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By G. T. Higgins

PREVIOUS workers1,2 have found evidence of exaggerated grain growth or secondary recrystallization on annealing sponge zirconium at temperatures high in the a, phase field, but no details of the orientation relationship between the secondary grains and "as-recrystallized" matrix were reported. In other hexagonal metals, namely dilute Mg-A13 and Cd-zn4 alloys, secondary recrystallization has been observed in which the secondary grains are related to the primary recrystallized structure by rotations about the c axis. These rotations are thus comparable with the rotations about the (111) axis observed in the secondary recrystallization of fcc metals. In the current work secondary recrystallization has been observed on annealing iodide zirconium at 800°C and the associated changes in crystallographic texture have been examined. The material employed was arc-melted iodide zirconium of the following composition: Impurity O H Fe Hf Pb I Ni C1 A1 ppm by wt 130 5 230 98 23 28 200 39 30 This was received as 0.25-in. plate, and, prior to the annealing studies, was cold-rolled to 0.040 in. Specimens 1 in. sq were chemically polished and annealed for various times at 800°C in a vacuum better than 5x 10-6 Torr. For metallographic examination specimens were first chemically polished and then anodized8 to enhance contrast between the grains when examined under polarized light. Changes in crystallographic orientation associated with the development of secondary grains were followed by (1011) and (0002) pole-figure determinations using a conventional Schulz goniometer in reflection. Filtered Cr Ka radiation was employed and great care was taken to avoid spurious re- sults due to the close proximity of the Bragg angles for the (1011) and (0002) reflections. Figs. 1 and 2 illustrate the change in grain structure on annealing at 800°C. After 24 hr the structure has ceased to be equiaxed due to the development of certain grains in preference to others. It is notable that the secondary grains do not grow to the extent observed in sponge zirconium.1,2 This appears to be due in part to the fact that normal grain growth is inhibited in the less pure sponge zirconium, with the result that the driving force for secondary recrystallization remains high, while at the same time the number of grains able to develop in the presence of the impurities is also smaller. As a consequence, in sponge zirconium those grains that do develop preferentially are able to grow into the fine -grained matrix without impingement, while in iodide zirconium the preferential growth of many grains leads to early impingement. The pole figures determined for specimens annealed for 5 min and 24 hr at 800°C are illustrated respectively in Figs. 3 and 4. These indicate that the dominant feature of the initial recrystallized texture consists of basal planes at an angle of 321/2 deg to the sheet surface, with a (1120) axis lying parallel to the

Jan 1, 1967

By Mark J. Klein

The behavior of nitrogen in Cr-0.12 at. pct Y was studied in specimens of varying interstitial concentration and thermal history. It was found that soluble nitrogen can be introduced into this alloy by increasing the concentrations of either oxygen or nitrogen. For low nitrogen concentrations the nitrogen in solution is low relative to that in unalloyed chromium. However, the nitrogen in solution increases with increasing nitrogen concentration, approaching that in unalloyed chromium. When the alloy is supersaturated with nitrogen, the nitrogen precipitates readily from solution as a chromium nitride. The stress -induced relaxation of nitrogen is influenced by internal oxidation or internal nitrification of this alloy. THE addition of small concentrations of reactive elements such as yttrium have been found to enhance the low-temperature ductility of chromium.&apos; However, the mechanism by which the ductility is increased is not known. It has been suggested that this effect is caused by a drastic reduction in the concentration of nitrogen retained in solution and therefore a decrease in the number of dislocations locked by nitrogen, a factor that has been associated with an increase in ductility.1,2 However, a change in the type of interstitial precipitate induced by yttrium could also contribute to enhanced ductility of the alloy, since chromium nitride precipitates appear to be embrittling.&apos; In this regard, it has been shown that yttrium scavenges nitrogen in chromium to form YN,4 thus reducing the embrittling chromium nitride phase. However, the change in nitrogen solubility induced by yttrium and the partition of nitrogen between chromium and yttrium nitrides are not known. The object of this investigation is to study the effect of yttrium on the behavior of nitrogen in chromium to obtain information relevant to the mechanism by which scavengers enhance the ductility of chromium. EXPERIMENTAL PROCEDURES The experimental procedures used in this investigation have been described in detail elsewhere.5,6 Wires of Cr-0.12 at. pct Y, 15 cm in length and 1 mm in diam, were drawn from rods 0.6 cm in diam supplied by the General Electric Co. The grain size of the wires after recrystallization at 1150°C was somewhat nonuniform, varying from 0.006 to 0.06 mm in diam. The interstitial analysis for the wires in ppm by weight was about 160 0, 80 N, 12 C, and <2 H. Heat treatments were carried out after encapsulation of the specimens in quartz tubes containing argon. Changes in interstitial concentrations, or interstitial "loading" as it is termed in this study, were generally accomplished by annealing in oxygen, ammonia or methane at 1150°C. The internal friction was measured using a conventional torsional pendulum enclosed in an evacuated chamber. Electrical-resistivity measurements were made at liquid-nitrogen temperature.

Jan 1, 1967

By M. S. Rashid, C. J. Altstetter

Allotropic transformations in cerium have been studied by dilatometric, resistometric, X-ray diffraction, and metallographic techniques. The dilatometric study indicated that, on cooling below O°C, the high-temperature fcc phase, y, transforms partly to the hexagonal phase, ß, and, on further cooling, to the collapsed fcc phase, a. The amount of $ phase present at room temperature is increased by repeated cycling through the a-y transformation. It has been shown metallograPhically that the y-ß transformation has many characteristics of a martensitic transformation. In contrast to the y-ß transformation the ?-a transformation does not give the manifestation of a shear transformation. Small cellular ? domains of random shape and size collapse to a in a short time with no apparent coordination with neighboring domains. The considerable confusion in the literature over the existence of more than one high-temperature fcc phase is discussed. Two such phases have been reported in the literature and an attempt is made in this study to clarify the situation. Twelve fcc and two hcp structures have been shown to be easily reproduced or eliminated. It is proposed that the two "additional" allotropes reported in the literature and fourteen of the phases detected here are not allotropes of cerium but are due to contamination. CERIUM exists in several allotropic forms, but there is some disagreement over what the forms are. Furthermore, the conditions favoring the presence of a particular allotrope and the nature of the transformations from one form to another are uncertain. The objectives of this research were 1) to ascertain the allotropic forms of cerium, 2) to establish the conditions under which the allotropes exist, 3) to study the effects of annealing and thermal cycling on the allotropic transformations, and 4) to study the transformation mechanisms. Dilatometric, resistometric, metallographic, and X-ray diffraction techniques were employed. The form of cerium commonly found at room temperature is fcc and is designated ?. A complex hexagonal phase, 8, forms when y is cooled to slightly below room temperature. At still lower temperatures the y fcc structure transforms to an fcc form with a much smaller lattice parameter, termed a cerium. A bcc form, 6, which exists just below the melting point (800°C), will not be considered further in this work. There is a substantial body of experimental evidence (reviewed by Gschneidnerl) which favors the acceptance of these four allotropes, though some investigators have tried unsuccessfully to observe the ß hexagonal form.&apos;-&apos; There is disagreement, however, over the phase-transformation temperatures, due, in part, to broad hysteresis and overlapping of the transformations between the a, ß, and ? forms. The transformations are also sensitive to prior thermal and mechanical treatment. The differing purity of cerium used by different investigators is undoubtedly a factor. Cerium is difficult to separate from other elements and is quite reactive, igniting spontaneously when it is filed in air. The highest purity of cerium to date is reported to contain several hundred parts per million by weight of impurities, and early investigations were carried out on cerium containing several percent of impurities. There have been reports of more than one fcc allotrope at room temperature. Gschneidner, Elliott, and McDonald5 obtained diffraction patterns of an fcc phase with a lattice parameter about 1 pct less than that of the ? phase, instead of the y phase, on slowly cooling cerium filings from 23° to -198°C and warming them back to room temperature. However, when the sample was heated to 447°C and cooled to room temperature it consisted of only the ? phase. They have designated this new fcc phase "a-? intermediate", and say it is quite sensitive to impurities. After prolonged high-temperature treatment of a powder specimen, Weiner and Raynor2 obtained a diffraction pattern of an fcc phase of lattice parameter about 1 pct less than the ? phase. This they called the y&apos; phase. It could not be reconverted to the y phase and is claimed to be different from the a-? intermediate phase.5,6 Dialer and Rothe3 reported two fcc phases* after cycling their powder specimens between room temperature and -192°C. Gschneidner, Elliott, and McDonald5 suggested that one of the fcc structures obtained by Dialer and Rothe was equivalent to their "a-? intermediate" phase. Table I presents some pertinent data on the proposed allotropes. For the ?(fcc)-ß(hexagonal) transformation

Jan 1, 1967

By W. O. Philbrook, R. H. Spitzer, F. S. Manning

A generalized mathematical model has been developed to describe the kinetics of the gaseous, topo-chemical reduction of porous hematite spheres. Gas-solid reduction is permitted at each of three advancing interfaces and is controlled by a complex series-parallel sequence of chemical and transport steps. Despite the fact that transport resistances are significant to the advance of each interface, little deviation from linear advance is predicted for the first 98 pct of reduction. Calculations to predict the movement of magnetite /wustite interface by a solid-state diffusion mechanism have been incorporated into the earlier dense-pellet model.&apos; The porous-pellet model is found to give a better description than the dense-pellet one for McKewan&apos;s measurements2 of interface movements in dense polycrystalline hematite reduced in hydrogen-water vapor mixtures. THIS paper reports a continuation of work"3" directed toward the better understanding of gas-solid reactions and the development of mathematical models that may be helpful in the design or control of ore-reduction processes. Laboratory studies of the reduction of single oxide samples in tube furnaces normally employ an abundant excess of pure reducing gas. Reduction may appear to be adequately described by a model assuming gas-solid reaction solely at the iron/wustite interface.&apos;&apos;&apos; However, when iron ore is reduced in either a fixed bed or an efficiently operated counter-current column, there are portions of the bed where the partially spent gas is no longer capable of reducing wustite to iron. Nevertheless, the formation of the intermediate reaction products, wustite or magnetite, can and does continue. In order to account for this aspect of the reduction of beds of particles, three semiempirical mathematical models were devised.&apos; One of these was for the limiting case of completely dense particles, and two alternatives were provided for porous particles. For purposes of the analysis, a dense pellet was defined as one in which the wustite and magnetite layers were impervious to the reducing gas when the atmosphere was capable of forming iron. In a porous pellet, the intermediate product layers were assumed to be sufficiently permeable to allow reducing gas to penetrate beyond the iron/wustite interface to form wustite and magnetite by removal of oxygen as a gaseous product rather than by a solid-state redfiction mechanism. Further progress required a better understanding of the reaction of the individual particles with the gas stream. A comprehensive mathematical treatment was developed&apos; to describe the continually changing interplay of transport and reaction steps

Jan 1, 1967

By J. W. Spretnak, J. N. Cordea

The gain boundary relaxation in high-purity aluminum, nickel, copper, and silver was studied by means of a low-frequency torsion pendulum. Both internal friction and creep at constant stress tests were conducted. A lognormal distribution in relaxation times was found to account for the relatively wide experimental internal friction peaks and the gradual relaxation behavior during the creep tests. This distribution was separated further into a lognormal distribution of relaxation time constants and a normal distribution in activation energies. A spread of up to ±6 kcal per mole in the activation energies accounted for the major part of the distribution. A "double-peak" internal friction phenomenon was observed in silver. The activation energies in kcal per mole derived from the grain boundary relaxation phenomena are 34.5 for aluminum, 73.5 for nickel, 31.5 for copper, and 41.5 for silver. It was found that the rain boundary relaxation strength in these metals increases with the reported stacking-fault energy. GRAIN boundary relaxation phenomena have been observed in a large number of polycrystalline metals and alloys. Numerous investigations have been conducted to study the structure of the grain boundary through this relaxation process. One of the first investigators was Ke1-4 who observed that the activation energy for grain boundary relaxation in aluminum, a brass, and a iron was about the same as that for volume diffusion. He concluded that the grain boundary behaved as if it were a thin liquid layer with neighboring grains sliding over one another. Leak5 conducted experiments on iron of a higher purity and observed that the grain boundary activation energy is comparable with that of grain boundary diffusion. He suggested that, in metals where this relationship holds, the damping may be caused by a reversible migration of grain boundaries into adjoining grains. Nowick6 has presented an interesting view of inter-facial relaxation with his "sphere of relaxation" model. A relaxed interface is represented as one where the shear stress is greater than the normal value along the edges and zero in the interior of the interface. The region of the stress relaxation is pictured as a sphere surrounding the interface. From his calculations Nowick concluded that the slip along an interface is directly proportional to its length. Therefore, the time of relaxation, T, depends on the size of the relaxation interface. This means that in the Arrhenius relationship, t = TO exp[H/RT], valid for atom movements, the relaxation time T is predicted to be proportional to the grain diameter through the pre-exponential term, TO. Since the internal friction can be given as Q-1 = ?j wt/(1 + w2r2), where ?J is the relaxation strength and w is the angular frequency, an increase in grain size at a constant frequency will shift the peak to a higher temperature. A great deal of work has been done to determine the exact relationship between the internal friction and grain size.1,5,7,8 In metals, the grain boundary peaks are found to be lower and broader than predicted theoretically.&apos; The above model can explain this by a distribution in the size of the interface areas, represented by a distribution in the parameter tO, and an overlap of spheres of relaxation, represented by a distribution in activation energies. Both these phenomena result in an over-all distribution in the relaxation time, which could affect the internal friction peak height, breadth, and also position. This relationship between the experimental data and theoretical calculations appears very promising in the study of interfacial relaxation mechanisms. THEORY A lognormal distribution in t can sometimes be used to adequately describe the spectrum of relaxation times governing an anelastic relaxation. wiechert9 originally suggested such a distribution to explain the elastic after-effect in solids. This choice is particularly applicable to grain boundary relaxation when considering Saltykov&apos;s work.&apos;&apos; He found a lognormal distribution in the grain sizes within a metal. Recently Nowick and Berry11 have introduced a log-normal distribution in T into the theoretical internal friction equations. The form of the distribution function is where z = In(r/rm), and Tm is the mean value of t. The parameter ß is a measure of the distribution and is the half-width of the distribution when is l/e of its maximum, IC/(O). Nowick and Berry have described the methods to obtain the parameters Tm, ß, and ?,J from experimental internal friction and creep test data. In the idealized case, where only one relaxation event occurs with one relaxation time, only ?J and T are necessary to completely describe the event, and 0 = 0. For the broader internal friction curves 6 is some positive number greater than zero. The larger the 6, the greater is the half-width of the distribution in In t.

Jan 1, 1967

By M. L. Rudee, R. A. Huggins

Samples of iron containing nitrogen or carbon have been given treatments similar to those used in cold-work peak (CWP) measurements and examined by transmission electron microscopy. It was observed that the unusual and nonreproducible behavior of the carbon CWP can be explained by a strong tendency for carbon to form grain boundary precipitates at temperatures below those used for CWP measurements. These precipitates dissolved at the temperatures used in the CWP measurements. There was no evidence for nitrogen precipitation at grain boundaries. There was no indication of precipitation along dislocations in either carburized or nitrided samples given treatments similar to those of CWP measurements. Although it is possible that subelectron-microscopic clustering had occurred, this observation supports the theories of the CWP that are based on continuous atmospheres rather than on individual precipitates. In an earlier paper,&apos; the present authors developed a new distribution function to predict the occupation of sites for interstitial impurity atoms around a dislocation. When this distribution was applied to the case of carbon and nitrogen in iron, it predicted that, if the temperature dependence of the concentration of solute atoms in the matrix was controlled by the presence of equilibrium carbide or nitride precipitates, the tendency for nitrogen to segregate to dislocations would be greater than that for carbon even though their binding energies to dislocations are identical. The cold-work internal-friction peak (CWP) is considered by most authors to be produced by the interaction of interstitial impurities with dislocations. Many investigators have studied the CWP in iron containing carbon and nitrogen and have observed a significant difference between its behavior in the two cases. In this paper a series of experiments will be reported that were initiated to determine whether the application of the new distribution function would explain the observed differences between the carbon and nitrogen CWP. Although it was found that the distribution function, pev se, did not explain the differences, the differences became clear, and some insight into the mechanism of the CWP was realized. Before reporting the present experiments, the literature pertaining to the differences between the carbon and nitrogen CWP in iron and the various mechanisms proposed for the CWP will be reviewed. LITERATURE REVIEW Snoek2 first observed the CWP in iron specimens containing nitrogen, but also reported a weak and unreliable peak in carburized samples. Later, Ke3 established that the CWP height was proportional to the degree of deformation. The presence of nitrogen alone would produce a peak of the same size as found in a sample containing both nitrogen and carbon, and KG concluded that the CWP was caused by nitrogen. In a discussion of G&apos;s paper it was reported that Dijkstra had investigated the CWP in samples that contained only carbon. He found it to be much smaller than the nitrogen peak and "unstable". KG et al.4 charged specimens of iron with both carbon and nitrogen. They observed that the carbon CWP was much smaller than that observed in nitrided samples, but that aging at 300°C caused the carbon peak to increase. A similar treatment produced no change in a nitrogen peak. Annealing at higher temperatures caused the height of the CWP in both the nitrogen and carbon samples to decrease. This behavior was also observed by Kamber et al. 5 who found that the activation energy for the annealing of the CWP was identical with the activation energy for the self-diffusion of iron. They concluded that the annihilation of dislocations by climb caused the reduction in the CWP height. Kamber et al. studied the "unstable" carbon peak in detail. They measured both the Snoek and CWP during various aging treatments. In carburized samples, aging at 100°C caused the Snoek peak to disappear, although the CWP peak remained small. However, a subsequent treatment for 5 hr at 240°C caused the CWP to reach a maximum. They proposed that an additional location for the carbon, other than whatever site produced the CWP, is present. In nitrided samples the CWP was completely developed as soon as a measurement was made; additional sites are not present. No explanation of either the additional site or the difference in the behavior of carbon and nitrogen was offered. petarra5 performed a systematic study of the effect of composition on the CWP. Using three kinds of "pure" iron, he showed that there was a residual CWP when the carbon and nitrogen concentrations had been reduced to less than that detectable by Snoek-peak measurements. He observed the same general annealing behavior and composition dependence as previous investigators, with the following exceptions. On first measuring the carbon CWP, it was found to be identical with the residual peak, and essentially independent of the carbon content. If the CWP was measured a second time in the same sample, it increased in size, but was still only about one-fourth the size of a CWP in a sample of the same iron nitrided to the same composition. On the other hand, a series of annealing experiments showed that the nitrogen CWP was not al-

Jan 1, 1967

By R. C. Ku, R. G. Davies

The stress-strain behavior of Fe-C and Fe-Ni solid-solution alloys has been investigated at 25°C. It is found that the rate of solid-solution strengthening is dependent upon the strain at which the yield stress is measured, the macroyield stress being much more concentration-dependent than the microyield stress. In fact the addition of nickel does not lead to any increase in the microyield stress of iron. The primary effect of increasing the carbon or nickel content is to increase the slope of the stress-strain curve in the microyield region; this effect has been correlated, by means of transmission electron microscopy, with a decreased ability of the dislocations to cross-slip. It is concluded that the Mott-Nabarro theory is a good description of true solid-solution hardening in these and other iron-base alloys. A.LL theories of the solid-solution strengthening1-4 indicate that the flow stress of an alloy increases both with solute concentration and "misfit" between the solvent and solute atoms. The functional relationship between strength, solute concentration, C, and misfit depends upon the particular theory. Mott and Nabarro1,2 and Schoeck and Seeger3 both predict a linear increase in strength with concentration, while Fleischer4 indicates that the strength should be proportional to C1/2; there are in the literature experimental observations to support both these compositional dependencies.1&apos;8 The experimental evidence used to support the theories is the change in macroscopic yield stress (strain, e, = 10-3) with composition. However, recent investigations have revealed that solid-solution strengthening in a Cu-Al single crystals7 and in Fe-V polycrystal-line" alloys depends upon the strain at which the flow stress is measured; a flow stress in the microplastic range (e = 10-6 to 10-5) is much less concentration-dependent than the macroyield stress. Since the theories of solid-solution strengthening are concerned in particular with the stress to move a dislocation in a dislocation-free matrix, they should only be compared with microyield-stress data; it will be shown that in a material deforming homogeneously the microyield stress (e = 10-6) is approximately the stress to move through the matrix those dislocations which have been nucleated by stress concentrations such as particles or grain boundary ledges.9-11 In contrast, the macro-yield stress is more complex in that it is affected by several phenomena: dislocation multiplication, dislocation interactions, and the ease of propagating slip across grain boundaries. For example, it is experimentally observed that when long-range order12&apos;13 or solute effects10 restrict cross alip the grain boundary

Jan 1, 1967

By P. L. Hendricks, J. W. Spretnak

The interstitial atom principally responsible for the yield point and strain aging in electron-beam-melted tantalum is identified by analysis of the kinetics of the return of the yield point after an increment of plastic deformation. Two sets of specimens contained two levels of oxygen with very low hydrogen contents and the third set had comparable oxygen and hydrogen contents. The activation energy for the return of the yield point agrees well with that for diffusion of oxygen for the first two sets of specimens. For the third set of specimens, the activation-energy value lies between those for diffusion of hydrogen and for diffusion of oxygen. The advent of the dislocation model of plastic deformation in metals has revitalized interest in the yield point and strain aging in bcc metals containing a certain minimum content of interstitial solute elements. Much theoretical and experimental work has been performed in recent years to elucidate the detailed mechanism of these phenomena. The purpose of this investigation is to attempt to identify the principal interstitial element responsible for the yield-point phenomenon in electron-beam-melted tantalum by analysis of the kinetics of the return of the yield point after an increment of plastic deformation. Some of the earlier theories of the yield-point phenomenon proposed a grain boundary film of iron carbide. Such models could not satisfactorily explain all features of strain aging and the yield-point phenomena. The most widely accepted explanation is that of Cottrell,1 later extended by Cottrell and Bilby.2 Strain aging is ascribed to "locking" of dislocations by interstitial solute "atmospheres". The yield-point phenomenon results when the dislocations are torn away from their atmospheres. The strain-aged condition is re-established after sufficient time to allow the interstitial atoms to diffuse to the dislocation lines and re-establish the locking atmospheres. Clearly, the Cottrell-Bilby model is concerned with the bulk of the grain and does not specifically involve the grain boundary. The recent modification of the Cottrell-Bilby model is a redirection of attention to the role of the grain boundary and the possibility of multiplication of a limited number of free dislocations rather than unlocking all of the dislocations. Theories have been advanced by Hahn3 and conrad4 which are modifications of the Cottrell-Bilby theory. The model proposed by Hahn indicates that, although the possibility of un- locking anchored dislocations is not excluded, it implies that unlocking is not necessarily required to explain yield drop. Locking of dislocations during the aging treatment is a necessary part of the theory; however, it assumes that dislocations once locked remain locked. It is suggested that the yield drop observed is a result of the following factors: 1) the presence of a small number of mobile dislocations initially, 2) rapid dislocation multiplication, 3) the stress dependence of dislocation velocity. In the case of bcc metals, locking is considered to be the means by which dislocations are immobilized. Cold working of the metal results in the generation of larger numbers of new dislocations and the stress dependence of the dislocation velocity accounts for yield drop observed. Conrad&apos; has proposed a model similar to the one just described which applies to strain aging of iron and steel and which logically could be extended to other bcc metals. This model also does not require large-scale unlocking of dislocations. It is proposed that, during initial loading of a specimen below the upper yield stress, a few dislocations are torn free of their Cottrell atmospheres at regions of stress concentrations. With an increasing stress, some multiplication of dislocations occurs by a double cross slip mechanism, thus giving a preyield microstrain. At some critical stress represented by the upper yield stress, sudden profuse multiplication of dislocations occurs, enabling plastic flow to proceed at a lower stress. In this model, microstrain, preyielding, and flow represent the movement of free dislocations. It should be noted that this model also requires the locking of dislocations by interstitial solute atoms for the occurrence of a yield point; however, unlocking of large numbers of dislocations is not required. If it is assumed that the yield point will return when some fraction of free dislocations produced during pre-straining are pinned, the number of solute atoms required to pin unit length of a dislocation line can be calculated when prestrain and reloading are done at the same temperature and strain rate. Since the migration of solute atoms back to the stress fields of dislocation lines is controlled by the diffusion rate of interstitial solute atoms, it is to be expected that the activation energy for strain aging would be identical to the activation energy for diffusion. It would also be expected that the strain aging observed will be controlled by the fastest diffusing species capable of producing locking over the temperature range investigated. The rate of yield-point return has been found to be adequately expressed by an empirical rate equation of the form: rate=Ae-Q/RT [1] where A = constant, Q = activation energy, R = gas constant, and T = absolute temperature. Cottrell and Bilby2 have expressed the number of atoms per unit length of dislocation line which arrive

Jan 1, 1967

By Robert E. Ogilvie, Zvonimir Ban

Oxidation experiments were conducted above 600°C to investigate the oxidation products formed on the surface of MoSi2. Results are presented which indicate that minor iron impurities play a key role in the oxidation behavior of MoSi2 above 600 °C. Based on considerations of the crystal chemistry of the oxidation products, MoSi2 with rhenium and iron additions was found to be resistant to oxidation in the pesting temperature range. AS early as 1914, Honigschmidtl observed that some silicides of molybdenum exhibited high resistance to oxidation at elevated temperatures. This fact did not arouse much interest until 1950, when Kieffer and cerwenka2 examined this property in more detail. They found that Mo-Si alloys with approximately 70 pct Mo (by weight) could be heated to 1600°C in an oxidizing atmosphere without any significant damage. The surface was found to be protected by the formation of an extremely thin silica glass layer which had no tendency to spa11 during subsequent thermal cycling. In 1955, Fitzer3 discovered that even solid bodies made of MoSi2 completely oxidized within a relatively short time when exposed to the air in the temperature range from 300° to 600°C. To describe this phenomenon he proposed the name "molybdenum disilicide &apos;pest&apos; ", clearly analogous to the previously observed "tin plague" ("tin pest") which, however, arises as the result of a phase transformation. Studies performed by Fitzer and, in particular, one published recently by Berkowitz, Blackburn, and Fel-ten,&apos; comprise the most extensive research to date on the pest phenomenon in MoSi2, as far as the fundamen- tal mechanism of the process is concerned. The first of these studies revealed the existence of a crystalline phase which appeared at the surface at 750°C and dissolved in the glassy silica layer at 1150°C. The logical assumption was that this phase was some reaction product of MOO3 and SiO2. The formation of a reaction product of this type seemed probable since it had been mentioned by Glemser and Lutz6 in a paper describing their studies of molybdenum oxides; however, this assumption was later disproved.8 It is our belief that information concerning the exact nature of this crystalline phase may be important for a better understanding of both pesting and the protection mechanism. Therefore, since the only available general description of the pest phenomenon was that of Fitzer, it was decided to reproduce his experiments. These experiments established that, in addition to the "pest" and "nonpest" temperature range, an intermediate region exists between 600" and approximately 650°C. This region is characterized by the appearance of a variable amount of yellow to orange colored crystals. The electron-beam microanalyzer was used to qualitatively determine their composition. Iron and molybdenum were found to be major constituents. This result can be explained based on the following facts: 1) iron, according to literature data,* is the most common impurity in molybdenum powder, and its content can be as high as 0.25 pct; 2) technical silicon powder usually contains iron; 3) steel ball mills are often used for the crushing and grinding of MoSi2. In order to clarify the exact role of iron, it was deliberately added to a stoichiometric mixture of molybdenum and silicon. The observed results corroborated the previous experiment, proving that iron (probably as some silicide phase) concentrates along the grain boundaries. I) EXPERIMENTAL PROCEDURE A) Oxidation of MoSi2 with Iron Additions. 1) Specimen Preparation. Specimens were prepared by both

Jan 1, 1967

By N. A. D. Parlee, M. M. A. El-Naggar, G. 8. Horsley

The apparatus was of a modified Sieverts type1&apos;2 with a reaction tube designed to function also as the cell component of an oxygen pressure gage. The reaction tube assembly is shown in Fig. 1 and described in Table I. The main body is a 1-in.-OD 15 mol pct calcia-stabilized zirconia tube. The ground-glass joint, g, the male part of which carried a prism for optical pyrometer use, was connected to the remainder of the Sieverts apparatus. The calibration of the cell (at its 1000°K operating temperature) for internal oxygen pressures (PO2in) in the range 0.2 to 10 9 atm was made against internal air pressures measured by mercury manometer and McLeod gage. At very low po2in values down to l<Tn atm the performance was checked by comparing pQ calculated from electromotive force measurement when the apparatus was filled with a) pure CO gas and b) a CO-CO2 mixture of the ratio CO-CO2 = 1:0.398, with Po, values calculated from the equilibrium constants of the following reactions at 1000°K:

Jan 1, 1968

By J. Weertman

The paper of Gifkins and Snowden considers the interesting but difficult problem of determining the stress dependence of secondary (steady-state) creep at low stresses. These authors have concluded that at stresses below 250 psi (2 x 107 dynes per sq cm) the secondary creep rate of lead is proportional to the stress (viscous creep) and is not proportional to the stress raised to about a fifth power. The experimental data considered by them were obtained on tests conducted at room temperature and at 50°C. The lowest stress employed was 50 psi (3.5 X 106 dynes per sq cm). The authors pointed out the main difficulty in determining the stress dependence of creep at low stresses. The creep tests must be run for very long lengths of time. However they made no estimates of when an experimental creep rate determination must be rejected because it does not represent a true steady-state or minimum creep rate. In order to be certain that a creep curve is within the steady-state region, the total creep strain should be of the order of 0.1 to 0.2. For a creep test of a year&apos;s duration this requirement implies that a secondary creep rate smaller than about 10-3 per hr cannot be measured reliably. The corresponding creep rate for a 10-year test is 10-6 per hr. The creep rates of the tests that were considered by the authors to prove the existence of viscous creep were of the order of or less than 10-6 per hr. One can conclude reasonably that this data does not prove unambiguously that large strain steady-state creep rate of lead is proportional to the stress in the stress range of 50 to 250 psi (3.5 x 106 to 2 X 107 dynes per sq cm). Another technique can be used to obtain the stress dependence at low stress levels. The creep rate is a very sensitive function of temperature. The creep rate can be increased by very large amounts merely by increasing the temperature. We carried out steady-state creep tests on lead single crystals25 at temperatures up to 320°C. We were able to obtain creep rate data down to stresses as low as 35 psi (2.5 x 10&apos; dynes per sq cm). Our smallest creep rate was 8 x 10-5 per hr. Thus we obtained large strain, steady-state creep rates to even lower stresses than were considered by Gifkins and Snowden. No evidence was seen for viscous creep. The creep rate was proportional to the stress raised to about a 4.5 power down to the lowest stresses. Since there is no reason to believe that changing the temperature should change the stress dependence of steady-state creep, we feel that large strain viscous creep does not occur in the stress range quoted by the authors for lead single crystals or large-grain polycrystalline samples of lead. This conclusion does not imply that viscous creep may nat occur in a lower stress range or in the same stress range for fine grain material or at creep strains very much smaller than 0.1. Support by the U.S. Office of Naval Research is acknowledged. Authors&apos; Reply R. C. Gifkins and K. U. Snowden We thank Dr. Weertman for his discussion and although, as we hope to show, we do not agree with his reservations, we do concur in stressing the importance of ensuring that creep rates are reliably obtained. Dr. Weertman appears to be content to accept n = 1 for low stresses with fine-grained material but not for single crystals. We believe our results show that the former result cannot be accepted without also accepting the latter. We will also show that the probable errors in our minimum creep rates are insufficient to alter our conclusions, that the criterion proposed by Dr. Weertman is arbitrarily restrictive and his alternative experimental approach possibly invalid. 1) A principal result of our Fig. 1(a) is that n = 1 for polycrystalline specimens at room temperature and 50°C for stresses below -250 psi. There was evidence that crystal slip and grain boundary sliding contributed approximately equaily to the overall strain in this low-stress regime. This implies that either a) grain boundary sliding controls slip within the grains or b) both grain boundary sliding and crystal slip independently occur according to mechanisms which give n = 1. Alternative a does not seem acceptable, so we were forced to consider b. This led us to reexamine work on bicrystals by Strutt and Gifkins and plot curves Fig. l(b). Previously Strutt et al. (loc. cit.), had merged these points with others using the Zener-Holloman parameter and thus, we now believe, had been led to overlook the behavior where n = 1. Curves C and D in Fig. l(b) did appear to confirm the hypotheses that n = 1 for crystal slip at these low stresses and the sliding curve F was similarly of the expected form. It was comparatively easy to find a quantitative theory to account for n = 1 for sliding and the similarity of curves C and D to curve F (all obtained from the same set of specimens) led us to feel that the single-crystal curves were valid. 2) We believe the secondary creep rates for both the polycrystalline and single-crystal specimens to be in error by factors c2. In Fig. 6 creep curves for polycrystalline specimens of lead(1) and lead(II) are reproduced as curves a and b, respectively, and curve c is for a single crystal at 100 psi. It is clear that, although the attainment of secondary creep rate takes 2 years for a and 150 days for b, thereafter the curve is linear for periods of 7 and -1 year, respectively. The single crystal has a linear portion commencing after 20 and extending to 90 days. Creep extension was measured directly using a traveling microscope reading to 0.01 mm on gage lengths marked on the specimens; the gage lengths

Jan 1, 1968

By J. Warner, M. J. Marcinkowski, B. Cullen, T. Prevender, J. Mcllwain, T. Carnahan, J. Pahlman, J. Demel, J. Munford

The following analysis was an outgrowth of a midterm examination given by one of the authors (M.J.M) in a course entitled Metallurgy 541 "Applications of Dislocation Theory&apos;&apos; at Iowa State University. Fig, l(a) shows the three-layer sequence of atoms lying in the (111) plane which characterizes the fully ordered AB3 fcc crystal, i.e., LI2 type. If any two-layer sequence of close-packed planes is constructed from Fig. 16)&apos; the structure would be hcp of the DO,, type. Consider for convenience that the circled atoms lie in the plane of the drawing while those shown square and triangular lie immediately above and below the plane of the drawing, respectively. It has already been shown&apos; that if a Shockley partial dislocation is passed over the plane of the paper, then the square atoms in Fig. 1(a) are displaced from their original positions as shown by the arrows in Fig. l(b). Not only is an intrinsic fault produced but the crystal is simultaneously disordered across the slip plane. In particular, 2AB bonds are converted to 1AA and 1BB bonds when referred to the area outlined by the solid line in Fig. 1. If, on the other hand, a Shockley partial is allowed to pass immediately above and immediately below the plane of the paper so as to displace the atoms in opposite directions as shown in Fig. l(c), an extrinsic fault is producedZ and twice the amount of disorder is introduced into the crystal as compared to the dislocation-produced intrinsic fault, if only broken first-neighbor bonds are counted. If an intrinsic stacking fault is produced by removing a close-packed plane of atoms in Fig. l(a) and displacing the two adjacent planes by 1/3a0[111], no wrong nearest-neighbor bonds are produced. Similarly, if an extra half plane of atoms with the same arrangement as any of those shown in Fig. l(a) is inserted between any two planes in the same figure, then an extrinsic stacking fault is produced in which once again no wrong nearest-neighbor bonds are produced. The latter two faults are bounded by Frank partial dislocations. Since, at least in the alloy CU3AU,3 nearly all of the ordering energy resides in the first nearest-neighbor interactions, intrinsic and extrinsic stacking faults and associated APB&apos;s of the Frank type are expected to have significantly lower energy than those of the Shockley type in CusAu in particular and quite likely in L1, and DO19 type alloys in general. Also, because of the higher degree of disorder plus loop interaction

Jan 1, 1968

By Victor A. Phillips

A series of strips of a Ni-12.7 at. pct A1 alloy were Prepared containing cubical y&apos;(NisAl) precipitates with edge lengths from 60 to 500A. A particle-free solution-tveated strip was included for cornparison. They weve cold-rolled 95 pct and the effects of particle size on the isochronal (1/2 hr) annealing behavior between 300° and 950°C studied (by hardness and light and electron microscopy). It ulas inferred that the particles deformed with the lnatvix becoming lamellae which remained coherent. Comparison with published data fov pure nickel showed that aluminum greatly re-tavded softening and recrystallization, but it made little difference whether or not particles were present. The presence of pakticles led to a heterogeneous distribution of precipitates after annealing at 700" to 750°C. Recovery was not detected. Recrystallization occurred by the growth of new grains into unrecrys-tallized material. In a previous study by the author,&apos; the growth of Ll2-type ordered yl(Ni3Al) precipitates was followed in Ni-12.7 at. pct A1 alloy as a function of aging at 600" and 700°C. The particles were showo to be cubical in shape in all sizes from 50 to 3000A and remained coherent. This work was used as a guide in preparing the starting structures for the present study of the effect of these particles on the annealing behavior of heavily cold-rolled strip. Another question of present interest was whether dislocation and particle hardening were additive, since the structures before rolling ranged from solution-treated to peak-aged to overaged. Also, precipitation might occur on annealing after cold-rolling. Reference may be made to other papers2"5 for previous work in this relatively unexplored field and only some recent work will be mentioned her:. phillips2 studied the effect of deformable 0 to 590A-diam cobalt particles on a Cu-3.23 pct Co alloy rolled 95 pct and found that the particles, which rolled out into thin lamellae, impeded softening and recrystallization. Tanner and servi3 likewise studied the annealing of cold-swaged Cu-2 pct Co alloy containing 150A-diam particles and found impeding effects. Haessner et a1.,4 on the other hand, found that incoherent 2-p-diam non-deformable particles of B4C (0.04 vol pct) tended to increase the rate of recrystallization of copper rolled up to 95 pct reduction. They attributed this to the formation of new grains at the particle interfaces. Humphreys and artin&apos; found that nondeformable silica particles in copper rolled to 30 pct reduction accelerated recrystallization if the particle spacing was large and retarded it if the spacing was smaller. Haessner et a1 4 also studied a rolled Ni-Cr-A1 alloy; however, the particles of y&apos;(Ni3Al)-type precipitate were not put in before rolling, but separated during the isothermal annealing at 750°C. No previous work appears to have been carried out on the effect of y&apos; (Ni3A1) particles on the annealing of Ni-A1 alloy. Hornbogen and ICreye7 redetermined the solubility c of aluminum in nickel as a function of temperature T and showed that it was given by c = 32.6 exp(-1940/RT). This relation gives aluminum solubilities of 15.1, 14.2, 12.0, and 10.7 at. pct at 1000°, 900°, 700°, and 600°C, respectively. The phase precipitated from the nickel-rich solid solution is fcc y1 (Ni3A1) which has a Cu3Au -type ordered structure8 and remains ordered up to 1000°C.B EXPERIMENTAL PROCEDURE The alloy used was identical with that used before. Chemical analysis showed 6.27 wt pct (12.71 at. pct) Al, the principle impurities being 0.065 pct Fe, 0.022 pct Co, 0.020 pct Cu, and 0.004 pct C. Bar stock of 1 in. diam was cold-swaged to % in. diam, cold-rolled to 0.300-in.-thick strip, and annealed at 900°C in dry hydrogen. It was cold-rolled to 0.100-in. thickness and solution-treated for 1 hr at 1000°C while sealed in a quartz tube in argon, quenching in iced brine with the aid of a device to snap off the nose of the tube. Lineal analysis gave an average grain size of 0.055 mm. Pieces of strip were aged at 700°C in vacuo for 30 min, 51/4 hr, and 1 week to produce nominal average particle widths of 60, 150, and 500A, respectively, as known from the previous work.&apos; The average diamond pyramid hardness was determined. The heat-treated strips were rolled from 0.100 to 0.005 in., a reduction of 95 pct, and the rolled strips stored at about -5°C. Small pieces were annealed within 1 week for 30 min at temperatures from 300° to 950° ±2°C in a horizontal vacuum furnace. Strips were withdrawn into a cooling zone, giving an estimated initial cooling rate from 950°C of about 50°C per sec. Average diamond pyramid hardnesses were determined on a lightly electropolished spot on the surface of each strip using 300-g load. Each point on the softening curves represents a separate annealed specimen. Sections containing the rolling direction were examined by optical metallography. Selected specimens were electrothinned to the center plane&apos; and examined by transmission at 100 kv in a Siemens Elmiskop I electron microscope. It is well-known that changes in the structure tend to occur when a deformed strip is electrothinned below a thickness of a few hundred angstroms, although this is less serious with a material such as nickel which has a high melting point, and also is apt to be less serious when particles are present. Observations were nevertheless confined to thicker regions of the foils with estimated thicknesses over 1000A. No changes were observed due to beam exposure.

Jan 1, 1968

By Frank Woolley, John F. Elliott

The high-temperatzrre solulion calorimeter has been modified and an extension dynamic analysis of i/s transient behavior has provided an improved basis for interpretation of the experimental data. The partial molar heats of mixing, Him, of aluminum, copper, and silicon in the corresponding binary liquid-iron alloys haz,e been measured directly at 1600°C. The resulls in kcal per g-alom are: THE high-temperature1,2 solution calorimeter was planned and designed to obtain directly the partial molar heat of solution of solute elements in a variety of liquid metals that might serve as solvents. Results obtained in the temperature range of 1000° to 1200°C were described in the two earlier publications. However, a long-term goal in the program has been to obtain measurements at 1600°C of the heats of solution of elements in liquid iron. Hence, subsequent to the work last reported,2 and based on the experience of the first two studies, the calorimeter system has been modified and operated at 1600°C to obtain measurements on the Fe-Si, Fe-A1, and Fe-Cu systems. This paper reports the results of the work. THE MODIFIED SYSTEM It was clear from the earlier results that the most precise measurements can be obtained with the high-temperature solution calorimeter when the solution time is less than approximately 30 sec. This can be achieved only when the bath temperature, Tb, is above the melting (liquidus) temperature of the solute material being dropped. A second point of importance is that the refractories used earlier liberated considerable water so that, although the oxygen potential of the atmosphere in the system was satisfactory for work with nickel and copper, it was too high for work with iron, silicon, and so forth. Third, for work at 1550" to 1650°C, an improved temperature-sensing unit is needed. The modified calorimeter in its latest form is shown schematically in Fig. 1. The refractory brick and the Kanthal-Super heating elements which formed the furnace for heating the solute addition have been replaced by a smaller resistance-heated tube furnace which is insulated with bubble-grain alumina. A more elaborate gas purification system was installed to maintain a satisfactorily low oxygen potential in the atmosphere of the calorinieter chamber and of the solute addition furnace. As was the case in the earlier work, at the beginning of a run the calorimeter chamber is evacuated and then filled with purified argon so that a total pressure slightly in excess of 1 atm is maintained during the run. When either of the furnaces within the enclosure attains a red heat, 6 pct H2 is added to the atmosphere. Throughout the run, gas from the calorimeter is circulated through a de-oxidation system at the rate of approximately 5 standard liters per min; the changeover time for the gas within the calorimeter enclosure is approximately 1 hr. The essential stages of the deoxidation system are: a copper furnace at 600°C, a drying tube of anhydrite, and a titanium furnace at 800°C. The oxygen potential of the gas stream in the purification system can be monitored at several points by a stabilized zirconia oxygen cell. This cell is invaluable in detecting the development of leaks in the container vessel and the gas circulating system. The installation of the solute-addition furnace allowed either of two types of temperature-sensing units to be mounted on a water-cooled probe. The first was a small optical device using a silicon diode that was

Jan 1, 1968

By E. A. von Hahn, T. R. lngraham

Cementation rates ulere studied by rotating an elec-tropolished or etched copper strip in aqueous solutions, of either perchloric acid or alkaline cyanide, containing silver ions. The rates of cementation were more rapid in acidic media than in cyanide media. In both, the rates varied with the rate of rotation of the copper strip. The deposits formed in the acidic solutions were finely divided, loosely adhering powders. Those formed in the cyanide solutions were dense and adherent. The presence of the deposits influenced the cementation rates. In the acidic solutions the rate was enhanced, possibly because of the increased cathodic area. In the alkaline solutions the rates were decreased in the presence of the deposits. This has been attributed to restricting the diffusion of the copper ion from the rnetal outward into the bulk of the solution. In an earlier paper1 the authors described a kinetic study of the cementation of palladium on copper in perchloric acid solutions. That work indicated that there were two stages in the palladium cementation process. The first, more rapid stage was consistent with rate control by the diffusion of Pd11 ions to the copper surface and/or by chemical reaction at the surface. The second stage was consistent with rate control by the diffusion of copper ions from the copper surface, through the deposit, out into the main body of solution. The effect of the type of deposit on the rate of cementation is of particular interest because it may be one of the primary features involved when large quantities of metal are to be cemented from solution. No substantial investigations of the effect seem to have been made. Accordingly, an extension of the previous work was arranged to study the cementation of silver on copper. This system was selected because of the convenience of the analytical methods, the previously established technology with copper, and the fact that the system could be studied in both acidic and alkaline media. By selecting perchloric acid and alkaline cyanide solutions as the media, it was hoped that some assessment might be made of the effects, on cementation, of having the silver ion present in a virtually uncomplexed state and in a highly complexed state. EXPERIMENTAL The cementation rates were studied, as previously described,&apos; by rotating a copper strip (1.0 by 23.2 cm) clamped to the peripheral surface of a lucite cylinder. The solutions were kept at constant temperatures (±0.05°C) under an atmosphere of purified nitrogen, and samples were taken periodically for analysis. The initial solution volume was 1000 ml and the sample volume 5 ml. The initial silver(1) ion concentrations were made low (0.5 to 1.0 x 10-4 moles per liter) to minimize the influence of the cemented deposit on rates. The solutions were prepared by dilution of suitable aliquots of silver perchlorate and silver cyanide stock solutions. Both stock solutions were prepared from purified silver powder (Johnson, Matthey, and Mallory Ltd.) with redistilled deoxygenated water, and they were kept under an atmosphere of purified nitrogen. To prepare the stock solutions, weighed amounts of silver powder were dissolved with nitric acid. For the AgC104 stock solution the silver nitrate solution was evaporated twice to near dryness with perchloric acid and then made up to volume: For the NaAg(cN)2 stock solution, the silver ions were precipitated with sodium hydroxide solution. The precipitate was filtered, washed thoroughly with redistilled water, dissolved with 1.1 times the required stoichiometric amount of sodium cyanide solution, and made up to volume. The small amounts of free perchloric acid and sodium cyanide present in the stock solutions were disregarded in the preparation of the solutions. The copper strips were cut accurately from 0.025-in. sheet (American Metal Climax OFHC brand) and annealed for 1.5 hr at 470°C in a stream of nitrogen. Analyses of the solution samples for silver and copper were done with a Techtron Model AA-3 atomic absorption spectrophotometer. Calibration standards of the same composition as the experimental solutions were prepared and analyzed simultaneously with the samples. No difficulty was experienced in the analyses, and the reproducibility was within 1 to 2 pct in both alkaline cyanide and perchloric acid solutions.

Jan 1, 1968

By Robert Maes, Robert de Strycker

The Fe-Ni-As phase diagram has been established by the study of about a hundred alloys, by microscopic observation, and by thermal analysis, with arsenic contents up to 50 pct. The iron and nickel arsenides present extensive solid-solution fields, owing to the substitution of nickel by iron and vice versa; the extent of the solubility field of each compound has been determined with an accuracy of ±1 pct. In the investigated range of compositions, the solidification reactions were established, and the temperatures of the invariant reaclions detevmined with a preciston of iZ°C in the most favorable and ±5°C in the least favorable cases. The isothermal lines of the liquidus surface have also been drazum, with an accuracy estimated at i5°C. Reactions in the solid state, which take place for the formation or the decomposition of certain phases , were investigated in detail. ThE constitution diagram of the Fe-Ni-As system is fundamental for the understanding of the properties of nickel speiss; these by-products of the extraction of certain nonferrous metals indeed often contain the three elements iron, nickel, and arsenic as main constituents. The Fe-Ni-As system has already been the object of earlier investigations. In 1932, Guertler and Savels-berg&apos; have presented some elements of the ternary phase diagram, for arsenic contents up to 55 pct (all percentages in this paper are given in weight percent), including the vertical section FezAs-Ni&s2. This investigation is, however, incomplete and certain anomalies suggested the necessity to verify the results published by these authors: the section Fe2As-Ni5AsZ, for example, is presented as quasi-binary, with a field of complete miscibility in the solid state, even though these compounds do not have the same structure. Recently, ~useck&apos; established an isothermal section at 800°C in the Fe-Ni-As system by X-ray diffraction and microscopic examination of water-quenched alloys. These techniques are sometimes inaccurate for the determination of the fields where alloys are liquid at the investigated temperature, and they may lead to erroneous conclusions when a compound exists at the investigated temperature but is not stable at room temperature and cannot be maintained by quenching. LIMITING BINARY PHASE DIAGRAMS The Fe-As constitution diagram has been the object of several investigations which have been reviewed by Hansen and Anderko.3 For the Ni-As phase diagram, a recent study has been effected by Yund.4 In this system, Heyding and calvert5 have determined the existence of a compound of unidentified structure at arsenic contents slightly higher than those corresponding to Ni5As2 and at temperatures lower than about 200°C; by analogy with iron and cobalt arsenides, this compound could correspond to the formula Ni2As, as suggested by Kulle-rud; although this is not definitely established. In the region of arsenic contents from 35 to 55 pct, Fried-rich7 detected anomalies in the solidification reactions; an interpretation of these anomalies was given by Hansen ,8 which assumed that the solidification reactions in practice are not in equilibrium, but are meta-stable. The main features of the Fe-Ni constitution diagram are the existence of a complete miscibility field, at least at high temperatures, for the fcc phase (which will be designated by My in the remainder of this work) and of a limited solubility field for the bcc phase (designated by Ma). EXPERIMENTAL METHODS The fundamental technique used in this investigation was microscopic observation, which allowed the determination of the reactions occurring during solidification of the alloys, and possible reactions in the solid state.

Jan 1, 1968

By H. E. Cline

Mechanical properties of the eutectic between CoAl and cobalt were measured over a range of- temnperatures and strain rates for a variety of microstructures produced by directional solidification and by thermo-mechanical processing. Directional solidification led to rodlike, lamellar, and irregular microstructures. The unusually high volume fraction of the cobalt-rich rods and the lurge spacing of the rods were explained by the phase diagram. The hot-worked structure consisted of fibers of COAL in a cobalt-rich matrix. The roonl- tevlperature strength of the uvrought material increased with decreasing grain size but the 1000°C strength decreased with decreasing pain size. At high temperatures the directionally solidified tnaterial was stronger and less strain-rate-sensitice than the hot-rolled material. The fine-grained hot-worked ma-terial became superplastic at high temperatures, with tensile elongations greater than 850 pct, while at root temperature this material was ductile and impact-resistant because of the ductile matrix. Fracture occurred in the directionally solidified material at elevated temperatures by inter phase separation and at roorn temperature by cracks in the intermetallic phase. Growth of these cracks was impeded by the ductile cobalt-rich phase. It was found that the CoAl intermetallic remains ordered at elevated temperatures. DIRECTIONAL solidification of eutectic alloys has been used to produce structures consisting of parallel rods or lamellae. Although the spacing of the phases depends on the growth rate, it has been observed to be of the order of 1 µ in many eutectics. A strong intermetallic phase has been used to reinforce a ductile matrix in the rod eutectic A1-Al3Ni and the lamellar eutectic Al-Al2cu.1 The microstructure of the eutectics A1-A13Ni and A1-A12Cu remained aligned after samples of these alloys were exposed to temperatures just below their melting points for long times. Stability of the microstructure at elevated temperatures makes directionally solidified eutectics a candidate for high-temperature applications. Recently Thompson4 has developed the Ni-NiMo eutectic containing 40 pct NiMo lamellae, giving a tensile strength superior to nickel-base superalloys. Unfortunately, this eutectic oxidizes rapidly at elevated temperatures. By mechanically processing a two-phase structure, one may reach strengths as high as 700,000 psi, as demonstrated by drawn pearlite.5 In this case the strengthening mechanism was thought to be related to the fine substructure formed during deformation.5 However, a heavily worked structure may recrystallize and coarsen at elevated temperatures. Some worked eutectics such as Al-Al2Cu,6 Pb-Sn,7 and Sn-Bi7 have shown unusually large elongations in tension when tested at elevated temperatures. This phenomenon of large extension, called "superplasticity", was related to the fine grain size of wrought two-phase alloys at elevated temperatures. A mode of deformation of "superplastic" material has been shown to be grain boundary sliding,&apos; which has also been observed during creep of polycrystalline materials.9 The Co-A1 system was chosen for this investigation after examining the phase diagrams of binary eutectics." The high melting point of 1400°C, the aluminum content which was expected to give oxidation resistance, and the properties of the intermetallic CoAl were the chief factors influencing this choice. This eutectic consists of a mixture of the intermetallic CoAl and a cobalt-rich solid solution. The intermetallic CoAl has a large range of solubility and a CsCl structure." From the similarity between CoAl and NiAl one would expect CoAl to be ordered at elevated temperatures; however, specific heat measurements" show a transition at 800°C. West-brookL2 has measured the hot hardness of CoAl and found a rapid decrease in hardness above 600°C. The tensile properties and stress rupture properties of as-cast CoAl-Co eutectic were measured by Ashbrook and wallace13 who report a room-temperature tensile elongation of less than 1 pct. I) EXPERIMENTAL A) Sample Preparation. Experimental materials were prepared by directional solidification, by hot working, and by powder processing. The starting materials were electrolytic 99.9 pct pure cobalt and 99.99 pct pure aluminum. 1) Directional Solidification. A vertical Bridgman apparatus heated by induction was used to directionally solidify cylindrical ingots $ in. in diam and 5 in. long. The apparatus was first evacuated and then an argon atmosphere was introduced to retard evaporation. The ingots were contained in an alumina crucible inside a graphite susceptor that rested on a movable water-cooled base. The base was lowered out of the induction coil at a constant rate. Eight of the ingots were solidified using a drive rate of 2.5 cm per hr, two of the ingots at 1.2 cm per hr, and one ingot at 10 cm per hr. The eutectic composition Co 10 wt pct A1 was used in all but one ingot which had the composition of the stoichiometric CoAl intermetallic, Co 32 wt pct Al. 2) Mechanical Processing. At 1000°C the eutectic Co 10 wt pct A1 is a mixture of an intermetallic phase, Co 21 wt pct Al, and a cobalt-rich phase, Co 5 wt pct Al.10 These phases differ from the stoichiometric CO 32 wt pct A1 and pure cobalt because of the large solubility of this eutectic at elevated temperatures." Four rectangular slab ingots, 4 by 1 by 12 in. high, of Co 10 wt pct Al, Co 5 wt pct Al, Co 21 wt pct Al, and Co 32 wt pct A1 were cast for hot rolling. The cobalt was first vacuum-melted, H2-treated for 20 min,

Jan 1, 1968

By B. Wilshire, W. J. Evans

W. J. Evans and 8. Wilshire SEVERAL recent investigations1-6 have shown that the strain, c, during transient and steady-state creep is well-represented by the expression: € = e0 + et(l - e-mt) + Esl [l] where Eo is the instantaneous strain on loading, ET the total transient strain, C, the steady creep rate! and m a constant relating to the rate of exhaustion of transient creep. However, it has been noted6 that deviations from this equation occur over the first 10 to 15 pct of the transient stage, when the creep rate, (. decreases more rapidly than is predicted by this equation. This rapid decrease has been attributed to a large change in work-hardening coefficient. It 1s widely accepted that steady-state creep results from a balance between the rate of strain hardcning h and the rate of recovery r (=-s(st) as: dE/dt = Es = r/h [2] Comparison of values obtained for h at the end of the initial extension and during steady creep suggests that h increases several fold during the transient stage. which has the effect of reducing the creep rate proportionally.7 To examine the dependence, on r and h, of the deformation behavior during transient and steady-state creep. a series of constant-stress creep tests was carried out at 413°C at 6000 psi using 70-30 a brass. Prelinlinary investigation showed that. with this material. the transient stage constituted a significant portion of the total creep life (-0.4tf. where tf is the time to fracture). The alloy. obtained from Metals Research Limited. was made from high-purity copper, 99.999 pct. and zinc. 99.99 pct. Heat treatment at 675°C for 4 1/2 gave a uniform grain size of 5 mm-1. Details of specimen preparation and creep testing procedures have been given previously.6 Values of h (?s/?E) were determined by measuring the instantaneous strain. ?E. which occurred on increasing the stress during creep by a small amount. ?s. Similarly. v (= -?s/ ?t) was derived from the incubation period. At, after a small decrease in stress.&apos; Several values of v and h were obtained throughout duplicate creep tests. using different stress increments in the range 300 to 800 psi. The accuracy with which Eq. [I] represents the present creep curves was established by determining the best value of the constants Es, Et, m , and 6, using a digital computer program based essentially on the graphical solution for this equation devised by Conway and Mullikan.9 About 40 strain/time readings were taken during transient and steady-state creep. Over most of the creep curve, the average difference between the measured reading and the calculated strain at the appropriate time was less than 0.0001. However.

Jan 1, 1969

By A. U. Seybolt, V. A. Phillips

Binary iron alloys containing 1 pct of Al, Cr, Mn, Mo, Si, Ti, or V, and 0.4 pct C, 1 pct Cr steels with and without 1.2 pct A1 or 2.0 pct Ti additions, were ion-nilrided at 550° to 600° in N-H mixtures. Nitriding increased the inicrohardne ss of all the binary alloys except those containing manganese or molybdenutn, and also hardened the heat-treated steels if aluminum or titanium urns present. Transmission electron microscopy revealed particle formation in all casts where hardening occurred. Electron diffraction gare positive identifications for ALN, CrN, and a, Si3N4 in the binary alloys, and AlN and CrN in the aluminum- cold chromium-bearing steels, respectil&apos;uly. Cubic VN with a, = 4.13A was tentatively identified. Particles, apparently of CrN, also formed in the base steel but did not increase the hardness very much. Chromium and vanadium formed nitride platelets on {001}° matrix planes, while titanium gave clusters <15A diam. Aluminum nitride precipitated at grain and subgrain boundaries, and within the grains. Silicon gave profuse precipitates of several Morphologies at grain boundaries and cubical particles within the grains. No effect of the alloy carbides on nitride precipitation was observed in the heat-treated steels. THE nitriding of steel has been a well-established commercial process for about 40 years, but in spite of this comparatively long period of use there have been few studies aimed at understanding the process. Most studies, like the early but very competent work of Jones and organ&apos; and nones.&apos; were concerned with establishing the pertinent engineering variables of steel composition, gas composition, temperature, and time. As far as the present authors are aware, there have been no studies of the composition, size, shape, or distribution of the nitrides formed in the nitriding of steel. Noren and Kindbom3 did, however, examine a few nitrided steels by surface replica electron microscopy, and were able to show the presence of car-bonitrides and AlN and TiN nitrides. pitsch4,5 and Hrivnak6 examined nitrided pure iron by transmission electron microscopy. Baird7 found manganese nitrides in Fe-1.6 pct Mn when nitrided at 650°C, using the same technique. In the present work, emphasis was placed on transmission electron microscopy because of its inherently better resolution, using principally binary alloys of iron containing 1 pct of alloying element. In addition, a few simple 0.4 pct C steel compositions were examined to investigate possible carbonitride formation. It was not anticipated that all of the added elements would form nitrides under the conditions used, but it was considered desirable to obtain direct experimental evidence on this point. It would be considerably easier to ascertain the presence of alloy nitrides by examining appropriate binary alloys in preference to relatively complex steels. The work reported here could have been done using orthodox ammonia-nitriding procedures, but an operating ion-nitriding equipment was available, and was therefore used for specimen preparation. EXPERIMENTAL DETAILS 1) Materials. Binary alloys were made up from vacuum-melted electrolytic iron with 1 wt pct additions of Cr, Ti, V, Al, Mn, Mo, and Si of about 99.9 pct purity. In addition, three steels were similarly made up—a basis steel with 1 wt pct Cr and 0.4 wt pct C and two steels with further additions of 1.2 wt pct A1 or 2.0 wt pct Ti, respectively. The materials were vacuum-melted and cast as 11-lb heats into tapered square molds of about 2 by 2 in. average cross section. The castings were forged and hot-rolled to 11/4 in. rounds. Discs of 4 in. thickness by about 1 in. diam were machined from the rods. Some of these discs were hot-forged and hot-rolled to about 0.020 in. thick, sand-blasted, and then cold-rolled to about 0.003 in. thick. At this point, the surface was cleaned by light etching with HC1, then washed, dried, and vapor-degreased prior to nitriding. 2) Ion-Nitriding Procedure. The type of ion-nitriding equipment used here is similar to that described by Jones and Martin.8 Briefly, a mixture of nitrogen and hydrogen at 5 mm total pressure is placed in a vacuum chamber with a dc potential of 450 to 500 v applied between the work (cathode) and the grounded metal vacuum enclosure (anode). Nitrogen ions are accelerated to the work where a thin layer of Fe4N forms on the surface and thus sets up a nitrogen concentration gradient. This causes nitrogen atoms to diffuse into the surface layers of the alloy forming a finely divided dispersion of alloy nitrides, causing hardening of the surface. In the work to be reported here. the nitriding was carried out at 550° to 600°C to be consistent with commercial nitriding practice. The temperatures cited are those measured by a thermocouple located under a platform on which the work was sitting. Except where otherwise stated, the mixture used in nitriding the binary alloys contained -2.0 pct N, balance hydrogen. The nitrogen concentration in the nitriding gas mixture used for the binary alloys was purposely kept lower than normally used in nitriding steels. 10 to 20 pct, in order to minimize Fe4N formation. In this way only the alloy nitrides would be present as a second phase. However, in the case of steels which would contain a- carbide phase along with as

Jan 1, 1969

By M. I. Jacobson, A. S. Yue, A. E. Vidoz, F. W. Crossman

An equation governing the concept of constitutional supercooling under the combined effect of concentration and temperature gradients was used to produce platelike Al-CuAl2 eutectic composites for mechanical properties studies. Compression specimens were prepared from a single-colony Al-CuA12 eutectic composite ingot, 2 in. in diam and 12 in. long. The specirrzens were cut such that the platelets were oriented parallel, 45 deg, and perpendicular to the compression direction. Since the ingot was of eutectic composition, The aluminum-rich matrix could dissolve 5. 7 wt pct Cu in solid solution, and therefore could be strengthened by precipitation hardening. Specimens were tested at room temperature and elevated temperatures in the unidirectionally solidified, solution-treated, and solution-treated plus aged conditions. The results were compared with those for the conventionally cast and extruded specimens. For the controlled material, the highest strengths were obtained with platelets oriented parallel to the compression axis. In the unidirectionally solidified condition, 0.2 pct offset yield strength was 32,000 psi; however, this was increased to 59,000 psi by solution treatment, and further increased to 90,500 psi by solution treatment and aging. The attainment of high compressive strengths in the Al-CuAl2 eutectic composites was interpreted in terms of the buckling of elastic CuAl2 platelets in the plastically deformed a aluminum matrix. SINCE the discovery of high-strength whiskers,&apos; scientists and engineers have made significant progress toward incorporating these whiskers into metallic matrices, forming composites for basic studies and structural application. The general procedure is to produce the whiskers first and then to bind them together with a ductile matrix. The production of whisker-reinforced composites requires tedious handling techniques,, particularly when it is desired to align the whiskers unidirectionally. Furthermore, the interfacial bond between the whisker and the matrix is frequently poor3 so that the resulting composite has strengths lower than expected. These disadvantages are generally true for any metallic composite produced by physically mixing the components. It is possible to eliminate these shortcomings by growing whiskers directly in the matrix material by eutectic solidification.4-8 In eutectic solidification, the matrix phase and a whisker phase are grown approximately simultaneously from a liquid of the same overall composition at the eutectic temperature. If the solidification process is controlled by varying the freezing rate, the temperature gradient, and the impurity content, platelike or filamentlike whiskers are produced parallel to the growth direction. The morphology of the grown-in reinforcement, i.e.. plates or rods, generally depends on the volume fraction9 of the dispersed phase present in the eutectic mixture. Since the unidirectional eutectic solidification is a one-step process, i.e., the liquid-solid transformation process, an excellent interfacial bond between the matrix and whisker is obtained. An additional advantage is that no special handling technique for whiskers is needed. In recent years, many investigators10-13 have studied the effects of growth variables on the micromorpholo-gies of binary eutectic alloys produced by controlled solidification. The study of their mechanical properties was initiated by Kraft and coworkers14-16 who found that the strength of cast A1-CuA12 eutectic alloy can be increased threefold by unidirectional solidification. In the A1-AL3Ni system, a strength of 50,000 lb per sq in, was reported for the unidirectionally solidified eutectic alloy, a value five times higher than for conventionally cast material. Thus, the unidirectionally solidified eutectics can be used as fiber-reinforced composite materials. In this paper, we shall first use an equation17 as a guide for the production of eutectic composites in general and the Al-33 wt pct Cu eutectic in particular. Experimental data supporting the theoretical prediction are given. Second, the compressive properties of the grown A1-33 wt pct Cu eutectic were thoroughly investigated in terms of platelet orientations, thermo-mechanical treatment, and temperature. The experimental data are interpreted in terms of a buckling model of fibers in elastic fiber-plastic matrix metallic composites. EXPERIMENTAL PROCEDURE Crystal Growth. The following experimental procedure was adopted for the production of controlled microstructures in the A1-33 wt pct Cu eutectic alloy. The controlled solidification was accomplished with a movable resistance-wound radiation furnace. Fig. 1 is a schematic drawing of the solidification apparatus. A water-cooled chiller was placed into a degassed high-purity graphite crucible containing the charge. Rubber stoppers wrapped with aluminum foil were used to seal both ends of the quartz tube through which a dried argon atmosphere was passed under a slight positive pressure. At both ends of the quartz tube, radiation shields were used to minimize heat loss. The quartz tube was held in place by two steel clamps and the furnace was drawn vertically by means of a steel cable against the steel truss which permits the furnace to move without touching the tube. The drive mechanism consisted of two pulleys, a counter weight.

Jan 1, 1969