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By C. G. Durdaller, W. H. Robinson, G. M. Pound

The nucleation rate of the a (pay) to 0 (white) tin transformation was measured as a function of temperature and a tin particle size using an X-ray diffraction technique. The powder specimens of a tin were essentially monodisperse and the small dinzension of the particles of these specimens was varied from 13 to 75 p. Several types of nucleation sites of differing potency were fbund to be operative in the nucleation process, but it could not be determined whether these sites were on the free surface of the tin particles or within the volume. Assuming that they were on the free surface, the average density of the most potent sites was calculated to be 2.5 to 5.3 x 10' sites per sq cnz through the application of a Poisson distribztion finction to the isothermal data. Analysis of the temperature dependence' of the rate constmts at a given fraction transformed suggests that the active sites are regions of higher free energy and not catalytic interfaces. Appreciable induction periods were observed at the lower temperatures of transformation. Experimental studies1 of solid-solid phase transformations have led to the belief that the new phase nucleates at structural imperfections. The purpose of the present work was to learn more about the mechanism of nucleation in solids and the nature of the singularities at which nucleation occurs. In this investigation nucleation rates in the isothermal transformation of gray to white tin were measured by an X-ray diffraction technique using essentially monodisperse powders of gray tin. This particular phase transformation was chosen for study because it presented fewer experimental difficulties than most others. The experimental temperature-control problems were minimal because the two phases coexist in equilibrium at 13.3"C, and measurable transformation rates occur at temperatures only slightly above room temperature. The growth rate of the P phase into the a2 is sufficiently fast to make the measured transformation rate equivalent to the nucleation rate, provided that the particle size of the samples is small enough; for the experimental temperatures used in this study, the particle diameter must be less than 100 p. EXPERIMENTAL TECHNIQUE The P tin used in this study was obtained from Capper Pass and Son Ltd., North Ferriby, Yorkshire, England, and was of 99.999 pct purity. It was transformedS to the a phase and ground into a fine powder in an agate mortar. This powder was separated by a Roller air classifier into seven fractions whose dimensions, as determined by microscopic measurement of many thousands of particles, are given in Table I and whose distribution of size within each fraction is given in Figs. 1 and 2. The shape of the particles was roughly that of an oblate spheroid,

Jan 1, 1964

By E. Hornbogen

The deformation mechanisms of a iron-phosphorus alloys were compared at 20oand —196°C. Alloying with phosphorus increases the resistance to slip, but has little effect on the resistance to twinning. The stress for onset of twinning is nearly independent of temperature, but there is an increasing tendency for cleavage along (112) twin boundaries with decreasing temperature and increasing phosphorus content. FIVE iron-phosphorus alloys and one high-purity iron (0.004 pct C, 0.004 pct N, 0.05 pct O) were vacuum melted and cast, then homogenized for 6 hr at 1100oC and water-quenched. Single crystals were cleaved from the coarse grains produced in this manner. The hardness was measured* on polished (100) surfaces of the crystals at 20" and -196°C. Laue back-reflection patterns indicated a deviation of not more than 3 deg from coincidence of the {100} plane with the surface. The deformation mechanisms were studied by relief effects on the polished surfaces. Yield points in compression (0.5 pct offset) were measured with polycrystalline material. At 20°C the addition of phosphorus to a iron leads to a change from slip to twinning as the main deformation mechanism, Figs. 1(a), (b). Between 2 and 4 at. pct P slip and twinning occur simultaneously. In alloys with more than 4 at. pct P twinning is the main deformation mechanism and slip was observed only in the neighborhood of twin intersections. All cracks at 20oC were on (100) planes, some initiated by twins.' From measurements made at-196oC, hardness and yield points of all the alloys were nearly constant and the same as the hardness of high phosphorus alloys that deformed by twinning at 20°C, Figs. 2 and 3. In the high-purity iron, plastic deformation at -196°C occurred by both slip and twinning, but deformation in the iron-phosphorus alloys appeared to be entirely by twinning. In the high phosphorus alloys a large number of cracks formed along the (112) twin boundaries and at intersections of twins, in addition to the (100) cleavage, Fig. 1(c). DISCUSSION In , iron, plastic deformation can occur either by slip or by twinning, depending upon composition,

Jan 1, 1961

By W. J. Wrazej

THE measurements on the formation of multi-layered scales on pure iron1 and the metal -lographic examination of the produced layer of FeO, Fe,O,, and Fe2O3 shown in micrographs2 throw much interesting light on this apparently well-known subject. Professor Paidassi announced2 that in a few months7 time further results are going to be published with regard to the growth of Fe2O3 and Fe2O3 layers on an Armco iron as a function of temperature. Because of the very thin layers of Fe2O3 which are shown by Paidassi (Fig. 10 of ref. 2) when samples were scaled in air at 700°C for 4 hr and because this is not in agreement with the present author's previous observations, the following experiment was recently carried out. Polished cylindrical samples 13/64 in. in diam and 1/4 in. long from electrolytic iron used for spectro-graphic work (Hilger, H.S. Iron rods, F.693) and an Armco iron sample 1/4 in. in diam of the same length were suspended in a muffle furnace on Nichrome wire and annealed in air for 4 hr at 700°C 5OC. Because of the known easy peeling off of the Fe2O3 layer which is mainly in the form of powder (purple red dust on the surface) the samples were protected against any draft and shock. After annealing, the samples were cooled in air and placed in the mount-

Jan 1, 1954

By E. Buehler, J. E. Kunzler

High-pu.1-ity molybdenum has been heat treated, melted, and zone refined and the physical and chemical changes that are produced by these processes have been studied by making resistance ratio measurements. Pronounced effects are observed that are associated with recrystalliza-tion at about 1200°C and with melting. Melting alone is found to result in a substantial purification by the evaporation of impurities such as iron. Zone refining is found to be reasonably effective with four passes producing a three-fold decrease in resistance ratio and a minimum ratio of 0.0003. With the aid of low temperature measurenzents, it has been shown that the build-up of a deposit of the material being zone refined on the radio frequency coil used for heating can lead to contamination of the sample. CONSIDERABLE interest in high-purity refractory metals for the study of mechanical properties has developed during recent years. Also the need for highly pure metals in certain fundamental studies, such as electronic band structure, has become quite widely appreciated. Molybdenum can now be produced with sufficiently high purity to make it attractive for such investigations. The most suitable measure of chemical purity of metals used for many of these studies is its resistance ratio, R,.,o,/Ro, During the purification of molybdenum by zone refining and its subsequent evaluation by this technique, a number of informative observations were made. These observations concern the effectiveness of zone refining, the volatilization of impurities at the melting point, and the recrystallization of molybdenum and appear to be pertinent to other refractory metals. Also, the usefulness of low-temperature resistance measurements as an analytical tool for evaluating the presence of chemical impurities and physical defects in metals is again illustrated. Samples of high-purity molybdenum of known mechanical history were heated to various temperatures between 800°c and their melting point. Resistance ratios of the samples were measured after they had been given a specified treatment. The data were used, along with mass spectrographic analysis, as an aid in interpreting the nature of the processes that occurred in conjunction with each treatment. Changes in the concentrations of chemical impurities and physical defects are typical of things that effect the low-temperature resistivity. SAMPLES The starting material was obtained from Westing-house Corp., Bloomfield, N.J. It was in the form of molybdenum rods, usually 1/8 or 3/16 in. in diameter. These had been previously processed from bars, 5/8 in, in diameter, originally reduced from 4 in. diam arc-cast ingots, by hot swaging at about 1300°c. In the final step, the temperature was lowered to about l lOO°C which resulted in the production of elongated grains. Typical grains were about 0.03 mm thick and 0.6 mm long. The molybdenum was quite pure as is indicated by the results of mass spectro-scopic analysis1 given in Column 2 of Table I. Other nongaseous elements not listed in the table were not detected. ZONE REFINING AND THERMAL TREATMENT OF SAMPLES Several sample rods, 8 to 10 in. long, were zone refined or were heat treated at several temperatures. Both types of operations were performed using 3 me-

Jan 1, 1962

By H. C. Chang, N. J. Grant

REEP studies and measurements in most in-V> stances are based on a relatively gross gage length. Even in some recent theoretical studies on the mechanism of creep, changes were followed by means of X-rays and metallography without regard for the behavior of the individual grains and grain boundaries.'" Analytical studies of creep have frequently indicated that more than one competing process is operative and that the ultimate creep performance depends on the effects of temperature, time, and strain rate as well as grain size.'-" he grains and grain boundaries are known to respond differently to these variables but the extent of the response is still little known, especially in poly-crystalline materials where the relative orientations of grains and grain boundaries are important. This paper reports some experimental observations of the behavior of the grain boundaries and their effect on the deformation in the grains. High purity aluminum was used to avoid complications of aging reactions, second phase, inclusions, etc. Experimental Procedure A small vertical nichrome wound furnace was built to permit direct loading on the test specimen. This furnace is capable of operating up to about 1300°F with reasonable temperature distribution. A ground rectangular quartz window, 1.25x0.5 in., is imbedded in the external stainless steel tube to permit observations of the creep process with a microscope. An argon atmosphere ,was provided to prevent oxidation. The quartz window caused a temperature gradient between the back and front surfaces of the specimen of 15" at 700°F. The temperature gradient could be cut down to 3°F along the length of the specimen by adjusting shunts across the furnace windings. An ordinary metallurgical microscope with a working distance of 14 mm was rebuilt so that it could be moved in three mutual perpendicular directions. Visual examination could be made with either a 30X eyepiece or a 15X filar eyepiece. Using an objective of focal length 24.3 mm and a numerical aperture 0.20 a total magnification of 120X or 240X could be obtained. High purity aluminum rated at 99.995 pct was supplied by the Aluminum Co. of America as % in. then the gage portion was further machined to 3/16 in. diam. The ends were Y4 in. diam and threaded to fit available specimen holders. Two opposite flat surfaces of the gage portion were obtained by milling, giving final dimensions of the gage portion of 3/4x3/16x3/32 in. Machined specimens were first electropolished in Jacquet's solution.' Reference marks were produced by pressing a thin sewing needle into the surface of the specimen. The specimen was then annealed at 900°F for 24 hr and at 1150°F for 12 hr. Typical macrostructures of specimens treated in this manner are shown in Fig. 1. The range of the grain size was 1 to 5.5 mm (see Fig. l), but most of the grains were of 2.5 mm and went through the whole thickness of the specimen. The specimen was re-electropolished and etched electrolytically to reveal the grain boundaries. In order to reveal the orientation difference of the grains, etch pits were produced on the surface of the grains by etching in a mixture of hydrochloric and nitric acids (HC1, 45 pct; HNO,, 10 pct; H,O, 45 , by volume). The specimens were very carefully put into the holders and furnace; yet even with this care, fine slip lines were developed on the specimen surface.

Jan 1, 1953

By R. J. Wasilewski

The resistivity of single crystal and of polycrystalline metal has been determined between 77° and 1500°K. At comparable purity, the resistivity of the poly crystalline metal differs from that calculated from the axial resistivity values. The observed anisotropy is briefly discussed. A zone refined titanium rod was obtained from F. J. Darnell.1 The hardness of this material varied between 52 and 64 Bhn, indicative of its high purity. Single-crystal specimens were cut out from a few large grains, elongated predominantly along <1120>. Resistance measurements were taken with specimens immersed in liquid nitrogen, solid CO,, and acetone, and at ice point, and then recorded continuously between room temperature and 1200" to 1250°C, throughout at least one full heating and cooling cycle at a rate of l° to 3°C per min. Four probe measurements were taken using spot-welded Pt wire 0.003 in. in diam as potential terminals, and the electromotive force drop was determined poten-tiometrically. A standard resistance, in series with the specimen, served to determine the dc current (generally about 80 ma) in the circuit. In order to eliminate spurious thermal electromotive forces, the circuit polarity was automatically reversed at 5-min intervals, and the mean of the two adjacent readings taken as the true electromotive force value. The discrepancy between the readings at reversed polarities was generally of the order of a few µ v, as all the spot-welded joints were contained within a volume of some 5 mm cube. The relative resistance (R T/R 273o) variation with temperature is tabulated below, and shown in Fig. 1, as measured during the first heating run. The discontinuous drop in resistance, corresponding to the a — ß transformation, started for both initial orientations at 1170°K; i.e., some 15°K above the accepted value of 882°C (1155°K). Judging by the temperature ranse of transformation—some 30°K for the single crystal and 20°K for the polycrystal-line specimen—this difference is believed caused by the solution of the oxygen present initially on the surface of the specimens. The general trend of the resistance vs temperature shown in Fi,;. 1 is in qualitative agreement with that previously reported for polycrystalline titanium metal. 2,3 Significant anisotropy is, however, indicated by the crossing over of the curves for <1120> and <0001> orientations at 273°, 650°, and 1000°K. This difference is most startlingly shown in Fig. 2, where instantaneous temperature coefficients (l/R273 x dR /dT) are plotted for both the first heat-

Jan 1, 1962

By H. C. Rogers, B. W. Roberts

Vanadium foils and wires, either cold-worked or recrystallized, show a ductile-brittle-ductile fracture sequence with temperature. At about 150°C the hydrogenated vanadium wires are found to be ductile. At room temperature the wires show brittle fracture, and at liquid nitrogen temperature the wires are again ductile, although to a lesser extent than found at 150°C. Hydrogenated cold-rolled vanadium foils have been found to fracture in unusually straight lines along the [100] texture directions. The hydrogen content required to show this [loo] texture fracture is limited to a few atomic percent in range. Hydrogen content above this range causes fracture to occur in random directions. PRELIMINARY experiments with hydrogenated vanadium foils indicated that the embrittling effect of the hydrogen on the vanadium, which was severe at room temperature, was reduced at both lower and higher temperatures. In order to investigate more quantitatively the ductility changes with temperature, vanadium wires were tested in tension at three temperatures. The reduction of area was measured and the fractures examined. Specimen Preparation—The material used was kindly supplied by A. U. Seyboltl in the form of M-in. rod. The nominal analysis was: 99.2 pct V assay, 0.2 pct C, 0.01 pct Si, 0.01 pct Fe, 0.015 pct Ca, 0.02 pct O,, 0.01 pct N2, and 0.003 pct H,. The specimens were 0.035-in. diam wires. These were prepared by cold-swaging the supplied rod to the final diameter without intermediate anneal. They were finished with long-bearing dies. The surface was then given a light polishing with 0 emery paper and degreased in trichlorethylene. An X-ray check indicated that the cold-swaged wire had a fairly strong [110] fiber texture. The wires were then recrystallized in vacuum in continuously pumped quartz tubes at two temperatures to give two different grain sizes. One group of wires was given 45 min at 800°C; another, 60 min at 1000°C. The microstructures in Fig. 1 show the wires after they have been electropolished and elec-troetched in 10 pct HCI. After the 800°C anneal, the vanadium grains had a diameter of 1 to 2p and there appeared to be a tendency to elongation in the longitudinal direction. However, the latter may be an etching effect. After the 1000°C anneal, the grains appeared to be equi-axed, but there was a very large spread in grain size, probably due to some impurity segregation in the wire, Fig. 1, right. The grain diameters varied between the limits of 1 to 150p. The small particles shown particularly clearly in Fig. 1, left, are also visible on the polished surface of all samples before etching and are undoubtedly carbides and nitrides of vanadium. An X-ray check indicated these annealed wires had a strong [110} recrystallization fiber texture. The hydrogenation was carried out in an iron retort with dry hydrogen flowing through it, the retort and contents being heated in a tube furnace with a hydrogen atmosphere. The hydrogenation temperature was approximately 500°C. The hydro-genation times chosen were approximately those which would be just enough to cause the vanadium to be brittle at room temperature and thus allow the greatest chance for ductility to occur at the other two temperatures. Part of the fine grained specimens were hydrogenated for 21/2 min at 490°C. Part of the coarse grained specimens were hydro-genated for 11/2 min at 515°C.

Jan 1, 1957

By F. W. C. Boswell, R. L. Cunningham, H. M. Weld

Chemical analysis shows the partition of the magnesium addition between the metal and the graphite is independent of whether the graphite is in the form of nodules or flakes. The bright central spot observed in nodular graphite polished sections is shown to be due to the structure of the nodules. DURING the past few years numerous papers have been published on the production1-7 and heat treatment" of nodular cast irons. However, very little information is available on the structure of the nodules and the reason for their formation. It would appear that an explanation of the phenomenon of nodulation must await a detailed knowledge of the nature of the nodule. Disagreement exists among various workers on such a fundamental point as to whether or not a nodule actually contains a microscopically visible, nongraphitic nucleus.9-11 Work was initiated with a view to obtaining definite information on this and other aspects of the problem. Chemical Separation and Analysis Microscopic appearance had indicated9-11 that a nongraphitic core might exist in nodules (Fig. 1). It appeared that a chemical comparison of separated nodules and flake graphite would be profitable, for if the core is nongraphitic a relatively large amount of certain elements would be found in the nodules as compared to the flake. This comparison could best be made by obtaining nodules and flake from the same melt of cast iron, part of which had been in-noculated with a suitable addition reagent for the formation of nodules. A 300 lb melt was produced. About half of this was innoculated in the ladle with an Fe-Si-Mg alloy to produce nodules and cast into keel blocks; the remaining half of the melt had silicon added in an effort to compensate for the silicon in the innoculant used in the other half of the melt and this was cast into similar keel blocks. The analyses of the resultant irons are given in Table I. Nodules and flake were chemically extracted from 2 kg samples of metal as described in the appendix. While this method dissolved the iron and chromium carbides, it did not dissolve the titanium, vanadium, and molybdenum carbides. These latter carbides could have been removed by nitric acid, but in other experiments it was found that it attacked pools of metallic iron entrapped in the nodules which had, until the nitric acid treatment, been protected from the attack of the sulphuric, hydrochloric, and hydrofluoric acids. It will be shown in the next section that entrapped iron exists in nodules but not in flake. On microscopic examination many tiny irregular particles were observed to accompany both the nodules and the flake. These were identified by tabling a sample of nodules from which a sufficient fraction was obtained for X-ray analysis. A good pattern of titanium carbide was obtained indicating that this was the predominant compound present. Since it was not possible to determine how completely the carbides could be removed mechanically and since their removal from flake is much more difficult, it was decided not to resort to any separation as this would render further comparisons more difficult. The samples were ashed in a combustion

Jan 1, 1953

By R. D. Nelson, D. H. Polonis

ThE eutectoid decomposition of 6 phase in the Cu-Sn system (32.53 wt pct Sn) has been studied by several investigators.1-6 On the basis of X-ray work, Iball and 0wen1 reported complete decomposition of 6 in powder specimens after 7 days at 300°C. Wang and Hansen followed the micro-structural changes during heat treatment of lump specimens and estimated 5 pct decomposition after 63 days at 300°C. Wang and Hansen suggested that the discrepancy between the decomposition rates of powder and lump specimens might be due to the excess surface free energy of powders. The present work involved 6 decomposition in copper-tin alloy powders containing 32.6 wt pct Sn. Alloy lump specimens exhibited entirely 6 phase after fairly slow cooling (air cooling) from above 350°C and were so brittle that they could be easily crushed to-200 mesh in a percussion mortar. X-ray diffraction study of the as-crushed powders (-200 mesh) revealed 100 pct 6 phase with very slight line broadening effects due to strain introduced by crushing. Only 6 phase was detected by X-ray diffraction in powders which were heat treated 4 hr at 450°C and air cooled to room tem-

Jan 1, 1960

By Harry A. Lipsitt, Rollins E. Hook, Attwell M. Adair

A necessary condition for a uniaxial stress distribution in compression testing is that the specimen end surfaces make full contact with the apparatus compression plates. In addition all compression surfaces must be machined perpendicularly to the loading axis. In general this condition is not sufficiently fulfilled in a simple apparatus. Therefore on application of the load the compression plate may first touch the specimen at one point only. This may cause crumbling of the specimen if the material under investigation is brittle (e.g., ionic crystals). It also precludes a precise study of the beginning of deformation as the effective cross sectional area is unknown. In addition a complex stress state is set up which renders quantitative work impossible, e.g., on dislocation density and arrangement as a function of stress. To overcome these difficulties a "self-adjusting" upper compression plate is required. A simple and reliable method of achieving this is shown in Fig. 1: A steel hemisphere is placed on the specimen. As soon as the compression plate (which no longer needs precise machining) makes contact with this hemisphere the load is uniformly distributed over the whole specimen surface, and a homogeneous uniaxial state of stress results. An advantage of the method is that the loading is always central, even when the specimen surface is not parallel to the compression plate (Fig. 1, dashed line). Therefore to a first approximation a uniaxial state of stress is maintained if the misorientation of the specimen end surface is small. Two typical stress strain curves of identically prepared sodium chloride crystals are shown in Fig. 2; curve 1 was taken without and curve II with the hemisphere under otherwise identical conditions. The improvement in the accuracy of defining the beginning of elastic and plastic deformation is clearly indicated. The writer wishes to thank the Deutsche Forschungsgemeinschaft for financial support, and Professor P. Haasen for providing facilities for this work.

Jan 1, 1962

By Ronald C. Koo

THE effect of grain size on the mechanical properties of the bcc metals has been a subject of intensive theoretical and experimental study.&apos;-l5 Quantitative relationships have been established experimentally between yield stress and grain size and between the ductile-brittle transition temperature and grain size in a number of metals.6"15 Much significance has therefore been attached theoretically to the grain size dependence. In all these experiments, different grain sizes were always achieved by annealing specimens at various temperatures. The implicit assumption was that any change in the dislocation substructure or in the distribution of impurities which might occur simultaneously with the production of various grain sizes had only a negligible effect on the mechanical properties. The validity of this assumption, however, is questionable. transformation in iron-nickel alloys is actually an extraneous phenomenon due to inadvertent compositional changes in the martensite if the heating rate is not sufficiently rapid. This complication can be avoided by up-quenching for the reversal treatment,5 and then the stabilization does not appear. Clearly, the lattice imperfections and strengthening produced by the reverse transformation are not responsible for the marked stabilization which has been observed by other investigators in these alloys. Data will be presented in this note to show that, at least in recrystallized tungsten of commercial purity, the difference in the ductile-brittle transition temperature of specimens annealed at various temperatures is more a result of a variation in the distribution of impurities rather than of the difference in grain size produced by the anneal. Ductile-brittle transition temperatures in tension were determined on powder-metallurgy tungsten specimens recrystallized at various temperatures. Tensile specimens having a gage length of 1.50 in. and gage diam of 0.18 in. were recrystallized at 1450°, 2000°, 2350°, 2550°, 2750°, or 2800" for 30 min in a vacuum furnace at a pressure of 1 x 10"5 mm of Hg and then tested at a constant extension rate of 8 x 10 per sec in an argon atmosphere from 100" to 800". Typical quantitative analyses of impurities are given in the Table. These results show that, within the precision of the analyses, see Table, annealing did not result in any detectable change in the impurity contents of the specimens, nor was there any detectable difference in purity between specimens having large differences in grain size annealed at the same temperatures . The results of the tensile tests yielded three distinct ductile-brittle transition curves approximately 225&apos; apart. As shown in Fig. 1, data of specimens annealed at 1450°C and those of specimens annealed at 2000°C (O) fell on Curve A. Data of specimens annealed at 2350" and 2550°C fell on Curve B, and those of specimens annealed at 2750" and 2800°C fell on Curve C. The decrease in ductility with increase in annealing temperature became so pronounced that one third of the specimens annealed at 2750" and two thirds of the specimens

Jan 1, 1963

By John D. Roach

DURING an investigation of the yttrium-hydrogen system aimed at producing solid yttrium hydride specimens containing various amounts of hydrogen, it was observed that yttrium containing approximately 2 wt pct H exhibited a tendency to crack and crumble to a powder on standing in air at room temperature. It was also observed that longer hydriding times, at a given temperature, increased this susceptibility to powdering without an increase in hydrogen content, also that moisture in the air is necessary for the observed effects to occur. Even if cracking did not occur, there was a continual formation of a light gray powder on the as-treated surface of the hydrided yttrium and this reaction continues until the entire hydrided piece has been reduced to a powder. Storing the hydrided specimens in the absence of air or removing the surface either by machining or grinding were effective means of preventing this disintegration of hydrided yttrium. In an attempt to determine the reason for this powdering phenomenon, the surfaces of a number of as-hydrided yttrium specimens were examined by X-ray techniques. In all cases the X-ray pattern obtained showed the major phase to be yttrium hydride (YH2) as would be expected since the specimens contained 2 to 2.2 wt pct H. In some cases a trace of yttrium oxide was observed. There was also a third phase present on the surface of these hydrided specimens which could not immediately be identified. This unknown phase was a face-centered cubic material, NaC1-type structure, with a lattice parameter of 4.855 and a calculated density of 5.914 g per cc. Very slight hand polishing of the surface of the hydrided yttrium specimens completely removed both the unknown phase and the traces of oxide so that only the yttrium hydride pattern remained. Based on the X-ray patterns the quantity of the unknown phase on the surface of the hydrided yttrium appeared to be directly related to the susceptibility of the material to powdering. Work at the Denver Research Institute on the yttrium-nitrogen binary system showed that yttrium nitride (YN) is a face-centered cubic material with a lattice parameter of 4.878A and a density of 5.890 g per cc. They also noted that this compound rapidly disintegrated to a powder on standing in air. The unknown pattern observed in the above specimens corresponds very closely to that of the nitride—fcc structure, 4.885 parameter, and density of 5.914 g per cc. The presence of this thin film of nitride on the surface of the hydrided specimens probably accounts for the observed powder formation and crumbling. The nitride reacts with the water vapor in the air (verified by private communication from Dr. C. Huffine, General Electric Co.) to yield yttrium oxide and ammonia. Ammonia is readily detected when hydrided yttrium specimens were allowed to stand in bottled moist air. The powder formed on the surface of the hydrided specimens was shown by X-ray analysis to be yttrium oxide. This reaction appears to occur primarily at the grain boundaries since discrete particles of yttrium hydride separate from the specimens during this powdering process. The reaction of yttrium nitride with water vapor is believed to be as follows: 2YN + 3H2O - Y203 + 2NH3. Despite the fact that this nitride is present only as an extremely thin surface film, if the above reaction is not prevented by removing this film from the surface either by machining or grinding, the reaction continues until the entire hydrided piece has been reduced to a powder. To account for this continuation of the reaction, it is believed that the following reactionalsooccurs: 2YH2 + 2NH3 -2YN + 5H2. The nitride produced by the latter reaction reacts in turn with water vapor. The reaction therefore becomes autocatalytic and continues until the hydride has been consumed and the entire piece reduced to oxide powder. The amount of nitride required to initiate this reaction is quite small and this nitrogen contamination can occur from a number of sources—hydrogen gas employed, minute leak in the hydriding apparatus or even from degassing of the reaction vessel itself. Longer hydriding times increase the possibility of nitrogen contamination and this is especially true when a dynamic gas system is employed in the hydriding process. The production of stable, solid hydrided yttrium is dependent on the complete absence of nitrogen contamination during processing. If such contamination does occur, powdering of the hydrided product can be prevented by removing the nitride from the surface e.g. grinding or by preventing access of air to the pieces e.g. sealing in wax or plastic. The author wishes to express his appreciation to General Electric Co. for sponsoring this research and for permission to publish the results of work under Subcontract AT-93.

Jan 1, 1962

By J. Gurland

THE microstructure of sintered carbides consists of particles of metal carbides, such as WC and TiC, embedded in a metallic binder which is usually a cobalt—or nickel-rich solid solution. One of the important factors influencing the strength of the alloys is the degree of dispersion of the carbide particles in the binder matrix. While it is generally accepted

Jan 1, 1960

By D. W. Levinson, L. E. Tanner

DURING the course of an investigation of the zirconium-iron-tin system the zirconium-iron system was reexamined up to 55 pct* Fe. The alloys pre- visible melting3 and X-ray diffraction studies were made of samples of the alloys. The ferromagnetic properties of ZrFe2were determined by Professor P. W. Selwood* using a modified Faraday balance.4 The zirconium-rich portion of the phase diagram is presented in Fig. 1 and compared with the work of Hayes et al.1 The maximum solubility of iron in ß is somewhat decreased while the eutectic temperature is raised. There seemed to be no change in the eutectic composition of 16 pct Fe. Since the base material was so low in iron content, it was possible to establish the maximum solubility in a between 0.017 and 0.025 pct Fe at the eutectoid temperature. The observation of fine ZrFe, particles in the micro structure of a specimen of 0.012 pct Fe alloy quenched from 700°C indicated that the solubility drops below this composition at 700° C and lower. Further study was made of the intermediate phase ZrFe2. wallbaum5 identified the compound initially as ZrFe2 with a C 15 (MgCu2) structure, placing it at 55 pct Fe stoichiometrically. Hayes et al.1 believed they found the phase at about 47.2 pct Fe and called it Zr2Fe3 but reverted to ZrFe, in the discussion of their paper.6 Jordan and Duwez7 confirmed Wallbaum&apos;s work as well as finding the same single-phase structure to about 62.3 pct Fe or Zr0-61 Fe2-18. In order to establish the ternary phase relations in the zirconium-iron-tin systema the exact position of this phase had to be known. This was accomplished by X-ray diffraction, visible melting, and metallographic techniques. Elliott8 obtained a single-phase ZrFe2 X-ray diffraction pattern from an alloy of about 55 pct Fe. This was confirmed in the present study with an alloy of 54.81 pct Fe. However, extra lines (attributable to a or ß zirconium) were found in diffraction patterns of the 47.42 and 49.83 pct Fe alloys. The melting characteristics of these same alloys were studied by suspending 47.42, 49.83, and 54.81 pct

Jan 1, 1960

By E. A. Calnan, B. E. Williams

IN the development of a new treatment for the prediction of deformation textures,&apos;-&apos; it was noted that for no metals are there experimentally determined tension textures with which the predictions may be compared. There is a considerable knowledge of drawing textures and previous workers have been content to consider these as equivalent to tension textures for the purposes of comparison. It is shown, however, in the new treatment that the tension and drawing textures are not necessarily identical, the radial compression exerted by the dies in the drawing operation producing some modification of the tension texture. In particular for the face-centered cubic metals it is predicted that for drawing the final texture should be [1ll] with a spread towards [211] (a more detailed derivation of this texture has been made by Calnan3). This has been amply confirmed by experiment, see Hibbard.6 For the pure tension case, however, the treatment predicts intermediate [1ll] and [loo] textures leading to a [211] end-point, while all previous treatments have predicted the final texture as [1ll] with in some cases an additional [loo] component. Thus evidence that the pure tension end-point is the [211], or at least that [1ll] and [l00] are not the final textures, should provide a valuable test of the new treatment. Accordingly some experiments were made on aluminum. Three aluminum specimens were examined in detail, one of cold-rolled high purity rod (99.99 pct), specimen A, and two of commercial extruded rod of purity 99.4 pct, specimens B and C. The initial annealing treatments were: A, 1½ hr at 400°C; B, 2 hr at 400°C; C, 1½ hr at 650°C. The principal difficulty is that of obtaining sufficient elongation before fracture occurs. This was overcome to some extent by giving a softening heat treatment, 1 hr at 300°C, after each 15 pct of extension. Vickers hardness measurements gave values before and after the softening treatment of about 30 and 28, respectively, in comparison with the initial value of about 19 corresponding to fully annealed material. From recent observations in this laboratory it is concluded that this small recovery corresponds to a polygonization process rather than recrystallization proper and consequently the preferred orientation is unaffected. At the higher extensions, however, some slight necking of the specimens took place and it was necessary to turn them down to a uniform cross-section before

Jan 1, 1953

By D. S. Hutton, W. C. Leslie

Thermal etch patterns developed on poly crystalline 3.5 pct Si-Fe by heating in hydrogen or in argon have been examined. The most prominent feature of the etching is the development of striations on grains with (100) planes near the plane of the surface. These striations are probably produced by the resoution of a random, high-energy plane into (100) facets of lower energy. THE thermal etching of iron and iron-base alloys has a long history. The phenomenon was observed by Osmondl more than 70 years ago. The literature on thermal etching between that time and 1951 was reviewed by Olney,2 and a briefer review appeared in 1958. 3 The only articles which have been found dealing with the thermal etching of silicon iron are those of Dunn and Lionetti4 and of Dunn, Daniels, and Bolton,5 and they reported only grain boundary etching. EXPERIMENTAL PROCEDURES A cast 3.5 pet Si-Fe alloy was given a metallo-graphic polish and etch, then placed in flowing purified hydrogen for 6 hr at 2200°F. The same specimen was later repolished and etched to remove the thermal etching. The specimen was then held in flowing purified argon at 2200°F for 72 hr. In both instances the specimen was rapidly cooled by being pulled up quickly into the cold zone of the furnace. All photomicrographs shown are of the surface as removed from the furnace. Oblique illumination was essential for observation of the thermal-etching effects with a light microscope and was used for all the photomicrographs. RESULTS AND DISCUSSION Grain boundary etching, grain boundary movement, and contouring within grains are illustrated in Fig. 1. The contours within a single grain followed behind the advancing grain boundary. To determine the average contour interval, or step height, white light was used in an interference microscope. The steps were of the correct magnitude to separate while light into its spectrum of colors. A green light was focused at the top of a contoured area, shifting to red across the field. By using the difference in the dominant wave length of red and green light,6 and counting the number of steps across the area, it was possible to obtain a value of about 80A for the average step height. Laue back-reflection patterns of four grains with contour lines showed that the grains had a (100) plane slightly inclined to the plane of the surface (± 5 deg). Insofar as this could be determined from their irregular traces, the contour lines within a grain had a common direction, <100> ± 5 deg.

Jan 1, 1961

By H. Margolin, E. Ence

In order to understand the effect of zirconium on properties of Ti-Cu-A1 alloys, Ti-Zr alloys were examined for the presence of ordering or compounds at the following compositions in weight percent: 24.1 pct Zr (lZr:GTi), 32.2 pct Zr (lZr:4Ti), 38.8 pct Zr (lZr:3Ti), 49.0 pct Zr(1Zr:ZTi). Alloys were prepared as 15-g buttons by non- consumable arc melting under argon atmosphere from Bureau of Mines titanium (Bhn 63) and Reactor Grade zirconium (Bhn 150). Weight losses during melting did not exceed 1 pct of the initial button weight. Prior to heat treatment, buttons were hot-rolled at 600" to 700°C to rods of about 6 mm diam. Contamination after hot-rolling was found to extend to a depth of less than 0.5 mm. Specimens for heat treatment were wrapped in molybdenum sheet, annealed in argon-filled quartz capsules, and quenched by breaking the capsules under iced brine. Annealing times were as follows: 700°C — 7 days; 600°C— 14 days; 575°C-1 and 2 months; 525°C-2 months; 500°C-2 months. Prior to heat treatment, all Ti-Zr alloys were vacuum annealed at 900°C to remove hydrogen. The reanneal of 575°C specimens for an additional month produced no observable microstructure changes. The results obtained by microstructure and X-ray diffraction are shown in Fig. 1, together with data of Hayes et al.&apos; No other phases than a or P were found. Small amounts of retained P were detected by X-ray in the 49 pct Zr alloy. The data of the present investigation suggests that ß and a transus boundaries are at considerably lower temperatures than those of Hayes et al. The work of Hayes et al. is based on sponge titanium and Bureau of Mines zirconium, both of which contained 0.15 pct 0. Since melting was performed in

Jan 1, 1962

By H. B. Probst

Mechanical twins were produced in zone-refined tungsten single crystals by explosive working at room temperature. These twins are parallel to (112) planes and have irregular boundaries rather than the classical plane twin boundaries. These boundaries aye grooved surfaces in which the grooves themselves are parallel to a <111> direction and the sides of the grooves appear to be par-allel to (110) planes. TWINS were produced in tungsten single crystals by explosive working at room temperature. These twins differ in character from any previously reported for tungsten; however, they are similar to those found in molybdenum after compression at -196°C.1 Deformation twins "resembling Neumann bands in ingot iron" have been observed in tungsten by Bech-told and Shewmon.2 This observation was made with sintered polycrystalline tungsten pulled in tension to fracture at 100°C and using a strain rate of 2.8 x 10-4 sec-1. More recently Schadler3 found deformation twins in zone-refined tungsten single crystals pulled in tension at -196"&apos; and -253°C. These tests were conducted using a strain rate of 3.3 x l0-4 sec-1, and the twin bands were found to be parallel to a (112) plane. Deformation twins in tungsten&apos;s sister metal, molybdenum, were observed by Cahn.4 These twins were produced by compressing small (0.7 mm) vapor-deproducedposited molybdenum single crystals at -183°C. The compression was performed &apos;by impact." By the use of precession X-ray techniques, Cahn was able to identify the twin plane as {112} and the shear direction as <1ll>. Mueller and Parker1 produced deformation twins in polycrystalline electron-beam-melted molybdenum by compression at -196°C. Their "loading rate" was 5000 psi per min which, judging from their stress-strain curve, corresponds to a strain rate of approximately 0.3 x 10-4 sec-1. These twin bands were found to be parallel to (1 12) planes; however, they differed in appearance from previously observed twins. In place of straight and parallel twin boundaries they were found to be irregular, jagged, and sawtoothed. The sides of the saw teeth were identified as (110) planes and irrational planes of a (111) zone. The twins observed in the present work in tungsten single crystals are similar in appearance to those of Mueller and Parker in polycrystalline molybdenum. The starting material used in this investigation was 3/16-in. diam commercial tungsten rod produced by powder-metallurgy techniques. This material was converted to a single crystal by the electron-bombardment floating-zone technique.= The process was carried out in a vacuum of 10-5 mm of Hg using a traversing speed of 4 mm per min. Segments (=2 in. long and 3/16 in. in diam) of two crystals (A and B) produced in this manner were studied. Crystal A received one zoning pass, while crystal B received two passes. The two crystals were explosively worked at Bat-telle Memorial Institute in the following manner. A 1/2-in.-thick layer of plastic was applied to the crystals to serve as a buffer in an attempt to prevent cracking. The composite, crystal and buffer, was then wrapped with 1/8-in.-thick DuPont sheet explosive EL506A2 and detonated in water at room temperature. Metallographic samples of the worked crystals were prepared, and back-reflection Laue X-ray patterns were obtained using unfiltered molybdenum radiation. RESULTS AND DISCUSSION Blasting the crystals as described above failed to prevent cracking. The crystals fractured into several fragments about 3/16 to 1/2 in. long; however, the fragments were of sufficient size to be useful for the subsequent study. The diamond pyramid hardness of the crystals after blasting was in the range 430 to 450 as compared with 340 for the as-melted material, which shows a definite hardening resulting from plastic deformation. These hardness values were obtained using a 1000-g load and taking readings only in sound portions of the crystals free of cracks. The crystals exhibited profuse twinning as shown in Fig. 1. No such structure is present in the as-melted condition. Most of these twins have jagged twin boundaries and are similar in appearance to those found in molybdenum by Mueller and Parker. The twins in both crystals were found to be parallel to {112} planes. This identification was made by using the conventional two-trace method. Subsequent efforts to describe these twins more fully were carried out on crystal A. If the longitudinal axis of crystal A is placed in the (001)-(011)-(Il l) basic triangle of the standard cubic stereographic projection, as in Fig. 2, then the two sets of twins shown in Fig. 1 are parallel to the (112) and (121) planes. Fig. 3 shows a schematic representation of a twin with jagged boundaries. This type of twin with a <111>

Jan 1, 1962

By P. K. Koh

Chi phase (body-centered cubic, a = 8.89A) was found in as-cast 23 pct Cr-10 pct Mo-Fe alloy as well as in heat-treated 316, 316L, 317, and modified 446 stainless steels. Chi phase resembles sigma phase in its metastability, chemical composition, and brittleness. Microstructure and some of physical properties of chi phase were developed. MOLYBDENUM has been established as a desirable alloying element for the enhancement of corrosion resistance in Cr-Ni steels and creep and rupture strength in high temperature alloys. On the debit side, however, the molybdenum addition has been known to stimulate u formation. When the molybdenum-bearing steels were subjected to prolonged heating at elevated temperatures, losses of corrosion resistance and/or ductility have been observed. Andrews1,2 first found the existence of a new phase among the anodic FeC13 extracts from type 316 stainless steel solution treated and then reheated from 800" to 1100°C. This phase was designated x and was identified by diffraction patterns as of body-centered cubic structure with a value equal to 8.89? and similar to that of a manganese. He found that the x phase in this steel always coexisted with s phase, but failed to distinguish one from the other by metallographic technique. No definite conclusion was drawn regarding the equilibrium temperature ranges of these two phases. The appearance of Andrew&apos;s work recalled an un- explained structure observed several years ago at the Allegheny Ludlum Research Laboratories during the investigation of an experimental alloy containing 25 pct Cr, 10 pct Mo, and balance Fe. X-ray diffraction patterns on the as-cast material revealed the presence of a body-centered cubic phase having a lattice parameter of 8.89?. The structure was sufficiently similar to that of y chromium that for a time it was thought that the structure might be caused by the presence of some undissolved electrolytic chromium particles. The alloy as-cast was so brittle that it shattered after the slightest hot reduction by hammer cogging. This paper gives the results of some metallographic and X-ray diffraction studies on x phase as found in several experimental alloys as well as a few molybdenum-bearing commercial stainless steels. The analyses of materials studied were as shown in Table I. Experimental Procedure Metallography: Solid specimens were polished mechanically and etched in boiling 50 pct HC1 solution in order to best delineate x and s phases in the alloys studied. X-Ray Diffraction: The difficulty of satisfactorily developing diffraction lines for s phase in solid specimens has been previously reported by Bindari, Koh, and Zmeskal.V or this reason all specimens used in this investigation were subjected to anodic

Jan 1, 1954

By E. S. Machlin, C. W. Chen

THIS investigation is concerned with the origin of the intercrystalline voids and cracks formed in metals and alloys subjected to stress at elevated temperature. There have been many suggestions in the recent literature relating to this problem. Greenwood&apos; suggested that the voids may be produced by vacancy condensation. Zener has stated that shear-stress relaxation across grain boundaries could initiate high tensile stresses at the regions blocking grain boundary slip and thereby cause the formation of cracks. Chang and Grant3 have described the formation of cracks at grain boundary triple points and have experimentally verified Zener&apos;s mechanism for the grain boundary regions in the vicinity of a triple point. Subsequent to the completion of this investigation, Gifkins4 developed a model which made use of Stroh&apos;s5 mechanism of fracturing to produce sub-microscopic fractures that subsequently grow by grain boundary slip. Chen and Machlin,6 in answer to Gifkins, described a model deduced from the present investigation, in which grain boundary slip provides both the stress to fracture at grain boundary jogs and the deformation required to separate fractured jog surfaces. The possibility of gas condensation to form intercrystalline voids and cracks is eliminated as a basic mechanism because such voids and cracks are developed in vacuum melted material containing minute amounts, if any, of gaseous impurities. In a theoretical evaluation of this problem, Machlin7 concluded that void nucleation by vacancy condensation during creep-rupture is improbable but that vacancy condensation on supercritical sized voids to produce growth is probable. This investigation was begun to evaluate the suggested mechanisms for intercrystalline fracture. In particular, in order to correlate vacancy supersaturation ratios produced in creep with those determined by Bal-luffi and Seigle8 as critical for , the nucleation of voids, specimens were obtained from the same heat of brass as used by the latter authors, through the courtesy of Dr. Seigle. The experiments conducted in this investigation fall into the following categories: 1) Brass—observation of voids produced under a variety of conditions, including creep under compression, to evaluate the mechanisms of void nucleation and growth. 2) Bicrystal experiments to check the mechanism of void nucleation deduced in this investigation. 3) Morphology of intercrystalline voids produced in a variety of metals. Each set of experiments will be described and discussed separately. Experimental Techniques A special creep-rupture test rack was constructed which made it possible to apply the stress to the specimen in a controlled atmosphere of inert gas, reducing gas, or vacuum. All the creep-rupture tests on a-brass (30 pct Zn) were conducted in nitrogen under a pressure slightly above atmospheric. Either dead weight loading or constant elongation rate loading could be applied with the load measured by means of a strain gage dynamometer. In order to obtain a coarse-grained crystal structure stable at

Jan 1, 1958