melting of aluminum of 99.996 wt pct starting purity in a graphite boat under helium atmosphere.8 A molten zone of 2 to 3 cm in length, which was maintained by induction heating. was passed along the length of the bar for eleven passes at a rate of 0.9 mm per min. An additional final pass was given at a rate of 0.2 mm per min. The center portion of the zone-melted bar was characterized by an electrical resistivity ratio between room temperature and 4.2° K of 8000 to 9000. Single crystals of 1 to 2 cm in length were removed from the center section of the zone-refined bar and electrolytic ally polished in a 2:l solution of methyl alcohol and concentrated nitric acid. The specimens were then chemically polished in Alcoa R-5 solution. X-ray analysis of the single crystals indicated the presence of striations or lineage substructure having misorientations as high as 2 deg. New, recrystallized grains were introduced into each striated crystal by the technique of artificial nucleation and growth, previously described.9 During the growth of the recrystallized grains at 300&apos; to 600°C in argon, it was sometimes found that a

Jan 1, 1962

By S. F. Reiter, You-Chao Liu, W. R. Hibbard

Cyril Stanley Smith in his classic 1948 Institute of Metals Lecture&apos; noted in the case of annealing twins that: "It is well known that approximately the same number of twins per grain and the same general geometry are maintained in large grains as in small ones, a fact that certainly suggests a mechanism such as the above where boundaries and twins grow proportionately together. If this view is correct, a spherical grain should have no mechanism for keeping its twins." Such a constancy of twins per grain would be of particular interest as a tool for the study of the origin of annealing twins. It has been proposed by Mathewson2 and later by Barrett3 that in face-centered cubic metals slip occurs in the {111} Plane by <112> shears which combine in pairs to produce the macroscopically observed <110> movement. This proposal is schematically inviting since <112> slip permits the atoms of one plane to move along the interatomic valleys of its neighbor rather than up the hills across the atom sites. There is strong experimental evidence? that annealing twins result from the growth of nuclei in the form of "twin faults" produced by single <112> shears. It is possible that more twin faults would form at low deformation temperatures than at high ones, because the more rigid lattice may increase the tendency to "freeze" the twin faults and prevent their dissipation in slip. This is suggested by (1) the greater resistance to slip at low temperatures and (2) greater tendency toward mechanical type twinning at low temperatures (a summary of these factors is presented by Seigle and Brick5). These considerations would suggest the following: a. Constant twin/grain ratio for specimens deformed constant amounts at a constant temperature, but annealed at various temperatures above the recrystalliza-tion temperature. b. Larger twin/grain ratios for re-crystallized specimens previously deformed constant amounts at lower temperatures. The purpose of this investigation is to test these considerations. One half in. rods of phosphorous deoxidized electrolytic copper and 70-30 alpha brass (68.36 pct Cu, 0.005 pct Pb, 0.01 pct Fe, 31.62 pct Zn remainder) were rolled to a thickness of 0.350 in., milled to specimens 0.350 X 0.437 X 2 in., and annealed at 700°C to an average grain size of 0.065 and 0.090 mm, respectively. These specimens of each metal were then rolled 50 pct reduction in thickness and annealed one hour under conditions which were all combinations of the following: Rolling Annealing Temperatures. Temperatures. °C °C -70 400 25 500 200 600 Standard metallographic techniques&apos; were used to prepare specimens. By the method of lineal analysis7 using a minimum of ten samples of fifty grains each for each specimen, the ratios of twins* per total grains, twins per twinned grain, twin families* per total grains and twins per twin family were determined. Recrystallized grain size was determined by A.S.T.M. comparison methods.8 All observations were made on the rolling plane. The results are tabulated in Table 1.

Jan 1, 1950

By M. F. Smith

BELOW the nose of the bainitic C curves in isothermal transformation diagrams, the rate of the austenite-to-bainite transformation usually decreases with decreasing temperature. However, in some steels and iron-carbon alloys, there is a noticeable acceleration in the initial reaction rate at temperatures just above Ms. Such speeding-up of the bainitic transformation would be understandable at temperatures just below Ms because of the catalytic effect of the martensite formed,&apos; but the reversal in isothermal kinetics just above Ms seems quite anomalous. This behavior was observed by Howard and Cohen&apos; in a 1.35 pct C steel and, on the basis of metallo-graphic examination, it was attributed to the formation of a thin plate-like product not belonging in the bainitic sequence. More recently, schaaber2 found two-stage reactions occurring in the vicinity of Ms in a number of steels, and suggested that the first stage might be the isothermal formation of marten-site, preceding the isothermal formation of bainite in the second stage. A decrease in the bainitic incu-

Jan 1, 1960

By D. L. Albright, R. W. Kraft, J. A. Ford

HE unidirectional solidification of A1-CuAl, eutec-tic specimens to produce an essentially parallel lamellar structure has been described previously.&apos; Ingots solidified in this manner ordinarily exhibit three macroscopic zones. In Zone I, at the head end of the ingot, a large number of slightly elongated grains occur in which the lamellae are highly distorted and twisted. After a few centimeters of growth, this distribution gradually changes to a small number of coarse grains elongated in the growth direction and in which the lamellae are quite regular, Zone 11. Zone 111, at the tail end of the ingot,

Jan 1, 1963

By G. M. Ault, G. C. Deutsch

The paper reviews the efforts made to utilize powder metallurgy to solve problems encountered when using alloys at high temperatures. The following subjects are discussed: comparison of wrought and sintered super alloys, sintered aluminum powder, porous materials for transpiration cooling, molybdenum, and cermets. TODAY, powder-metallurgy techniques are be-JL coming increasingly important, producing materials which at the present time cannot be made by any other method. Among these materials are high melting-point metals such as tantalum and tungsten, porous metals for filters and lubricant-containing bearings, electrical contacts and electrodes (i.e., tungsten-copper), cutting tools of the cemented carbides, and magnet alloys. In addition, the powder-metallurgy industry has grown because, through the application of its methods, shaped parts, such as gears, can be produced at tremendous rates with a low scrap loss in comparison with manufacture by casting or forging and machining. In the past few years, by utilizing powder metallurgy, several approaches to the problem of high temperature materials have been investigated. In this paper the authors will review some of the studies on application of materials having properties above 1350°F. Since their experience lies in the aeronautical field, possible uses of powder-metallurgy techniques in the production of aircraft en- gines will be emphasized. A large portion of the work is classified, but such a restriction has not eliminated any field from discussion, although limiting the amount of detail it is possible to present. The development of high temperature alloys from powders and porous metals for cooling will be discussed as well as research done on molybdenum and molybdenum alloys, cermets, and intermetallics. Some studies on the utilization of cermets will be considered along with special problems that have been revealed through these investigations. Special interest in certain factors of sintered aluminum powder (SAP) makes it desirable to discuss this material although its use temperature is below the 1350°F limitation set for this paper. High Temperature Alloys from Powders In general, components made from powders for room-temperature application have been investigated with the primary purpose of taking advantage of the high production rates and economies made possible by powder metallurgy. From the standpoint of properties, the ojective of the powder metallurgist has been to obtain a product comparable to the cast or wrought product that is to be replaced. Comparisons of the properties of alloys made by powder-metallurgy methods with those of similar compositions made by casting and forging are reported in the literature.12 In many cases equivalent

Jan 1, 1955

By F. W. Aul, R. C. Glenn

EXTRACTION techniques are of particular importance in determining size, shape an: crystal structure of particles smaller than l000Å in steels and other alloys. However, artifacts that can arise during the preparation of extraction replicas may lead to erroneous conclusions. The purpose of this note is to illustrate some of these artifacts and the misinformation that can result from their presence. An alloy of iron with 0.8 pct Cu was investigated in the following conditions: 1) Solution treated 3 days at 925°C in dry hydrogen and quenched in water. Aged in steps to precipitate copper, as follows: heated to 700°C, held 1 day; then furnace cooled to 50O°C, held 3 days; then furnace cooled to room temperature. 2) Solution treated 3 days at 925OC in dry hydrogen and furnace cooled to room temperature. 3) Solution treated 3 days at 925OC or 17 hr at 1100°C in dry hydrogen to dissolve all copper, then quenched in water. A normal parlodion dry-extraction technique was employed after etching the specimens with super picralP or with 2 pct nital. A wet-extraction method

Jan 1, 1962

By J. G. Faller, L. P. Skolnick

The distribution of cobalt and vanadium over non-equivalent crystallographic sites in C14-type Zr(VCo), alloys has been investigated. An anomalous X-ray scattering technique developed by Skolnick, Kondo. and lavine7 by which the separation in the scattering factors of two similar atoms can be enhanced was employed. Six alloys spanning the pseudobinary section ZrV1.6Co0.4-ZrVO.6CO1.4 at 10pct steps showed a nonrandom compositionally dependent distribution. Specifically, at high vanadium content cobalt preferentially occupied sites of type (6h) and vanadium, sites of type (2a; at low vanadium content the reverse was observed. In addition to the distribution fraction the structural parameters x and z were obtained. There was no significant deviation of these parameters from those obtained in the ideal C14 structure. Certain suggestions are made to account for the observed nonrandomness in the distribution of atoms on the two types of sites. INTERMETALLIC compounds of formula AB2 iso-morphous with MgCu2, MgZn2, and MgNi2 are known as Laves phases. Because Laves phases exhibit high symmetry and coordination numbers, the highest possible for an AB2-type compound,1 they are among the most frequently observed compounds in nature. In recent years interest has centered about the purely transition metal Laves phases2-&apos; in efforts to understand the function of atomic size and electronic structure in the formation of these compounds. It has been observed that pseudobinary Laves phase systems often show a variation of structure across the phase diagram. Such a system is the ZrV2-ZrCo2 in which the structure varies from cubic MgCu2 to hexagonal MgZn2 to cubic MgCu2.4 Some understanding about the conditions under which the second modification is stable can perhaps be gained by studying the distribution of cobalt and vanadium atoms on lattice sites in the MgZn2 modification of the system ZrV2-ZrCo2. In both the MgZn2 and MgNi2-types there exist nonequivalent positions open to occupancy by the B element, whereas in the MgCu2 prototype all sites are equivalent. Skolnick, Kondo, and La-vine7 have developed an anomalous scattering technique suitable for this type of investigation. Whereas the influence of size on the formation of a Laves phase is well recognized, no substantial evidence has been put forth in support of the size ratio dependence of a particular prototype. Berry and Raynor8 suggested that RA /RB ratio does indeed affect the type of structure that is chosen, MgZn2 compounds tending to cluster about 1.225 while MgCu2 compounds were found at larger deviations from this ratio. Dwight,3 however, from a study of 164 Laves phases does not believe this generalization to be justified. Electronic effects are certain to play a part in the stability of Laves phases in general and in the choice of a structure type in particular. For example, size along would favor the formation of Laves compounds of Ti, Zr, Hf, Ta, or Nb as the A element with nickel or copper as the B element. The absence of such is attributed to an unfavorable electron : atom ratio by Elliott and rostoker.4 Early experiments of Laves and witte9 with pseudobinary and pseudoternary systems of the three prototypes established the dependence of crystal structure upon electron: atom ratios. They observed that the MgCu2 structure dissolved elements of higher valency until the electron: atom ratio of =1.8 was reached; the MgZn2 likewise dissolved elements of lower valency replacing zinc. witte,6 from calculations of the electron : atom volumes of Brillouin Zones, obtained limits of stability for the prototypes MgCu2 and MgZn2. Elliott and Rostoker4 used these limits with considerable success in the all-transition element Laves phases they investigated. According to witte,6 compounds between the electron :atom ratios of 1.80 and 2.32 were of the MgZn2 type; those above and below exhibited the MgCu2-type structure. On the basis of these limits and an assumed valency of zirconium based upon the near tetra-valence of titanium, Elliott and Rostoker obtained valencies for the first transition series elements. For the Laves phases with which this investigation is concerned, ZrV2 and ZrCo2, the authors calculated electron :atom ratios of 2.54 and 1.56, respectively. These ratios are for the MgCu2-type structure and straddle the stability band of the MgZn2 modification. One could, therefore, predict that a pseudobinary system ZrV2-ZrCo2 should pass through the MgZn2 modification in traversing the composition diagram from one end to the other. Implicit in this assumption is a smooth change of the electron: atom ratio from 2&apos;54 to 1.56. MOSS10 states that his finding the low temperature structure of ZrCr2 to be C15 instead of C14 alters greatly Elliott&apos;s valency of zirconium and hence the assumed valencies of the other metals. Such a quantitative correlation of structure with electron : atom

Jan 1, 1963