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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 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 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 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.' 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 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'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

By P. E. Arnold, G. S. Ansell

RELAXATION in metals has been studied in detail by many workers in recent years.1-5 These studies have shown that there is an energy-loss peak observed in a metal placed in mechanical resonance at low frequencies which may be correlated with various metallurgical processes. These experiments have been largely used to study single-phase materials. In order to study the effect of a finely dispersed second phase in a metal matrix upon this phenomenon, the relaxation behavior of an aluminum-aluminum oxide SAP-Type alloy in both the fine-grained as-extruded and coarse-grained recrystallized conditions was investigated by the use of internal-friction measurements. The alloys studied, designated MD 2100, consist of a matrix of commercial-purity aluminum containing a finely dispersed second phase of aluminum oxide. The aluminum oxide is present in this alloy in the form of fine platelets approximately 130A units thick and several microns on edge. The mean free path betwen dispersed platelets is approximately 0.5 p. The grain size of this alloy is extremely stable at temperatures as high as the melting temperature of the aluminum matrix. In the as-extruded condition the grain diameter is several microns, while in the recrystallized condition it is several millimeters in diameter. The damping characteristics of the alloy samples were determined using a torsional-pendulum device. The internal-friction constant was determined for this alloy in both the fine-grained as-extruded and coarse-grained recrystallized conditions over the temperature range from 343" to 923°K at frequencies of 0.9, 1.3, and 1.8 cycles per sec. An internal-friction peak was observed in testing the fine-grained alloys which was not observed for the coarse-grained alloys. This peak, which might be associated with a type of grain-boundary relaxation, was observed at each of the three different test frequencies for the fine-grained sample. The temperature at which the relaxation peak occurred for each of the three different frequencies is shown in Table I. From these data an activation energy of relaxation for each pair of frequencies was determined by comparing the temperature shift of the relaxation peak with frequency between each of the test frequencies, assuming that an Arrhenius-type rate equation is applicable. The activation energy of relaxation determined from these data is also shown in Table I. The mean value of the activation energy was about 6 kcal per mole. The activation energy for the relaxation process determined in this investigation indicates that the relaxation associated with the grain boundaries in this aluminum-aluminum oxide SAP-Type alloy is quite a different process than grain boundary relaxation in single-phase aluminum alloys. In these latter alloys, the activation energy for relaxation has been found to be the activation energy for self-diffusion, approximately 36 kcal per mole1,2 Where the activation energy is the same as the activation energy for self diffusion, it has been proposed that the relaxation phenomena is dependent upon vacancy formation and motion. It is apparent therefore, that, in this aluminum-aluminum oxide SAP-Type alloy, the relaxation must be due to another type of atom transport. It has been shown previously in studies of the high-temperature, low-stress, steady-state creep behavior of as-extruded aluminum SAP-Type alloys, that the activation energy for steady-state creep is one that may be characterized by the nucleation of dislocations from the grain boundaries. It is proposed that the relaxation behavior observed here is due to a similar effect. In this case, the internal-friction peak is a resonance behavior due to the time-dependent nucleation of dislocations from grain boundaries in the sample. A process of this type would have an activation energy which is undoubtedly stress-dependent and of the form Q = Q, + (dQ/du)u

Jan 1, 1962

By E. I. Salkovitz, F. W. von Batchelder

DURING the last few years several papers1-' have been published in which internal friction measurements have been used to determine the quantity of carbon or nitrogen dissolved in a iron. This method is based on the fact that, in pure Fe-N and Fe-C alloys, nitrogen and carbon cause peaks in the internal friction vs. temperature curve; at a frequency of 1 cycle per sec (cps) these peaks appear at $-200 and +360C, respectively, and if internal friction is expressed as Q-1, which is equal to times the logarithmic decrement, this figure will, by coincidence, give the weight percentage of nitrogen or carbon in solid solution.' In most of the studies published, very pure iron (Puron) was used. In one case the influence of manganese on the behavior of nitrogen in a iron was mentioned.4 It would be of great value, especially for the study of aging and related phenomena, if this method could be applied to commercial mild steel with norrnal percentages of manganese, phosphorus, sulphur, etc. As a rule, in such steels carbon and nitrogen are present together, and the amounts of these elements in solid solution should preferably be determined separately. The fact that their internal friction peaks appear at different temperatures (+36° and + 20°C in pure iron) seems promising for such a selective determination. It is necessary, however, that the peaks are narrow enough not to interfere with one another, and further, that there is no effect from carbon on the behavior of nitrogen in stress induced diffusion, and vice versa. According to Fast,' however, in the presence of manganese the nitrogen peak gets wider and appears at a higher temperature nearer the carbon peak, and thus the prospects for selective determination are reduced. (The carbon peak was not affected by the presence of manganese.) But even if fully quantitative de- terminations of the two elements are not attained, some relative figures on the sum of them and an indication of which one is the predominant one, would be of value. Some results from experiments along these lines will be reported here. An internal friction measuring device was assembled mainly following a description by KG." The measurements were also carried out as reported in that paper. Table I gives the chemical compositions of the four different materials used in this investigation. All materials were drawn to wires with diameter about 0.8 mm, and the analyses refer to these final shapes. Determination of Nitrogen Peak Wires from steels A, B, and C were decarburized in wet hydrogen (about 30 pct H2O) at 700°C until no carbon or nitrogen could be found by chemical analysis. No peak was then found in the internal friction. The wires were further annealed at 580°C for 16 hr in hydrogen bubbled through a solution of 6.8 pct NH3 in distilled water. Chemical analyses gave 0.04 pct N in A and C, and 0.06 pct in B. After annealing at 580°C for 15 min in a lead bath and water quenching, the internal friction was immediately measured. The resulting curves are shown in Fig. 1. At these high values of the internal friction the accuracy is comparatively poor; at Q-1 - 0.030 it is estimated to be 0.002. In order to make possible a calculation of the activation energy for diffusion of nitrogen, measurements were made at two different frequencies. Steel A shows rather broad peaks, and their temperatures can hardly be expected to be very accurate. Steels B and especially C are better in this respect. The finding of Fast' that manganese broadens the nitrogen peak is con-

Jan 1, 1953

By T&apos Ke, ing-sui

NUMEROUS investigators have observed that internal friction accompanies cold-working of metals and the effect of annealing is to reduce this internal friction.1,2 However, - most of the experiments were made at high stress amplitudes and the principal purpose was to study the increase of internal friction as a result of the applied cyclic stress during measurement. In order to study the internal friction introduced by cold-working applied prior to the measurement, the stress level applied during the measurement of internal friction must be sufficiently small. The results of measurement are significant and can be used for a base of comparison only when the applied cyclic stress is so small that the internal friction is independent of stress amplitude. Internal friction of cold-worked metals under small stress level has been studied by a number of workers8 -" he internal friction was measured around room temperature with a frequency of vibration of the order of kilocycles per second. The purpose of this paper is to report a study of the change of internal friction when severely cold-worked aluminum was annealed at successively higher temperatures until it was completely recrys-tallized. The measurements of internal friction were made over a range of temperature extending from room temperature up to the temperature of prior anneal. The frequency of vibrations used was about one cycle per second. The apparatus used for the internal friction measurements to be reported in this paper was a torsion pendulum with the specimen in wire form as the suspension fiber. The description of this apparatus and the method of measurement have been previously given.7,8 The applied stress was sufficiently small SO that the magnitude of internal friction is independent of stress level at each temperature range concerned. Corresponding to this stress the maximum shearing strain on the surface of the specimen is of the order of l0-5 and lower. The in- ternal friction (Q-1) is reported as 1/p times the logarithmic decrement. Internal Friction Versus Temperature of Anneal: Fig. 1 shows the internal friction measurements performed upon 99.991 pct aluminum subjected to 95 pct reduction in area. The final diameter of the wire is 0.033 in. This figure gives a general survey of the effect of temperature of anneal and of temperature of measurement. The internal friction of the cold-worked specimen was first measured at room temperature. It was then annealed at 50°C for one hour and the internal friction measured at 50°C and at room temperature. The same wire was successively annealed at higher temperatures for one hour and measurements were taken at the annealing temperatures and lower temperatures as before. Such a procedure was followed in order to stabilize the internal friction at the temperature of measurement so that during the measurement which generally takes about half a minute, there is no detectable change in internal friction. This series of measurements .was made up to 450°C. After each annealing a short test piece of the specimen, which had received the same past thermal and mechanical treatments, was taken out for metallographic examination. It is seen from fig. 1 that up to the annealing temperature of 250°C we have the following observations: for any given temperature of measurement, the internal friction is lower the higher the temperature of prior anneal. When the annealing temperature is 290°C or higher, the internal friction at the annealing temperature drops abruptly to a value which is much smaller than that for the previous curve. Metallographic examinations showed that the recrystallization of the specimen was completed after the annealing at 290°C. Fig. 1 shows that, as far as internal friction is concerned, there is no abrupt transition between the processes of recovery and recrystallization. Averbach has also reached the conclusion that recovery may be a process analogous to recrystallization on the basis of X ray extinction measurements in brass." The effect of annealing temperature upon the internal friction at room temperature is shown by curve I of fig. 2. In this figure the internal friction at room temperature was plotted as a function of annealing temperature. It is seen that the internal friction decreases rapidly at first with an increase

Jan 1, 1951

By R. H. Schnitzel

Internal-friction peaks have been observed in tungsten single crystals at about 300° and 400°C. The characteristics of these peaks are similar to interstitial peaks observed in other bee metals; therefore, the origin of these peaks appears to he the Snoek mechanism. The interstitial responsible for the peak at about 300°C has not been identified. Carburizing increases the magnitude of the peak at about 400°C; consequently, it appears reasonable to suppose that the specific interstitial associated with this peak is carbon. The activation energies associated with the 300° and 400°Cpeaks are about 35,000 and 45,000 cal per mole, respectively. INTERNAL - friction peaks resulting from the stress-induced diffusion of interstitials (Snoek relaxation peaks) have been frequently observed in bee metals.1-5 Attempts to detect Snoek relaxation peaks in tungsten have, however, not been fruitful.' Failure to find Snoek peaks in sintered tungsten can perhaps be attributed to one or more of the following difficulties: a) the relatively low purity of the sintered tungsten; b) the lack of extensive metallurgical knowledge about tungsten-interstitial alloys, such as suitable interstitial dosing and quenching procedures; and c) the inconsistency of some of the interstitial analyses of tungsten, which reflects itself in one's inability to be sure of the nature of the specimens. This present investigation did not overcome all of these difficulties for successful tungsten internal-friction measurements. Some of these difficulties still persist and new difficulties were encountered during the course of this investigation. Nevertheless, the use of electron-beam tungsten single crystals having somewhat greater purity levels than sintered tungsten combined with appropriate carburizing and quenching procedures permitted a reasonable attempt to be made. As a consequence, internal-friction peaks were observed in these tungsten single crystals at about 300° and 400°C. These peaks were found to be unstable, since they annealed rapidly away during a sequence of internal-friction measurements. Hence, it was necessary to construct an apparatus having a faster heating rate to study some of the details of these peaks. From the behavior of these peaks as well as our knowledge of similar peaks in other bee metals, one can reasonably conclude that these peaks are caused by residual interstitial impurities within these crystals. Further investigation of these peaks after the application of various metallurgical treatments lent credence to this supposition. EXPERIMENTAL TECHNIQUE The internal friction of tungsten single crystals was measured using two different pieces of apparatus both of which are of essentially the same conventional design, namely the KE type of torsion pendulum. The important difference between these two types of apparatus was in the attainable heating rate and method of protection of the specimen from atmospheric contamination. The apparatus designated "number 1" was enclosed in a vacuum chamber which was heated by an externally mounted furnace. It had a slow rate of heating which was estimated to be about 4°C per min from room temperature to about 350°C and then about 1°C per min to 600°C. The internal friction of tantalum was measured with this apparatus and the established Snoek peaks were found.' These tantalum peaks in the temperature range from room temperature to 400° C served as a check for the apparatus. The apparatus designated "number 2" having a faster heating rate than number 1 was not elaborate. It consisted of a mounted nickel tube to which split heating elements were attached. Argon was used as the protective atmosphere. The measured heating rate was about 12° to 15°C per min whereas the cooling rate was somewhat slower at about 10° C per min because of the increased difficulty encountered in stabilizing the temperature. No surface oxidation of the specimen was noted after any test. This apparatus was also checked with the known peaks of tantalum.1 The preparation of the single-crystal specimens for internal-friction measurements consisted of centerless grinding the crystals from an approximate 0.200 in. diameter to 0.030 to 0.040 in. in diameter, and then electropolishing them to about 0.020 in. in diameter. Single crystals processed in this manner are designated as being in the virgin condition. Since the length of crystal varied from 3 to 9 in., the test frequency varied from about 1 to 2 cps. The frequencies of measurement, axial orientations, and chemical analyses for the various crystals are listed in Table I. The controlled addition of carbon into tungsten is a difficult problem. Attempts to find the critical conditions necessary for an equilibrium treatment were not fruitful. Therefore, a simple nonequi-librium method was used. The addition of carbon to these crystals consisted of appropriately combining three treatments—carburizing to achieve a case, annealing to partially dissolve the carbon into the

Jan 1, 1965

By J. H. Frye, S. G. Holder, E. E. Stansbury

Internal friction studies on annealed and cold-worked pure silver and alloys of silver with 4.5 atomic pct each of Cd, Sn, and Sb are reported. Small amounts of cold work, introduced by stretching pure silver, decrease the internal friction; large amounts of cold work, by wire drawing, cause this decreased internal friction to rise. Results of severol anneoling histories on the room-temperature in-ternal friction indicate a rather complex recovery and recrystallization behavior. A rather system-atic alloy effect is observed for the elements of Period V-B in silver in both the annealed and cold-worked states. DURING recent years internal friction measurements at very small stress levels have been interpreted in terms of structural models and mechanisms occurring within the metal or alloy.These measurements have been made over wide ranges of frequency of vibration and of temperature. While the effects of impurities, alloying, and plastic deformation have been studied by numerous investigators, no investigations of the effect of a series of solutes related by their position in the Periodic Table on a given solvent seem to have been reported. The present paper reports internal friction measurements on silver and on certain silver-base solid solutions to determine the values of room-temperature internal friction associated with varying amounts of plastic deformation and after different annealing

Jan 1, 1957

By Nicholas J. Grant, Yoichi Ishida, Arthur W. Mullendore

An inert particle -marker technique was developed to provide a direct measurement of grain boundary sliding during creep in tile interior of aluminum specimens. Groin boundary sliding in the interior as measured by this technique was found to be nearly the same or slightly lower than that measured on the surface. These data disagree with those obtained by the grain-counting technique developed by W. A. Rachinger. In tests where both techniques were used, the grain-counting technique gave large and variable values of grain boundary sliding. It is shown that the grain-counting technique gines erroneozcs results because of a preferred direction of grain growth during creep. A question which has long plagued those who study grain boundary creep is whether or not surface measurements yield a true representation of the deformation in the interior of a specimen. The first attempt to measure grain boundary sliding in the interior of a creep specimen was made by Rachinger.1 His technique is based on the measurement of average grain diameters, both parallel and perpendicular to the tension axis, followed by a calculation of the grain elongation from these measurements. The difference between total elongation, Et, and the calculated grain elongation, Eg, is considered to be the result of grain boundary sliding, Egb. Surprisingly large values of Egb/ Et (90 pct) came out of creep tests of pure aluminum at temperatures above 250°C (480°F), utilizing the Rachinger technique. This value is very much larger than the values of 8 to 15 pct measured by numerous investigators on the surface of a specimen. Values obtained on the surface by Rachinger, however, were consistent with those measured by the displacement of reference scratches. Chaudhuri and Grant2 repeated the Rachinger method for A1-10 pct Zn, and found the same large values of Egb/Et inside the specimen. However, from purely geometrical considerations, grain boundaries cannot slide without grain deformation; therefore, they questioned the validity of Rachinger's grain-counting method. Several authors2,3 have suggested that grain boundary migration during high-temperature deforma- tion may tend to restore the equiaxed grain shape in order to minimize interfacial energy. Rachinger4 tested this hypothesis and found that it did not hold. Grains elongated by rapid extension retained their elongated shape during a subsequent slow creep test. It appears that some other factor was responsible for the abnormally high values of .Egb/El. McLean and Gifkins5 made a survey of the effect of grain size on the ratio Egb/ Et, and proposed that the high values were the consequence of a small grain size. They failed to explain the low value of Egb/Et which Rachinger observed on the surface of the small grain size specimens, and suggested that the surface effect on the value of Egb/Et does not always occur. Many of the disagreements arising from Rachinger' s work stem from the fact that there was only one method of estimating grain boundary sliding in the interior of a specimen, and that method was of an indirect nature. If a marker line of some sort could be introduced inside of the specimen, one could make measurements just as clearly as on the surface. In the present investigation, the technique utilizes a layer of finely dispersed oxide particles inside the specimen introduced by hot press-bonding of two pieces of aluminum. Rachinger attempted a similar technique but with the oxide distribution he obtained there was so much interference with grain boundary motion that quantitative measurements were not attempted. MATERIALS AND EXPERIMENTAL PROCEDURE A) Materials Preparation. Two pure aluminum rods (impurity content in percent: Si, 0.002; Cu, 0.004; Fe, 0.002; Mg, 0.000: Zn, 0.000; V. 0.001) 1 in. diameter by 2 in. high were jacketed end to end in a 4-in.-diam cylinder of commercial-purity aluminum, 4 in, high, which had a l-in.-diam hole. The l-in.-diam mating surfaces of the two pure aluminum rods had been electropolished initially. This interface provided the oxide-film internal -marker plane after the hot press-bonding process, see Fig. 2. The composite was annealed for 1 hr at 900 F and hot upset more than 50 pct reduction in height in one step. The resulting slab was then rolled to 1/2 in. thickness; the pure aluminum test material was cut out and annealed at 900°F for 1 hr and cold cross-rolled to 1/8 in. thickness. The sheet was machined into specimens with a 1/8-in.-square cross section and a 1/2-in. gage length. The following heat treatment was given the specimens: Specimen 5A series: annealed at 1000°F for 5 min for grain-size control and then cooled to 700°F and held for 15 hr for stabilization.

Jan 1, 1965

By Edward J. Felten

THE oxidation resistance of chromium and Fe-Cr alloys is increased by small additions of yttrium or other rare earth metals.1,2 In addition, the presence of the additives increases the resistance of these alloys to spalling of the external oxide above 1000°C. This ability to prevent spalling appears to be related to the formation of an internal oxide in alloys containing yttrium or the other rare earth metals. The internal oxide is found in the form of a filamentary growth concentrated in the grain boundaries of the unoxidized metal. In alloys containing yttrium this internal oxide was found to be either Y2O3 Or YCrO3.' In an earlier report,' the growth of the external oxide was found to be controlled by diffusion through the oxide layer. Thermal balance studies were used to establish the kinetics of external oxide formation. In this related study the rate of growth of the internal filamentary oxide has also been studied. The results obtained indicate that the growth of the internal oxide is also diffusion controlled. Internal oxidation appears to occur in at least two ways. Using copper alloys containing small amounts of silicon, Rhines 3 found that between 600" and 1000oC a subscale was formed which consisted of particles of silica dispersed in the metallic matrix. The conditions requisite to internal oxidation as suggested by Rhines are: 1) a solubility of oxygen in the alloy, 2) the ability of oxygen to diffuse at an appreciable rate into the alloy, 3) the possibility of the formation by the alloying element of an oxide more stable than the oxide of the host metal, and 4) a relatively low solubility of this oxide in the metal. These conditions are fulfilled for a number of other copper alloys.3-5 Furthermore, the relationship between the depth to which the internal oxide is formed and the oxidation time follows the simple parabolic law.6 The activation energy for copper containing small amounts of silicon, germanium, iron, or manganese as calculated from Rhines data6 is about 48 kcal per mole. In some cases the internal oxide is found segregated at the grain boundaries, especially near the the surface. Observations of this type of oxide formation have been reported by stead,7 Rhines,* and Lustman. Evans" cites these cases as examples of the simultaneous movement of anions and cations during oxidation. Furthermore, Evans states that the presence of a minor constituent with a high

Jan 1, 1962

By Y. C. Liu

An analysis is presented to show that the formation of rolling textures in fcc metals can be rationalized in terms of flow mechanisms operative during the rolling process. First, a general approach used by Calnan is followed, where the rolling process is approximated on the basis of two axes, p and Q. In this treatement there are two separate sets of slip systems, one for each axis, and it is shown that a homogeneous rotation can he achieved by restricting the slip systems for the two axes to share common slip directions Then, two criteria are used to select the active slip systems for the axis P: they must have relatively high resoloed shear stresses, and dislocations on these slip systems must interact attractively in order to lower total energy content Finally, a method of analysis is introduced to locate the end position of an axis by knowing its acti7.e slip systems. The result of the analysis indi- cates that two main flow mechanisms operate in fcc metals. The ideal orientation derived from one oj-them is (8 13 21) (21 8 13) which is very close to the (358) (523) orientation observed experimentally on the rolling texture of copper. This flow mechanism should only he operative in metals containing dislocations extended into partials separated by less than five times their lattice parameter. The ideal orientations derived from the other flow mechanism are a combination of (1 10} (112) and a spread of orientations with (110) parallel to the rolling plane. This type of ideal orientations corresponds to those observed in the rolling texture of silver 30:70 brass, and binary alloys with high alloying content. This flow mechanism should be operative in any fcc metal regardless of its stacking-fauIt energy. When a polycrystalline metal is subjected to a large amount of plastic deformation, it is generally observed that grain orientations alter and align themselves towards certain positions, eventually reach-

Jan 1, 1964

By Paul A. Beck, M. N. Parthasarathi

By determining the (220) pole figure for OFHC copper rolled to 96 pct R. .A., the occurrence of four texture components of the type (135) [211] was confirmed. It was found that the total volume fraction of material close to the four symmetrical orientations of this type is larger than the volume fraction of the other components put together. THE rolling texture of copper was described by early investigators1'" as a mixture of components of the (110)[l12] and (112) [11l] types. Other studies, still using the qualitative photographic method of texture determination arrived, instead, at orientations of the type (135) [533] or (135) [211] for copper3'4 and at the closely related "Z-texture" for a fee nickel-iron alloy.5 The prevalence of this type of orientation, near (123) [412], in the rolling texture of aluminum and of copper was later confirmed by means of quantitative diffractometer methods.' However, in a recent paper7 Jones and Fell stated that the (110) [112] and (112) [111] double texture was in better agreement with the measurements of Young's modulus for cold-rolled copper.' These authors also expressed their belief that the "roll texture" can be determined by means of two photographic quasi-fiber texture patterns taken with sheet specimens rotated around the rolling direction and the transverse direction, respectively. Jones and Fell found7 that the results obtained from such patterns for cold-rolled nickel did not agree with any of the orientations mentioned above, but they suggested that the observed diffraction spots may have been brought about by the overlapping of reflections due to the (110) [112] and (112) [11l] double texture components. Jones and Fell concluded that the (123) 14121 type orientation is inconsistent with their patterns. They also stated, without offering any supporting evidence, that this orientation is inconsistent with the (220) pole figure. "Ideal orientations" are often used for a very rough description of the principal orientations encountered in a texture, It is, however, well to remember the fact that, no matter how "accurate", these ideal orientations are only schematic representatives of a continuous distribution9, which often (as in the case of rolled copper) includes extensive orientation spreads. The attempt by Jones and Fell7 to use elastic modulus data in deciding between various ideal orientations in the rolling texture of copper neglects this fact. The inadequacy of two-dimensional "axis density figures" in describing orientation distributions in sheet textures was previously discussed.9 It was also pointed out9 that there is no reliable evidence to prove that orientation distributions derived by the "quasi-fiber method" from rotated sheet specimens are fully equivalent to the corresponding information obtainable from quantitative pole figures. The view that a sheet texture could be adequately determined by means of two photographic quasi-fiber texture patterns is obviously erroneous9. The question as to the consistency with the (220) pole figure of ideal orientations derived from the (111) and (200) pole figures is, on the other hand, certainly very relevant. Since no quantitative (220) pole figure for cold-rolled copper appears to be available in the literature, the following work was undertaken. EXPERIMENTAL METHOD An extruded rod of OFHC copper, 1 in. in diam, was given alternate rolling (30 to 35 pct R.A.) and

Jan 1, 1962

By R. G. Garlick, H. B. Probst

Tungsten single-crystal specimens of various orientations were deformed in tension at room temperature. Slip traces indicated both (112)(111) and (110) (111) slip; however, about 10 pct plastic dejormation was required bejore these traces could he seen. Resolzled shear-stress considerations indicated that at least some of the particular systems observed were not those on which slip initiated hut were secondary systems. This is highly probable, considering the high plastic strains involved. Analysis of the stress data with respect to possible slip systems indicated that slip must have been initiated at stresses below the proportional-limit stresses measured. ALTHOUGH there is general agreement that slip deformation in fcc and hep metals takes place on the plane of close packing and in the direction of close packing, there is no such agreement for slip in bcc metals. It is generally agreed that the close-packed direction (111) is the slip direction, but investigations have led to conflicting descriptions of the slip plane. As Hoke and Maddin1 point out, there are essentially four points of view. 1) Deformation in bcc metals is composite shear on (112) and (110) planes or on nonparallel (110) planes, and any apparent slip on other planes can be accounted for completely by slip on these planes. Chen and Maddin have reported this to be the possible case for molybdenum." 2) Slip occurs in the (111) direction and is limited to {110), {112), and (123) planes (the three closest packed planes of the lattice). 3) Slip occurs in a (111) direction, but not necessarily on planes of close packing (banal slip). 4) Slip occurs in those directions and on those planes for which ß, the ratio of Burgers vector to interplanar spacing, is a minimum. The slip systems of the bcc metal tungsten have never been fully determined, although several investigators have reported pertinent results.3"7 The present work was initiated to determine the active slip systems in tungsten at room temperature, the critical resolved shear stresses associ- ated with these systems, and the orientation dependency of operative systems. These features of tungsten deformation at room temperature have never been reported in the literature. The authors find this somewhat surprising, particularly in view of the availability of tungsten single crystals since the advent of electron-beam zone-melting techniques and the widespread interest in refractory metals. It would seem apparent that such work has been attempted but the results have not been reported, possibly due to the conflict with deformation theory. The results of the present work conflict with any straightforward description of deformation based on the proposed explanations of slip in bcc metals. Although these conflicts have not been resolved, a presentation of the problem seems in order and should be of value to others working in this field. MATERIALS AND PROCEDURE Single-crystal tungsten rods of 1/8-in. diameter were grown from undoped commercial rod by one-pass electron-beam zone melting in apparatus previously described by witzke.8 Representative analyses of the rod before and after melting are given in Table I. There was no detectable zoning of impurities during melting. Buttonhead tensile specimens, as shown in Fig. 1, were machined from single crystals. Two flats 90 deg apart were ground in the gage length of each specimen. These flat surfaces facilitated the analysis of slip traces. No attempt was made to position these flats with respect to the crystal orientation. The worked surface layer of the machined specimens was removed by electrolytic polishing in a NaOH solution. Tensile-axis orientations were determined by standard Laue back-reflection techniques. The sharpness of the Laue spots indicated that the crystals were free of strain.

Jan 1, 1964

By E. S. Machlin, S. Weing

GRAIN boundary stress relaxation has been the subject of several investigations in recent years, but as yet the phenomenon is not well understood. One of the major difficulties has been the lack of a sufficient amount of data with which to evaluate any proposed mechanism. Little information is available on the effect of small amounts of substitutional solutes on grain boundary stress relaxation. It is with this important phase of the problem that this investigation is concerned. The influence of substitutional solutes on grain boundary stress relaxation has been recently investigated in copper by Pearson: and in aluminum by Dorn et al.' Pearson studied the effect of zinc, gallium, germanium, and arsenic on the relaxation peak of OFHC copper.* The pure OFHC copper decreased the peak intensity and a second peak appeared at a higher temperature. This latter peak was termed the alloy grain boundary peak. At the lowest binary concentration studied, approximately 1 atomic pct, the primary peak was almost completely obliterated. Pearson found that the activation energy calculated from the alloy grain boundary peak for all solutes, irrespective of the concentration, was 44,000 cal per mol. Pearson concluded that the increase in activation energy from 33 to 44 kcal per mol is not continuous but abruptly changes from the lower to the higher value. As no attempt was made to investigate the intermediate range of concentration and hence calculate the possible variation of the activation energy for the initial grain boundary peak, this conclusion is hardly valid. In contrast to these results, Dorn et al. studied the effect of zinc, silver, copper, germanium, and magnesium on the grain boundary stress relaxation of aluminum. No change in the energy of activation was observed for binary alloys of the flrst four solutes, but a linear increase was found for increasing concentration of magnesium. Saturation was not found up to the maximum of 1.6 atomic pct. The energies of activation were obtained by plotting the horizontal displacement of the dynamic modulus curve vs temperature for two vibrational frequencies. As the modulus is proportional to the square of the frequency, this requires the measurement of the torsional frequency over a range of temperature. However, the technique does not lead to an unambiguous interpretation of the grain boundary

Jan 1, 1958