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By D. Walton, W. C. Winegard, W. A. Tiller, J. W. Rutter

It is shown that the cellular substructure observed in binary alloy crystals grown from a melt of known concentration can be eliminated by the proper choice of growth conditions. For a given solute concentration, there exists a critical ratio of temperature gradient G in the melt to the rate of solidification R of the crystal, i.e., of G/R, which must be exceeded before the cellular structure can be eliminated. A secondary substructure is observed which is related to the cellular substructure. IN crystals grown from the melt, a prismatic substructure has been observed by Buerger,1 Pond and Kessler,2 and Rutter and Chalmers." This structure is columnar in the direction of growth and appears as a network of hexagonal cells in the plane of the solid-liquid interface. Rutter and Chalmers3 have shown that this substructure occurs as a result of the presence of a layer of high impurity concentration in the melt adjacent to the solid-liquid interface. The formation of the substructure is accompanied by a redistribution of this impurity in the neighborhood of the interface. The structure can be controlled by proper adjustment of the variables in the solidification process such as a rate of solidification and the temperature gradient in the liquid. The redistribution of solute during the solidification of metal crystals has been treated theoretically

Jan 1, 1956

By John T. Norton

N order to attempt to arrive at a better under-Jl standing of the whole basic problem of sintering, these remarks will serve as an introduction for discussion that is included and will, perhaps, help to isolate specific questions which need to be answered or to suggest some definite avenues of investigation which should be followed. To bring some sort of logical order into the presentation, I will consider the various types of interaction between the metal to be sintered and the atmosphere which surrounds it, depending upon whether the phenomena are essentially chemical or physical in nature. For example, when the only necessary criterion for the satisfactory sintering of a certain powder is the removal of an oxide skin, then the problem of choosing a suitable atmosphere is primarily chemical; however, if a special surface condition as a consequence of the oxide skin removal is necessary for particularly effective sintering, then the problem becomes a physical one. Of course, the two aspects overlap considerably, but it may be possible to make a distinction in principle if not in practice. The chemical characteristics of the phenomena will be emphasized, since these are the better known. Metal-gas reactions involved in sintering are controlled primarily by the thermodynamics of the processes involved. In which direction will a reaction go and how far before it stops? The answer is to be found in the magnitude of the free energy change associated with the reaction. If a constituent is to be removed from the specimen as completely as possible or if a constituent is to be formed in the specimen as completely as possible, then one chooses conditions which are far from equilibrium so that the reaction is driven toward completion. On the other hand, if the composition is to be maintained at a desired value, then conditions are adjusted as closely as possible to the equilibrium point. This aspect of the problem is susceptible to quite precise analysis, provided, of course, that the significant reactions can be recognized and the required thermodynamic data are available. Conversely, if one asks how fast the reaction goes or how far it proceeds in a given time, the answer is frequently much more difficult to answer in quantitative terms. Yet the rate-con trolling factors of the reactions may be of primary importance in the success of a particular operation, especially where competing processes are at work. Both equilibrium and rate factors must be understood if a clear picture is to be obtained. For instance, in a process for carburizing titanium dioxide, is the difficulty of obtaining a stoichiometric Tic due to a true limitation of the equilibrium or simply to a very slow rate of reaction? An example of this appears in the work of Kalish and Mazza.' They showed that the oxygen content of sintered iron compacts was lower when sintered in pure hydrogen than in the case where the hydrogen was diluted with either argon or nitrogen. The equilibrium oxygen content of the iron would be the same in the two cases, since it is determined by the ratio of the partial pressures of water vapor and hydrogen and this pressure ratio is unchanged by dilution. The rate of oxygen removal, however, under the conditions of a constantly replaced furnace atmosphere, depends upon diffusion and thus upon the concentration of hydrogen in the furnace atmosphere. Possibly the clearest way to illustrate the interplay of these two factors is to consider in more detail some of the typical metal-gas reactions. Adsorbed Gases It is common experience that fine metal powders with their very large surface areas often contain large quantities of gas. This gas, which results from exposure to air or perhaps from some step in the

Jan 1, 1957

By David P. Shoemaker, Clara B. Shoemaker

It has been shown for an important class of complex transition intermetallic compounds (a, P, R, 6, and p phases) characterized by "normal" coordination [CN12 (icosahedral), CN14, CN15, CN16/ that interatomic distances nay be calculated to a good approximation as the sum of characteristic atomic radii. Two radii, one for major ligands and one for minor ligmds, are specified for each atom, except in the case of CN12 where only a miaaor-ligand radius is specified. The same appears to be true of transition-metal phases of simpler struc-ture: Laves phases (CN12, CN16), and p-tungsten phases (CN12, CN14). In the case of known examples of the more complex phases, a simple rule is given which specifies these radii. However, only a fraction of the known examples of the simpler phases obey this rule closely. To include the latter phases the rule may be modified by considering the radii as linear functions of the weighted average of the Pauling CN12 radii of the two kinds of atonzs, with the radii weighted according to the over-all chemical composition of the alloy. With very few exceptions interatomic distances for both tlze complex and the simpler transition phases can b$ predicted with this modified rule to within 0.06A. ManY intermetallic compounds are known of composition A,By, in which A is a transition element to the left of the manganese column in the periodic table and B is a transition element in or to the right of it. Frequently the coordination numbers (CN) found in these compounds are CN12 (icosahedral), CN14, CN15, and CN16 (called "normal" coordinations by Frank and Kasperl). Well-known examples are the cubic and hexagonal Laves phases which have CN12 and CN16, and the 0-tungsten (CrsO) phases which have CN12 and CN14. In the more complicated (often ternary) phases, such as the a phase,2 the Beck phases p3 and R~, the 6 phase,5 and the p p atoms occur with CN12, CN14, CN15, and (except for a) CN16; in many cases several crystallographically independent atoms of one particular CN occur in the asymmetric unit. A large number of independent interatomic distances are found in these complicated phases, varying from 20 in the a phase to 94 in the 6 phase. These distances show a large spread; they vary, for example, from 2.358 to 3.278A in the 6 phase. In our analysis of these distances we found that in each of these compounds every atomic position can be characterized by either one or two radii. The CN12 positions are characterized by a single radius, The higher coordinated positions are characterized by two radii, namely: the CN14 positions by 4 in the direction of the twelve "5-coordinated" ligands3 (called 'minor" by Frank and Kasperl) and by r:, in the direction of the two "6-coordi-nated" ligands (called "major" by Frank and Kasper); the CN15 positions by r15 for the twelve minor and r:, for the three major ligands; the CN16 positions by rlE for the twelve minor and r:, for the four major ligands. We have expressed the experimentally determined interatomic distances in observational equations as the sums of the appropriate pairs of these characteristic radii and the value of these radii have been determined by the method of least Squares. Despite their wide range, the interatomic distances could then be predicted by the sums of these atomic radii with an average deviation in any one compound of 0.06A or less. The results are summarized in Table I. Inspection of the radii thus obtained shows that in the structures in Table I the radii (in A) are given to a first approximation by the simple relationship: Where CN is the coordination number (12, 14, 15, or 16), and A = 1 for major ligands and = 0 for minor ligands. The interaLomic distances can be predicted within about 0.1A by sums of these atomic radii. Another phase belonging in this group with CN12, 14, 15, and 16 is the y phase & B7, in which A is molybdenum or tungsten and B is iron or cobalt. Recently the M%C phase has been refinedE and the observed distances also agree well with those calculated with Eq. [I]. (In the original determination of the structure of W6FeV7 the F$(II)-W(II1) distance was erroneously given as 2.84A, but we have recalculated it fro? the published parameters and found it to b? 2.57i4, in good agreement with the value of 2.6A predicted with Eq. [I.].) Many binary transition alloys are known to crystallize with the simpler structures having "nor-

Jan 1, 1964

By P. G. Shewmon

If interfacial equilibrium is maintained at the interface between a growing precipitate and the supersaturated matrix, so that solute diffusion alone determines the growth rate, the precipitate shape should evolve toward that characteristic of the dendrites found in solidification. However, this shape is rarely observed in precipitation reactions proceeding at high temperatures where interfacial equilibrium is usually felt to prevail. Thus some other stabilizing factor must enter, to keep the interface smooth. It is shown that a slow interfacial reaction (low interfacial mobility) will stabilize the interface, while transformation stresses have a IN studying the kinetics of phase transformations such as solidification or proeutectoid precipitation at high temperatures, it is customary to assume that equilibrium exists across the interface and that the rate of the reaction is determined by the rate at which heat and solute diffuse to and from the interface. In the case of precipitation, such an assumption predicts an almost infinite rate of initial growth. It is generally stated that the rate cannot be infinite and that during some initial period the rate must be determined not by solute diffusion but by an interfacial reaction, i.e., transferring atoms across the interface. The duration of this much weaker stabilizing eFfect and impurities tend to enhance instability. It is also concluded that a sets an upper limit on the wavelength of the perturbation that can give instability. Thus initially all flat or smoothly curved particle interfaces will be stable even if their growth is diffusion-controlled. Proeutectoid precipitation in the Fe-C system is considered in some detail and it is shown that the experimental results can only be rationalized if the growth rate of ferrite in steel transformations is determined by a slow interfacial reaction for all hut a few orientations between the two phases. initial period has never been clearly established, but it is generally assumed to be too short to affect any measurable results.' Several authors have pointed out that in the case of interfacial equilibrium any bump in the surface will grow out ahead of the planar interface due to the higher gradient in front of it.2j3 Thus the interface will be unstable with respect to an irregular interface with points (plates) propagating rapidly out ahead of the interface into the supersaturated phase. Recently, Mullins and Sekerka have given equations for the stabilizing effect of surface tenion.~ They found that for particles with a radius of curvature of 1 p or greater the stabilizing effect of surface tension will be completely overcome by a supercooling, or supersaturation, of as little as

Jan 1, 1965

By J. W. Spretnak, G. W. Cunningham

A study has been made of the growth and disappearance of voids in the interface of pressure bonded copper. The formation of visible voids is primarily due to spheroidization and coalesence of microvoids produced during the application of pressure. The microvoids could be prevented from forming by the application of high pressures or by increasing the ductility of the copper. Migrating grain boundaries were found to be more effective in void removal, than stationary grain boundaries. DURING the course of an investigation on the mechanism of pressure bonding, it was found that voids formed in the bonding interface which inhibited migration of the interfacial boundary and grain boundaries in the bond region. Therefore, an effort was made to determine the nature of the voids and how they form, grow, and disappear. This paper reports the results of such an investigation. The existence of interfacial voids is not solely a characteristic of massive components of metal which have been bonded by the application of heat and pressure, but is a phenomenon which has been observed in sintering as well. Simonsen attempted to study the sintering process by hot-stage microscopy and thereupon observed the formation of interparticle porosity as sintering proceeded. It was assumed that the porosity was due to grooves created at the location where grain boundaries joined the surface of the particle. Pranatis, Castelman, and seigle2 have also observed voids along the areas of contact in wound-wire specimens used for sintering studies. They did not discuss the point in detail since this behavior was not general, but they did suggest that the voids might develop as a result of stresses along the interparticle contact area. In previous investigations on pressure bonding, workers3 have suggested that voids may exist in the region where mating surfaces are placed in intimate contact, but the existence of the voids was not verified and no attempt was made to study the growth and disappearance of these voids. Durst noted the existence of pores in roll-clad structures prepared by cold reducing two sheets to force them in contact and then annealing to improve the bond. Since his unbonded regions contained a gas which he assumed to be insoluble, he proposed a mechanism which consisted of spheroidization of the unbonded regions and a growth of the contact area, but no speculations were made regarding disappearance of the gas filled pores. One interesting comment made by Durst was the suggestion that flattened voids with sharp corners which are produced during roll bonding will have a greater driving force for spheroidization than the more rounded pores created by pressing metal powders and thus spheroidization and neck growth will occur at lower temperatures. In this study it was necessary to demonstrate conclusively that voids can actually exist in the interfacial bond area. Experimental work was then directed toward a study of the mechanism whereby the voids grow and subsequently disappear.

Jan 1, 1963

By Lawrence H. Van Vlack

The energy of the y-iron grain boundary was determined to be 850 ergs per cm2 at 1105°C. The a/a and the a/y boundaries possess somewhat less energy. The microstructures of several iron alloys are discussed in terms of the interfacial energy relationships. THE dependence of the shape of liquid interfaces upon their energies has been studied for some time.1"3 Recently, Smith' concluded that many of the microstructures observed in metals may be attributed to the energies of the interfaces between the grains and phases. While the energies of liquid surfaces have been measured by numerous different methods: only two attempts have been made to determine experimentally the energy of surfaces involving crystalline solids. Udin, Shaler, and Wulff8 used a procedure introduced by Berggren7 to measure the surface tension of solid copper. It consisted of determining the load required on a thin copper wire so that the surface tension was counteracted, and no net strain resulted. Bailey and Watkins8 sed a different technique and were able to determine both the surface tension of copper and the tension of the copper grain boundary. They measured the contact angle which liquid lead makes against a copper surface. They then calculated the above energies from the surface energy of liquid lead by using the Pb vs. Cu/CuY dihedral angle and the surface groove angle formed during thermal etching. They obtained a value of 1800 dynes per cm for the surface tension of clean copper and approximately 640 dynes per cm for the tension of copper grain boundaries. The former value was somewhat higher than Udin's value of 1500 dynes per cm. This paper includes a determination of the energy of the y-iron grain boundary. In addition, the micro-structural relationships of several other metallic and nonmetallic phases with iron were examined and an attempt was made to interpret the observed structures in terms of interfacial energy relationships. Theoretical Considerations In a three-phase material containing a solid and two liquids, there may be two solid/liquid interfaces, one liquid/liquid interface and one inter- granular interface. Liquid/liquid interfacial energies can be measured directly. Therefore, by determining the energy of such an interface and by measuring the required interfacial angles: the energies of the interfaces involving solids may be obtained.10 They may be shown schematically as in Fig. 1. The above procedure requires the following assumptions: 1—The interfacial energies are, in general, unaffected by boundary orientation, and 2— the shapes of the interfaces are unaltered between annealing and sectioning for microscopic examination. The first assumption is good to a first approximation as shown by Dunn and Lionetti11 except for a few critically orientated boundaries. Two conditions may alter the shape of a boundary upon cooling: 1—Precipitation of dissolved material upon one side of the interface, and 2—a change in volume during the transition from one phase modification to another. The former must be detected by microscopic observation. The latter may become appreciable in systems containing an interface between two liquids which solidify after annealing. However, possible movement of the two-liquid interface may be checked in the system diagrammed in Fig. 1 by measuring 8, for example, and comparing it with its value as calculated from the other interfacial angles by: tan8, C11 05 COS- o- + cos 8, cos- The choice of a suitable pair of liquids is limited by several factors. The relative values of the several

Jan 1, 1952

By Lawrence H. Van Vlack

DISCUSSION, H. L. Burghoff presiding C. S. Smith (University of Chicago, Chicago)—The author is to be congratulated on his valuable contribution to the extremely meager absolute data on interface energies in metallic systems. It is interesting to note that the ratio between a and r iron boundary energies is approximately the same in the quaternary alloy with silicon, carbon, and sulphur as in the binary Cu-Fe alloy. A value for the copper grain boundary energy can be obtained from the author's data, Tables IV and VI, by utilizing the energy ratios of the following pairs of interfaces: copper-sulphide/copper, copper y iron, y iron/y iron, y iron/ copper, and copper/copper. This gives a value of 595 erg per sq cm for the free energy of the copper grain boundary. Despite this circuitous route and the assumption that the y iron boundary is identical in alloys with and without sulphur and does not change between 1105" and 100O°C, this figure is in remarkably close agreement with other values of the copper boundary energy, obtained by equilibration against lead and against the free copper surface. It therefore appears either that impurities do not greatly affect the grain boundary energies or that boundaries in even nominally pure metals are already sufficiently contaminated so that further change has little effect.

Jan 1, 1952

By F. H. Wilson, E. W. Palmer

Brass mills are familiar with a recurring problem which reveals itself during deformation of annealed metal as an opening up of cracks which are suggestive of a grain boundary pattern. A typical example is seen in Fig 1, which shows part of the convex surface of a cartridge brass disc which was slightly dished by the punching operation. Another illustration of the same type of defect was found in the surface of a finished cartridge case which split open on firing. These cracks, shown in Fig 2, were away from the split but indicate the presence of the type of weakness which permitted the splitting. Usually the weakness consists of separate cracks, the lengths of which are of the same order of magnitude as the grain size prior to the final anneal. Their typical appearance in a polished section is shown in Fig 3. This structure was found below the surface of a fractured tensile-specimen that had been cut from a large cartridge blank showing the defects on its convex surface. While the pattern formed by these cracks suggests a grain boundary origin, the cracks bear no relation to the currently existing grain structure. Thus Fig 3 shows that the grains have grown up to cracks already present. Since it is doubtful that the cracks were present in the metal before the anneal, they must have formed during the anneal but prior to recrystallization. The term "fire-cracking" has been generally applied to cracking that occurs during an anneal under the influence of internal stress, but refers more specifically to obvious macroscopic cracking attributable to the presence of a low melting phase, usually lead. Since the type of cracking described above may occur when the lead content is very low, we have considered it a somewhat different phenomenon, and have called it "inter-granular parting." While most examples involve cartridge brass, intergranular parting has also been observed in the fabrication of large seamless tubes from discs of both 85/15 red brass and 70/30 cupro-nickel. Similar cracking in nickel silver was investigated by Jones and Whitehead,1 who showed that it could occur during healing or cooling. That which occurred on heating they called "fire cracking," and they suggested that, a transformation at about 320°C might account for its occurrence. It was felt in this laboratory that the observed parting was probably one aspect of the general observation, first made by Rosenhain and Archbutt,2 that a tendency toward intergranular fracture under tensile stress increases with increasing temperature and decreasing rate of strain. In this case the stress involved would be internal. The rate of strain would be exceedingly slow, a localized internal creep. Reference to the literature uncovered no efforts to extend the observations of Rosenhain to conditions involving only internal stress. Accordingly, an exploratory research, sufficient in detail to satisfy us as to the probable truth of this explanation of the observed intergranular parting, was undertaken. The internal stresses present during the early stages of an anneal (prior to recrystallization) would be from two sources: residual stresses developed during deformation, and thermal stresses caused by uneven heating and expansion. Thermal stresses would vary widely according to shape, size and manner of heating, and can be considered as supplementary to residual stresses. It seemed necessary to determine the stress and temperature conditions under which parting would occur in a relatively short time, and then to establish whether or not in- ternal stresses may persist to an extent adequate to cause parting at such temperatures. (Jones and Whitehead1 and Moore and Beckinsale3 made tests which indicated that stress relief required an appreciable time.) During the course of the research the desirability of studying the effect of grain size became apparent, and this factor is one of the major variables of our investigation. Intergranular Parting under Tension at Elevated Temperatures In early experiments, hard 70/30 brass tensile specimens, with unknown residual stresses, held for 10 min. at applied stresses from 30,000 to 40,000 psi at temperatures from 300 to 350°C, showed no macroscopically visible cracks when unloaded and cooled, but cracks very similar in appearance to those observed in commercial practice were revealed in these specimens by pulling them to fracture. Annealed specimens, on the other hand, showed no cracks in such experiments, apparently because they deformed plastically at stresses below those necessary to cause parting in a reasonable time. Hence, the specimens used for this study were first strengthened by cold tensile elongation, giving them an unavoidable residual stress pattern (determined largely by grain size and orientation) which would, however, correspond in direction, at least, to the stress pattern obtained under stress at temperature. A variation in these residual stresses might be expected with variations in grain size, but following any given anneal the reproducibility of stress pattern should be as good as that of the grain size measurement. With no information as to the effect of the amount of prior deformation, tests were conducted on specimens given the same cold elongation, using a stress applied at temperature which was a constant proportion of the stress required to produce this elongation. In

Jan 1, 1950

By A. N. Holden, W. E. Seymour

DURING the last several years, the U-Zr system has been studied at many laboratories as one of the research programs sponsored by the Atomic Energy Commission. The equilibria in part of this system have been difficult to determine, although the phase diagram from 0 to 60 atomic pct Zr has been established with reasonable certainty. Existing diagrams of the system vary appreciably beyond 60 atomic pct Zr, particularly with regard to the existence of an intermediate phase. Most existing diagrams show a transformation or reaction horizontal near 600°C. In 1955, a collection of uranium phase diagrams' was prepared at the Battelle Memorial Institute and the U-Zr diagram in that collection contained a questionable region in the vicinity of 60 to 80 atomic pct Zr. Summer-Smith" has published a phase diagram of the system that shows no intermediate phase. Summer-Smith did his work with powders and found only the uranium and zirconium eutectoid mixture from X-ray patterns of material annealed below 600°C. Mueller3 at Argonne National Laboratory did similar work with filings, and he found that initially there was a pattern of an intermediate phase, but on long-time annealing

Jan 1, 1957

By Peter Greenfield, Paul A. Beck

Thirty binary systems of vanadium and chromium group transition elements with second and third long period transition elements were explored in regard to the intermediate phases formed. It was found that the phases predominating in these systems are s, AB type with ordered a-tungsten or C8 structure, close-packed-hexagonal with small unit cell dimensions and, finally, phases isomorphous with 1-manganese. IN recent years, considerable information has become available concerning the intermediate phases in binary systems of the transition elements. Thus, the s phase has been found to occur in most of the binary systems of vanadium, chromium, and molybdenum with the group of elements manganese, iron, cobalt, and nickel.' It was observed that, while the rr phases formed by chromium with manganese, iron, or cobalt possess a considerable temperature range of stability, particularly in the Cr-Co system, the corresponding s phases with molybdenum are limited to a temperature range of less than 400" above about 1200°C. Goldschmidt' reported v phases of tungsten with iron and cobalt, and these are apparently stable only at (and above?) 1400°C." Exploratory work in this laboratory with Fe-W and Co-W alloys of approximately 60 atomic pct W annealed at 1300°C did not produce X-ray patterns suggesting the presence of a phase. It appears then that the phases of iron and cobalt with the chromium group elements decrease in stability as the two components are chosen from long periods further removed from each other. From the available information, it might be concluded that the controlling factor is the increasing difference in atomic radii between the components. In contrast to the a phase, the phases formed by iron and cobalt with chromium group elements' are stable only when the latter have large atomic radii (molybdenum and tungsten); the corresponding phases with chromium do not occur. When the difference in atomic size becomes still larger (r,/r,, approaching the ideal value of 1.225), the u and p phases are replaced by Laves phases (AB,), as in the alloys of iron and cobalt with columbium," tantalum." and titanium."-" However, atomic size certainly cannot be the sole determining factor, since, for instance, in contrast to the very stable (Mo, Co)p phase, no such phase occurs in the Mo-Ni system even though the atomic diameters of cobalt and nickel are nearly the same. Similarly, chromium and cobalt form a a phase in a wide temperature range," but the corresponding s phase in the Cr-Ni system is missing. It has been shown that the composition of the u phase in various binary and ternary systems of transition elements in the first long period may be correlated in a fairly quantitative manner with the number of electron vacancies. The influence of electronic structure is probably present also in binary and ternary phases' and to some extent, apparently, even in Laves phases." " Although the absence of phases in the Cr-Ni and Mo-Ni systems has not as yet been explained on the basis of electronic structure, it appears reasonable to suspect a connection. One of the great difficulties in arriving at well founded rules in regard to the alloying behavior of transition elements lies in the lack of reliable information concerning the details of their electronic structure in the metallic and alloy form. The theoretical penetration of this field appears to be beset by very considerable difficulties, even when the complications due to alloy formation are disregarded. Another great source of uncertainty is the scarcity of phase diagram information even for binary systems of the transition elements so that only a very limited basis is provided for generalizations as to the occurrence of intermediate phases. For instance, very few binary phase diagrams of second and third long period transition element systems have so far been published. The present work was undertaken in order to survey the various types of intermediate phases occurring in 30 binary systems of elements of the group vanadium, columbium, tantalum, chromium, molybdenum, and tungsten with the elements rhenium, ruthenium, rhodium, palladium, and platinum. For most of these binary systems phase diagrams are very incompletely or not at all known, as will be further reviewed.*

Jan 1, 1957

By Sheldon Rideout, E. L. Kamen, B. S. Lement, Paul A. Beck, W. D. Manly

The 1200°C isothermal sections of the following ternary phase diagrams were investigated: Cr-Co-Nil Cr-Co-Fe, Cr-Co-Mot and Cr-Ni-Mo. In all these systems the u phase was found to form extended solid solutions. Two new ternary phases of unknown structure were identified. The existence range of intermediate phases of transition elements was correlated with 3d electron vacancy concentrations. THE occurrence of extensive ternary d solid solutions in the Cr-Co-Ni and in the Cr-Co-Fe systems was described in a brief note.' More recently d- solid solutions were also found in the Cr-Fe-Mo system by two independent groups of investigators.2,3 The existence of binary d phases in the V-Co and V-Ni systems, predicted in ref. 1, was experimentally discovered recently by Duwez and Baen and independently by W. B. Pearson, J. W. Christian, and W. Hume-Rothery.5 Duwez and Baen stated two general conditions for the occurrence of the d phase in alloys of the transition elements: "(1) The atomic diameters of the two metals do not differ by more than 8 per cent. (2) One of the two metals has a body-centered cubic structure while the other is face-centered cubic, at least in one of its allotropic forms." In the course of an extensive research program conducted at this Laboratory under the sponsorship of the NACA, several ternary systems, containing d solid solutions and also certain new ternary phases, were investigated. The present report describes the investigated portions of the 1200°C isothermal sections of the following ternary phase diagrams: Cr- Co-Ni, Cr-Co-Fe, Cr-Co-Mo, and Cr-Ni-Mo. It was found that the range of existence of the d phase in these four ternary systems, as well as in one of two ternary systems which were investigated by others, can be fairly consistently described in terms of electron vacancy concentrations. This supports the suggestion of Sully and Heal" that the d phase is an electron compound. Experimental Procedure The ternary alloys were prepared by vacuum induction melting in zirconia and alumina crucibles. Lot analyses of the metals used are given in Table I. Specimens of all alloys were annealed at 1200°C in an atmosphere of purified 92 pct helium and 8 pct hydrogen mixture. Alloys consisting mainly of

Jan 1, 1952

By D. K. Das, P. A. Beck, S. P. Rideout

IN a previous publication1 1200°C isothermal phase diagram sections were given for the Cr-CO-Ni, Cr-Co-Fe, Cr-Co-Mo, and Cr-Ni-Mo ternary systems, in which the a phase formed narrow, elongated solid solution fields. The present investigation is concerned with the 1200°C isothermal sections of the Co-Ni-Mo, Co-Fe-Mo, and Ni-Fe-Mo ternary systems. A prominent feature of these systems is the presence of narrow, elongated µ phase fields. The crystal structure of the phase designated as µ both here and in the previous publication1 was determined by Arnfelt and Westgren.2 For the (CO, W)µ phase, named by them Co,W, (and also frequently designated as a), these authors found that the crystal system is hexagonal-rhombohedra1 and the space group is D53d — R3,. Westgren and Mag-neli3 later found that isomorphous phases exist in the Fe-W and the Fe-Mo systems (these phases are often referred to as < and E, respectively). Henglein and Kohsok4 stated that the phase described by them as Co7Mo,; (otherwise frequently designated as c) is also isomorphous with the above three. The Co-Fe-Mo system was investigated at 1300°C by Koester and Tonn,5 who found a continuous series of solid solutions between (Co, MO)µ and (Fe, MO)µ Koester6 also indicated similar uninterrupted solid solutions in the Ni-Fe-Mo system. However, since the Ni-Mo binary system does not have a phase isomorphous with F, Koester&apos;s diagram is expected to be erroneous. No data appear to be available in the literature concerning the Co-Ni-Mo system. The face-centered cubic (austenitic) solid solut,ions of iron, nickel, and cobalt, which are quite extensive in all three systems at 1200°C, are here designated as the a phase. The body-centered cubic (ferritic) solid solutions, based on iron, are designated in this report as the ? phase, in conformity with the nomenclature used previously.&apos; Experimental Procedure The alloys were prepared by vacuum induction melting in zirconia and alumina crucibles. The lot analyses for the metals used have been given.&apos; The number of alloys prepared was 46 for the Co-Ni-Mo system, 65 for the Co-Fe-Mo system, and 113 for the Ni-Fe-Mo system. The compositions of these alloys were selected with due regard to maximum usefulness in locating phase boundaries. The alloy specimens were annealed at 1200°C in an atmosphere of purified 92 pct helium and 8 pct hydrogen mixture. Alloys consisting almost entirely of the face-centered cubic austenitic a phase, or of the body-centered cubic ferritic c phase were double-forged with intermediate annealing. The double-forged specimens were then final annealed for 90 hr at 1200 °C and quenched in cold water. Alloys containing considerable amounts of any of the other phases could not be forged. Such specimens were annealed for 150 hr at 1200°C and quenched. Microscopic specimens of all alloys were prepared by mechanical polishing, in many cases followed by electrolytic polishing. Description of the polishing and etching procedures used and tabulation of the intended compositions of the alloys prepared are being published in two N.A.C.A. Technical Notes.7,8 , Many of the alloys were analyzed chemically and, in general, the results are in excellent agreement with the intended compositions. X-ray diffraction samples were prepared by filing or crushing homogenized alloy specimens and by reannealing the obtained powders in evacuated and sealed quartz tubes. After annealing for 30 min at 1200°C the tubes were quenched into cold water. X-ray diffraction patterns were made with unfiltered chromium radiation at 30 kv, using an asymmetrical focusing camera of high dispersion. X-ray diffraction and microscopic methods were used jointly to identify the phases present in each specimen. The amounts of the phases in each alloy were estimated microscopically. The phase boundaries were located by the disappearing phase method. The results were used to construct 1200°C isothermal sections for the three ternary phase diagrams. The accuracy of the location of the phase boundaries determined in this manner is estimated to approximately ±1 pct of each component. The portion of the three phase diagrams lying between the µ, P, and 6 phases on the one hand, and the molybdenum corner on the other, has not been investigated. Recently Metcalfe reported0 a high temperature allotropic form of cobalt on the basis of dilatometric results and of cooling curves. In the present work no attempt was made to search for the new phase in the cobalt corner of the Co-Fe-Mo and Co-Ni-Mo systems. No alloy was prepared with more than 80 pct Co; the alloys used were intended to locate the boundary of the a phase saturated with cL. The microstructures of the quenched a alloys near the cobalt COrner gave no suggestion of an in-suppressible transformation On quenching. The location of the boundaries of the a + ? two-phase fields in the Fe-Ni-Mo and Fe-CO-MO systems was determined entirely by the microscopic method. The face-centered cubic a alloys near the ? field transform partially or wholly into the body-centered cubic ? phase on quenching from 1200°C to room temperature. The ? formed in this manner has an

Jan 1, 1953

By J. W. Downey, J. B. Darby, L. J. Norton

THE only previous investigation of the phase equilibria in the Ta-Pd system was reported by Greenfield and Beck.1 Their work (actually a portion of a much broader survey) was limited to the composition range 50 to 75 at. pct Ta and to a single temperature, 1000°C. The results indicated that no intermediate phases were present at this temperature. They pointed out that this was an unexpected result in view of the fact that niobium, which belongs to the same group in the periodic table as tantalum and has essentially the same atomic size, forms a o phase with palladium.&apos; Also, tantalum in combination with rhodium,&apos; iridium,&apos; or platinum&apos; stabilizes the s phase. By analogy, the Ta-Pd system would also be expected to contain a s phase. The present investigation was therefore undertaken to explore more fully the phase relationships in this system. Alloys were prepared by arc melting on a water-cooled copper hearth in an argon-helium atmosphere. The purity of the starting materials was greater than 99.9 pct. The weight losses on melting were less than 1 pct and therefore the alloys were not analyzed chemically. Specimens were wrapped in molybdenum foil, encapsulated in quartz capsules under a vacuum of at least 1 x 10-5 mm of Hg, annealed as indicated in Table I, and water quenched. Optical and X-ray metallography were used for identifying the phases present in the annealed and quenched alloys. The alloys were resistant to attack by several acids; however, a sodium cyanide electroetch and an immersion etch containing 1 part HF, 1 part HNO3, 2 parts H2SO4, and 5 parts H2O by volume were found satisfactory. The X-ray diffraction patterns were taken with a Straumanis-type Debye-Scherrer camera and filtered copper or chromium radiation. A summary of the phases found in this investigation is presented in Table I. No attempt was made to determine the composition limits of the various phases. The present results indicate that this system consists of two terminal solid solutions separated by at least four intermediate phases at the approximate compositions Ta3Pd, -TaPd, TaPd,, and TaPd3. The Ta-rich solid solution, containing less than 10 at. pct Pd at 1150°C, is in equilibrium with a o phase which is stable in the vicinity of 25 at. pct Pd. The latter phase is also in equilibrium with a bct phase at the equiatomic composition. At high temperatures it appears that the Pd-rich solid solution extends to at least 66.6 at. pct Pd and is in equilibrium with the bct phase. When annealed at 900°C, a sample containing 66.6 at. pct Pd transformed to an unidentified phase designated as X. An X-ray diffraction pattern of this phase contained sharp low-angle lines while the high-angle lines were characteristically diffuse. The observed d-spacings and relative intensities for lines in the low-angle region are presented in Table 11. In the vicinity of 70 at. pct Pd an intermediate phase having the TiA13-type structure is formed. It is stable to at least 1100°C, and presumably dissolves congruently into the ter-

Jan 1, 1963

By A. T. Aldred

HIS note reports the existence of several new scandium intermetallic compounds of the A2B and AB stoichiometries where the A element is scandium and the B element is from group VIII or IB of the periodic table. Alloys were arc melted from high-purity materials using 2-g charges. Typical lot analyses for the materials used are given in Table I. Chemical analyses were not made on the alloys as there was little or no weight loss on melting. After annealing the specimens for 14 days at 600°C and water quenching, metallographic and X-ray techniques were used to determine the occurrence of the various phases. Table II lists the relevant data for the A2B phases. The Ti2Ni structure,2 has ninety-six atoms in a face-centered cubic cell, whilst the Al2Cu structure is body-centered tetragonal.3 The occurrence and stability of the various A2B type phases in transition metal alloy systems has recently been considered by Nevitt.4 The Ti2 Ni-type phases occur over a relatively narrow range of radius ratios from 1.14-1.26 with A partners mainly from the titanium group and B partners predominantly from the cobalt group. This suggests that both a favorable relative size of the atoms and a favorable electron concentration are necessary conditions for the existence of this structure type. A12Cu-type phases involving Ti group elements as A partners are formed with B partners from the cobalt and nickel groups, predominantly the latter, and have a higher radius ratio (1.27-1.29) than the Ti2Ni-type phases. The occurrence of both Sc2Pd and Sc2Co can be rationalized in terms of these considerations but SczNi is anomalous because of its high radius ratio. The radius ratios are calculated from the Goldschmidt CN12 radii and it might be postulated that the scandium atom is reduced in size in the compound. Unfortunately the apparent atomic size of scandium in the compound cannot be calculated from a knowledge of the structure and lattice dimensions. The crystal structure of the Sc2Au compound could not be identified from the powder diffraction pattern, but it is interesting to note that it is isostructural with a series of A2Au phases where A is a rare earth element.5 Pertinent information concerning the AB phases found in this investigation is given in Table 111. All the phases have the ordered bcc CsCl structure. The occurrence and stability of CsC1-type phases have recently been discussed by Dwight,7 who concludes that the relative sizes of the atoms do not appear to be a controlling factor (the radius ratios of all the known phases vary between 0.985 and 1.439) but that the occurrence of the phase is predominantly dependent on the relative positions of the A and B partners in the periodic table. As a measure of the stability of a given CsCl phase it has been customary to define a lattice contraction on alloying, DAB — dAB, where DAB is the AB interatomic spacing as calculated from the Goldschmidt CN8 radii and dAB is the AB interatomic distance in the compound (= v3/2 ao). Values of the parameter DscB -dScB for the compounds found in this investigation are given in column 5 of Table III and are plotted in Fig. 1. If the lattice contraction does in fact reflect the stability of a phase then Fig. 1 shows two very interesting trends when the position of the B partner in the periodic table is considered. Firstly, within any given group the stability increases in order on going from the first to third long period. Secondly, within any given period the stability increases in order as the B partner is taken from the copper, nickel, and cobalt groups. In the case of the second long period, the lattice contraction reaches a maximum at ScRh and then decreases to ScRu. The same trend could

Jan 1, 1962

By S. E. Hasko

It is the purpose of this note to report the crystal-lographic data for nine new B5A compounds* having the Cu5Ca structure, with A a rare earth and B a transition element, Co, Ni or Cu. In previous papers, some magnetic data1 and preparation and crystallo-graphic data2 for other B5A compounds having the same structure have been reported. Crystallographic data for these compounds are shown in Tables I and 11. These results are in agreement with others of this series reported previously by Wernick and ~eller.&apos; The abnormally large atomic volume of Yb metal3 is not manifested in Ni,Yb, when one compares it with the compounds reported here and the data of reference 2. This is not true for the compound YbAl,, having the cubic Laves structure (MgCuz), to be discussed in other papers.4&apos;5 Thus, it appears that Yb has a valence of 3; i.e., the 2 s and Id electrons are lost to the conduction band.4&apos;5 Lattice constants for four of these compounds prepared by levitation melting have been reported by Nassau, Cherry, and wallace.&apos; The lattice constants

Jan 1, 1961

By S. E. Haszko

Fused alumina or silica crucibles were used as the containing vessel. X-ray powder photographs were taken with CrKa radiation and the use of Straumanis type Norelco cameras of 114.6 mm diam. Crystallographic data for these compounds are shown in Table I. These results are in agreement with others of this series reported previousiy by Wernick and Geller.l The abnormally large atomic volume of Eu and Yb metal3 is manifested in EuA12 and YbAl2, when one compares them with the compounds reported in Ref. 1. However, the behavior of Yb in the Ni compound is the same as that observed in Ni5Yb having the Cu5Ca structure.4 Thus, it appears that Yb has a valence closer to 3 only in the Ni compounds; i.e.. the 2s and Id electrons are lost to the conduction band. 1,4 Europium in EuAl2, appears to have a valence closer to 2. In previous work.&apos; X-ray patterns of ingots of NdCo2 indicated a multiphase material with faint indication of the presence of a phase having the MgCu2 structure. It was thought that NdCo2 formed peri-tectically from the melt, resulting in a multiphase system when cooled under nonequilibrium conditions. An X-ray pattern of a sample from a melt cooled more slowly than in past work showed that the major phase was NdCo2. The lattice constant, Table 1, is in excellent agreement with the value one can predict from the data of Ref 1. One of the other phases was identified as Co,Nd. The author wishes to thank J. H. Wernick for his guidance in this work, and D. Dorsi for the preparation of these compounds. &apos;J. H. Wernick and S. Geller: AIME Trans., in press. &apos;J. H. Wernick and S. E. Haszko: to be published. &apos;F. H. Spedding and A. II. Daane: Progress in Nuclear Energy, Series 5, Eds.: H. M. Finniston and J. P. Howe, McGraw-Hill Book Co., 1956. &apos;S. E. Haszko: to be published. &apos;J. H. Wernick and S. Geller: unpublished work. 6J. 11. Wernick and S. Geller: Acla Cryst., 1959, vol. 12, p. &apos;162. The Influence of Hydrogen on the Lattice Parameters of Ti-Sn Alloys A. Coucoulas and H. Margolin A reinvestigation of the lattice parameters of Ti-Sn alloys by the present authors has revealed consistently higher c and a values than those obtained by Worrier. The difference is most pronounced in the c-parameters which are, therefore, used as a basis of comparison. This discrepancy was not due to air contamination, since precautions were taken to exclude this possibility. Specimens for Debye-Scherrer photograms were prepared by arc-melting 15-g buttons of Bureau of Mines titanium and 99.99 pct Sn, with compositions of 6, 8, 10, and 12 at. pct Sn. These buttons were forged under an oxygen-acetylene torch to 1/8-in. sq rods to produce relatively fine grained material. Scale and some surface were ground off, and the rods, after wrapping in molybdenum and titanium sheet, were vacuum annealed 15 min at 800 °C to remove hydrogen. Heat treatment of one of the samples at 875°C to produce ß and reveal a at the surface showed no surface contamination. Following the vacuum treatment, the specimens were wrapped in molybdenum and annealed for 1week at 800°C under two atmospheres of argon. After water-quenching, the rods were ground so that the thickness tapered to 0.1 mm at the tips. The ground specimens were then recapsuled as previously and reannealed 1 hr at 800°C to remove cold work. The

Jan 1, 1961

By W. A. Wood, H. L. Wain, R. I. Garrod

The mechanical behavior of recrystallized chromil~m of high purity has been studied, principally in torsion and to a lesser extent in tension, at temperatures between —196oand 350oC. Depending upon the conditions of test, the material may show brittle or ductile behavior or an intermediate or subduc-tile state having some of the characteristics of each. This latter state existed at temperatures between approximately ±50°C and was characterized by a) extensive creep at stresses well below the normal fracture stress, b) nonelastic loading/unloading effects during creep, c) strain softening under cyclic loading, and d) final failure of a brittle type. Suggestions are made on the dislocation processes and interactions which give rise to subductile behavior The ductile-brittle transition in bee metals has been studied mainly by tension and bend tests. These methods, however, favor crack propagation which may follow too closely on initiation for detailed study of the transition itself. For work of this nature, therefore, other modes of deformation less favorable to crack propagation may be preferable. This paper describes a study of the ductile-brittle transition in chromium which is based mainly on torsional testing although a few subsidiary experiments were made in tension. It appears to reveal at the transition an intermediate state that cannot properly be described as either brittle or ductile. Torsional tests on chromium have been made by other workers1 but not, as here, primarily for study of this intermediate state. EXPERIMENTAL The chromium, in the form of swaged rod, was prepared by techniques already described.&apos; The particular material used was one in which the main impurities were 0.03 wt pet 0 and 0.006 wt pet N and one in which transition from ductile to brittle states in torsion conveniently fell at about room temperature. For torsion, test specimens were from 5/16-in.-diam rod to provide test portions 1-1/4 in. long by 7/32 in. diam, a twist of 1 deg thereby corresponding throughout this paper to 0.0015 surface shear. The specimens before test were annealed for 2 hr at 1200°C in vacuo, which left them with a re-crystallized grain size of about 0.01 mm, and then electropolished. They were tested under dead-weight loading in an apparatus in which they could be surrounded by a furnace or cooling chamber, tests in practice being made at various temperatures between -196" and +350°C. For tension tests, cylindrical specimens were prepared in a similar manner and tested at room temperature under dead-weight loading. RESULTS (TORSION) Subductile State. The state described above as intermediate between brittle and ductile may be perhaps best defined by reference to torque/twist curves at various temperatures. These are grouped in Fig. 1. Below about -50°C the material was brittle, in the sense that it exhibited little plastic deformation under stress and fractured by cleavage along planes of maximum resolved tension, which in torsion produces the well-known helical type of fracture. The deformation is typified by the curves for -196" and -150°C in Fig. 1; it shows a slight but progressive deviation from linearity above a certain torque, here about 50 lb-in., until fracture occurs at about 95 lb-in. A feature to which it is desired specially to call attention is that under none of the loads did the specimens show significant creep.

Jan 1, 1964

By James A. McGurty, Walter J. Koshuba, Samuel G. Gordon, Gilbert E. Klein

ONE of the problems encountered in working with metals at elevated temperatures is the instability resulting from solid-solid diffusion at a -common interface. A determination of the nature and magnitude of this phenomenon is important as related to structural properties of materials potentially useful in high temperature applications. This paper is concerned with the solid state reaction between metallic molybdenum and beryllium at elevated temperatures. In the older literature,&apos; there were no known inter-metallic compounds in the system Be-Mo, and the list of beryllium intermetallics was rather small. New compilations have been made by Smithells&apos; and by Taylor," listing all the then known beryllium binary intermetallic compounds. In addition to these, some new phases have just been reported&apos; in the system Zr-Be and some further compounds of the type MBe,3 have been currently described. The new compound MoBe,, which is reported upon in this paper differs considerably from the above mentioned MBe13 group, and will be discussed in detail. Diffusion Study The nature of the solid diffusion at a Mo-Be interface was determined by sealing a beryllium rod inside a molybdenum capsule and heating at a temperature of 2000°F&apos; (1100°C) for 100 hr. The molybdenum capsule was fabricated from % in. swaged molybdenum rod obtained from the Fansteel Metallurgical Corp. The beryllium metal was obtained from Brush Beryllium Corp. as % in. cold-drawn rod. This material assayed 99.05 pct Be and contained as impurities 0.84 pct Be0 and 0.19 pct Be2C. The molybdenum capsule was % in. in OD x 2 in. long. To prepare it, a concentric hole 0.250 in. + 0.001 in. — 0.000 in. in diam was drilled and reamed in one end of a rod to a depth of 1 &apos;/2 in. A 1 in. long beryllium rod 0.250 in. + 0.000 in. — 0.001 in. in diam was pressed into the molybdenum capsule. A molybdenum plug 0.250 in. & 0.001 in. in diam x 9/16 in. long was then used to seal the beryllium in place. The capsules were placed in a molybdenum resistance furnace and heated at 2000°F (1100°C) for 100 hr. On cooling, the specimens were cut and examined metallographically. Fig. 1 is a micrograph at X250 of a portion of the interface from a transverse section. Four phases are clearly visible, with sharp boundaries between them. Phase A is a section of the molybdenum capsule; phase B is the molybdenum-rich intermetallic composition MoBe,; phase C is the beryllium-rich compound MoBe13; phase D is a section of the beryllium rod. All phases were readily polished to a high metallic luster. The molybdenum-rich phase has a pronounced purple tinge. The beryllium-rich phase (C) is only slightly darker than the pure beryllium. In polarized reflected light, however, it shows striking birefringence between crossed Nicols. The black areas represent flaws or pores in the material. A small representative amount of powdered material from each of the phases was carefully removed under the microscope with a diamond tool. With this material, powder X-ray diffraction patterns were made for the identification of each phase. Table I lists the X-ray diffraction spacings and corresponding indexes characteristic of these intermetallic compounds. Synthesis To establish the formula of the new intermetallic compound, X-ray diffraction patterns were made from powders obtained from solidified melts of known composition. The syntheses were made by

Jan 1, 1952

By W. C. Hagel, H. J. Beattle

DURING an earlier examination of high-temperature alloy, A-286, the presence of an unknown intermetallic compound was verified by X-ray diffraction. Owing to its prominent appearance at grain boundaries, the arbitrary name of G phase was assigned.&apos; Low-silicon, vacuum-melted heats were found to contain no G phase, and this investigation was initiated to determine the influence of silicon on G-phase formation; additional work was undertaken to extend existing data on other intermetallic compounds and the aging reactions in this group of alloys. Taylor and Floyd2-4 observed that the Ni3Al phase (y&apos;) and the Ni8Ti phase (7)) are the only equilibrium intermetailic compounds in nickel ternary alloys containing up to 25 pct Cr and 10 pct Ti or Al. They found that y&apos; can dissolve considerable nickel, chromium, and titanium, although the stoichio-metric composition of 7 remains fixed. Nordheim and Grant5 confirmed that age hardening of 80 pct Ni-20 pct Cr alloys of the Nimonic-80 type is due to precipitation of y&apos;, where aluminum is partially replaced by titanium. They suggest that optimum hardness and ductility result from increasing the titanium to aluminum ratio toward the end of the y&apos; solubility range and from increasing total titanium and aluminum content to the maximum limit permitted by processing. Such information is necessary for those seeking to improve the service-temperature range and long-time structural stability of high-temperature components. Experimental Methods Compositions of materiais studied. are listed in Table I. Alloys D, E, and F possess representative A-286 analyses; silicon increases from less than 0.02 to 1.75 pct in alloys A to H; in alloys I to K, titanium decreases from 2.24 to 0.39 pct, and aluminum increases from 0.1 6 to 240 pct. Alloys A and D were solution heat treated for 4 hr at 1700°F, oil quenched and aged for 0.5, 2, 6, 12, 30, 70, 200, and 1000 hr at 1200°, 1300°, 1400°, and 1500°F. Therefore, a total of 33 specimens was required for each

Jan 1, 1958

By S. Pearson, L. Rotherham

Measurements have been made of the variation of internal friction with temperature for OFHC copper, and for a series of binary solid solutions of high purity copper with zinc, gallium, germanium, arsenic, and silicon, to investigate the effect of alloying elements in substitutional solid solution on grain boundary viscosity. The apparatus used was of the torsional pendulum type developed by KeI1 modified so that the specimen and vibrating system could be maintained in a high vacuum. The activation energy for grain boundary relaxation in copper is 33,000 cal per mol. This is considerably less than the activation energy for self-diffusion, in disagreement with Ke&apos;s theory2 that the two activation energies should be the same. All the alloying elements increase the activation energy for grain boundary relaxation to approximately 44,000 cal per mol, increasing the grain boundary viscosity at a given temperature. The results are discussed in terms of theories of grain boundary slip put forward by MottQ and by Ke.+ Experiments have also been made to investigate the effect of small amounts of oxygen on the variation of internal friction with temperature for copper. EXPERIMENTS described in this paper were designed to investigate the effect of alloying elements in substitutional solid solution on grain boundary viscosity, using the internal friction method developed by Kel for measuring grain boundary viscosity. It was considered desirable to make the system under investigation as simple as possible by making experiments on a comprehensive series of binary alloys of copper with the elements immediately following it in the periodic table, i.e., zinc, gallium, germanium, and arsenic. These elements are within the range of favorable size factor for solution in copper, and the systems have been extensively investigated by Hume-Rothery and his co-workers." Later, in order to study the effect of the relative size of the solvent and solute atoms, experiments were made on a series of Cu-Si alloys, since the apparent atomic diameter of silicon when in solution in copper—the diameter necessary to assign to the solute atoms to account for the lattice constant of the solid solutiona—is almost the same as that of the solvent atoms. Preliminary experiments were made to measure the variation of internal friction with temperature for pure copper. Ke made some experiments on copper," but found that the curves obtained were not reproducible in consecutive experiments. The copper was maintained in an argon atmosphere during the experiments but, although he took precautions to exclude oxygen, Ke came to the conclusion that the precautions were not entirely satisfactory, and that the lack of reproducibility must be due to absorption of oxygen by the copper. Experiments have therefore been made to investigate the effect of small amounts of oxygen on the variation of internal friction with temperature for copper. Previous Work Ke made extensive experiments on high purity aluminum and was able to show that the grain boundaries behave viscously at high temperatures. He found that the relative rate of movement of the grains could be expressed as Where v is the velocity of slip, A is the constant, u is the shear stress, H is the activation energy, R is the gas constant, and T is the absolute temperature. By assuming that the boundary layer was one atom thick, he obtained a value for the viscosity which, when extrapolated to the melting point, gave good agreement with the viscosity of the liquid metal at the melting point. Ke also made experiments on other high purity and commercial purity metals:, and on some alloys." " He came to the conclusion2 that the activation energy for grain boundary slip was the same as for self or volume diffusion and for steady state creep in single crystals. Rotherham, Smith, and Greenough" have shown recently that the activation energy for grain boundary slip is not the same as for self-diffusion in tin,

Jan 1, 1957