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By Horace Pops, L. L. Isaacs

SOLID-STATE transformations at low temperatures are frequently studied by optical metallography. Greninger and ooradian' and Hull and Gar-wood2 have examined the martensitic-type transformations in 0-phase Cu-Zn alloys during continuous cooling below room temperature. The lowest range of temperatures in the apparatus described by these investigators is limited to approximately 110°K. Present studies of reversible first-order phase transitions near liquid-helium temperatures have necessitated the design of a new cold-stage cryo-stat for optical metallography. The features of interest of this instrument are as follows: a) temperatures down to 4.Z°K are obtainable; b) the specimen is always under vacuum, thereby avoiding the condensation of moisture; c) specimens can be rapidly cooled or heated at varying rates, thus permitting studies of transformation hysteresis. Fig. 1 shows the details of the cryostat. All major parts are made of type 304 stainless steel. Both helium and nitrogen cans are Heliarc-welded to the helium filling tube, permitting the use of a common shielding can. Hence, the over-all weight and the area of the evacuated surface are mini- mized. The copper sample holder is screwed into the bottom of the helium can. To assure good thermal contact between the sample holder and the refrigerant, an indium ribbon is placed on the threads

Jan 1, 1964

By J. M. Roberts, D. M. Barnett

The activation energy required to break a pinned dislocation line away from its condensed atmosphere of impurity atoms is calculated as a .function of applied stress, without neglecting line tension. Reasows are presented for not assuming the effect of line tension to be negligible when considering the problem of freeing a small segment of dislocation from an impurity atmosphere. The dislocation is considered to he pinned at each atomic size along its length and the pinning points are assumzed immobile. The development is a refinement of the origznal cottrell-bilby1 theory. The solution is compared to recent approximations developed by cottrell3 and Haasen5 in which line tension con- IN 1949 Cottrell and bilby1 considered the problem of determining the force required to pull a dislocation away from its condensed atmosphere of impurity atoms. They also examined the effect of thermal fluctuations on this force. The dislocation line was pictured as bowing out in a triangular loop under the action of an applied stress, and the activation energy necessary to free the dislocation from its atmosphere was calculated as a function of stress, line energy, and dislocation-solute atom interaction. siderations were neglected. A qualitative explanation of the yielding process in terms of the activation of Frank-Read sources is presented, but the lack of a realistic solution to the dynamic dislocation problem involved prevents an extension of the model at present. A self-consistent correlation between the present calculations and experimental data for delay time associated with yielding and the temperature dependence of the upper yield stress was made. Favorable agreement was noted. It is concluded that extension of the original Cottrell-~ilby' theory which includes line tension effects can just as well describe the yielding process as other approximations3,5 which neglect line tension. Cottrell and Bilby found the form of the activation energy vs stress curves to be almost independent of the line energy and the interaction energy (i.e., these parameters only affected the activation energy U by a scale factor). A check of the theory was accomplished by comparison with the experimental data of McAdam and Mebs2 for the lower yield stress as a function of temperature. cottrell,3 in 1957, attempted to obtain a simple closed-form solution for the activation energy as a function of stress by linearizing the quartic equation relating displacement of the dislocation line and applied stress. It was argued that since the contribution to the line energy/atomic plane of a dislocation is made by the long-range stress field of the dislocation through a term of the type (Gb3/2p)ln A/ro, where

Jan 1, 1963

By E. S. Bumps, W. F. Craig, M. Baeyertz

Metallurgists have looked at fractures macroscopically for many years and have evolved a vocabulary in which such words as "cleavage," "brittle," "shear," "ductile," "granular," "fibrous," and "silky" are used to describe the appearance of the fractured surface; but the meaning of these words in terms of metal structure is not well established. Observations of the structural meaning of "brittle" and "ductile" fractures in plate steels have been made, notably, by Kramer and coworkers1 and by Tipper.2 Grossman3 has studied the fracture of tempered martensite and combinations of ferrite and martensite. Notwithstanding these and other less concerted attacks on the problem, present understanding of fracture rests more on assumptions and logic than on experiment. It is the purpose of this paper to add a little to the growing fund of experimental observations of the nature of fractures in steel. The particular fractures to be described were obtained in conventional impact testing of an ordinary structural steel shape. In impact tests of the Charpy type, the specimens fail in a characteristic manner that depends on the steel and the temperature of testing. With ordinary structural and many other steel products, an appropriate range of testing temperature will cause a considerable change in the energy absorbed before fracture. This change is known as the energy transition and is accompanied, more or less closely, by alteration in the appearance of the fracture. At testing temperatures below the transition, the terms "brittle," "cleavage," or "granular" are used to describe the fracture; above it, "ductile" or "shear" are often used. Within the transition, the fracture changes from "brittle" to "ductile" by a progression in appearance, wherein the "brittle" portion of the fracture becomes restricted to a smaller and smaller central area of the fracture, as the testing temperature is raised and the "ductile" type of fracture is approached. All this is well known to metallurgists. The specimens under consideration are of the conventional V-notch Charpy type. They were taken from a structural steel shape of the following analysis: C Mn P S Si 0.17 0.46 0.009 0.029 0.03 Both longitudinal and transverse specimens were tested and examined. Fig 1 shows the energy values plotted against testing temperatures in the usual way. The curves for both longitudinal and transverse specimens show an energy transition, although the maximum energy absorbed at testing temperatures above the transition is greater in the case of the longitudinal specimens. Fig 2 illustrates the changes in the macroscopic appearance of the fractures that are associated with the energy transitions shown in Fig 1. Macrographs of the fractured surfaces of the specimens have been identified with the fracture ratings at intervals on each fracture curve. The numerical fracture rating on the ordinate of Fig 2 indicates the percentage of the area of each fracture that was considered to be "brittle" on macroscopic observation. Such rating of the fracture type in impact tests is now customary in many laboratories. Hereafter the specimens will be identified by reference to Fig 2 as 90 pct "brittle," 80 pct "brittle," and so on, in accordance with this macroscopic evaluation of the appearance of the fractured surface. The discussion of the fractures is divided into three parts. The first two are concerned with the mode of fracture and its relation to general structural features. As the same metal-lographic features occur in both longi-

Jan 1, 1950

By H. Biloni, G. F. Bolling

The microsegregation in tin specimens containing 0.2, 0.5. or 1 wt pct Pb has been studied m detail. The specimens were grown from the melt in a controlled fashion and exhibited a well-developed cellular substructure. In general, a severe microsegre-gation can be observed in all the photomicrographs presented. Some observations of special interest are: the distribution of a second phase, the presence of a eutectic in several forms, the evidence for dif- THE Smialowski or cellular substructure which forms during solidification has been extensively studied during the past decade.'* Many of the im- *Most references to the cellular substructure except for the last 2 years are reviewed by Winegard.' portant characteristics of this substructure, such as its occurrence and variability with growth conditions, its association with the phenomenon of constitutional supercooling, and its effect on dislocation production and mobility, have received quantitative fusion of solute in the solid, and the enhancement of segregation at a dislocation subboundary network ("striations"). On the basis of the metallographic observations, it can be deduced that the segregation observed is representative of the solute segregation produced during crystal growth. Some deductions are also made about the interplay of the two substructures, cells and striations, and about the mode of cellular growth. investigation both experimentally and theoretically. However, the concentration profile of the solute segregated during crystal growth has not been examined in detail. Tin crystals grown from melts containing various concentrations of lead have been most extensively studied. In a recent investigation of Sn-Pb alloys, Kramer et a1.2 were able to measure the effective solute distribution coefficient, k,, at the most advanced points of the solid-liquid interface, over a large range of growth conditions, finding it to approach the value of k,, the equilibrium distribution coefficient. As will be shown, this must lead to drastic segregation. Another recent study of several Sn-Pb alloys was made by Plaskett and winegard3 who investigated the variation of growth conditions

Jan 1, 1963

By R. D. Carnahan, J. E. White

A study of dispersion strengthening in TD-Nickel (nickel plus 2 vol pct Tho2) was conducted employing microstrain techniques at ambient room temperature. It was found that optimum strength was due primarily to the incorporation of stored energy developed by a variety of thermal-mechanical treatments. The relatively low strength of the recrys-tallized condition implies that the dispersed particles themselves offer only token resistance to deformation. The development of resistance to large-scale recovery or recrystallization at temperatures near the melting point requires a more extensive sequence of strain-anneal cycles than does the development of optimum strength. A micro-Bauschinger effect was observed which appears to be related to the lattice resistance to the movement of free dislocations. The effect was nearly identical to that in pure nickel indicating that the presence of the dispersed phase and considerably increased dislocation density (stored energy) only alters the number or effectiveness of barriers. THE early stages of deformation of engineering materials can be conveniently studied by utilizing strain-gage techniques which permit resolution of strains less than 5 X 10-7 in. per in. for testing in four-point bending (Carnahan and white1). The present investigation, part of a continuing study on the very early stages of deformation, was designed to reveal the true role of a dispersed phase in promoting high strength in a commercially available dispersion-strengthened alloy. Although this technique has been used for some time to study microdeformation in pure metals and alloys, it has just recently received attention as a means of investigating dispersion strengthening. Studying the very early stages of deformation in alloys which depend upon a finely dispersed inert phase for strength may prove to be a very important method for a better understanding of these materials. It is essential to obtain considerable clarification of actual dislocation movement and the kinds of deformation barriers which exist before optimum properties can be designed into this type of material with any degree of confidence. Considerable research on a variety of dispersion-strengthened materials has resulted in two different schools of thought regarding the strengthening mechanism. One faction2-4 favors the idea that the particles themselves resist the motion of dislocations. The criterion for yielding is the fracture of the dispersed second-phase particles due to an array of piled-up dislocations. Other invesfigators5-a have shown that particles are effective primarily by allowing a greater buildup of stored energy or dislocation density through thermal-mechanical treatments in the composite than the pure matrix material. The particles themselves, then, are not exclusive obstacles, but the complex network of particles, dislocation tangles, subboundaries, and grain boundaries are strength determining. The development of such a complex dislocation network in SAP has been studied recently in some detail by Goodrich and Ansell. The ability of dispersion-strengthened alloys to resist softening or recrystallization is also of considerable importance; however, the criteria for maximum stability may not necessarily be those for maximum strength. In this study, in addition to the evaluation of the microstrain properties of TD-Nickel, it is felt that considerable clarification of the true dependence of strength and stability on the dispersed phase is shown. I) MATERIAL AND PROCEDURE TD-Nickel is a dispersion-strengthened alloy developed by the E. I. DuPont de Nemours Co., which contains 2 vol pct thoria (Tho2) in a pure-nickel matrix. The average ThO2 particle size is approximately 0.1 p and the interparticle spacing is less than 1 u. The material was supplied by DuPont in two conditions: hot-extruded bar stock, and stress-relieved cold-rolled sheet 0.025 in. in thickness. The bar was extruded at 2200°F from a cold-pressed and sintered billet. The sheet stock was prepared from the extruded material by a process involving ten or more 50-pct cold reductions by rolling with intermediate anneals at 1800° to 2000°F. Test specimens used in this study were prepared in the form of rectangular parallelepipeds measuring 0.375 by 1.375 in. in thicknesses ranging from 0.025 to 0.040 in. Samples prepared from sheet and extruded stock were mechanically polished before heat treatment and were handled with extreme

Jan 1, 1964

By Y. L. Yao

A scale based on existing data for the mutual solid solubilities of metals in binary systems has been compiled. This scale is useful for estimating the relative magnitude of two solubilities, provided that these two metals do not form a continuous series of solid solutions. In his classic work on the theory of metallic solid solutions, Hume-Rothery proposed that, other things being equal, a metal of lower valency should be regarded as more likely to dissolve one of higher valency than vice versa. He called this the "relative valency effect". Later he found that the application of this general principle was limited to the three univalent metals: copper, silver, and gold. In dealing with alloys of these metals with metals of higher valency, Hume-Rothery stated, it is usually found that the solid solution of the univalent metal is of the greater extent.&apos; The question of whether there is a systematic trend in comparing the relative magnitude of mutual solubilities, if valency is not considered a criterion, naturally arises. The present paper proposes a "mutual solid solubility" scale on an empirical basis. The order of its arrangement is determined by the relative magnitude of mutual solid solubilities. Some applications of and inferences from this scale are given. ORIGIN AND SCOPE OF THE SCALE An extensive survey of over 400 binary phase diagrams shows that, with certain exceptions and within certain limitations, metals can be arranged in the following order: Na Zn Cd Ga Bi Ge Sb As Hg Sn Si Mg Li Ba In Tl Pb Al Ca Be Mn Cr Re W Mo Cu V Ta Fe Ru Cb Co Ti Hf Ni Os Zr Ir Pt Au U Rh Ce Pd Ag Th so that a metal higher on the scale tends to have a higher solubility in a metal lower on the scale than vice versa. some experimental solubility data are given in Table I. These data, unless otherwise specified, are taken from Hansen and Anderko.6 Throughout this paper, the term "solubility of A in B" is taken to mean the maximum solid solubility of A in B in atomic percent, while the maximum solid solubility of B in A in atomic percent is called "reciprocal solubility". The exceptions found in the above-mentioned survey are: Al-Ag system, 20.34 at. pct Al in Ag, 23.8 Ag in Al; Mg-Pb system, 5.9 Mg in Pb, 7.75 Pb in Mg; As-Sn system, vanishingly small amount of As in Sn, a large As primary solid solution; Cd-Hg system, Cd in Hg <Hg in Cd; Mg-T1 system, 5(?) Mg in ßT1, 15.4 T1 in Mg; W-Ti system, -21 W in ßTi, -25 Ti in W; Zr-Ag system, probably small amount of Zr in Ag, 20 Ag in ßZr.7 Considering the large number of examples, the exceptions are few. It is remarkable that metals may be so arranged without considering other factors such as size, crystal structure, electronic structure, and so forth. A limitation to the use of the scale is the fact that it cannot be tested for two metals forming a continuous series of solid solutions. It is interesting to point out that when the continuous solid solutions have a miscibility gap the critical composition is

Jan 1, 1961

By P. K. Foster, A. McNabb

A consideration of the literature shows the inadequacy of Fick&apos;s Laws to describe the diffusion of hydrogen in steels below 400°C. These laws are modified an the assumption that hydrogen is delayed at fixed sites in the lattice. Approximate and exact solutions of the resulting nonlinear system are derived for simple geometrical shapes. The results qualitatively account for the observed anomalous behavior. Experimental methods for verifying the theory are suggested. 1 HIS paper presents a new analysis of the diffusion behavior of hydrogen in steel based on a physical model which supposes that hydrogen atoms wander in a random manner through the crystal lattice, but tend to get trapped or delayed at certain fixed sites uniformly distributed throughout the metal. These sites, which will be called traps, are regarded merely as potential wells of significantly greater depth than those encountered in regular regions of the crystal lattices and no assumptions are made concerning their nature or origin. The results of experimental studies of the diffusion of hydrogen in iron and steel have usually been reported in the literature in terms of a diffusion constant D derived under the assumptions that the hydrogen concentration C is governed by Fick&apos;s laws.1 Fig. I is a composite of published graphs of the man. ner in which the values of D, so derived, vary with temperature. It is convenient to consider this material in two categories; the high temperature results above 400°C, and the results at lower temperatures. The graphs 2, 3, 4, 5 in the first class lie within a factor of three of each other and are relatively consistent compared with the low-temperature values. There is an increasing divergence in values of D with decreasing temperature till at room temperature they are spread over three orders of magnitude. Small values of D have been obtained for work-hardened specimens.&apos; It is evident that D is a function of other variables besides temperature in this range and that these neglected variables are in some way connected with the work hardening experienced by the specimen. In view of evidence for an interaction between hydrogen in solution and dislocations9&apos;10 and adsorption on crack surfaces,&apos; some doubts must be entertained about the validity of Fick&apos;s laws and their associated physical model of noninteracting particles in random motion through the medium. More direct evidence of their inapplicability to the diffusion of hydrogen in steel was first produced by Darken and smith." Consider the permeation of hydrogen through a plate of thickness a under a boundary concentration Co at the ingoing, and zero at the outgoing, face. If Fick&apos;s first law1 is valid, the steady state flux P, through unit area is DCo/a. In addition, the concentration C varies linearly throughout and Qo, the mean quantity of hydrogen in the medium, is co/2. Compare Qo with Q1 the mean quantity required to saturate the same specimen to a uniform concentration G. In this case Ql = Co and hence the ratio

Jan 1, 1963

By N. A. Tiner, Saara Asunmaa

The early stages of nucleation of vacuunz-deposited gold coatings on electropolished surfaces of pure nickel and binary alloys of Ni-A1 and Ni-Ti have been studied, employing carefully controlled temperature and vacuum conditions. The preferential nucleation of gold on slip-plane edges on the crystal surfaces gave rise to a very pronounced decoration effect which was used in studying the morphology of the pain boundaries, etch pits, and slip planes on crystal faces. Characteristic surface patterns were observed with local dimensional variations. Most pronounced geometric patterns were ohserved in the pain boundaries of nickel and on the crystal faces of Ni-A1 alloy. The nucleation behauior of gold indicates contamination on the Ni-T1 alloy and the getter properties of titanium are presented as a tentative interpretation for the detected contamination. The markings and imperfections on cleavage surfaces of crystals have long been observed by optical microscopy.1,2 Surface-replica techniques are also used to detect the smallest steps and structural details on crystal surfaces by electron microscopy. Recently, Bassett3-5 and Sella, Conjeaud, and Trillat 6 have shown that, when gold is deposited onto a rocksalt cleavage surface, there is preferential nucleation at steps and slip-plane edges on the crystal surface. This gives rise to a very pronounced decoration effect which is invaluable for revealing the lattice steps on a cleavage surface. According to Bassett,3 gold atoms arriving during vacuum evaporation at the crystal surface have a certain mobility on the surface after arrival, particularly at elevated temperature. If a significant

Jan 1, 1964

By E. C. Kersey, R. J. Gennone

MetALLOGRAPHIC investigations of composites of zinc alloys and aluminum have been made to study the effects of various thermal treatments on the zinc-alloy grain size and diffusion of zinc into the core material. The use of various alloys of zinc has necessitated the development of a universal etchant which will allow microscopic examination of the zinc grain size regardless of the composition.

Jan 1, 1960

By D. Kuhlmann-Wilsdorf

A new theory of work hardening is developed which rests on only a few simple principles and is applicable to a wide variety of materials and dislocation structures. It explains, qualitatively, the general characteristics of the three-stage shear stress-shear strain curve of fcc metals, as well as the most important features connected with easy glide. The value of, the work-hardening coefficient in stage 11, is derived quantitatively, from first principles, and is shown to be insensitive to many changes in detailed dislocation behavior. The low rate at which energy is stored during mechanical working in stage 11, the dependence of slip line length on stress, and the so-called Cottrell-Stokes law are explained. Although the theory is primarily developed for fcc metals and alloys, it is largely applicable also to some other materiuls, and in particular apparently to poly crystalline simple steels in theh linear range of hardening. FOR pure fcc metals and alloys, after many different pretreatments and under a great variety of testing conditions, the well-known three-stage work-hardening curve is commonly observed. Moreover, the work-hardening coefficient in stage 11, 011, bears an almost constant relationship to G, the modulus of rigidity, such that K = G/Brr" = 300, within a factor of about 2 either way. The very fact that the three-stage curve and the value of K are so very persistent, can hardly be understood except on the assumption that some quite simple phenomena are responsible. In this light all available theories of work hardening must be judged unsatisfactory: Each of them is based on some quite specific dislocation model, while it is known that metals with similar values of K may have widely different dislocation structures, for example, dislocation tangles in the case of pure fcc metals, and piled-up groups of dislocations in a-brasstype alloys. Thus, while a particular theory might conceivably represent a special case with a reasonable degree of accuracy, it cannot possibly have illuminated the underlying principle. Another severe criticism applying to the presently most widely discussed theories is that they employ empirical or even quite unexplained parameters in order to arrive at a numerical value of K. This indicates that some vital aspect of the work-hardening process has remained unexplained. In the present paper, a new theory of work-hardening is developed which does not suffer from the above shortcomings. It is derived from first principles, and is founded on the realization that the underlying causes for the three-stage work-harden- ing curve and for the persistence of the numerical value of O,, must be few and simple. As a first step it is shown herein that the experimental oklservations on "easy glide" can be explained on the assumption that in this stage dislocations multiply, beginning in a number of restricted area:;, and from there penetrate into crystal regions still substantially free of glide dislocations until a quasi-uniform dislocation distribution has been established. During "easy glide", the resistance to the movement of the foremost dislocations, advancing into still largely a dislocation-free regions, is believed to control the flow stress. This resistance is determined by various factors, among them the reaction of the dislocations against bowing-out into loops, which is due to their line tension. Without such bowing-out no dislocation multiplication would occur, but the corresponding contribution to the flow stress stays practically constant all through stage I. According to the present theory, stage TI begins as soon as there are no more areas left into which newly formed dislocations have not yet penetrated, i.e., as soon :is a quasi-uniform dislocation density has been attaned. Regardless of how, in detail, the dislocations should happen to be arranged at the end of "easy glide", whether in pileups or tangles, on one glide system or on several, the stress necessary to overcome the line tension of the segments must now increase, because the dislocation density increiises while the average free dislocation length decreases. It is argued that all other contributions to the flow stress stay at about the same level as in stage I, and that the said increase in the stress necessary to bow out dislocation segments into loops is responsible for the major part of work hardening in stage 11. Stage TII of the stress-strain curve is explained by largely follouing the ideas of Seeger and his co-workers; however, it is pointed out that the start of stage m may on occasion indicate the onset of "conservative climb" instead of cross slip. Indirect evidence indicates that linear work hardening persists even under the profuse action of cross slip, but at a lower rate. Only when, in addition to cross slip, climb operates extensively, does the work-hardening rat,. drop sharply, ultimately down to zero. BRIEF SURVEY OF EXPERIMENTAL EVIDENCE The stress-strain curve of crystals of many different substances are qualitatively similar. No significant permanent plastic deformation takes place below the so-called "critical resolved shear stress". As the applied stress is raised beyond this level. yielding occurs with little or no work hardening and

Jan 1, 1962

By H. H. Hausner, H. S. Kalish

IN recent years zirconium and beryllium have become of great interest because of their special properties. Zirconium is known for its remarkable ability to absorb the gases oxygen, nitrogen and hydrogen, has extensive use as a getter in electron tubes and has indeed become the primary metal in the manufacture of photoflash bulbs. Beryllium is of interest because it is light metal and as such could supplement aluminum and magnesium in light metal applications. The late development of zirconium ductile at room temperature produced by both the iodide and calcium reduction methods has stimulated frequent articles on this metal in the recent literature. Beryllium is so closely akin to zirconium crystall-ographically that some investigators are of the opinion that beryllium should be ductile at room temperature if it were pure enough. The crystallographic relationship of beryllium and zirconium, the interest created in Be-Zr alloys where the zirconium is believed to function as a remover of solid solution gas in beryllium and thus increase the ductility of the beryllium rich alloy, and the amenability of these metals to powder metallurgy methods stimulated this approach to an investigation of the system Be-Zr. Preliminary work showed that a zirconium compact melted when pressed in contact with a beryllium compact and sintered at 1250°C, without any apparent final bond between the two. A search of the literature revealed nothing pertinent about the Zr-Be system or about any zirconium - beryllium alloys. In 1936 Misch³ vaguely identified the compound ZrBe2 and reported that it has a deformed cubic structure. Two patents," , were issued to Mach-lett Laboratories in 1943 and in 1946 regarding the addition of small amounts of zirconium to beryllium in order to improve the ductility of beryllium so that it may better be used for X ray windows. In considering the alloy formation of beryllium with other metals Raynor thought it unlikely that zirconium would have any solid solubility in beryllium. From this indefinite information nothing could be ascertained about the possible use of Zr-Be alloys or the use of these metals intimately. A brief preliminary study of the system Zr-Be by powder metallurgy methods was undertaken to provide regions for more intense studies of Zr-Be alloys and as a guide to a formal phase diagram determination. The investigation described in the following pages was completed in less than three weeks. The usefulness of this rapid method to facilitate phase diagram studies and new alloy investigations will be shown. Materials and Procedure Zirconium powder was produced from crystal bar stock of high purity supplied by Foote Mineral Co. The crystal bar was converted to hydride at 730°C, crushed, and the hydride decomposed in purified argon at 850°C. 60 pct of the powder passed through a 325 mesh screen, 40 pct of the powder was —140 mesh, +325 mesh and the average particle size of the total was 8 to 12 microns. The beryllium powder was used as re-

Jan 1, 1951

By N. Brown

From the theories of flow and fracture it is shown that the difference in reciprocals of the transition temperatures (OK) is a quantitative measure of temper ernbrittlement. Experimental data are given which support this conclusion. STUDIES of temper embrittlement have been made with various viewpoints; some involved a study of the kinetics of the reaction,&apos;,2&apos;" others were concerned with changes in the mechanical properties," . and still others investigated the structural differences between the embrittled and unembrittled states by means of the microscope," -ray ,&apos; measurements of electrode potential," and electrical resistivity." In all these studies, the difference in impact properties was the criterion for distinguishing between the embrittled and unembrittled states. By common agreement the difference in transition temperatures is now taken as a measure of the degree of embrittlement, and this measure is used as the quantitative measure upon which studies of the phenomenon are based. Vidal and Jolivet"&apos; suggested that the degree of embrittlement was the same whether measured by impact or by a slow bend test. Their conclusion was based on tests at constant temperature. Jaffe and Buffum" using the impact and slow bend test showed that, for a given degree of embrittlement, the difference in transition temperatures varied with the method of testing. Hultgren and Chang" showed that the difference in transition temperature produced by the V-notched Charpy impact test was not the same as the value produced by the keyhole-notched impact test. This is a very fundamental point because there can be no true measure of temper embrittlement unless it is invariant with respect to the test method. Theory The purpose of this analysis is to show how the transition temperature depends on the stress distribution and the state of the material. The criterion for fracture may be stated as follws: where iF is some function of the principle stresses and F is a critical condition depending on the state of the metal. Similarly yielding occurs when Where is another function of the prin-ciple stresses and Y is a critical value depending on the state of the material. There is some controversy as to the exact form of the function f,.(u,, u,, us) but most experimental data give the following criterion:= where 8, and 6, = 21 or 0. Combinations of 6, and 8, give the various criteria such as the normal stress, the hydrostatic tension, and the maximum shear stress laws. Agreement is general that the octahedral shear stress law adequately describes the yield condition. where the bracketed factor will be called the design factor and depends on the stress distribution. Whether the metal decides to yield or fracture is given by the condition that The effect of temperature and strain rate upon Y has been studied by various investigators, It has been shown by MacGregor and Fisher" that

Jan 1, 1955

By R. E. Ogilvie, J. I. Goldstein

The a and y solubility limits in the Fe-Ni phase diagram have been redetermined at temperatures above 500°C. Both a diffusion-couple and a quench and anneal technique were used. The solubility limits were measured with an electron-probe micro-analyzer. The nickel concentration at the phase boundary is increased below 700°C and the a solid-solubility range is much larger than had been previously measured. The solubility limits are also extrapolated to 300°C. It is suggested that the solubility of nickel in a FeNi reaches a maximum in the temperature interval 400o to 500°C. THE equilibrium diagram has been of great use in the field of meteoritics, where the phase relations between kamacite (a) and taenite (?) in metallic meteorites can be described by means of the Fe-Ni diagram. The study of metallic meteorites by electron-probe microanalysis has cast some doubt on the accuracy of the presently available Fe-Ni diagrams.1, 2 Recent thermodynamic studies of the Fe-Ni system also suggest that the diagram may be in error.3 For these reasons the high-temperature (800o to 500°C) part of the diagram was redetermined. INTRODUCTION The currently accepted Fe-Ni diagram is that of Owen and Liu.4 Above 910°C, there is a region of complete solid solubility, ? (fee). Below 910°C, the a (bee) phase is stable in pure iron. The effect of increasing amounts of nickel is to stabilize the y phase. The phases that form when Fe-Ni alloys are heated or cooled bear little relation to the equilibrium diagram. If an alloy is cooled from the y state and held at a temperature within the a + y field, no evidence has been found for the occurrence of the y - a transformation.5 If the alloy is cooled to low enough temperatures the y phase breaks down into a supersaturated bee phase called a2. In fact, in alloys over 27 pet Ni the y phase is retained at room temperature.6 The a, phase has the same composition as the original y. The temperature at which a2 forms, the M, temperature, has been determined experimentally.&apos; A state of equilibrium can be approached by cooling below M, to form a2 and then reheating the alloy into the two-phase region of the diagram. The y phase will then begin to precipitate out of the a2 phase and grow. The growth of the phase, however, is quite slow. Using the interdiffusion coefficients -Da of Goldstein et al.,8 it is estimated that it takes about 1 year to grow a 10-µ-wide region of ? at 700°C in a 5 pet Ni alloy. Owen and Liu4 used the technique just described to form the equilibrium phases. The phases present were determined by means of X-ray analysis. The accuracy of their diagram depends on the number of alloys available near the phase boundary at a given temperature. In this study two different techniques were used to determine the a/a + ? and ?/a + ? solubility limits. The inherent accuracy of both techniques was greatly improved over that used by previous investigators because the phase-boundary compositions were measured with an electron-probe microanalyzer. PROCEDURE The two methods used to determine the Fe-Ni diagram are the diffusion couple (D.C.) and the quench-and-anneal (Q.+A.) techniques. In the first method, diffusion couples whose diffusion path goes through a two-phase region of the phase diagram were used. A description of the technique used for making the diffusion couples has been described in a previous paper.&apos; After the diffusion treatment a discontinuity in the resultant concentration vs distance profile was measured. The nickel concentrations in the a and ? phases at the interface of the discontinuity are the solubility limits of the a and ? phases in the phase diagram at the diffusion temperature. If the interface com-

Jan 1, 1965

By J. H. Brophy, A. L. Prill, H. W. Hayden

An error lzas been found in the conventional way of determining the time exponent of linear shrinkage for the solution-precipitation stage of liquid-phase sintering. Large amounts of shrinkage due to initial rearrangenzent result in erroneously low exponents and tni si dentification of the rate-controlling process. Two alternative, mathematically correct, methods of calculation are applied to existing data on Fe-Cu, WC-Co, and Tic-Ni-Mo. This results in reidentifi-cation of the rate-controlling process and somewhat better agreement with related data. In each case the solution-precipitation process is solution-controlled and not diffusion-controlled. THE liquid-phase sintering process has been the object of a considerable amount of research for many years. Linear shrinkage vs time data at various sintering temperatures have been used recently in an attempt to identify the prevailing mass-transport processes in a number of metallic and nonmetallic systems. There is an analytical error inherent in the methods previously used for handling data during the "solution-precipitation" stage of shrinkage which must be recognized before the correct rate-controlling processes can be determined. It is the purpose of this paper to show how the error has affected previous conclusions and to suggest corrections. A number of mechanisms have been proposed to explain experimental observations during sintering in the presence of a liquid phase. The earliest of these is due to Price, Smithells, and williamsl who attributed the observed growth of the solid phase to the simultaneous solution of smaller particles and growth of larger particles. From the work of Lenel et al.2,3 and Gurland and Norton4 has come the suggestion that the liquid-phase sintering process may be divided for analysis into three steps: 1) rearrangement upon formation of the liquid phase; 2) solution and reprecipitation of the solid phase in the liquid; and 3) "coalescence" or a final stage of sintering, characteristically slower than the solution-precipitation process. The sequence of steps is shown schematically in Fig. 1. Kingery5 presented a thermodynamic and kinetic analysis of the first two "stages" of the liquid-phase sintering process in which the functional dependence of lineal shrink- age on time at temperature was used to identify the rate-controlling mass-transport process. Table I summarizes the time dependences and processes considered by Kingery.5 This method of data presentation has been employed by Kingery and coworkers for Fe-CU,6 WC-Co, and a number of nonmetallic systems," and bv Whalen and Humenik for Tic-Ni-Mo and Fe-cu.8 In each of these studies, the rate-controlling step during the "solution-precipitation" stage was identified from the slope of the curve in that stage on a logarithmic plot such as Fig. 1. However, in all of the previous studies, at a certain composition, relatively large amounts of shrinkage due to rearrangement preceded the solution-precipitation stage. Under these conditions, the larger the amount of rearrangement shrinkage the

Jan 1, 1965

By Paul A. Farrar, Harold Margolin

The system Ti-Cr has been re investigated From 40 to 100 pct Cr. The high-temperature modification of TiCr, was found to exist in the temperature range from 1365 where it terminates in the eutectoid reaction TiCr,(TI)* — HE chromium-rich region of the Ti-Cr system was investigated by Vogel and Wenderott,&apos; Mc Quillan,&apos; Van Thyne et dl.,&apos; and Cuff Duwez and Taylor determined the crystal structure of the low-temeperature modification of TiCr, to be fcc a = 6.943A and Levinger&apos; discovered the existence of a second (high-temperature) modification of TiCr, and determited its crystal structure to be hexagonal a = 4.932A, c/a = 1.617i. No information was obtained as to the temperature range over which each modification of TiCr? existed; therefore the present investigation was initiated. I) Experimental Techniques Alloys employed for the delination of this system were prepared from iodide titanium and high-purity chromium. The purity of these materials is as follows: Iodide titanium: purity 99.99 pct; major impurities—carbon 0.0001 pct; oxygen 0 to 0.002 pct; nitrogen 0 to 0.002 pct; silicon 0 to 0.005 pct; manganese 0.001 pct; copper 0.001 pct (Foote Mineral Co., Lot 609-29). Chromium #1: metallic purity 99.997 min.; interstitial content—oxygen 0.27 to 0.46 pct; hydrogen 0.028 to 0.038 pct; nitrogen 0.0002 pct (Ave-quipo Inc.). Chromium #2: purity 99.9 pct; major impurities—carbon 0.01 pct; oxygen 0.013 pct; nitrogen 0.02 pct; silicon 0.01 pct; sulfur 0.03 pct; iron 0.01 pct (Fulmer Research Institute Ltd.). A total of sixteen alloys of thirteen different compositions was prepared in the range from 40 to 95&apos; *All percentages are given in weight percent. pct Cr. The compositions of the alloys prepared were as follows: Ti-40, 45, 50, 60, 62, 64, 66, 68, 70, 80, 85, 90, and 95 pct Cr. Two buttons were prepared of the 66, 90, and 95 pct Cr alloys. The 40 pct Cr and one of the 66 pct Cr alloys were prepared from the chromium # 2. All the other alloys were prepared from chromium #1. The alloys were arc-melted as 25-g buttons in a copper-hearth glass-walled furnace7 under an inert atmosphere of high-purity helium. The alloys were sintered at 250 amp and melted twice at 350 amp for 30 sec with the buttons being turned over between melts. Weight losses during melting were determined and in the range 45 to 68 pct Cr they were found, in all cases, to be less than 1.25 pct of the total alloy weight. A number of the high-chromium alloys shattered during cooling from either the first or second melt, which made the weight loss considerably larger than usual. The 70 and 80 pct alloys lost approximately 5.7 pct of their total weight, the 85 pct alloys 1.5 pct, the 90 pct alloy 2 pct, and the 95 pct alloy 3 pct. However, it is felt that the actual composition of the alloys in this region is probably within approximately 1 pct of the intended composition, as a large portion of the material lost was that due to shattering after melting. Nominal compositions were therefore used in plotting data and referring to the alloys. The alloys were cut into specimens, wrapped in molybdenum sheet, and encapsuled in argon-filled quartz or Vycor tubes for heat treatment. The heat-treatment times and temperatures are given in Table I. The specimens were quenched in iced brine (I.B.Q.) following heat treatment. The standard techniques of grinding, polishing., and etching were used in preparing the specimens for metallo-graphic examination. For alloys below 68 pct Cr

Jan 1, 1963

By Paul A. Farrar, Felix Ermains, Harold Margolin

The systems Ti-Crand Ti-Vhave been reinvesti-gated in the region up to 40 wt pct alloying addition using both conventional and rapid quenching techniques. The Ti-Cr eutectoid temperature was determined to be at 667° & 10° C and 14.5 wt pct Cr. The solubility of the Cr in a Ti was found to be less than 1 pctat 700"C. The P transus of the Ti-V system was found to be depressed to 510°C at 40 wt pct V and the solubility of V in a Ti was found to be less than 2 wt pct at 700°C. Investigation by a. d. McQuillan1-3and m. k. McQuillan4 on the systems Ti-Co, Ti-Cr, Ti-Cu, Ti-Fe, Ti-Mn, Ti-Ni, and Ti-V has cast doubt as to the position of the ß/a + ß boundaries in many of these systems. Their investigations were carried out using hydrogen pressure and/or rapid quenching experiments, as opposed to the conventional quartz capsule techniques employed by most other investigator.&apos;" By these methods, the ß/a + ß boundary was found to be lower than that obtained by conventional techniques in all except the Ti-Fe system. In the latter, the ß/a + ß boundary was essentially the same as the boundary obtained by conventional technique.7&apos; On the basis of rapid quenching results in the Ti-Cr system, M. K. McQuillan4 placed the eutectoid temperature below 550°C whereas other investigations using conventional techniques had placed the eutectoid variously as between 650&apos; and 700°C,5 between 675&apos; and 700°C,6 between 650" and 675°C,7 at 670°C,8 and above 625"C.la9l3 In order to check these results, a reinvestigation of four of the systems was undertaken using both conventional and rapid-quenching techniques. The Ti-Fe and Ti-Mn systems will be dealt with in anoth er paper, with only the Ti-Cr and Ti-V systems being discussed here. EXPERIMENTAL TECHNIQUES Alloys employed for the delineation of the systems under investigation were prepared from iodide titanium sheet capsules containing the alloying materials,

Jan 1, 1962

By E. C. van Reuth

FIFTY-three alloys have been examined in the Fe-W and Co-W alloy systems in an attempt to verify the finding of o phases in these systems as reported by Goldschmidt.&apos; The alloys were examined metallographically and by X-ray diffraction. The 10-g specimens were made by powder metallurgy techniques. Very fine, high-purity powders were compressed in a double-acting die at 120,000 psi after hydrogen reduction. All compacts were then sintered for 200 hr at 950°C in a helium atmosphere. Metallographic investigation and X-ray diffraction proved this time to be sufficient to allow complete homogenization before the subsequent high-temperature anneal. Each specimen was then sealed into an evacuated silica capsule and annealed at 1400"or 1500 C (except two) for 25 hr. (The 60 pct Fe and 55 pct Co alloys taken to 1610"and 1680°C respectively were held at these temperatures for 1hr. However, since these structures were at equilibrium before the anneal, and in view of their resultant structures, it is assumed that they reached equilib-

Jan 1, 1960

By J. E. Hilliard, H. E. Cook

It is shown that for systems having a miscibility gap the spinodal composition (c,) in the vicinity of the critical temperature (Tc) is related to the equilibrium composition (c,) by where cc is the critical composition. This expression is exart for the limit T — Tc and is a good approximation down to (T/Tc) - 0.9. If the miscibility gap meets the composition of the pure components THE recent theoretical treatment by cahn1,2 on spinodal decomposition of solid solutions has revived interest in methods of estimating the chemical spinodal, * i.e., the locus on a binary phase By use of the appropriate expression, the spinodal can be drawn on the Phase diagram almost by inspection with an accuracy comparable to that of lengthy calculations in which a free-energy function is fitted to the phase diagram. Satisfactory agveemenf is also obtained with spinodals comPuted from experimental free-energy curves. where G is the Gibbs free energy of the homogeneous solution and c the atomic fraction of component 2, the derivative being evaluated at constant temperature (T) and pressure (P). (These subscripts will hereafter be omitted from the partial derivatives.) If experimental measurements of G as a function of c and T are available in a single-phase region above the spinodal, then these can be extrapolated to obtain a series of metastable free-energy isotherms in the two-phase region, and from these isotherms a series of spinodal compositions can be calculated. Because the value of is very sensitive to experimental errors, an elaborate analytic procedure is required for

Jan 1, 1965

By L. F. Mondolfo

An investigation of the relationship between properties of the elements and type of binary diagram formed was conducted. It was found that, for each type of equilibrium diagram, the factors for the size, valence, electronegativity, period, melting point, entropies of fusion, and sublimation calculated for each pair of elements cover a range of values. However, these factors show sufficient relationship to the equilibrium diagram so that the correlation of several of them can be used to predict the type of diagram formed, or at least limit the choice to only a few types. ThE goal of the metallurgist concerned with alloy development has always been to find a method that predicts the properties that can be obtained when a certain metal is added to another one. In most cases a qualitative predictiton of properties can be made if the equilibrium diagram is known. However, this means that for new metals the alloy development has to start with the experimental determination of the equilibrium diagrams. Because this determination is at least as complicated and time-consuming as the determination of the properties themselves, most alloy development has taken place by trial and error, and the study of the equilibrium diagrams has followed rather than preceded the creation of new alloys. Alloy structures and properties depend on the interaction between electrons and a complete knowledge of these interactions would permit prediction of structure and properties of alloys. Unfortunately direct measurement of these interactions is extremely difficult and somewhat doubtful and only properties that depend on them can be measured easily and with certainty. Study of the relationship between properties of the elements and equilibrium diagrams is not new. Besides the well known Hume-Rothery rule of the necessity of an atomic diameter fit within 15 pct for extensive miscibility in the solid, and the wide knowledge of the effect of such factors as size, electronegativity, electron-atom ratio on solid state features,"&apos; work relating to liquid state and liquid-solid reactions can be found in the literature. Of particular interest is the work by Axon,3 who investigated the effect of size and melting point on a selected number of eutectic and monotectic dia-

Jan 1, 1962

By R. E. Reed-Hill, J. L. Martin

Kinking is an important deformation phenomenon in poly crystalline a zirconium. The crjlstallo-gvaphic features of the most important form of kinking have been determined with the aid of twins formed at 77°K in grains previously kinked at high temperatures. It has been .found that the kink-band boundaries correspond to walls of edge dislocations with (1150) Burgers vectors and dislocation lines parallel to (1070). The present observations imply that basal slip is an important secondary-slip mode in polycrystalline zirconium. Previous single-crystal studies13 did not veveal this mode Other evidelzc.e for (0002)(1120) slip is also presented. ThE first studies of kinking in hexagonal metals were made by orowan,1 using single-crystal cadmium wires. He suggested that this was a new de- formation mode in metals, different from ordinary glide or twinning. Next, Hess and Barrett2 studied zinc-crystal rods in compression, and were able to offer an explanation of the phenomenon described by Orowan. They concluded that kinks required no new deformation mechanism and were a special form of deformation band that developed gradually and solely from basal glide. Similar kink bands were then observed by Washburn and parker3 on zinc crystals deformed in tension at low stresses and high temperatures. In titaniun,4 kink bands associated with {1010}<1120> prism slip have been observed in coarse-grained specimens. Magnesium5 and rhenium6 have also been observed to kink in conjunction with their basal- and {1010} prism-slip systems, respectively. Yttrium has (1010) as a predominant slip plane, but no observations of kink bands were reported.7 Since no previous investigations of kink bands in zirconium have apparently been made, this study was proposed. Its aim was to determine the crys-tallographic features of a type of kink band frequently observed in polycrystalline zirconium. EXPERIMENTAL APPARATUS All tests were performed on a type TTC Instron machine. The cross-head speed usually chosen in tension or compression was 0.02 in. per min. Ten-

Jan 1, 1964