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By R. E. Smallman, J. C. Terry

J. C. Terry and R. E. Smallman (Llniuersity of Birmingham, England)—In a recent publication53 Wood and Westbrook have reported the results of an investigation of the tensile behavior of fl-phase AgMg alloys. These results agree in broad outline, but differ in the details, with those obtained in the above laboratory and, consequently, some discussion of their paper would seem appropriate. In our experiments, tests were carried out on extruded wires, 2 mm diam, in a hard-beam tensile machine, and while an oil bath was used for the tests up to 150°C, above this temperature the oil bath gave rise to serious contamination of the specimens and hence tests above 150°C were made in vacuo. This procedure is different to that adopted by Wood and Westbrook. The ß-phase alloys exhibit differences in mechanical behavior when they are tested in different temperature ranges. In agreement with Wood and Westbrook, three characteristic ranges are observed which may be classified as low, intermediate, and high temperatures, respectively. Our experiments show that in the low-temperature region, the shape of the stress-strain curves is similar to that reported. However, in addition, it is observed that the temperature at which the low-temperature region ends is markedly dependent on strain rate, and increase with increasing strain rate as shown in Fig. 18. The temperature at which a transition from the low to the intermediate temperature takes place is about 0.4 to 0.45 of the absolute melting point, Tm. This transition temperature coincides with that at

Jan 1, 1963

By D. K. Deardorff, Haruo Kato

D. K. Deardorff and Haruo Kato (U. S. Bureau of Mines)—We wish to refute the 1875" 20°C value that Giessen, et al., report as the transformation temperature of hafnium. Although these authors state that their work along this line will be reported later, we can't leave their value undiscussed, for we believe it to be 125°C too high. Our value of 1750° 20°C, which the authors mention, has been substantiated in our laboratories by the use of three other methods. The first method of substantiation was by heating and cooling curves using a hafnium/tungsten thermocouple, the couple having first been calibrated against a t/Pt-10 pct Rh couple. The second method was by quenching and metallography of dilute Hf-Ta alloys. The third cussion, it may be pointed out that the observations of Rogers referred to large unidirectional strains where the internal cracks or voids appeared only after a strain of 32 pct or more. On the contrary the internal fissures observed, as a result of fatigue cycling, occurred for a total extension of some 5 pct and furthermore followed the directions of the slip zones. Finally, it is not our contention, as implied in Dr. Alden's last paragraph, that the tensile stress is an important factor in crack propagation. Indeed, in connection with the reference to the companion report, special note is made of the fact that "Deformation was apparently concentrated in grains which have a slip plane nearly perpendicular to the specimen axis and thus near the plane of maximum applied shear." This dependence of the growth of fissures on the orientation of the slip planes with respect to the direction of maximum applied shear is clearly shown in work on the torsional cycling of single crystals which has been submitted for publication. method was by heating and cooling curves with W/W-26 pct Re thermocouple. Counting the original resistometric method, four different methods have yielded 1750" 20°C as the transformation temperature of hafnium. All our work on determination of the hafnium transformation temperature has shown that the specimen under test must be quickly heated to and through the transformation temperature if the lowest possible transformation value is to be determined; otherwise a higher value not representative of pure hafnium will result. Speed was emphasized in all methods. In our resistometric work the corresponding voltage, amperage, and temperature readings were taken quickly and the transformation temperature was usually reached within 5 min total heating time. In the thermal analysis work involving Hf/W or W/W-26 pct Re thermocouples the transformation temperature was attained within three minutes total heating time, this time being less because the two variables were

Jan 1, 1963

By R. E. Smallman

R. E. Smallman (University of Birmingham, England)—Recently, Tedmon and Ferriss11 have determined the yield stress parameters oi and ky for tantalum by measuring the lower yield stress as a function of grain size 2d and fitting the results to a relationship of the form They report that although ky , which is taken to be a measure of the dislocation locking strength, is small (- 2 to 4 x 106 cgs units) a substantial yield drop is nevertheless observed in a normal tensile test. Niobium gives a similar result,12-14 as pointed out in the original work by Adams et a1.,12 and in order to check this apparent anomaly the yield-stress parameters of electron beam-melted niobium have recently been reanalyzed15 by the Luders strain technique. In this method the strain hardening part of the stress-strain curve is extrapolated to zero plastic strain; the intercept on the preyield portion of the curve is taken to give oi, whilst the difference between oi and the lower yield stress gives kyd-1/2. The results indicate that ky increases with increasing grain size and hence, a plot of vs d-112 yields an apparent ky, which is lower than the true value. A similar effect could account for the small ky found in the relatively pure tantalum used by Tedmon and Ferriss. The variation of ky with grain size shows that dislocations are more strongly locked in coarse-grained specimens than in fine-grained samples. In niobium, this may be attributed to the fact that the dislocation density in the fine-grained material is higher than that found in the coarse-grained samples which are given a sufficiently prolonged anneal to remove any residual substructure and, since the metal contains only a small amount of interstitual impurity, a variation in locking occurs. By contrast, application of both the grain size analysis and the Luders strain method to yield-stress data from commercially pure vanadium containing a large amount of interstitial impurity gives consistent values of oi and ky, with ky independent of grain size and temperature. Electron microscope observations show minor variations in dislocation density from grain size to grain size, but in any case in this material the dislocations are heavily locked with precipitate. On yielding new dislocations are generated and, as a consequence, the importance of any differences in dislocation density between the various specimens of different grain size is considerably reduced. It is perhaps significant that Adams and lannucci,16 working with a grade of tantalum containing a higher interstitial content than that used by Tedmon and Ferriss, prepared the specimens of different grain size by annealing in the temperature range 1500" to 2000° C to minimize any differences in dislocation structure, and found that ky had a value of 1.04 x 107 cgs units, independent of testing temperature. Such behavior is consistent with the dislocations being locked by carbide precipitates so that the generation of free dislocations is an athermal process. The recent work of Gilbert et al.17 also shows that in tantalum there is no significant variation of ky with grain size provided it contains 150 ppm of oxygen. In this case, however, the dislocations are not locked by precipitate and ky is temperature dependent. C. S. Tedmon and D. P. Ferriss (authors' reply)— We would like to thank Dr. Smallman for his interesting comments and discussion to our paper, "The Dependence of Yield Stress on Grain Size for Tantalum and a 10 pct W-90 pct Ta Alloy".18 It was suggested that perhaps the relatively small values obtained by us for ky of tantalum could be attributed to the same cause that accounts for the apparently small values of ky that result when it is determined by the Luders Strain technique. Since our values were obtained by plotting the lower yield stress vs the reciprocal of the square root of the grain size, it is not clear how this could be the case. The values of ky in this experiment have been calculated, using the Luders strain technique. With this method, values for ky on the order of 2 x 105 to 5 x lo6 cgs units were obtained. In spite of this rather large variation, the magnitudes are still small, and there appeared to be no good correlation between ky and the grain size or the yield stress, probably because of the difficulty in accurately extrapolating the work-hardening portion of the curve back to zero plastic strain. As was shown in the original data,18 there was little work hardening in any of the curves, at any temperature. In his discussion, Dr. Smallman also points out how ky has been observed to increase with increasing grain size, when determined by the Luders strain technique. There are at least two possible explanations for this. In the first case, if it is assumed that the bulk of the interstitial impurities are concentrated at the grain boundaries, then, of course, the available grain boundary area would decrease with increasing grain size, thus presenting less area for the interstitials, which would then presumably increase the concentration within the grains, thereby increasing the locking of the dislocations. In the second case, the increase in ky with increasing grain size would be attributed to the nature of the grain boundary itself. One of the several ways of deriving the Hall-Petch equation19 is based on the stress concentration arising from a pile-up of dislocations at the boundary. The ability of the stress concentration to unlock a source in a neighboring grain would depend on the strength of the grain boundary. As is well-known, the nature and struc-

Jan 1, 1963

By G. W. Powell

G. W. Powell (Ohio State University)—Appleton and Bever measured the quantity Es which, for a solid torsion specimen, is basically an average quantity. Es is the amount of energy stored in a solid torsion specimen strained to a surface shear strain of divided by the total number of gram-atoms of alloy in the specimen. It would seem more meaningful and rigorous to deal instead with the quantity which is the energy stored per gram-atom of an alloy uniformly strained to the shear strain . The purpose of this discussion is to demonstrate that as a function of y is readily obtained from the torsion data. radius of the torsion specimen, shear strain at the surface of the torsion specimen density of the alloy, atomic weight of the alloy, and total energy stored in unit length of the torsion specimen. The energy stored in unit length of an elemental tubular section of the torsion specimen is, as given by Appleton and Bever, where E is expressed as calories per gram-atom. The energy stored in unit length of the torsion specimen is

Jan 1, 1963

By W. C. Leslie

W. C. Leslie (Edgar C. Bain Laboratory for Funda mental Research)—This investigation, with its com bination of high-purity metal, calorimetry, and metallography, will serve as a model for annealing studies for a long time to come. The evidence for a competition between recovery and recrystalliza-tion is particularly convincing. The demonstration of edge-nucleated recrystallization was so clear that it may obscure the necessity for other types of "nucleation" sites; otherwise, single crystals of aluminum could not be recrystallized after cold work. At least three types of sites have been found to operate in iron: 1) high-angle boundaries, probably in the same manner as in aluminum, 2) matrix sites, 3) inclusions or second-phase particles. In each instance, the cells developed during cold work and perfected during recovery are the "nucle for recrystallization. Observations by ourselves and others of the dislocation structure of cold-worked metals and of the structural changes that occur during annealing have led us to doubt the validity of the basic assumption of the Lucke-Detert theory, and of the modification developed by Gordon and Vandermeer, that during recrystallization of a metal containing foreign elements in solid solution a high-angle boundary is ad vancing into a cold-worked matrix having a random distribution of solute atoms. We contend that an es sential part of the cold-working and annealing of solid solution alloys is the trapping of solute atoms by the low-energy "wells" afforded by individual dislocations and by dislocation arrays. If cells are formed during cold work, the cell walls are stabilized by this concentration of solute atoms. Thus, solutes inhibit recrystallization not only by decreas-ing the rate of high-angle boundary migration, but also by preventing the formation of high-angle boundaries by subgrain growth or coalescence, i.e., solutes can inhibit both "nucleation" and growth. In addition to stabilizing the dislocation Structure, the solute-dislocation interactions may produce clusters of solute atoms which are not as readily assimilated into the recrystallized grains as are individual solute atoms. There is an additional complication. The dislocation structure formed upon cold working a dilute solid solution may not be the same as that formed during cold working of the pure solvent metal. The solute can either enhance or minimize the formation of cells during cold working. Both effects have been observed in binary alloys of iron. The annealing process is inextricably connected with the mechanisms of strain hardening and solid solution hardening. Although the correlation between experimental boundary migration rates and the predictions made from the theoretical equations are impressive, it should be mentioned that in at least four other instances (Pb-Ag and pb-Au,15, Fe-Mn,16, Fe-Mo)17 the agreement was rather poor. In brief, while it is probable that the migration of high-angle boundaries is held back by solutes in the manner described, this is only a partial explanation of the total effect of solutes upon recrystallization of cold-worked alloys. Paul Gordon and R. A. Vandermeer (author's reply)— The authors first wish to thank Dr. Leslie for his compliments of this work. It is perhaps worth pointing out that some of Dr. Leslie's remarks are directed toward subject matter covered in two earlier papers in our work.18,19 We agree with Dr. Leslie's main contention that the exact nature of the metal structure in the vicinity of a boundary should have an effect on the boundary migration. The theory of Lucke and Detert does not take such detail into account, nor does it account for orientation effects on the migration rates. We assume that since our data checks the theory so well, the effects of detailed structure are statistically averaged out by the polycrystalline techniques used just as are the effects of orientation factors.

Jan 1, 1963

By E. A. Steigerwald

E. A. Steigerwald (Thompson Ramo Wooldridge, Inc.1— he authors' results clearly indicate that cracking can be produced by the hydrogen pressure developed during a charging operation. This type of cracking or blistering has also been observed in polycrystalline materials24"28 when the charging conditions are sufficiently severe and is often referred to as irreversible embrittlement since it cannot be removed by a baking treatment. There are additional data, however, which must be considered before a pressure theory can be generally employed to account for all failures which occur as a result of hydrogen. In many cases, hydrogen embrittlement in a tensile test or in delayed failures under static loads is a reversible phenomena which cannot be simply explained on the basis of preexisting cracks generated by the charging operation. It is this aspect of the problem which has prompted many investigators to seek mechanisms other than hydrogen pressure to explain their results.24'n728 Fig. 15 indicates an example where, under specific experimental circumstances, hydrogen embrittlement can occur at liquid nitrogen temperatures. In this case, which has been previously decribed,'' specimens were charged with varying quantities of hydrogen, immediately quenched, and tested in liquid nitrogen (-320°F). A companion set of identical specimens were charged, aged at 300°F to remove the hydrogen, and also tested at -320°F. When the current density was greater than lo-' amp per sq in., embrittlekent occurred in both sets of specimens, indicating that cracking had occurred during charging and the embrittlement, as in the case of Fe-Si single crystals, was irreversible. At current densities between approximately 103 and lo-' amp per sq in, the embrittlement was present only for those specimens which contained hydrogen during the testing sequence. The embrittlement was therefore reversible with respect to the aging and charging operations. Since extensive hydrogen movement would not be expected at -320°F, it is difficult to reconcile these data with a mechanism which requires pressure and pressure dependent growth of preexisting cracks. There are other features of hydrogen embrittlement such as the reversibility of the incubation time for delayed failure with respect to applied stressg0 and the influence of prestraining31 which are also difficult to explain using a pressure model. Any general mechanism of hydrogen embrittlement will have to consider the reversible aspects of the embrittlement data as well as the irreversible portion which has been clearly presented for the Fe-Si crystals and which is consistent with a pressure model. A. S. Tetelman and W. D. Robertson (authors' reply)—he authors agree with Dr. Steigerwald that a general mechanism of hydrogen embrittlement must be applicable in all cases where embrittlement occurs. Dr. Steigerwald's experiments were performed on an iron alloy which has an extremely complex microstructure, and therefore does not lend itself to the direct and detailed observations that can be made in Fe-Si. The change in the characteristics of cracks as a consequence of annealing at 300°F is not really known in detail but it is probable that stress-relaxation (blunting) occurs, dislocations produced near the crack tips will be pinned by carbon atoms, and hydrogen will be lost to the atmosphere. Any, or all of these effects of annealing will alter the ease with which a crack subsequently propagates under applied stress. A quantitative treatment of the problem must take these effects into account. Since diffusional processes are presumably eliminated at -320°F, the general mechanism proposed by Dr. Steigerwald's colleagues cannot be operative at this temperature. A detailed discussion of the general' inapplicability of this mechanism has been presented elsewhere. However, the data presented by Dr. Steigerwald in his discussion can be explained in terms of a pressure model. Crack propagation under internal pressure P and applied stress occurs when where is the total energy expended in creating new surface area and by plastic work at the crack tip. The total crack length increases with increasing current density, since we have shown that it systematically increases with hydrogen concentration and Dr. Steigerwald has shown that hydrogen concentration increases with current density. For large L (high current density) Eq. [I] can be satisfied even if P = 0 and the embrittlement process does not require the presence of hydrogen. Specimens charged at a lower current density will con-

Jan 1, 1963

By Kenneth A. Moon

Kenneth A. Moon (U.S. Army Materials Research Agency)—The authors are to be congratulated for a very interesting and valuable paper. Their discussion of the structural implications of the results shown in their Fig. 5, however, requires a small correction. The model of Speiser and Spretnak with 0 = 1 and z' = 2 is perfectly reasonable for the Ti-O a phase, but Eq. [3] is valid only for solutions sufficiently dilute that the number of empty sites excluded by more than one filled site is negligible. The composition at which intrinsic saturation occurs therefore cannot be deduced from Eq. [3], but but must be decided by consideration of the structural details of the phase in question. In this case, intrinsic saturation is expected not at the composition Ti3O but at Ti2O, because Ti2O has the anti-Cd structurel4 for which each filled octahedral site has two nearby empty sites, one in the hexagonal plane immediately above it, and one in the similar plane below it. The other two models, with ?=1/3 and 1/2, imply a distinction between octahedral sites in pure titanium which is not easy to justify. The problem of extending Speiser's and Spretnak's treatment in a general way to more concentrated solutions will be the subject of a forthcoming publication by the writer. M. T. Hepworth and R. Schuhmann, Jr. (authors' reply)—The authors wish to thank Dr. Moon for calling to their attention the paper by Holmberg which presents the results of X-ray studies of Ti-O solutions ranging from 0 to 33 at. pct 0 and quenched from various annealing temperatures between 400" and 1800°C. Within these ranges, Holmberg found three types of phases: 1) At high oxygen contents (above 25 at. pct) and low annealing temperatures, he found the anti-Cd(OH)2 structure referred to by Dr. Moon. In this structure each titanium atom is in contact with 3 oxygens and each oxygen is in contact with 6 titaniums, the "available" oxygen sites corresponding to every other layer of octahedral sites in the titanium matrix. The limiting composition is Ti2O. However, this anti-Cd(OH)2 structure was not observed for samples containing 25 at. pct 0 or less. 2) For the specimen containing 25 at. pct 0 annealed at 400°C an ordered Ti3O structure was observed. This structure is related to the anti-Cd(OH)2 structure but differs from it by providing only two oxygens adjacent to each titanium atom and thus is consistent with the model represented by Eq. [5] in our paper, with 6 = 1/3, z' = 0. 3) For dilute solutions and for more concentrated solutions annealed at higher temperatures, the structure corresponds to that of the metal with random distribution of oxygens among all the octahedral sites. Thus, it is interesting to observe that the thermo-dynamic indications of ordering in the vicinity of Ti3O can now be supported qualitatively at least by Holmberg's X-ray evidence of the existence of an ordered phase of the composition Ti3O. That is, for solutions with oxygen contents close to that of Ti3O, both the thermodynamic data and the X-ray data are more consistent with models based on the ordered structure of Ti3O than they are with the model which Dr. Moon suggests corresponding to "intrinsic saturation" at Ti2O.

Jan 1, 1963

E. R. JETTE*—The way this ternary was developed there are two directly determined points on each of the iso-thermals except the 700° isothermal, where I believe there is only one. How were the end points determined, and what was the basis for it? Whose work formed the basis for the silver copper line ? M. B. BEVER †—At most temperatures the authors determined three points of the isothermal line. For example it can be seen from Fig 3 and 4 how three points for the 600°C contour line were obtained. The authors took two additional points for each temperature from the copper-silver binary diagram contained in Hansen's volume on constitution diagrams. It is correct that the 700°C contour line is based only on one point in the ternary field which was found by a slight extrapolation of Fig 4. R. I. JAFFEE*—Are the tie lines representing phases in equilibrium parallel to the silver-copper boundary ? M. B. BEVER—Are you asking that as a matter of principle ? R. I. JAFFEE—I assumed that would follow from principle. I wonder if that is in accordance with the authors' ideas too. M. B. BEVER—I do not believe the authors obtained any information on the tie lines in the two-phase field. Of course, in the limiting case of very low gold contents the tie-lines approach to the silver-copper boundary, but generally in the two-phase field I do not think that the tie-lines have to be parallel to the boundary. E. R. JETTE—1 am quite sure they do not have to be parallel. You cannot tell from this work in which direction they go. E. A. GULBRANSEN*—Were any pycnometric measurements made to check the lattice parameters of the alloys ? M. B. BEVER—I did not hear any-

Jan 1, 1950

By Hsun Hu

C. G. Dunn (Geneva1 Electvic Reseavclz Labo,vatory)-Dr. Hu16 has obtained a number of rolling and annealing texture results that partly agree with those of Dunn17 and Dunn and Kohl8 for experiments of a similar nature. I would like to discuss some of the points of agreement as well as some of disagreement and then present some unpublished data as a contribution to the work on textures. Firstly, there is agreement on the components produced during a 70 pct cold-rolling reduction of a (110) [001 ] single crystal; there is agreement on the forma- tion of a (110) [001] recrystallization texture provided recrystallization occurs at 800°C or higher; and there is agreement on the formation of (120) [001] components provided recrystallization occurs below 600°C. There is some disagreement on the low-temperature recrystallization since I also obtained a substantial amount of a (110) [001] component while the author obtained only (120) [001] components. I also discussed the differences between low- and high-temperature recrystallization (which included further annealing changes in the samples on long

Jan 1, 1962

By J. D. Meakin

J. D. Meakin (The Franklin Institute Laboratories)— In a recent paper Garofalo12 has shown that a number of experimental creep results can be represented by the empirical relation In this expression ? is the steady creep rate, s is the applied stress, and A is a constant at a given temperature; a and n are adjustable parameters. Garofalo has shown that Expression [6] approximates to a power function at low stresses and a simple exponential function at high stresses. Among the data used by Garofalo are the results we published for creep of copper." For these results we found that the best correlation was an exponential law with different parameters in the low-and high-stress region, respectively. That is, i = A exp qs where A and q have different values above and below a critical stress a,. In Ref. 13 are listed a variety of observations which support the proposal that different mechanisms are operative at stresses above and below a,, and it is not felt appropriate to repeat those observations here. The purpose of this note is to demonstrate that, although the representation used by Garofalo does fit the experimental data very well, this fit cannot be used to conclude that only one mechanism is rate-controlling. The argument is best made graphically and is illustrated in Fig. 9. The continuous curves 2 and 3 represent pairs of simple exponential functions which intersect at i = 10-5. The curve 2 closely resembles the copper results in that a change of slope of 2:1 occurs at i = 10-5; the two functions shown are in fact: e = 10-7 exp (1.150) and ? = 10-6&apos; exp (0.576s) For purposes of comparison, curve 3 represents two exponential functions with a change of exponent of 3:1 and curve 1 has the exponent 1.150 throughout. It is quite clear that a satisfactory straight-line fit is obtained on a Garofalo plot for all three curves. The curves represent processes which have either a single stress exponent or two ex- ponents in a ratio as high as 3:l. It must, therefore, be concluded that the ability to obtain a linear dependence between log i and log (sinh cyo) cannot be taken as evidence for a single activated process. In fact, to some extent the way the experimental points quoted by Garofalo lie about a best fit straight line on the log (sinh as) plot indicates that two processes are indeed occurring. This is seen in Figs. 7(c) and 8(c) of Ref. 12 where it is particularly evident that the experimental points deviate from the straight line in a manner similar to curves 2 and 3 of Fig. 9. It is, of course, recognized that the generally used exponential form is an approximation to the hyperbolic sine function which is not valid for exponents of less than 1.2, e.g., qs < 1.2. The only curve in Ref. 12 which is affected by this restriction is Fig. 6(b) where the deviation from a In ? vs s

Jan 1, 1964

By T. S. Lundy, J. Askill

J. Askill and T. S. Lundy (Oak Ridge National Laboratory)—Moore has proposed a simple correlation between the activation energy for solute diffusion in fee metals and the atomic volume of the diffusing species using both tracer and chemical-diffusion data. The first point we wish to make is that it is wrong to attempt such correlations without separating the two types of data. Activation energies obtained using tracer techniques cannot, in general, be directly compared with those obtained from chemical-diffusion experiments. A knowledge of the variations of chemical potentials with composition is necessary and chemical-diffusion data must be corrected for such variations, even for dilute alloys, before a comparison is possible. Secondly, for nickel, iron, aluminum, and lead, Moore neglected a number of recently published works, e.g., Al26 and Mn54 in aluminum,46 cr51 in nickel,47 and Fe55 in iron.48 These and others should have been used. If one considers only the tracer diffusion data, there is left no simple correlation of the type proposed by Moore. For example, in the case of solute diffusion in aluminum the only reliable tracer data listed by Moore are for zinc and aluminum. The nickel, cobalt, and iron data of Agarwala49 are representative of near-surface diffusion-not bulk diffusion. In conclusion we suggest that for tracer diffusion data in these fee metals there is no justification for proposing any simple correlation of activation energy with atomic volume using the limited data that are presently available. R. H. Moore (author&apos;s reply)—The writer has proposed a simple correlation which is useful in estimating the internal consistency of diffusion data. The accuracy of the correlation is, of course, a function of the number of data available. Lundy and Askill take issue with the writer&apos;s decision to include data for the systems: nickel, iron, aluminum, and lead, taking the view that the data are insufficient to establish the correlation. The writer agrees that the data are insufficient and has cau- tioned the reader that the correlation is tentative in these instances. Inclusion of these systems is justified by the interesting trends the correlation reveals. For example, the distinction between interstitial and substitutional diffusion may be clearly established, Figs. 4 and 6, and the behavior of transition elements and nontransition elements is indicated to parallel the behavior illustrated by the silver and copper systems. Lundy and Askill have singled out the aluminum system for special criticism. The writer chose to discuss the data for diffusion of iron, nickel, and cobalt in aluminum in the terms used by the original authors9 and has included the comments of Balluffi.l0 The writer did not intend the reader to conclude that data for these elements should correlate with data for the nontransition elements as Lundy and Askill have evidently assumed. Iron, nickel, and cobalt form intermetallic compounds with aluminum, so the activity coefficients of these elements may be expected to deviate markedly from unity. This may account for the low frequency factors observed by Hirano.9 The nontransition elements, on the other hand, yield relatively simple phase diagrams with no evidence for intermetallic compound formation as in the case of iron, nickel, and cobalt. In dilute solution, Henry&apos;s law should be closely obeyed, the activity coefficients should not deviate markedly from unity, and the effect on the activation energy should not be large. The accuracy of the correlation applied to these systems will improve as the data is extended. It does not seem unreasonable to conclude that its extension should be encouraged.

Jan 1, 1965

By James C. M. Li

James C. M. Li (Edgar C. Bain Laboratory for Fundamental Research)—Professor Weertman has suggested the interesting possibility that dislocation tangles are formed by helical formation of dislocations stopped by long-range stresses or by jogs. Such a possibility is similar to that of "mushrooming"374 in the respect that a dislocation must first be stopped and then interact with vacancies. The effect of short-range internal stresses which may exist at the time a dislocation is stopped has not been considered. It seems that the effect of these internal stresses may be just as important as, if not more than, that of the interaction with vacancies. The internal stresses produced by dislocations of

Jan 1, 1964

By R. I. Jaffee, R. W. Wood, H. R. Ogden, D. N. Williams

D. W. Morgan, D. H. Polonis,and R Taggart (Uuivevsity of Washington)—Dispersion hardening in titanium-copper alloys is of particular interest to us in view of our current research activities in phase transformations in this system. We should like to raise questions concerning several points in the paper. The flow sheet for fabrication and heat treatment (Authors&apos; Fig. 2) indicates that 0.045 in sheet is treated in air for a period of 30 min at 1625&apos; F. Were any surface coatings used to reduce oxygen contamination at this stage? One might ask the same question about the 8-hr annealing at 1400F. Contamination during fabrication and heat treatment of such thin sections could be considerable without some protection. Although the authors state that no analyses were made, they note that contamination masks the distinction between base strengths of the different alloys. In this connection, what fabrication and heat-treatment procedures were used in obtaining the comparison specimens of unalloyed titanium? It would seem that oxygen contamination must cast doubt on the reliability of the proposed strength-mean free path relationship deduced from the data (Authors&apos; Fig. 5). It is usual to evaluate dispersion hardening on the basis of yield strength rather than ultimate tensile strength, and accordingly we have replotted the authors&apos; Fig. 1 to include yield strength. The yield strength data do not justify a discontinuity of 3 p at either 70" or 1000 OF. Can the authors substantiate their conclusion 1) with additional evidence? Otherwise it seems that they have succeeded only in pointing out the possibility of a linear relationship between yield strength (or Uts) and the logarithm of the nleall free path, comparable with that demonstrated for iron-carbon alloys (Authors&apos; Ref. 2). Work in our own laboratories has shown that the hardness of the phase Ti,Cu is 235 Vpn, and that of a 1.5 pct (at.) (2 pct wt) supersaturated solid solution of copper in titanium is 190 Vpn. This small difference in hardness would suggest that Ti2Cu should not be a very effective dispersion-hardening phase. D. N. Williams, R. W. Wood, H. R Ogden, RI. L Jaffee (authors&apos; reply)— This discussion brings out some interesting points with respect to the interpretation of our results, and also raises some questions regarding the experimental technique. We shall consider the latter questions first. Contamination during heat treatment was prevented by performing all heat treatments in argon-filled Vycor capsules. Fabrication was done in air, with the usually observed scaling. Scale was removed

Jan 1, 1962

By R. C. Gifkins

R. C. Gifkins (CSIRO)—In this paper evidence is put forward to support the idea of grain boundary shearing in aluminum at 4.2°K and the phenomenon is explained in terms of a low-temperature "equicohesive temperature". It is stated that these findings show that grain boundary shear cannot be ruled out in any situation by temperature arguments alone. We believe, from our own recent study of "apparent grain boundary sliding&apos;&apos; at temperatures below 0.45 Tm, that it can be ruled out on temperature arguments alone.45 Our experiments were made principally with magnesium and a Ms-A1 alloy ("Magnox A12"). Careful examination of offsets of marker lines or steps at grain boundaries produced by deformation at room temperature (-0.3 Tm) showed many of these to result from curvature over narrow zones along the grain boundaries. A significant residuum did, however, appear as a sharp offset or step. It was found that the mean value of this step rose to a small value during the first 0.5 to 1 pct strain and then remained at this level with further strain. Moreover, exactly the same values were obtained (at the same stress) at 75°C instead of 21°C. That is, in this range of temperature the "apparent sliding" was not temperature-sensitive. At 125°C and above there was sliding which increased with strain and which was temperature-dependent. When this temperature-dependent sliding was used to calculate the sliding to be expected at room temperature, this underestimated the "apparent sliding" by a factor of 104. The conclusion drawn is that the "apparent sliding" consists of shear localized in a zone of a width measured perhaps in microns, whereas it seems that true sliding occurs on the boundary surface.46 A model for such localized shear has been developed in general terms, following a similar model of Urie and Wain.47 Other strong evidence for low-temper- ature sliding has been based on the offsets of marker lines consisting of a substructure seen using the electron microscope to resolve these.48 We have repeated this work and found that the effects can be accounted for in terms of cracks in an oxide film which is produced when the substructure is etched up; these cracks form over zones of shear rather than at actual interfaces. However, in aluminum at room temperature (-0.3 Tm) there is no "apparent sliding" which is optically detectable. We suggest that, when the temperature is much lower (and possibly the rate of strain higher, too), as in the experiments of Chin et al., then aluminum behaves like magnesium at room temperature, and a narrow zone of shear develops to accommodate differences in strain across the grain boundary. Such a zone could well give rise to triple-point cracks. It is hoped to investigate these suggestions further. B. Y. Chin, W. F. Hosford, Jr., and W. A. Backofen (authors&apos; reply)—It is interesting to have Dr. Gif-kin&apos;s comments, although it is somewhat difficult to reply in detail without the reference containing the work that he describes. Apparently though, he does find a low-temperature temperature-independent sliding that would seem to be related to the observations reported here. Perhaps some of the difficulty has semantic origins, growing out of the distinction between (&apos;true sliding" and "apparent sliding".

Jan 1, 1965

By Robin O. Williams

Robin 0. Williams (Oak Ridge National Laboratory)— The authors have questioned the degree to which the coherency strains between the iron-rich and chromium-rich phases are isotropic as proposed in Ref. 5 on the basis of the difference between the elastic properties of the two phases. The relative magnitude of the stresses is determined by the moduli as shown by Eqs. [2], [3], and [4] of Ref. 34. However, the moduli of the two phases have no direct bearing on the uniformity of either the stress or strain within either phase. The idea that the strains are isotropic within each phase (but normally of different magnitude and always of different sign) is based entirely upon the experimental observation that X-ray line broadening has not been detected even when the particles become rather large. It has not proven possible to grow the particles sufficiently large that they lose coherency. Based upon this lack of line broadening one can estimate an upper limit for the nonuniformity of the strains within each phase as follows. It is considered possible to detect line broadening if it is as great as 10 pct of the separation of the K, doublet for the (211) line using chromium radiation. The doublet separation would correspond to a total strain of 0.0017 such that the total variation of lattice parameter relative to the average lattice is now k0.05x0.0017 or something less than ± * For the present case the strain in each phase is roughly 0.002 such that the variation of strain within a phase will not exceed 5 pct. It is stated that the expression derived for strengthening for the hydrostatic straining as observed in this system would substantially overestimate the magnitude due to dislocation flexure. This is contrary to the conclusion reached in the original paper34 for the present range of particle sizes. What is the lowest temperature at which a has been observed to form in this alloy? M. J. Marcinkowski, R. M. Fisher, and A. Szirmae (nutlzors&apos; reply)— -Williams&apos; arguments based on X-ray findings for a chromium-rich precipitate and an iron-rich matrix strained to a common lattice parameter are certainly convincing. This being the case, there are no shear components of strain associated with the precipitate-matrix aggregate to interact with the shear components of the dislocation stress fields, contrary to the opinion expressed by the present authors. On the other hand, the present authors, in spite of this error, did not expect the shear interactions to be significant. The chief objection to Williams&apos; model in the present case is that the various segments of the dislocation line are assumed to pass from one potential valley to the next independently of neighboring segments. This is only true for a highly flexible dislocation line, i.e., one whose radius of curvature is something less than the center to center distance between precipitate particles which amounts to about 90A in the present alloy. In order to maintain this curvature, an externally applied shear stress of at least 230,000 lb per sq in. would be required or about four times the observed stress. It is therefore concluded that the dislocation lines move rather rigidly through the lattice. This being the case, the forces on the dislocation resulting from the hydrostatic interaction between the stress fields of the edge-dislocation components and the precipitate particles should average out to zero; that is particles above the below the slip plane produce forces on the dislocation of opposite sign and therefore will cancel when averaged over the entire length of the dislocation. On the other hand, since the dislocation is not perfectly rigid, Williams&apos; model may lead to some strengthening, but far less than that predicted. A second and equally serious objective to using Williams&apos; strengthening model for the present alloys is that profuse wavy slip due to the motion of screw dislocations played a predominant role not only in the unaged alloys but in the fully aged ones as well. Since the screw dislocation has associated with it only shear components of stress the hydrostatic strengthening model no longer applies. In view of these arguments the present authors must reject Williams&apos; model of strengthening as being pertinent to the present alloy system. The present authors have made no detailed study of the lowest temperature at which a forms in the quenched ferritic alloys. None was ever observed n the alloys aged at 500°C so that forma-tion must occur at temperatures higher than this and was therefore not a factor in the present study.

Jan 1, 1965

By I. R. Kramer

I. R. Kramer (Martin Co.)—In a recent paper Nakada and Chalmers24 reported some observations of effects of surface conditions on the stress-strain curves of aluminum and gold single crystals. It is of interest to compare these observations with the results published previously in this journal and to comment on their general conclusions. In brief, Nakada and Chalmers concluded that the removal of the surface layer of a prestrained specimen lowered the stress-strain curve for aluminum but not that for gold. Further, they concluded that the surface work hardening of aluminum is confined to a depth not more than l0-3 cm. In our results25 published previously, it was pointed out that when prestrained specimens of aluminum and gold were polished to reduce the thickness upon reloading the initial flow stress decreased markedly. Further if a sufficient amount of metal was removed, the yield point failed to appear. With continued application of the load the stress-strain curve became coincident with that of the virgin crystal. We have found this behavior in some 100 determinations to hold consistently for gold, aluminum, and copper in both single and poly-crystalline specimens. The amount of strain required before the curves coincided depends upon the amount of metal removed but it is usually less than 0.01. This type of behavior is the same as that reported for metarecovery by other investigators.29 For aluminum specimens which have been prestrained and then heated to temperatures above 50°C we have consistently found that the stress-strain curve was typical of the orthorecovery28 type. In this case the stress-strain curve always lies below that of the virgin specimen. With respect to Ref. 24 the curves for aluminum are always below that of the virgin curves, while those for gold become coincident. This observation indicates at least for aluminum that the specimens must have been heated to a temperature high enough to cause recovery by an alteration of the internal dislocations. In addition, a recovery would be expected because of the removal of the surface work-hardened layer. Nakada27 had reported that, with his particular apparatus in which a perchloric acid polishing solution was used, the temperature of the specimen increased 65°C. The curves presented in Ref. 24 for gold do not permit one to detect the initial flow stress upon reloading after the surface-removal treatment. In fact, contrary to the method used by Nakada and Chalmers, the change in the stress-strain curve produced by a surface-removal treatment cannot be described in terms of a decrease in stress at strains much higher than that at the initial flow stress because of the coincidence of the curves at the higher strain values. With regard to the depth of the work-hardened surface layer, our data show for aluminum single crystals (7.5 by 0.3 by 0.3 cm) that the initial flow stress remained constant after 12 x 10-3 cm had been removed from the thickness. This depth was independent of the prior strain. For gold crystals this depth is somewhere between 10 x 10-3 and 20 x 10-3 cm. Y. Nakada (author&apos;s reply)— Kramer states,28 "for aluminum specimens which have been prestrained and then heated to temperatures above 50°C, we have consistently found that the stress-strain curve was typical of the orthorecovery28 type. In this case the stress-strain curve always lies below that of the virgin specimen." However, Cherian et a1.26 discovered that aluminum polycrystals annealed at 32" and 100°C showed the metarecovery behavior. They showed that the orthorecovery behavior did not appear until the crystals were annealed at 150°C. Kramer suggests28 that the drop in the flow stress of aluminum crystals after the surface removal by electropolishing24 may be due to the recovery caused by the temperature rise which may occur during the electropolishing.27 However, as indirectly stated in Ref. 24, the current density used in these electro -polishing experiments was 0.15 amp per sq cm. According to ref. 27, this current density should cause a temperature rise of only 40°C. This may cause the metarecovery but not the orthorecovery. Furthermore, as stated explicitly in Ref. 24, the surface removal was accomplished by chemical etching as well as by electropolishing. The results were the same for both electropolishing and etching. During the etching, the specimen temperature did not rise above 35°C. Some aluminum crystals were placed in water at 35° C for 30 min. These crystals did not show the decrease in flow stress. Therefore, it is quite clear that the flow-stress drop after the surface removal is not caused by a high-temperature recovery. However, as Kramer points out,28 it is quite possible that the internal dislocation structure may have been altered because of the removal of the highly work-hardened surface layer. However, how much this rearrangement contributes toward the flow-stress decrease is not known at present.

Jan 1, 1965

By Frederick Forscher

Frederick Forscher (Nuclear Materials and Equipment Gorp.)—It is gratifying to see another series of experimental results that essentially reconfirms our reported observations of "Strain-Induced Hydrogen Embrittlement in Zirconium" (F. Forscher: AIME Trans., 1956, vol. 206, p. 536, noted as Ref. 3 of paper). However, several important considerations may have been overlooked, or—at least—have not been specifically pointed out. It is the purpose of this discussion to present some of these considerations. The statement is made that "the equilibrium concentration of hydrogen in solution at 20°C in zirconium is approximately 10 ppm; i.e., no zirconium hydride precipitates are formed at or below this hydrogen content." This is perhaps the case in the unstressed condition. In the presence of triaxial (plastic) strain however, even as little as 1.4 ppm H2 (Forscher&apos;s Figs. 6 and 11) will cause porosity near fracture in 20°C tests. The necked-down region that develops during a tensile test provides the triaxiality necessary for these pores to open. Both Beevers&apos; and Forscher&apos;s micrographs show that porosity is concentrated in the necked region. So-called "pure zirconium" containing about 10 ppm H2 also shows pronounced porosity near fracture (Beevers&apos; Fig. 3). Since it is generally agreed that such porosity is

Jan 1, 1965

By W. A. Rachinger, C. Graeme-Barber, R. L. Bell, R. C. Gifkins, T. G. Langdon

R. L. Bell. C. Graeme-Barber, and T. G. Langdon (Imperial College. London)— The internal-marker technique developed by Ishida, Mullendore, and Grant has enabled them to make some interesting observations on the role of grain boundary sliding in creep. Certain of their conclusions are supported by our own similar experiments on Magnox AL80 (Mg-0.8 pct Al) specimens containing several markers, full details of which will be published shortly. In particular, we would agree that: 1) Using the internal-marker method, there is little difference between Egb, the contribution made by grain boundary sliding to the total strain, measured at the surface and in the interior of a specimen. 2) The measurement of the change in grain shape during creep leads to an underestimation of the grain strain, and hence an overestimate of Egb.. However, the discrepancies between the values obtained by this method and those obtained using markers are not as great as Tables IV and V of Ishida, Mullendore, and Grant would suggest; see below. The authors&apos; Eq. [I] which is used to compute Egb from the transverse displacement ITt of longitudinal marker lines is not given in the reference quoted,&apos;&apos; where in fact only relations for Egb in terms of the longitudinal displacements of markers were developed. As first pointed out by Gifkins and Gittins,12 a problem arises in the use of longitudinal markers. and we will show that Eq. [1] underestimates Egb in the interior by a factor of 2. In Fig. 12, two grains X and Y have become displaced by the vector AC which lies in the plane of the grain boundary ABCD separating them. A longitudinal marker has been split by this displacement into the two parts LA and CAW. If these were surface grains the transverse displacement, Ut. could be obtained by viewing normal to the "top" surface. If interior, a section through CD parallel to the top surface would show the same result, provided the longitudinal internal markers delineated planes normal to the top surface. (This is an essential feature of the markers not pointed out in the paper.) The important point is that the quantity Ut tan B (=BE=DF) only gives the elongation due to the one component AB of the sliding. The elongation V/tan 8 (=GD) due to the component AD must be added to produce the total elongation resulting from the boundary displacement AC. If the grain boundaries in a poly crystalline specimen are randomly oriented with respect to the stress axis it follows that In the interior of a specimen the two sums depend for any difference simply on the definitions "top&apos;&apos; and "side". On the surface it is possible that the two sums could differ somewhat. In either event it is clear that the authors&apos; Eq. [I] underestimates Egb, and in the interior, and perhaps at the surface also, the appropriate formula is given by The suggested modification probably makes little difference to the comparison between surface and interior values of Egb where both were obtained from marker measurements. For the estimation of the correction becomes extremely important where the boundary contribution is large. In our own work on magnox, for example, we have obtained values of as large as 70 to 80 pct, under conditions of high temperature and low strain rate. The use of planar markers transverse to the stress axis would simplify the comparison between surface and interior behavior, because measurement of the longitudinal offsets Us of these markers could be summed to give the total elongation di-

Jan 1, 1965

By J. Richter, D. Schulze

J. Richter and D. Schulze (Deutschen Akademie der Wissenschafte zu Berlin)—Introduction. In a recent paper R. G. Garlick and H. B. Probst reported on experimental results of investigations of room-temperature slip in zone-melted tungsten single crystals.17 In the paper it was pointed out that slip lines could be detected with an optical microscope only after about 10 pet plastic strain of the crystal. In our investigations we could observe slip lines in tungsten single crystals of defined orientations already with an elongation of 0.02 to 0.03 pet.18"9 Experimental Technique and Results. The tungsten single crystals were produced from 4 to 5 mm sintered rods* as starting material by electron- beam zone melting. With single-zone-pass melting a speed of 0.5 mm per min was used, while three-pass melting could be handled at a speed of 3 mm per min. Crystal axis orientations were located in the shaded area of the stereographic triangle, see Fig. 6. Orientation 1 is located at about 18 deg and orientation 2 at about 5 deg on the great circle from [011] to [ill]. This corresponds approximately to the orientations P and M referred to by Garlick and Probst. Our single crystals had a length of about 70 mm and were profiled solely by electrolytic means, leaving grip ends at both ends of the crystals. Between the latter, a cylindrical crystal of 45 to 50 mm length and about 2.4 mm diam was obtained. The crystals were deformed at room temperature in a commercial tensile-testing machine to obtain a strain of 0.02 to 5 pet. The average strain rate e = eP/t for all tensile tests amounted to approximately 10 -6 to 10-5 per sec, with ep representing plastic strain and t the duration of applied stress. In Fig. 7 a crystal is shown elongated by 0.03 pet. The picture was obtained by means of an optical microscope. Figs. 8 and 9 give electron-microscopic pictures of slip lines of crystals elongated by 0.07 and 1.1 pet, respectively. For crystals with the orientation 1, see Fig. 6, only the two main slip systems (101)[111] and (110)[111] were found. With the crystals of group 2 the two main slip systems are again evident, with

Jan 1, 1965

By M. van Swaay, C. E. Birchenall

A. S. lBrling (Johnson, Matthey & Co. Ltd., Laboratories)— Because of its initial emphasis upon the production of membranes by powder metallurgy and by normal casting and rolling techniques, this paper is of considerable interest to those concerned with the design and application of industrial diffusion units. As the subsequent performances of the three grades of palladium were not compared in detail, it can perhaps be concluded that specific permeabilities were very similar. A short table in which the absolute diffusion rates obtained by the Authors with their three grades of palladium were compared with those of other investigators18-25 would, however, have been of particular value in view of the very variable results obtained with this membrane material. The Authors state early in the paper that the permeability of the thoriated samples decreased in much the same way as that of the nonthoriated samples. Later, they emphasize that sintered palladium without thoria was very susceptible to poisoning and did not respond as well as the other materials to the decontamination treatment. These results, which suggest that sintered membranes are less effective than those produced by normal methods, have considerable industrial implications, and amplified experimental details would be very welcome. The results of the Authors differ in one important respect from those of other investigators. Thus, no "bleeding" was required to maintain a constant rate of diffusion, although Davis, Darling, and De Rosset found this to be necessary. Davisz3 found that "bleeding" was necessary even when the hydrogen had already been purified by diffusion through a palladium tube, and it would be of value to know the purity of the gas stream emerging from the purification train shown on Fig. 1 of the Authors&apos; paper. The Authors show that diffusion rates varied according to the square root of the pressure difference providing that the palladium membrane was not contaminated in any way. This finding is in agreement with the results of those workers2,18,19,23,24 who diffused their hydrogen through the membrane into a partly or completely evacuated system.Those workers who did not find this square-root law dependence did not have a partial vacuum on the downstream-side of the membrane.&apos;&apos; The difference between the two experimental con- ditions appears to be significant, as the absolute diffusion rates per sq cm of diffusion area are lower when the square-root law dependence is not observed. While the effect could be attributable to poisoning of the membrane it is conceivable that a positive pressure on the downstream side of the membrane might influence the mechanism of diffusion. In view of the capricious behavior of palladium, factors of this type, which are likely to influence its industrial significance, should be carefully considered. M. van Swaay and C. E. Birchenall (authors&apos; 9-eply) — Our Eq. 191 may be compared with several others for hydrogen diffusion in palladium: D = 5.95 x exp (-5770/1)&apos; D = 3.55 x 10"3 exp (-5550/)&apos; D = 4.3 x 10"3 exp (-5620/1&apos;)&apos; Other values are given in the literature, but in many cases surface poisoning may have affected the results. No analysis was performed on the hydrogen gas stream after purification. It should be noted that the presence of liquid nitrogen traps near the heated membranes may have set up convection currents and provided the equivalent of "bleeding." The question of whether a partial vacuum existed on the downstream side of the membrane is not clear. Does it imply that there is something unique about the permeability measured near one atmosphere pressure? We do not believe that there is. When square root pressure dependence is not observed, diffusion rates are not measured. Is "absolute diffusion rate per sq. cm. of diffusion area" equivalent to permeability? The terminology is new to us. In any case we doubt very much that pressures of the order of several atmospheres can affect the mechanism of diffusion.

Jan 1, 1962