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By Robert E. Green

Experiments were performed in order to investigate the influence of magnitude of driving force, recouery, and previous heat treatment on grain boundary migration in deformed aluminum crystals. The frequency of occurrence of strain-free grains possessing Preferred crystallographic orientations was studied both as a function of heat treatment and as a function of amount of deformation of the matrix crystal. Aluminum of such composition as to exhibit precipitation-hardening behavior was used. CONSIDERABLE work has been devoted to the factors influencing grain boundary migration in metals.1'52 Aust and Rutterl-9 have studied grain boundary migration into matrix crystals containing a striation substructure, which provided a thermally stable driving force during the course of the migration experiments. These authors state that, while variations in the striation pattern were sometimes observed, it was possible to obtain reasonably uniform and reproducible striation structure by careful control of the solidification conditions. Admittedly, this source of driving force is a unique one and has served well in numerous experiments. However, although the striation substructure provides a thermally stable driving force, the subject of its reproducibility from crystal to crystal is questionable. In fact, Aust and Rutter3 attribute the scatter shown in some of their experimental points and several anomalies in boundary migration rates to variations in the substructure driving force along a single specimen. A further limitation on striation-induced driving force is that the driving force cannot be varied over wide ranges in a controlled manner. More often used as a source of driving force is the strain energy stored in a crystal during plastic deformation. This type of driving force has the disadvantage that it is not thermally stable due to recovery taking place simultaneously with the grain boundary mobility measurements. On the other hand, this strain-induced driving force is very reproducible from crystal to crystal since it is very easy to grow single crystals possessing the same purity and crystallographic orientation and then to strain them identically. In order to measure grain boundary migration rates two different methods are primarily used. Most often the technique employed is the heat-cool-etch method1' which involves thermal cycling, while the other technique, developed by Graham and Cahn11 using an X-ray diffractometer and goniometer furnace, involves continuous heating only. Thus the influence of thermal cycling vs continuous heating is a factor to be considered in grain boundary migration rate measurements, particularly in cases where the source of driving force is the strain energy stored in the deformed matrix, and recovery is likely to occur. Numerous recent investigations have shown that extremely small impurity additions to zone-refined metals exert a marked effect on grain boundary migration rates1-5, 9, 12-27 and a few have considered the effect of the distribution of impurities.28-35 The concentration of impurities and their distribution as influenced by heat treatment must also be taken into account in migration-rate studies. In the present article consideration is given to the influence of the magnitude of driving force, recovery, and previous heat treatment on grain boundary migration rates. In order to vary the driving force over a large range it was necessary to use as a source of driving force the energy stored in the matrix crystal during plastic deformation. A majority of the investigations were performed on aluminum specimens which were of such compositions as to exhibit precipitation-hardening behavior.

Jan 1, 1965

By M. J. Saarivirta, P. P. Taubenbla

This paper presents some high-temperature properties of copper-zirconium conductor alloy compared to copper-chromium alloy. Definite superiority of the copper -zirconium alloy over the copper-chromium alloy at high temperatures is shown. RECENT investigations have shown that cold-worked copper-zirconium alloy possesses good room-temperature strength, ductility, and conductivity and maintains most of its strength at temperatures up to 450°C (840°F). As a result, this alloy is now used for many applications, such as commutator segments, resistant welding wheels and tips, rectifier bases, electrical contacts, and so forth. Early investigations1-3 have shown that the maximum solid solubility of zirconium in copper is close to 0.15 pct and the alloy containing Cu-0.10-0.15 pct Zr exhibits the optimum mechanical and physical properties. Results2 have also shown that the alloy has better elevated temperature strength and ductility than copper-chromium and copper-silver alloys. The present investigation was undertaken to learn more about the elevated temperature properties of copper-zirconium alloy and to compare these properties with those of the copper-chromium alloy. WORK PROCEDURE The commercial copper-zirconium alloy, Amzirc was selected for this investigation. Because this alloy is composed of oxygen-free high-conductivity copper and 0.10-0.15 pct Zr, it was believed that possible disturbance from impurities would thus be negligible. Copper-chromium alloys used in this investigation contained 0.40 and 0.70 pct Cr and balance copper. The Cu-0.40 pct Cr alloy was a commercial brand, whereas the Cu-0.70 pct Cr alloy was made from OFHC copper and Cu-5 pct Cr master alloy. It was made in a graphite crucible under argon gas cover and cast. In the preparation of specimens, all three alloys were treated to give the optimum properties; thus the Cu-0.15 pct Zr alloy was solution annealed at different temperatures to determine the desirable solution annealing temperature. It was then cold worked and aged at 375" to 400°C (705" to 750" F). A solution annealing temperature of 1000°C (1830°F) was selected for the copper-chromium alloys because this temperature is widely used in commercial practice. The same alloy was aged at 450°C (840°F) after solution annealing and cold working. It was found that the maximum precipitation hardening of the copper-chromium alloy occurred at this temperature. When aged after solution annealing, the aging temperature was 500°C (930"F) for both alloys. The following properties were determined: 1) Tensile properties as a function of temperature. 2) Effect of solution annealing temperature on high-temperature tensile properties. 3) Stress to rupture strength at 350° and 400°C (660"to750°F). 4) Impact strength. 5) Electrical conductivity and resistivity as function of temperature. 6) Thermal expansion.

Jan 1, 1961

By Margaret V. Doyle, R. W. Powers

INTERNAL friction measurements, carried out as functions of temperature, have been used extensively to obtain data on the mobility of interstitial impurities in the Group V metals, vanadium, colum-bium, and tantalum. For a given frequency of vibration, the internal friction peaks at a temperature which depends principally on the particular metal and interstitial impurity. Relaxation times and corresponding activation energies are determined from a knowledge of such peak temperatures for various vibration frequencies. These experimentally determined relaxation times are related to the average jump frequencies of the interstitial impurity atoms using the model of Snoek1 and can be related to macroscopic diffusion coefficients as shown by Polder.2 In these Group V elements, the impurity whose diffusion rate has been the hardest to pin down by the internal friction technique has been carbon. The experimental difficulties associated with carbon in these metals were not evident in the earliest investigation carried out by Ke on tantalum.3 The carbon peak was thought to occur near 140°C at 1 cps on the basis of the enhancement of the height of this peak measured on specimens which had been coated with colloidal carbon and heated in vacuo at 1200°C. Presumably on the basis of similar evidence, Wert identified a peak also near 140°C at 1 cps in columbium with the diffusion of carbon in that element." Later, the difficulties of admitting carbon into these metals without simultaneously introducing oxygen were pointed out by Ang and Wert- nd by Marx, Baker, and Sivertsen.6 The latter suggested that the peaks attributed to carbon in tantalum and columbium might arise from the presence of traces of oxygen, adventitiously absorbed during the carburization. Such suspicion was confirmed, at least in tantalum, when it was found possible to prepare C-Ta specimens without contamination by oxygen. Specimens sci prepared, aitnough high in carbon content, gave no evidence of a damping peak near 140°C.7 Recently, the authors were able to Show that carbon diffuses in tantalum at a rate only slightly slower than that for nitrogen.8 At 1 cps, the carbon peak lies at 34g °C, only a few degrees above the nitrogen peak at 341 °C. However, the two could be distinguished by a different stability with respect to aging at 400 °C and by a different dependence of peak height on solute concentration. On the basis of this experience with tantalum, it appeared worthwhile to search also for a carbon peak in columbium in the vicinity of the nitrogen peak." In this report, the location of the carbon peak in columbium is made known and its position relative to the nitrogen peak is compared with the authors' previous findings in tantalum. In addition, a second source of internal friction seen only in specimens of very high purity is discussed. Columbium was obtained from the Fansteel Metallurgical Corp. as either 30 or 40 mil diam stock. The manufacturer gives the following analysis as typical of this material: 99.4 pct minimum Cb, 0.10 pct maximum C, 0.5 pct Ta, 0.04 pct Ti, 0.02 pct maximum Si, and 0.01 pct maximum Fe. Wires 13 in. long were degassed near 2200°C for 4 to 16 hr in an ultimate vacuum better than 2.10" mm Hg in an apparatus described previously.8 This treatment reduced the oxygen and nitrogen damping peaks observed in the as-received material to less than 0.0001 in Q-1 above background. The latter value varied somewhat from specimen to specimen in the range 0.0004 to 0.0008, depending chiefly on the wire diameter and the frequency of vibration. The high temperature evacuation left the specimen in a rather soft condition, the Vhn being reduced to 40 from a value near 121 in the as-received conGi~iur~. The gram size was about the diameter of the specimen. After outgassing, specimens were loaded with carbon by absorption of such hydracarbons as methane or ethylene. Carbon was also added to a few speclrnens by heating them at

Jan 1, 1958

By G. Meyrick, H. W. Paxton

Observations on the tensile deformation of single crystals of austenitic stainless steels as a function of composition, orientation, and temperature are described and compared with relevant data for other alloys. Crystals free from second phases show sharp yield points followed by Lüders' extensions of up to 20 pct. The critical resolved shear stress is strongly temperature-dependent increasing fourfold between 423O and 77°K. A temperature-independent low rate of hardening follows the Luders' extension and is frequently associated with overshoot. Unlike pure metals where Proficse cross slip usually occurs at the end of linear hardening, this stage is terminated either by cross slip or by slip on the conjugate system, the particular node apparently depending upon initial orientation and composition. The presence of 6 ferrite or martensite has a profound effect upon the magnitude of the yield stress and the shape of the stress-strain curve. In experiments on transgranular-stress corrosion cracking of austenitic stainless steels in boiling magnesium chloride, several workers1'2 have shown that increasing amounts of nickel tend to reduce the probability of specimen failure. Reed and paxton3 have observed in single crystals that the macroscopic crack plane changes as the nickel content is increased. For 18 pct Cr-8 pct Ni, the crack plane is sensibly perpendicular to the applied tensile stress; for 20 pct Cr-20 pct Ni the crack plane is (100). The average crack-propagation speed is much lower in the 20 pct Ni crystals. Furthermore, the possible importance of stack-ing-fault energy in nucleation and growth of cracks has been suggested by a number of workers. While the general effect of variations in stack ing-fault energy appears to be quite well-correlated with observed variations in cracking characteristics, each of the theories assigns rather different detailed reasons for these effects. Because the stack ing-fault energy of austenitic steels is believed to be increased with increasing nickel content, and because some theories of trans-granular cracking postulate a mechanical stage in the crack propagation (rather than relying entirely on electrochemical solution), it appeared to be of some interest to investigate the mechanical properties of a series of different compositions of aus-tenite single crystals. These experiments were considered of intrinsic value in view of the relative scarcity of such data on fcc alloys. This paper gives the results of some experiments carried out with this aim in mind, and suggests various 'other experiments which may be helpful in future studies. The experiments are also of interest in view of the recent interest in obtaining higher-strength steels by control of the imperfection content of austenite; although the compositions are not directly comparable, the results are still probably valuable. Comparisons with experiments on other fcc alloy crystals are made where possible to see how well the general pattern of behavior is understood. EXPERIMENTAL PROCEDURE The alloys used in this investigation were vacuum-melted heats of nominally 20 pet Cr-20 pet Ni-60 pet Fe, 20pctCr-16 pct Ni-64 pct Fe, and 20 pctCr-12 pet Ni-68 pet Fe.* Analyses of the material are

Jan 1, 1964

By Phillip A. Stoll, Young Ku Yoon

ThE deterioration of the magnetic properties of silicon-steel core materials during service (magnetic aging) is quite undesirable. Although some information about the effects of impurity elements on magnetic properties is available, 1,2 magnetic aging that occurs at low temperatures has not been extensively studied. Moreover, the microscopic techniques used by earlier workers were not suitable for study of fine metastable phases that are precipitated at relatively low temperatures. Recently, several investigators3,4 successfully used transmission electron microscopy in the study of low-temperature precipitation in Fe-C, Fe-N, and Fe-Mn-C alloys. To investigate metallurgical factors that affect magnetic properties after aging, the microstruc-tures of steels having different magnetic-aging

Jan 1, 1964

By L. F. Pease, J. H. Brophy

A phase diagram for the Ta-Zr system is presented. The system is of the minimum-melting point type with the 0-zirconium phase decomposing monotectoidally at 785°C and 95.5 at. pct Zr. The minimum solidus temperature is 1875°C and the temperature of the top of the monotectoid loop is 1775°C. Techniques employed included X-ray diffraction and fluorescmce, electron microprobe analyses, diffusion couples, metallography, and melting-point measurements. Errors due to interstitial solutes and in melting observations are particularly common in this system, and their occurrence is discussed. SEVERAL versions of the Ta-Zr phase diagram have been reported in the literature.lm7 Williams et al.' report a diagram of the minimum-melting point type with a monotectoid reaction at 800°C and 12 wt pct Ta. The minimum in the solidus occurs at 1820°C and 25 wt pct Ta, while the top of the monotectoid gap is located at 1780°C and 80 wt pct Ta. The experimental techniques employed were metallography, electrical resistance variation with temperature, dilatometry, X-ray diffraction, and direct observation of melting by the technique of Pirani and ~lterthum.' Experience in the Nb-Zr phase diagram has shown that small changes in the interstitial content can cause large shifts in the positions of the phase boundaries. Small amounts of inter -stitials can cause similar changes in the Ta-Zr system and may be responsible for the wide variations in the phase diagrams previously reported.'-' The authors15 have found that alloys containing 0.75 wt pct 0 and 1.0 wt pct Ni with tantalum contents from 19 to 85 at. pct often contain a lamellar or cellular precipitate after annealing above 1400°C. This precipitate is very similar to that reported by pollack,12 Ralls," and Donlevy17 for the Ni-Zr system. In the present investigation, a wider variety of experimental techniques and improved alloy purity were applied to the resolution of errors in diagrams for this system as they now appear in the literature. New results have been obtained in the areas of alloy homogeneity and purity. Errors in the common techniques of direct melting observation in binary alloys have been demonstrated. In the commercially important high-tantalum region, the more accurate metallographic method of solidus determination has been employed. EXPERIMENTAL PROCEDURE Nominal analyses of the materials employed are given in Table I. The zirconium was low hafnium reactor grade iodide crystal bar, and the tantalum was in the form of high-purity sheet. Powders were impossible to use because of gas content. Alloys were melted on a water-cooled copper hearth, with a thoriated tungsten-tipped nonconsumable electrode in 2/3 atm of Zr "gettered" argon. Alloys were

Jan 1, 1963

By D. T. Peters, J. C. Bisseliches, J. W. Spretnak

The pain boundary relaxation phenomenon in high-purity copper, 0FHC copper, and a precipitation-hardenable alloy o-fCu-2 uit pct Co has been studied by internal ,friction and elastic aftereffect techniques. The data were analyzed by assuming the broad distribution of relaxation times observed obeys a lognormal distribution law which enables calculation of the relaxation strength. Grain size had no effect on relaxation strength, although the peak width increased with increasing grain size and decreasing temperature. A double grain boundary peak was produced in high-purity copper by annealing to produce secondary recrystallization. The activation energy measured for 99.999 pct Cu is 37.5 * 3 kcal per mol and 46.5 kcal per mole for OFHC copper. A small peak in the Cu-Co alloy at about 220°C at 1 cps was deduced to be the grain boundary peak. Its height increased and its activation energy decreased with increasing aging time. Except for erratic peak positions the observations were consistent with the theory of pain boundary sliding. BEFORE the mechanism of the grain boundary internal friction peak in metals can be satisfactorily explained, the detailed characteristics of the relaxation process must be documented. Of interest are the effect of grain size on relaxation strength, the high-temperature background, and peak width and position. The effect on the grain boundary peak of a precipitate at grain boundaries and of the change in distribution of the particles with aging time must also be explained by any existing or forthcoming theory. The model which has received the most attention was proposed by KG' and zener2 and proposes that the anelastic strain results from sliding of adjacent crystals at grain boundaries. The sliding is limited by the interlocking of grain corners. It follows, according to this model, that the relaxation strength is independent of and the relaxation time is proportional to the grain size. The proportionality between grain size, D, and relaxation time, t, has been confirmed by K&' and Bisseliches . In this case, the internal-friction peaks of various specimens can be superimposed by plotting Q-' as a function of the parameter vD exp H/RT where v is the frequency and H the activation energy. However, the data of Starr et 01.' and Leak6 fit better to a parameter containing D to an exponent near two. A meaningful relationship is not always deducible from the shift of peak temperature with grain size. KG7 demonstrated that a twofold variation in grain size obtained by varying the amount of cold work followed by identical recrystallization anneals will cause a peak shift that is too large to be accounted for even by an exponent of two. Since the decreased grain boundary area existing with a larger grain size is exactly compensated for by an increased sliding distance, the relaxation strength should not decrease with increasing grain size. The height of the internal-friction peak has generally been observed to be rather insensitive to grain size as long as the average grain diameter does not approach the specimen diameter. Exceptions have been reported by Koster, Bangert, and Lang8 for copper, and by Leak6 for iron. The observations for copper could well have been confused by the presence df 0.3 pct0. The possibility that the peaks may simply be increasing in width with increasing grain size and that the relaxation strength, which is proportional to the area under the peak, may remain constant was not examined. his point has been checked in this investigation using high-purity copper. Atomic mechanisms to account for damping by sliding at grain boundaries have been proposed by KG7 and Mott. KG predicts the activation energy to be identical to that for self-diffusion. Mott's "island" model suggests the activation energy is nL where n is the number of atoms in an island and L is the latent heat of fusion per atom. Other authors have felt that a value equal to the activa-

Jan 1, 1964

By J. T. Norton, N. J. Grant, I. S., Servi

Coarse grained high purity aluminum was tested in creep at temperatures of 400° to 1200°F to develop subgrain structures. Measurements of subgrain size, distribution, and rotation were made from X-ray diffraction patterns. Subgrain size and distribution were checked metallographically and the size was compared with average slip band spacing. The slip family was determined for several specimens. THE interest and research recently evident abroad in the role of subgrain formation and polygon-ization as a contribution to the creep of metals at elevated temperatures is deserving of greater attention in this country. Such metallic subgrains can be defined as macroblocks existing within the grains. The general observation has been that the macro-blocks which belong to the same grain have a maximum difference in orientation of a few degrees. In spite of the considerable amount of work that has been done since Jenkins and Mellorl observed the "division of existing crystals into smaller units when deformation occurs at an annealing temperature," the subject of subgrain formation is only now receiving truly active discussion and investigation. The existence of subgrains has been revealed by metallographic methods, as in the work of Jenkins and Mellor,1 and by X-ray methods, first applied to this problem by Homes.' Hirst3 and Calnan and Burns4 applied the back-reflection Laue technique to the study of coarse grained specimens. Wood et al.5 and Greenough and Smith' examined the ring obtained with a back-reflection camera for the study of fine grained specimens. In addition to the above, the transmission technique was used by Wood.6 A special technique was developed by Guinier and Tennevin8 in order to improve the resolution. Metallographically, the subgrains have been observed directly on the surface of deformed specimens by Wood et al.,3 or have been made evident on repolished surfaces by applying a suitable etching reagent. The latter technique, first suggested by Lacombe and Beaujard,9 was then improved by Wyon and Crussard.10 Subgrains can be formed in single crystals after small amounts of bending followed by heating after this cold work, or during deformation at elevated temperatures. The first phenomenon was analyzed by Cahn11 for the simple case of pure bending followed by annealing. Cahn suggested a mechanism of subgrain formation based on the dislocation theory and called this phenomenon "polygonization." He extended this mechanism to the more complex case of local bending, such as the bending which may occur when a polycrystalline specimen is deformed in tension. Cahn's suggestion was later found quite consistent with the results obtained by Dunn and Daniels." An explanation has been presented recently regarding the formation of subgrains during deformation at elevated temperatures by Chang and Grant.'" In general, there are two schools of thought on the subject. One, according to Wood et al.,5 is that subgrain formation is a mechanism of deformation which is operative under certain conditions in the same way that the slip process is the mechanism of deformation which is operative under other conditions. The boundaries between the subgrains undergo a viscous flow which contributes substantially to the deformation of the material. The second, according to Cahn,13 Wyon and Crussard,10 and Chang and Grant,18 is that subgrain formation is the effect of simultaneous deformation and annealing and is,

Jan 1, 1953

By D. H. Baldwin, R. E. Reed-Hill

DURING the course of experiments involving oxygen equilibrations with a high-purity Pd-5 at. pct Rh alloy, the appearance of a subscale was noted. Most of the heat treatments in a pure oxygen atmosphere were performed at 900°C. The presence of the subscale was noted when the oxygen partial pressure was in excess of approximately 95 mm, up to 1 atm, the highest pressure used. According to available thermodynamic information' on the free energy of formation of Rh2O3 (the only reliably reported solid oxide of rhodium), this oxide should not be stable under these conditions, nor, of course, any oxide of palladium. Extraction of the subscale from the matrix was affected by treatment with aqua regia, and the resulting X-ray diffraction powder pattern is shown in Table I. This pattern is not that of Rh2O3, nor that of any known rhodium or palladium oxide. It can be indexed on a hexagonal lattice with a. = 5.22Å and co = 6.0Å. In addition to this unknown material, there was a weak Rh2O3 pattern. An X-ray fluorescence analysis of the powder gave 3214 palladium counts per sec and 5381 rhodium counts per sec, thus indicating the likelihood of a double oxide of palladium and rhodium. In view of the fact that the above result was obtained on a single sample, it is perhaps best not to insist upon the above ratio of about 0.6, but possibly to tentatively assume 0.5 or 1/1. The small amount of Rh2O3 in the X-ray pattern might have occurred on cooling, and it seems possible that the double oxide, below some temperature level, is not as stable as Rh2O3. To examine this point, some of the extracted double oxide was heated on a sheet of pure palladium in air at 900°C, and allowed to furnace-cool over a period of several hours. The X-ray diffraction pattern of the powder showed approximately the same intensity of Rh2O3 and the "hexagonal" oxide as before, but, in addition, a rather faint pattern of another crystalline species made its appearance. This finding again suggests partial transformation of the major (double) oxide to other oxides on cooling from 900°C. Application of the phase rule shows that only one equilibrium oxide (subscale) could have been present at temperature. Vacuum-fusion, oxygen analysis of the extracted subscale showed 7.7 ± 0.7 pct O. Combining this information with that of the X-ray fluorescence analysis suggests the formula PdRhO. This compound should have an oxygen content of 7.07 pct, which is within the range of error of the oxygen analysis. However, until a more careful stoichiometric study is made, it is suggested that the formula be written

Jan 1, 1965

By C. H. Samans, G. F. Tisinai

HARDENING and embrittlement of the ferritic chromium stainless steels at temperatures near 885 °F have been known for a long time.' However, no satisfactory explanation has been given. Both ordering and precipitation hardening have been suggested. Fisher, Dulis, and Carroll2 discovered a chromium-rich body-centered-cubic precipitate in embrittled alloys. Subsequently, Williams' and Wright4 also have found evidence of this body-centered-cubic constituent. William's hardness, electrical resistance, and magnetic studies led to his proposal of a new constitutional diagram for the Fe-Cr alloys. The new feature of this diagram is the eutec-toidal decomposition, below about 970°F, of the s phase into two stable body-centered-cubic solid solutions, one rich in iron and the other rich in chromium. An observation of Heger5 that the amount of s phase has increased and the amount of chromium-rich body-centered-cubic phase decreased in the interval 5000 to 32,600 hr at 900°F, even though the alloy increased in hardness, casts some doubt on this diagram. If precipitation hardening causes the embrittlement, the precipitate probably is always coherent with the matrix, since no evidence of overaging has been reported. It cannot be stated positively, however, that Fisher's body-centered-cubic constituent is the embrittling phase. According to Preston's data,6 such a chromium-rich phase should have a parameter less than about 0.5 pct larger than that of the iron-rich matrix lattice. Moreover, the constitutional relationships whereby Fisher's constituent forms, and whether it is stable, metastable, or a transition phase, are not yet completely clear. The recent studies of Wright4 and of Lommel,7 as well as the earlier studies of Becket8 and of Hochmann,9 have shown that 885°F hardening occurs in relatively pure Fe-Cr alloys. No evidence of its occurrence or absence in chromium itself has been reported. The rate of hardening in high purity alloys seems appreciably slower than that in alloys containing larger amounts of impurities (chiefly carbon and nitrogen). This may be due merely to the absence of hardening and straining effects from precipitated carbides and/or nitrides. These observations on high purity alloys make it seem unlikely that 885 °F hardening is caused by a constituent containing other than iron and chromium atoms, e.g., carbides and/or nitrides. Wright,4 Lommel,7 and Lena and Hawkes10 emonstrated the accelerating effects of a finely dispersed precipitate of (probably) chromium nitride on the hardening reaction. This appears to be evidence that lattice straining increases the rate of nucleation of the hardening constituent. Some new observations on 885°F hardening are reported here. They show an effect of preheat treatment that should contribute to a better understanding of the 885°F hardening phenomenon. They also clarify a discrepancy which exists in the literature. Some investigators have reported most rapid hardening at 885", whereas others have reported it at 930°F. The present work also shows that 885°F hardening does not occur in electrolytic chromium, and that any long range ordering type of reaction affecting any sizeable part of the volume is unlikely. Materials Studied Table I shows the currlposition of the alloys used in this investigation. In these alloys carbon and nitrogen are present in roughly similar amounts. Presumably both elements precipitate, as carbides and/or nitrides, during the heat treatments given.

Jan 1, 1958

By O. D. Sherby, J. E. Dorn

For elevated temperature-constant load creep tests of a solid solution alloys, the creep strain is a function of a temperature-compensated time parameter 0 = je H/RT dt. The activation energy H is equal to o constant of about 36,000 cal per mol. The substructures resulting from a given creep stress condition are functions of the creep strain independent of temperature. Each new creep stress gives a new unique set of grain substructures; this is one of the factors responsible for the failure of the mechanical equation of state for creep. IN this report an attempt is made to correlate the creep properties of dilute a: solid solutions in aluminum with the subgrain structures that are developed during creep. The possibilities of such correlations have already been suggested by Wood et al. and others1-" who demonstrated that the subgrain structures are functions of the creep stress, creep strain, rate of creep, and temperature. Investigations by Sherby and Dorn' have shown that the creep strain, E, at constant load for dilute a solid solutions of aluminum is given by the functional relationship: e = f(8,u,) [1] where: 0 equals te-AH/RT = temperature-compensated time; t, time; AH, activation energy, - 35,800 cal per mol; R, gas constant; T, absolute temperature, above 400°K; and u,, initial creep stress. Consequently, it was anticipated that the subgrain structure that develops during a constant load creep test should also correlate with any two of the three significant variables C, 8, and Another possible correlation between the subgrain structure and the creep variables is obtained by differentiating Eq. 1 with respect to time, whence the creep rate, 2, becomes: = (2L) (2) =f (, u,) e-AHRT [2] or: e = F (c e H/RT, 0) [3] For the minimum creep rate, ;,, 8 is solely a function of U, as revealed by Eq. 1. Consequently, at the minimum creep rate Eq. 3 reduces to: = F (eAH/RT) [41 Correlations between U, and i, eAH/RT were found valid for solid solution alloys of aluminum where AH was a constant of about 35,800 cal per mol. The parameter ;, eH/RT is identical to the Zener-Hollo-mon parameter8," used by them in evaluating the tensile properties of copper and other metals. Eq. 4 suggests that the subgrain structure developed during secondary creep might be correlatable with either of the two variables 2, e H/RT or u,. Some of the solid solution aluminum alloys which were discussed in an earlier report' were also used in the present investigation. Sheets of these alloys were homogenized, cold rolled from 0.100 to 0.070 in. in thickness and then recrystallized to about the same grain size. Their chemical composition and grain size are recorded in Table I. Creep specimens were selected with their tensile axes in the rolling direction. The details for creep testing have been described10 and will not be repeated here. All creep tests were performed under constant load conditions. Experimental Results and Discussion Metallographic Structure of Creep Specimens: In order to obtain a preliminary concept of creep on the metallographic structure of high purity aluminum, the various ruptured specimens previously used to obtain the creep data for pure aluminum were polished and etched electrolytically in a dilute solution of fluoroboric acid. Oblique illumination was used to reveal the substructures which, for convenience, are shown in correlation with the vs. ;, eH/RT curve in Fig. 1. It is necessary to emphasize that the data for the curve refer to the various secondary stages of creep whereas the micrographs refer to the fractured creep specimens. Nevertheless a regular and systematic correlation is observed between E, eAH/RT (or the creep stress) and the micro-structure at fracture. For In (e, eAH/RT) = 42.3, which refers to creep at a high creep rate and a low creep temperature, the fractured aluminum specimen, as shown by the micrograph in the upper right-hand corner of Fig. 1, exhibited extensive deforma-

Jan 1, 1954

By B. Fazan, O. D. Sherby, J. E. Dorn

McLean's technique was employed to determine the effect of temperature on the contribution of grain boundary shearing to the total creep strain in pure aluminum over the range of 610° to 747°K. The contribution of grain boundary shearing at the same stress was found to depend upon a temperature-compensated time, where the activation energy AH was practically identical with that for total high temperature creep. SEVERAL outstanding investigations by McLeanl-' have demonstrated that the total creep strain in polycrystalline aluminum at 473°K arises from microscopically detectable slip, subgrain tilting, and grain boundary shearing. Whereas microscopically detectable slip arises from dislocations that move out of the grains, subgrain tilting is due to entrapment of dislocations of like sign in subgrain bound-arles. Consequently, creep in polycrystalline aggregates appears to be the resultant of two mechanisms, namely, migration of dislocations and grain boundary shearing. This suggests that an appropriate law for creep should contain two additive terms ?1 = ?d + ?yb where the total creep strain, ?1, depends on the sums of the creep strains arising from motion of dislocations, ?d, and from grain boundary shearing, ?yb. But extensive investigations5 over wide ranges of alloys, grain sizes, temperatures, and stresses have shown that the total creep strain is quite accurately dependent on the single term functional relationship ?1 = f (?), s = constant where s is the stress (constant),* ? = te-?H/RT, t is the time under stress, AH is the activation energy, R is gas constant, and T is absolute temperature. Since Eq. 2 was found to be valid over those ranges where appreciable grain boundary shearing is observed, it appears probable that the activation energy for grain boundary shearing might be identical with the activation energy for migration of dislocations. Thus, under a given stress, it could be thought that where fd and fgb represent the appropriate functions for each mechanism of creep. The primary objective of this investigation was to obtain a direct check on the accuracy of this hypothesis. Experimental Procedure and Results Rolled aluminum sheet (99.987 pct Al), 0.100 in. thick, was used in this investigation. Creep specimens having a 0.25 in. wide, 3 in. long gage section were so machined that their axes were in the rolling direction. All specimens were annealed for 9 hr at 894°K before testing to produce a mean grain diameter of about 0.1 in. One face of each specimen was polished electrolytically in 10 pct HBF4. In order to permit accurate measurements of grain boundary shearing, the polished surface was lightly scribed with a ruling machine accurate to ±0.0001 in. to give a uniform grid of lines which were 0.01 in. apart. Although it was thought that surface working might modify the creep behavior in the vicinity of the scribed grid lines, this technique nonetheless was employed because such local differences in creep properties should not modify seriously the fractions of the total creep strain due to grain boundary shearing or to migration of dislocations. All creep tests were conducted under constant load with an initial stress of 250 psi. The specimen tem-

Jan 1, 1955

By Laurence Pellier

Electron microscopical studies were made of the effect of sensitization at 1200oF on a Type-.104 stainless steel with high carbon and low nitrogen and oxygen contents, after solution annealing and after cold working. The loci of the carbide precipitates in the early stages of sensitization were followed in dry stripped plastic replicas. Some observations were made by direct electron transmission on thinned films. Intragranular dislocations showed a high degree of stability through the annealing necessary to produce sensitization. I HE present work was undertaken to determine the effect of sensitization, at 1200°F, for 1/2 hr, on the electron microstructure of a Type-304 stainless steel with high carbon, and low nitrogen and oxygen contents, after solution annealing and after cold working. Many electron microscopical studies of sensitization of 18-8 stainless steels have already been made. Most of them utilized extraction replicas, from which the morphology and composition of the precipitated carbides could be established.'-" ry stripped replicas were seldom used for such studies, although it was demonstrated that they are applicable, in general, to EurveYs of the general microstructure of many alloys' and, in particular, to the observation of precipitated carbides in austenitic stainless steels.3

Jan 1, 1963

By T. E. Davidson, C. G. Homan

This report deals with a study of the effects of extreme hydrostatic pressure on a polycrystalline material which exhibits a high degree of elastic anisotropy. Metallographically prepared polycrystalline bismuth samples were subjected to pressure levels up to 20,000 atm in a piston type gas-liquid system. The observed structural changes consisted of deformation localized along the grain boundaries, which appears to be a boundary migration phenomena, and widespread slip and cross slip. Subsequent deformation is progressive with increased pressure, and is substantially different in type from the deformation characteristic of uniaxial compression. A large amount of interest has been shown in recent years in the effects of extreme pressure on metals. In this connection, many investigations into the effects of pressure on physical and mechanical properties and reactions have been undertaken. Due primarily to the experimental difficulties involved, there has not been a great deal of study of the structural changes resulting from exposure of metals to extreme pressure. It has been difficult, for instance, to produce a true hydrostatic stress state in many of the extreme pressure devices used, and also to directly examine specimens metallographically before and after pressurization. The results of a preliminary investigation into one of the effects of extreme pressure, and its associated true hydrostatic stress state, on the structure of metals are discussed herein. Metals exhibit varied degrees of anisotropy in their physical and mechanical properties. Significant among the anisotropic properties is the modulus of elasticity, which varies by a factor of as much as three in some of the fcc metals, and by much larger factors in some of the less symmetrical elements. As a result of the variation of the modulus of elasticity with crystallographic direction, shear stresses will be induced in polycrystalline samples under true hydrostatic compression. Depending on several factors, these shear stresses could become of suffi- cient magnitude to cause localized plastic deformation. Presented herein are some of the structural changes observed in polycrystalline bismuth as a result of exposure to hydrostatic pressures of up to 20,000 atm. Although several other materials in both bicrystal and polycrystalline form are also currently under investigation, bismuth was chosen initially, due to its low symmetry and moderately high degree of anisotropy in the elastic properties. The fact that extreme hydrostatic pressure can induce structural changes in some elements in the polycrystalline state is of importance in itself. However, it may also be a factor in many of the other extreme pressure effects. For instance, this localized plastic deformation could substantially lower the recrystallization temperature, thus altering the effects of extreme pressure on this phenomenon. Also, as commented on by ridgman,' the hysteresis in the polymorphic transition of polycrystalline bismuth under extreme pressures could possibly be attributed to structural changes brought about by unequal compressibility. Therefore, to accurately determine the true effects of extreme pressure on metallic substances, one first must determine if any structural changes due to hydrostatic compression are also simultaneously occurring. The purpose of this work has been to determine whether the shear stresses induced by hydrostatic pressure in an anisotropic polycrystalline material, such as bismuth, could reach a magnitude great enough to cause plastic deformation and to study the resultant structural changes and effects. THEORY In a metallic crystal, the elastic properties are dependent upon the crystallographic direction and plane. Depending upon the degree of anisotropy of the elastic properties and other factors, internal shear stresses of sufficient magnitude to cause localized plastic deformation may be induced in polycrystalline material by true hydrostatic compression. The following highly simplified two-dimensional model of two adjacent grains in a polycrystalline aggregate under hydrostatic pressure serves to schematically demonstrate how these shear stresses arise in an anisotropic material.

Jan 1, 1963

By H. H. Podgurski, Hsun Hu

Large cryslals of high-purily iron (99.996+ pcl) cannot be obtained by the usual strain-ameal technique. Repealed phase transformation by thermal cycling prior to crilical deformation improves the capabilily of cryslal growith but fails to yield satisfactory crystals. Imperfect columnar crystals can be produced by the phase-transition method. The addition of a small amounl (0.005 wl pet) of nilrogen IT was reported'-4 that for metals of very high purity the usual procedures of the strain-anneal technique fail to produce large crystals. This was eliminates practically all the difficulties in crystal growth by the normal strain-anneal procedures. An actual example is presented, showing that most parts of a strip have been converted into a large crystal by this method. The addition of nitrogen, which can be removed from iron with less difficulty, is believed to be more desirable than carbon additions for the same purpose. thought to be due to the strong tendency for recovery in the high-purity metals: hence the critically strained matrix undergoes polygonization instead of recrystallization upon annealing for crystal growth. Talbot1,2 succeeded in overcoming this difficulty by adding 0.03 to 0.04 pct C to high-purity iron before critical deformation. followed by annealing in hydro-

Jan 1, 1965

By E. Gregory, A. Coucoulas

Carbm dioxide, which exists metastably as a constantly subliming molecular solid in a normal room-temperature environment, has been shown to exhibit many microstructural features which are similar to those observed in metals and ceramics at temperatures approaching their melting points. An examinution has been made of some of the factors affecting a brittleness condition known as "smzdiness" which occurs in solid carbon dioxide. It has been shown to be highly dependent on manufacturing and storage conditions and is thought to be a marked intergranu-lay brittleness which results from a combination of excessive grain growth and a concentration of gas-filled pores at the grain boundaries. In the course of an investigation carried out to explain certain physical and mechanical properties of solid carbon dioxide, observations were made of the microstructure and fragmentation of samples after fabrication and storage under varying conditions. Many similarities between the structures of solid carbon dioxide observed under ambient conditions and those existing in metal and ceramic systems at temperatures approaching their melting points have been observed. There are, however, important differences between solid carbon dioxide and the common metallic and ionic solids which result primarily from the differences in the nature of the bonding forces. Despite these differences, the relative ease with which certain microscopic observations can be carried out, may make solid carbon dioxide a useful material model for the physical metallurgist and the ceramist. It could also prove a valuable material for educational purposes where it is required to illustrate grain phenomena which normally can only be seen with the aid of a high-temperature microscope, and after prolonged chemical or thermal etching.

Jan 1, 1963

By G. T. Horne, P. J. Wray, S. Kinoshita

CONSIDERABLE evidence exists for a strengthening mechanism operative at intermediate temperatures in bee metals containing interstitial solute atoms. The strengthening is indicated by a maximum in the ultimate tensile strength1 as well as the fatigue

Jan 1, 1965

By H. Sigurdson, T. V. Cherian, C. H. Moore

The phenomenon of recovery of cold-worked metals is interesting not only because of its practical importance but also because of its fundamental significance in solid state reactions. Although extensive investigations1,2 have already been made in an attempt to discover the mechanics of the recovery process, many of the observations have not yet been satisfactorily correlated to provide a completely consistent model for the process. The wide differences in the recovery rates of various properties can be cited as a typical example of one of the difficulties that are encountered. Frequently, for example, the electrical resistance will have almost completely recovered before any recovery in tensile strength can be detected. Of course, such differences in the recovery rates of different properties might be explained by assuming that each property is a unique function of the work-hardened state, and consequently each property exhibits its own unique recovery rate. The assumption that different properties are uniquely related to the work-hardened state cannot be denied. On the other hand, the properties that recover at different rates often exhibit more or less parallel changes upon work-hardening. This suggests that the microstructural changes attending recovery are not exactly the reverse of the changes attending work-hardening. Several types of imperfections must be postulated in order to account for this apparent anomaly. The different recovery rates for various properties, then, are due to the different recovery rales of the type of imperfection to which each property is most sensitive as well as the unique dependence of each property on the cold- worked state. This concept assumes that a simple model of the work-hardened state consisting only of one type of imperfection, such as Taylor's type of dislocation patterns, is inadequate to cope with the diversified phenomena attending work-hardening and recovery. Although current models for the work-hardened state are not useful for describing all aspects of the recovery process, the general trends of the recovery of each postulated type of imperfection as a function of time and temperature should be at least qualitatively deducible from the rather well developed laws of kinetics of reactions in the solid state. Consequently, recovery data might prove useful for elucidating some aspects of the complexities of the work-hardened state of metals. A preliminary attempt to study work-hardening by investigating recovery rates of cold-worked metals is outlined in the following pages of this report. Experimental Procedure Many properties recover when cold-worked metals are annealed below their recrystallization temperature. Therefore, electrical resistivity, thermal electromotive force, X ray diffraction line widths, X ray diffraction line intensities, elastic spring back, density and other physical and chemical properties have been used to study the recovery process. Major interest, however, has generally been directed toward the recovery of the mechanical properties such as hardness, yield strength, and tensile strength. But a search of the literature suggests that the effect of recovery on the true stress-true strain curve has been neglected, in spite of the current recognition of the fundamental importance of such an investigation. An investigation on the effect of recovery treatment on the true stress-true strain curves in tension, therefore, was undertaken in the present study. Commercially pure aluminum (99. + pet Al) in the form of 0.100 in. thick rolled sheet of 2S-O aluminum alloy was selected as the material for this investigation because rather extensive correlatable data are already available on the recovery of some of its properties. Tensile specimens having a 6 in. long gauge section and a uniform reduced section width of 0.500 in. were machined from the sheet in accordance with a design that has previously been reported.3 All specimens were selected with their axes aligned in the rolling direction. In order to eliminate the effects of previous work-hardening and the effects of machining, the specimens were annealed for 15 min. at 750°F before testing. During tensile testing the loads were measured by means of a proving ring (sensitive to 1/2 lb) in series with the specimen.4 Strains were determined from the extension of a rack and pinion strain gauge sensitive to a strain of + 0.0001. The stress was recorded as the true stress, namely

Jan 1, 1950

By Nicholas J. Grant, H. C. Chang

TRANSCRYSTALLINE fracture surfaces of the cleavage type have been examined by microscopy and X-rays for several metals.' These investigations revealed that the fractured surfaces were not flat and invariably had cleavage and other deformation markings on them. On the other hand, the study of inter crystalline fracture surfaces has been limited. Perryman, in a recently published paper on the inter crystalline fracture of ß-brasses,' found that a thin layer of heavily deformed metal was invariably associated with these surfaces. Furthermore, the thickness of this layer was found to depend on the orientation of the grain boundary surface with respect to the applied stress. The mechanisms of grain boundary sliding and intercrystalline fracture have been presented in two previous papers,which described certain aspects of the deformation of a 20 pct Zn-A1 alloy. It is the purpose of this paper to present some observations on the structure of intercrystalline fracture surfaces and to correlate the structure of such surfaces with the mechanism of intercrystalline fracture. Experimental Techniques—The high purity 20 pct Zn-Al alloy was generously supplied by the Research Laboratories of the Aluminum Co. of America. Two sizes of specimen were used; the first had two parallel flat surfaces of dimensions 1x0.17x0.09 in. and the second was round with a 0.25 in. diam. A grain diameter of 1 to 3 mm was obtained by annealing the specimens at 1000°F for 24 hr. The specimens were then air cooled. The specimens were subjected to creep at 500°F and 2300 psi. The rupture times ranged from % to 3 hr, with one room temperature tensile test. It has been mentioned previous1y" that the intercrystalline fracture surfaces of this alloy, when tested under the conditions given above, are sharply defined. In the optical examination of the fracture surfaces, whenever possible, magnifications of at least X250 were used. The locations of the regions examined, both optically and by X-rays, were selected to give several fracture surface orientations with respect to the stress axis and to the specimen surfaces. This was possible for the X-ray studies since the grain diameters were large compared to the X-ray beam. A film to specimen distance of 3 cm, a 1 mm pinhole and Cr radiation were used for the Laue back reflection pictures.

Jan 1, 1957

By G. R. Wilms

A study has been made of the structural changes in polycrystalline high purity aluminum during the tertiary stage of creep under conditions of constant tensile load. It appears that there is no basic modification in the particular mechanism of deformation that characterized the preceding secondary stage of creep, but that the changes in crystalline structure produced during the tertiary stage are only a consequence and not a cause of the accelerated strain. Intercrystalline fissures were observed on entry into the tertiary stage, and these might supplement the accelerated rate of strain owing to local stress concentrations. There is evidence that the formation of these fissures may be associated with the presence of surface imperfections, and it is suggested that a more generalized treatment of the results may explain certain creep characteristics of commercial alloys. IN previous work'-4 a study was made of the changes produced when specimens of annealed aluminum were deformed at various temperatures and rates of strain, especially under conditions leading to creep under constant tensile load. It was shown that, as the temperature was increased or as the rate of strain was decreased, elements of the substructure produced within the grains became coarser, and with the strain rate constant at a given temperature, their size tended to an equilibrium value. The preliminary process of the breaking down of the grains into a substructure was identified with primary creep.' The subsequent equilibrium, condition was associated with secondary creep. The question then arose whether the tertiary stage corresponded to any further significant change in the substructure. The question is also of interest in view of the opinion, expressed for instance by Andrade,5 that the tertiary stage is merely an accelerated rate of strain due to the reduced area of section of a specimen under continuous tensile load, and the other opinion, as suggested by the observation by Sully, Cale, and Willoughby6 of a tertiary stage in com-pressive loading, that this third stage is a real effect in its own right. The object of this paper is to record some observations on the tertiary stage of high purity aluminum. Experimental Procedure The material was aluminum of 99.98 pct purity as previously used. The specimens had a rectangular section of l/8 x l/2 in., and extensions were measured over a 1 in. gage length. After machining to shape, the specimens were annealed to give a standard grain size of 0.2 mm and then electropolished. The general procedure involved metallographic and X-ray diffraction examination at progressive stages of elongation (marked by arrows on the curves shown in Figs. 1 and 2), the specimen being extended to fracture under constant load at a given temperature. The X-ray tests were made by the back-reflection method from a stationary specimen, using CoK radiation. The longer edge of the micrographs in the paper corresponds to the direction of applied stress. Results The previous work showed that, in the secondary stage of creep in aluminum, three basic types of structure could be developed according to the temperature and rate of strain. These were: 1—slip, which predominated at the lower temperatures and higher rates of strain and produced the finest and least perfect substructure; 2—cell structure, which superseded slip as the temperature was raised and the rate of strain decreased and which was characterized by a coarser and more perfect structure and an absence of slip lines; and 3—a stage termed "boundary microflow," which predominated at still higher temperatures and lower rates of strain when the cell size had increased and become comparable

Jan 1, 1955