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By E. N. Smith, J. C. Redmond

The increasing need for materials capable of withstanding higher operating temperatures for various applications such as gas turbine blading and other parts, rocket nozzles, and many industrial applications, has brought consideration of cemented carbide compositions. The well known usefulness of cemented carbides as tool materials is attributable to their ability to retain their strength and hardness at much higher temperatures than even complex alloys. However, it has been found that the temperatures encountered in cutting operations do not approach by several hundred degrees1 those involved in the applications mentioned above where the interest is in materials possessing strength and resistance to oxidation at temperatures of 1800°F and above. At these latter temperatures, the tool type compositions which are made up essentially of tungsten carbide are found to oxidize very rapidly and to produce oxidation products of a character which offer no protection to the remaining body. As a further consideration, the density of the tungsten carbide type compositions is high, from about 8.0 to 15.0. The refractory metal carbides as a class are the highest melting materials known as shown by Table 1 which summarizes the available data from the literature for the carbides of the elements which are sufficiently available for consideration for these uses. The density is also included in the table, since as mentioned above it is an important consideration in many of the applications for which the materials would be considered. It has been established that in the tool compositions the mechanism of sintering with cobalt is such as to result in a continuous carbide skeleton and that the properties of the sintered composition are thus essen- tially those of the carbide.2 On the hypothesis that this mechanism holds to a greater or less degree in cementing most of the refractory metal carbides with an auxiliary metal, it appears from Table 1 that titanium carbide compositions would offer possibilities for a high temperature material. Titanium carbide has extensive use for supplementing the properties of tungsten carbide in tool compositions. Although the literature contains several references to compositions containing only titanium carbide with an auxiliary metal,3,4,5,6 it may be inferred from the meager data that such compositions were deficient in strength and were considered to have poor oxidation resistance.7 Kieffer, for instance, reports the transverse rupture strength of a hot pressed TiC composition at 100,000 psi as compared to up to 350,000 psi for WC compositions. The work described herein was undertaken to determine the properties of compositions consisting of titanium carbide and an auxiliary metal and to improve the oxidation resistance of such compositions. It appeared possible that the inclusion of one or more other carbides with titanium carbide might improve the oxidation resistance and also that this might be more desirable than other means from the point of view of maintaining the highest possible softening point. Consideration of the available carbides in Table 1 suggests tantalum and columbium carbides because of their high melting points and general refractoriness. The work on improving oxidation resistance was concentrated on the addition of tantalum carbide or mixtures of tantalum and columbium carbide. The auxiliary metals used included cobalt, nickel and iron. It was also desired to learn the general physical properties of these compositions. Experimental Procedure The compositions used in this study were made by the usual powder metallurgy procedure applicable to cemented tungsten carbide compositions. The powdered carbide or carbides and auxiliary metal were milled together out of contact with air. In some cases cemented tungsten carbide balls and in other instances steel balls were used to eliminate any effect of tungsten carbide contamination. A temporary binder, paraffin, was then included in the mix and slugs or ingots were pressed with care to obtain as uniform pressing as possible. The ingots were presintered and the various shapes of test specimens were formed by machining, making the proper allowance for shrinkage during sintering. Thereafter the shapes were sintered in vacuum at temperatures of from 2800 to 3500°F. Final grinding to size was carried out by diamond wheels under coolant. The titanium carbide used contained a minimum of 19.50 pet total carbon and a total of 0.50 pet metallic impurities as indicated by chemical and spectrographic analysis. It was found by X ray diffraction examination with

Jan 1, 1950

By J. B. Clark, F. N. Rhines

brittlement or notch sensitivity progressively increases. Further, in contrast to results obtained with the impact test, the notch strength for the large specimens does not reveal a 500°F embrittlement range. The notch sensitivity as determined with the 0.3-in. specimen of 4340 steel given the stepped austenitizing treatment has been discussed elsewhere. This quantity as measured for the 1.1-in.- diam notch tensile test and given in Fig. 3, is taken to signify that reduced notch sensitivity is encountered in the 600" to 800°F tempering range for specimens given the stepped austenitizing treatment. The stepped austenitizing treatment may, there- fore, be of use in promoting deeper hardenability for a 4340 steel while at the same time giving reduced notch sensitivity in the high-strength range in which this steel is now being used. Acknowledgments The work reported was supported by the U. S. Navy Bureau of Aeronautics. The authors are indebted to the Bureau of Aeronautics for granting permission to publish results of this research and to N. E. Promisel, H. Hessing, and J. Maltz for their interest.

Jan 1, 1958

By M. N. Shetty, A. C. D. Chaklader

RECENTLY, it has been demonstrated that a considerable densification and interparticle bonding can be achieved if a pressure is applied to a powder compact while the material of the compact is undergoing either a decomposition reaction' or a polymorphic transformation.' The term "reactive hot pressing" has been coined to identify this process in which a phase change is combined with pressure to achieve interparticle bonding. This process is based on a principle which postulates that there is an enhanced reactivity and mobility of the molecular species at the phase-transformation temperature and this effect is utilized for interparticle bonding in powder compacts. This note summarizes the results obtained in an attempt to utilize this technique to produce ceramic-metal composites. In this case, a decomposition reaction of a compound (which after decomposition yielded an oxide) was used to achieve interparticle bonding in ceramic-metal composites. The reactive hot pressing was carried out in a Phillips induction heating unit, using either a graphite or a high-temperature steel die which functioned as both the susceptor and the hot-pressing component. The die was heated to the desired temperature in a helium atmosphere. All cermets produced by this technique were based on alumina as the ceramic phase. Different metal phases such as iron, copper, and chromium were used to study the effect of varying the metal phase on the properties of the composite. a Mono-hydrate (Boehmite) was mixed with different proportions of metal powders (-325 mesh) in dry condition in a mortar and pestle. No special precautions were taken for proper mixing. The mixtures were then compacted into a cylindrical form having an approximate dimension of 1 cm in diameter and 1 cm in height. For this compaction an ordinary

Jan 1, 1965

By L. S. Birks

The bainite transformation in a 3.5 pct Ni-1.25 pct Cr steel was studied under various conditions of cooling and stress. Several characteristics may be specified: 1) transformation in the bainite region (925° to 575°F) is very little affected by the manner of cooling from the austenitizing temperature at 1600°F to 575°F)tothe upper limit of bainite transformation at 925°F; 2) starting time for the bainite transformation is the same order of magnitude for either isothermal transformation or continuous cooling, but the rate of transformation is somewhat greater for isothermal transformation; 3) tensile stress accelerates both isothermal and continuous cooling transformation, and 32,000 psi stress changes the form of the isothermal transformation diagram to correspond in appearance to the continuous cooling diagram; 4) transformation for nonlinear, continuous cooling may not be determined directly from the linear, continuous cooling transformation diagram, but may be predicted by assuming first that the fractional amount of austenite transformed in a given small temperature interval depends on the approximate linear cooling rate during that temperature interval and then by summing stepwise over the whole temperature range. IN a previous publication' an X-ray spectrometer was described with which the X-ray diffraction from a specimen could be observed continuously under controlled temperature and tensile stress. This instrument has now been applied to a study of the austenite-bainite transformation in a Ni-Cr steel for both isothermal and continuous cooling conditions, with and without stress. Certain characteristics of the transformation lead to a method of predicting the amount of transformation to be expected at a given temperature for any type of cooling curve. Material and Specimen Preparation The steel chosen for the investigation was a Ni-Cr steel having the composition in the following percentages: 0.30 C, 0.27 Mn, 0.019 P and S, 3.50 Ni, and 1.25 Cr. In order to fabricate specimens suitable for the X-ray spectrometer, a 1/4 in. plate was ground down to 0.060 in. and then cold rolled to about 0.035 in. Next it was heat treated by quenching in oil from 1650°F and tempering at 1200°F for 1 hr. Then it was etched in dilute nitric acid to reduce its thickness to 0.014 in. and cut into blanks in the shape of flat tensile specimens 3 1/4 Vi in. long, 7/16 in. wide, with a notch % in. long and 7/32 in. wide; see Fig. 1. X-Ray Technique Since the X-ray spectrometer has been described in detail elsewhere,' only a brief outline of the principles will be repeated here. A focusing, pow- der-diffraction arrangement' was used, as shown schematically in Fig. 1, and the specimen was mounted vertically in a vacuum furnace (not shown in the figure). The X-rays, moving in a horizontal plane, enter and leave the furnace through beryllium windows. As shown in the figure, X-rays diverging from the line source A are diffracted by the specimen B and converge at the detector slit C. The detector D and the slit C may be set at the proper angle in the horizontal plane to receive X-rays diffracted by either the face-centered phase (austenite) or the body-centered form (ferrite, bainite, martensite). The specimen is heated by electrical conduction between connectors E, and E,, and a Pt—Pt-10 pct Rh thermocouple spot-welded to the center of the notched region on the side away from the X-ray beam indicates the temperature continuously on a Brown recorder. Temperature control is exercised manually with a variable transformer on the input to E,-E,. Any desired time-temperature relationship is easily obtained by first drawing the desired curve on the temperature recorder chart and then adjusting the variable transformer during the run so that the thermocouple

Jan 1, 1957

By Nicholas J. Grant, David S. Bloom

An investigation of the Cr-Ni system has revealed that there exists a eutectoid transformation at about 1180°C. 'The transformation in chromium implied by the eutectoid reaction was detected at about 100°C below its melting point. Associated with the eutectoid transformation, a metastable transition structure has been found. THE Cr-Ni phase diagram is shown in current literature to be a simple eutectic system in which the high chromium end of the diagram is incompletely determined, Fig. 1. The last investigation of this system was undertaken in 1936.' Because of limitations in metal purity, especially of chromium, and temperature measuring techniques, the diagram should be accepted with some reservations, as was indicated by Hansen.V or examwle.-, the wresence of the compound Cr²Ni, with a tetragonal structure," remains unverified and incompatible with the simple eutectic diagram. The work reported here began because of discrepancies that appeared in experimental studies in the binary alloys Cr-Ni and in the ternary system Cr-Mo-Ni. The existing binary Cr-Ni diagram failed to provide a complete explanation of observations made by microscope, X-ray, and thermal analyses. Experimental Methods The materials employed were of a higher degree of purity than were available to previous investigators. The Mond nickel used had a nominal purity of 99.87 pct, while the electrolytic chromium analyzed 99.03 pct with the major impurity being 0.5 to 0.7 pct oxygen with some iron. All alloys were melted in a vacuum furnace to remove dissolved gases, sufficient carbon was added to the charge to combine with all the oxygen as CO. Final analysis determined the carbon as about 0.02 pct and the oxygen around 0.06 pct or slightly more. Stabilized zirconia crucibles and thermocouple protection tips were used throughout and contributed no detectable impurity to the melts, as long as the oxygen in the chromium was kept low. Heats averaged about 250 g, which permitted about 2 in. of the thermocouple protection tips to be submerged. The temperature drop across the thermocouple protection tip was determined to be about 3°C, a minor source of error. The alloys, after removal from the vacuum furnace, were placed in a furnace operating in a purified argon atmosphere for the thermal analyses. An- nealed wolfram-molybdenum thermocouples provided the primary means of temperature determination, though a Pt-Pt-10 pct Rh couple was employed for a check when possible. A sensitive, high-speed Leeds and Northrup Speedomax recording potentiometer indicated the thermocouple output. X-ray diffraction patterns were obtained primarily on a Norelco unit, which permitted diffraction angles only up to 45" (28 = 90"). In general, either rotated or stationary solid samples were used, because it later evolved that many samples were susceptible to transformation resulting from the cold working involved in pulverizing. It was also noted that rotating a sample sometimes suppressed weak lines, so, usually, samples were not rotated. Later a high temperature camera was adapted for use at temperatures up to 1400 °C on the Norelco unit utilizing both solid and powdered samples. Unless otherwise noted, all X-ray patterns were made with a chromium tube and a vanadium filter. Further-

Jan 1, 1952

By N. J. Grant, C. Stein

A more complete determination of the chromium-rich portion of the Cr-Ni phase diagram was made, based in part on resistivity measurements. The existence of a eutectoid reaction at 1215°C,made,based in addition to the previously reported eutectic reaction at 1343°C, was confirmed. Metallographic studies, lineal analysis, and diffusion-couple evidence were utilized to support Metallographicand extend the findings of the resistivity measurements. Delineation of the a chromium solvus line shows that the maximum solubility of nickel in a chromium decreases rapidly from 25 wt pct Ni at the eutectoid temperature to 16 wt pct. Ni at 950°C. IN recent years alloys of high chromium and nickel content have become of more interest as better performance of metals at higher temperatures is sought. It has become increasingly important, therefore, that the Cr-Ni binary diagram, which is composed of two of the elements commonly found in many high temperature alloys, be known more accurately. In particular, the chromium-rich portion of this diagram has for a long time remained incompletely determined and has been reported in the literature with a great deal of conflicting evidence. In general, electrolytic chromium of nominal purity was used by most of the earlier workers, who, except for Jenkins et al., made no further attempt to purify the metal. In the present redetermination of the chromium-rich portion of the Cr-Ni phase diagram, every effort was made to use the purest component metals available and to retain this purity throughout the preparation of the alloys and their subsequent handling. Early work by Voss, Bain," and Phebus and Blake4 indicated that the Ni-Cr binary diagram was a simple eutectic system with rather extensive terminal solid solutions. Later, Nishigori and Hamasumi," Tasaki, Weaver and Jellinghaus,' Matsunaga, and Jette, Nordstrom, Queneau, and Foote attempted to determine the limits of the phase fields. Except for Jette and coworkers, the other investigators agreed that the temperature of the eutectic reaction occurred between 1320" and 1340°C and at a composition of 50 or 51 pct Cr. There was, however, considerable disagreement as to the melting point of the chromium-rich alloys and the limits of the solid-solution fields. As a result of the studies of Jenkins et al., the liquidus and solidus curves up to 80 and 90 pct Cr, respectively, were outlined. In addition, the solid-solution phase fields at higher temperatures had been investigated and showed only two phases. The boundary of the chromium-rich a phase was not determined precisely according to these authors, but indications were that it tended to confirm the earlier work of Nishigori and Hamasumi. A more recent investigation by Taylor and Floyd,'" using X-ray methods, essentially corroborated the diagrams proposed by Jenkins et al., and by Wise and Eash (see Fig. 1). Again, no indication of a third phase in the chromium-rich portion of the diagram appeared. The earlier observations, however, are not substantiated by the modifications to the Ni-Cr binary diagram proposed by Bloom and Grant." In the investigation carried out by Bloom and Grant, X-ray methods showed that an eutectoid reaction existed at approximately 1180°C, in addition to the eutectic reaction at 1343°C (see Fig. 1). Their determination of the melting point of pure chromium was 1930°C (later revised to 1903"C)." Experimental Procedure and Results The chromium used for this study was electrolytic chromium, made available by the United States

Jan 1, 1956

By J. J. Gilman

Examination showed that characteristic cleavage step patterns are observed on the cleavage surfaces of undeformed, slipped, bent, twinned, compressed, and indented zinc crystals; and the effect of temperature is discussed. Dimples were seen to produce cleavage steps in a treelike pattern in otherwise undeformed crystals. The steps seem to originate when cracks intersect screw dislocations. IT has been known for a long time that the path of fracture in polycrystals may be discontinuous (see Jaffe, Reed, and Mannl for review). Recently, Kies, Sullivan, and Irwin2 have proposed, and given evidence, that crack propagation is discontinuous within individual crystals as well. Other evidence has been given by Low.' When discontinuous cracks within a crystal join together to make a macrocrack, the lamellae between each set of two cracks are torn somewhere, forming small cliffs. These cliffs appear as lines when the cleavage surface is observed microscopically.4,5 The lines have been called vein, tree, and riverlike markings by various authors, and they have sometimes been mistaken for fissures. The descriptive term cleavage steps is used in this paper. Cleavage steps vary in height over a wide range of values, from molecular dimensionsG to lor. and larger. Kies, Sullivan, and Irwin,2 as well as George,' have shown that the gross cleavage step patterns for plastics, polycrystalline metals, and for mono-crystals are sometimes similar. Thus, they depend mostly on the mechanical variables that prevail during cleavage and are relatively insensitive to the structure of the material. For example, parabolic markings2,7,8 sometimes result when cracks open up ahead of, and not coplanar with, the main crack front. If the advance crack has the same velocity as the main crack, their intersection line is a parabola, otherwise it is a hyperbola or an ellipse. The patterns are strongly affected by differences in crack velocities. This results in chevron patterns which point to the place of origin of the main crack. It is the purpose of this paper to demonstrate the existence of a mechanism of cleavage step formation which is a continuous rather than a discontinuous process. Also, certain characteristic step patterns are described, and the strong effect of temperature is shown. The specimens were zinc monocrystals (grown from 99.999+ pct pure metal). These were cleaved at room temperature and at — 196°C. Results and Discussion Cleavage step patterns are highly variable from point to point on a given specimen, as well as from one specimen to another. Although the patterns shown in the photographs are typical, they have been selected for graphic illustration. Figs. la and lb compare undeformed crystals that were cleaved at —196 °C and room temperature, respectively. Cleavage at room temperature (Fig. lb) resulted in a higher density of high steps (dark black lines) and enhanced the visibility of the fine background markings. Deformation by simple slip caused no marked change in the step patterns until the glide strain reached about 1.0. But, as Fig. lc shows, the density of high cleavage steps was greatly increased by large glide strains. Corrugations lying perpendicular to the slip direction may also be seen in Fig. lc. These are caused by deformation bands. The cleavage resistance of the crystal of Fig. lc was very high compared to undeformed crystals (estimated by the force on a needle required for cleavage). Striking and varied cleavage step patterns were observed on bent crystals. Two characteristic patterns that were observed on crystals bent at 25°C, and cleaved by reverse bending at —196°C, are shown in Figs. 2a and 2b. The first, Fig. 2a, consists of V-shaped lines similar to the parabolas of other materials2,7 Fig. 2b shows a pattern that is the equivalent of Fig. la, consisting of faint background lines with a few higher step markings. Cleavage of bent crystals at room temperature resulted in Figs. 2c and 2d. Now, the cleavage step lines show a strong tendency to follow one of two perpendicular paths. In Fig. 2c (bent once), many of the cleavage step components that lie parallel to the bend axis are assembled into irregular lines. In Fig. 2d (bent twice), the cleavage steps again tend to consist of two perpendicular components, but neither of the components is assembled into lines. Also, the step density is higher.

Jan 1, 1956

By A. E. Dwight, P. A. Beck

A search was made for ordered phases of AB3 composition in various combinations of Ti- and V-group elements with CO-and Ni-group elements. Three new TiNi3-type phases ZrPd3, HfPd3, and HfPt3 were found. In addition, twelve new Cu3Au-type phases TiRh3, Tilr3, ZrRh3, Zrlr3, HfRh3, Hflr3, VRh3, VIr3, CbRh3, Cblr3, TaRh3, and TaIr3 were also found. The lattice contraction for all three structures considered increases with increasing relative size of the A atom, suggesting that it is mostly the A atom that cont~acts. It was noted that, for the same radius ratio the lattice contraction is larger when the A atom is Ti than if it is Cb OY Ta. It is well known that elements or disordered solid solutions, which have structures with spherical close-packing, may be described in terms of various stacking schemes of close-packed layers. Stacking of the type abab corresponds to the hexagonal close-packed structure, and stacking of the type abcabc corresponds to the face-centered-cubic structure. In binary alloys of the first, second, and third long period transition elements various AB3 phases occur with close-packed ordered structures. It was observed that these ordered structures also may be described by suitable stacking of close-packed ordered layers, Fig. 1, as first shown by Laves and Wallbaum for TiNi3.' It is clear that the units of translation in such a close-packed layer consist of four atoms, one of which (black circle) is atom A and the three others (empty circles) are atoms B. Because of the alternation of A and B atoms in every second row of each layer, the unit-cell dimension in the layer is equal to the sum of the diameters of atoms A and B: a0 = 2(rA + rB). Stacking of such layers in the sequence abab results in a hexagonal close-packed structure of the MgCd, type. The unit-cell dimension in the basal plane is approximately double of that for the disordered hexagonal close-packed structure, but in the direction of the hexagonal axis it is about the same, so that 2co/uo = 1.63 in case of spherical close-packing. Ordered hexagonal close-packed structures of this type were found to occur in MoCo3,2 WCo3,, and UPt, .4 When the ordered layers shown in Fig. 1 are stacked according to the scheme abcabc, the resulting ordered structure is of the AuCu, type (cubic). Structures of this type were found to occur in TiPt3,5 CrPt,,' CrIr,,' and URu, .4 Finally, the stacking scheme abacabac of the same ordered layers results in a hexagonal close-packed structure of the TiNi3 type.' In this case, the unit-cell dimension is doubled not only in the basal plane, but also in the direction of the hexagonal axis, so that co/ao = 1.63. Structures of this type were found to occur also in TiPd3,5 ZrPt,," and UPd,.4

Jan 1, 1960

By C. Chiou, D. P. Seraphim

The effect of clustering on the superconducting properties of Al-Zn alloys has been studied by the ballistic induction techniques. The superconducting critical temperature, T,, changes when zinc-rich clusters are formed. The change in T, depends on the concentration and may be positive or negative, but always correlates with an effective decrease in the solute concentration of the alloy. Reversion after clustering effectively returns a 5 at. pct Zn alloy to the quenched state. These methods might be use&lly extended to the Al-Mg system, where X-ray data are difficult to obtain. In very dilute Al-Zn alloys, as in other tin,' indium, aluminum,2 or tantalums base solid solutions, there is a decrease in the superconducting critical temperature, Tc, roughly proportional to the temperature independent resistivity, i.e., -0.2°K per pS2cm. With increasing solute concentration, the T, generally reaches a minimum and then increases4 to a value well above that for the pure solvent. The change of T, with solute concentration follows an empirical formulation involving two constants which correlate with the scattering cross section of the impurities. As will be shown below, the Al-Zn alloys more concentrated than 1or2at. pct do not follow the empiricism, probably because they are unstable even when rapidly quenched.5 However, it seems possible to study at least the later stages of solute clustering by precise measurements of the 1', following various thermal treatments. A few experiments on quenched alloys, aged alloys, and tests on reversion are reported here. The heat treatments selected for obtaining the quenched and aged states were mainly deduced from the work of Dash and Fine.6 For the quenched state, specimens were homogenized at 480°C, quenched to -160°C, and immediately transferred and mounted in liquid nitrogen. Measurements on the superconducting properties and residual resistivities were then made at helium temperatures, after which the specimens were aged at room temperature for 3 to 5 hr, i.e., much longer than the time required for clustering to be essentially completed. The superconducting properties and residual resistivities were once again examined. To reach the reverted state of the A1-5at. pct Zn alloy, the aged specimen was heated for 5 min at 200°C and then tested as above.

Jan 1, 1963

By B. H. Kear

Clustering of slip bands in different systems has been observed in both ordered and disordered Cu3Au crystals compressed in the <110> orientation. Certain features of the slip band patterns are explained in terms of reactions between dislocations with Burgers vectors at 120 deg; in a few rare cases, the slip band evidence suggests that the Products of such reactions form diffuse tilt boundaries between the differently slipped regions of the crystal, similar to the known behavior of ionic crystals, but not nearly so well defined. WHEN crystals with orientations favorable for multiple slip undergo plastic deformation, slip may occur in different systems in localized regions, so that clusters of slip bands are developed. This phenomenon has been observed in fee1-4 metals and also in ionic crystals having the sodium chloride structure.5-8 In the ionic crystals, the boundaries formed between the differently slipped regions of the crystal assume characteristic orientations and are associated with macroscopic tilts that are plainly visible on the sides of the crystal. Recently, this interesting feature was explained in terms of the formation of diffuse low-angle boundaries as a result of interactions between families of glide dislocations in the different systems meeting in the boundaries.9 This paper describes an attempt to obtain similar evidence for boundary formation in an fee crystal. The alloy Cu3Au was chosen for the present study simply because this material is currently being used in a general study of differences in deformation behavior of the ordered and disordered phases of this alloy, which will be described elsewhere. EXPERIMENTAL PROCEDURE The two specially oriented compression specimens used in the present study were prepared from a melt-grown single crystal by careful cutting, grinding and polishing. The finished specimens were about 6 mm by 2 mm in cross section by 6 mm tall, with their ends parallel to (101) and sides parallel to (111) and (121); the broad faces of the specimens were made parallel to (711). Both specimens were annealed in an evacuated quartz tube at 850oC for several hours, slowly cooled to 500°c, and then quenched into water in order to obtain the disordered state for the alloy. One of the specimens was partially ordered (with S- 0.8) by reannealing at 350oC for 100 hr. After these annealing treatments, both of the specimens were electropolished. 10 Finally, the specimens were compressed in the [loll orientation and their stress-strain curves were recorded. The deformation was carried out in increments of a few percent strain. At each stage in the deformation the specimens were unloaded, removed from the compression jig, and examined optically for slip bands. Before reloading, the specimens were repolished, so that the observed slip band patterns were characteristic of a particular stage in the deformation. EXPERIMENTAL RESULTS Fig. 1 show!; the stress-strain curves for the ordered and disordered specimens and also indicates the stages 1, 2, and 3 where the deformation was interrupted for examination of slip bands. The curves show marked differences in flow stress and in work hardening rate in the two specimens, as observed by previous workers.11,12 Also, it was found, in agreemement with the observations of Taoka and Sakata,&apos;3 that the plastically deformed disordered alloy showed the characteristic coarse slip bands of alloys, whereas the ordered alloy exhibited a fine slip band structure similar to that of pure metals. Slip Band Observations. In what follows, the description of the slip band patterns, with accom-

Jan 1, 1962

By Shozo Saito, P. A. Beck

Mettrllographic and X-ray diffraction study of Cb-Co alloys in the Composition range of 7 to 33 nt. pct Cb, after annealing at 1175 °&apos;, showed that near 25 al. pct Cb on MgNi,-lype hexagonal Laves Phaseexists in a narrow composition range, and that an MgCl- type cubic Laves Phase occurs between approximately 27 and 32.6 ut. pd Cb. Lattice parameter and density measures indicated that, in both phases. the deviations from proper Loves sloichimetry result from the substitution of cobalt atoms for some 0f the columbium atoms. Tlle same phases occurant 1000&apos;C, together with an additional phase of unknown structure, which appears between the hexagonal Laves phase and the cobalt-bose terminal solid solutions KOSTER and Schmid&apos; identified a phase corresponding to the composition VCo,, and more recently the crystal structure of this phase has been determined.&apos; In the Ta-Co system Korchynsky and Fountain recently found two intermediate phases at the composition Taco,, one of them metastable. In contrast to the V-Co and the Ta-Co systems, in the Cb-Co system no intermediate phase has been found4 at the composition CbCo,. The present investigation was undertaken in order to reexamine the question of the existence of such a phase. EXPERIMENTAL PROCEDURE Twelve alloys were prepared by arc-melting in a water-cooled copper crucible under helium atmosphere. Electrolytic cobalt and 99.9 pct pure colum-bium powder have been used as starting materials. It was found that melting losses can be reduced by compressing the colunlbium powder in the form of thin pellets before melting. For the alloys used the melting losses were not higher than 1 pct. The intended compositions of all alloys and the chemical analyses of three of them are given in Table I. Specimens from all alloys were annealed in evac- uated fused silica tubes at 1175°C for 3 days and quenched in cold water. A second set of specimens of most alloys was annealed at 1000°C for 7 days and then quenched in cold water. The annealed and quenched specimens were examined metallographically, using the following etchant: 60 pct glycerine +20 pct H,NO, + 10 pct HF + 10 pct water. Powder specimens for X-ray diffraction were prepared by crushing annealed solid specimens in a mortar. Alloys containing 27.3, 28, 29.7, and 32.6 at. pct Cb annealed at either 1175" or 1000°C were very brittle and it was found unnecessary to reanneal the powders. However, alloys containing 24.8 at. pct Cb, or less, especially those annealed at 1000°C, were much less brittle and re-annealing was required to remove the strains present in the crushed powders. In each case reannealing was done at the same temperature at which the corresponding solid specimens were annealed and it, too, was followed by quenching in cold water. In many instances X-ray diffraction patterns were also taken of the polished and etched solid specimens and compared with the corresponding X-ray diffraction patterns obtained with powders. The X-ray diffraction patterns were taken with an asymmetrical focusing camera, using CrK radiation. For precision lattice parameter measurements some X-ray diffraction patterns were taken with a symmetrical focusing camera, again using CrK radiation. EXPERIMENTAL RESULTS A microscopic examination of the alloys annealed at 1175°C revealed that the alloy containing 25.5 at. pct Cb was composed of a single phase, but that the 24.8 at. pct Cb alloy did contain a small amount of a second phase, identified by means of X-ray diffraction as having a fcc structure, undoubtedly the terminal solid solution based on cobalt. Apart from the few very weak lines corresponding to this minor phase, the X-ray diffraction patterns of these alloys could be well interpreted in terms of a MgNi,-type hexagonal Laves phase structure. The indexing of the X-ray diffraction pattern, Table 11, yas based on the lattice parameter values a, = 4.740A and c,

Jan 1, 1961

By W. K. Hardy, H. H. Stadelmaier, L. J. Huetter

The ternary system Co-Sn-C was studied in the cobalt-rich region. The liquidus projection ulas established and two fonr -phase reactions were found. An isothermal section at 950°C was worked out. In the region studied the following phases were observed: cobalt-rich solid solution, graphite, binary compound y -cobalt-tin, and a ternary compound. As a result of the limited solubility of carbon in liquid cobalt-tin alloys, the investigation was limited to the cobalt-rich region. Tin contents up to 32 at. pct were studied. Cobalt of 99.99 pct purity, tin of 99.97 pct purity and synthetic graphite of 99.93 pct minimum purity prepare the alloys. Carbon determinations of all alloys were obtained by gas volumetric analysis. Samples were investigated microscopically and by X-ray diffraction using CoK, and FeK, radiation. Cooling curves were obtained with a number of alloys to determine the temperature of the four-phase reactions. The thermocouple was calibrated with the melting points of high-purity silver and copper. In the region studied the following phases were observed: Cobalt-rich solid solution (face-centered cubic) Graphite. Binary compound y (solidifies congruently at composition Cop~n)&apos;. Ternary compound k which is face-centered cubic with superlattice and nonferromagnetic.&apos; In Fig. 1 the fields representing the projections of the liquidus surfaces were determined by microscopic investigation and are labled by their primary phase. In the field labled C graphite is the primary phase. During solidification in this field much of the primary graphite was expelled through the surface of the melt. It could not always be established microscopically whether the remaining graphite was primary or purely eutectic. Therefore it was not possible to determine accurately the boundary curve which drops from the binary eutectic el at 1309 "~~ to the point of the four-phase reaction at F. The ter-nary carbide is the primary phase in the field labled k. To the right of this field the primary graphite is consistently nodular whereas flake graphite is observed at tin contents somewhat below F. The ternary carbide does not appear to solidify congruently. The graphite is attacked in a peritectic reaction along the boundary between k and C. Thus no graphite is observed in alloys in the k field. In alloys right of the boundary between k and C the graphite nodules are located in the center of the k crystallites, further documenting the peritectic nature of the reaction with the graphite. A four-phase reaction was found at F and 1120 &3"C. The most likely reaction is L+ CY-Co + C — k. Below the temperature of the binary eutectic ez at 1112" a second four-phase reaction was observed at E and 1100 lt3"C. It is the ternary eutectic L — CY-Co + k + y. Figs. 2(a ) to (e) show microstructures of the ternary alloys in the as-cast condition. Fig. 2(a) shows the eutectic a-Co + C (with some primary graphite) with the carbide k in the grain boundaries. Fig. 2(b) shows primary cobalt (dark areas) and the eutectic a-Co + k which is formed along F-E.

Jan 1, 1961

By R. B. Russell

The expansion coefficients of hexagonal (a) zirconium have been calculated from the lattice expansionparameters of both coefficientsofhexagonallow and high hafnium alloys in the range 0° to 600°C. It is found parametersofboththat the coefficients are straight-line functions of the temperature and that the effect of hafnium is to depress the mean coefficients by about 1 pct at room thattemperature and 9 pct at 600°C. The cubic (ß) form was stabilized so that its coefficient could be determined from 400&apos; to 900°C. COEFFICIENTS of thermal expansion for hexagonal-close-packed (a) zirconium were determined up to 600°C (1112°F), without any interference from the effects of preferred orientation, by measurement of the lattice parameters obtained from a symmetrical back-reflection focusing X-ray camera. This paper combines the results for a 1.2 atomic pct hafnium alloy from an earlier report&apos; with those for hafnium-free zirconium. The problem confronting the investigator is essentially that of getting sharp, high-angle diffraction lines which represent the material at a known constanl. temperature and chemical composition. In order to do this, it was necessary to use the proper X-ray emission wave length (Co K was chosen) and to have a fine-grained metal whose atomic spacings would be free from effects of cold work (the specimen was annealed) and to prevent a changing composition owing to gas absorption during the heating of the metal to temperature (the sample was heated in a vacuum). A summary of the effect of temperature on properties is listed in Table I which gives data for ordinary zirconium, as well as new values for the low hafnium metal. The coefficients of the linear thermal expansion that have been reported are given in Table 11. The discrepancies shown may be explained perhaps by the effect of preferred orientation, and McGeary and Lustman2 have done this successfully for sheet metal. The differences in texture cannot explain all the differences in expansion coefficient shown in Table II. liesults by the author agree most closely with those of Kroll.3 Chemical analysis of the high hafnium metal pre- viously reported1 showed that it was 98.22 atomic pct (97.40 wt pct) pure. The low hafnium metal was dehydrogenated Westinghouse crystal bar, designated SMZ-137A. Its analysis was as given in Table 111 (chemical analyses 5377, 5431, and 5432).

Jan 1, 1955

By M. G. Nicholas

The influence of deformation, relative movement and surface cleanliness on the strength of room -temperature "interparticle" bonds between copper surfaces has been studied. No bonding resulted when clean surfaces were merely pressed together, even under pressures of 50,000 psi. Bonding resulted, however, when clean surfaces were simultaneously pressed and moved relative to each other, some bonding occurring no matter how small the pressure or relative movement. Exposure of the clean surfaces to various chemicals inhibited bonding, none at all being produced by small relative movements. The size of the movements which first produce bonding between exposed surfaces depends on the nature of the chemical, being less than 0.002 in. for cleansing reagents and greater than 0.004 in. for lubricants, water and hydrogen sulfide. It is concluded from the experimental data that the prime requirement for bonding is the dispersal of surface films such as oxides and adsorbed contaminants. THE formation of interparticle bonds during the room-temperature compaction of powder metallurgy components greatly increases the ease of handling in subsequent production operations prior to sintering. The strength of unsintered compacts follows the same general trends as their density and hardness, but quantitative data are extremely Scarce. Quantitative correlation of the data on the overall strength of a compact with that of the individual interparticle bonds is virtually impossible due to the extremely complex geometry of powder compacts. Qualitatively, however, the strengths of unsintered compacts can be correlated with variations in parameters known to influence the extent of cold bonding, and hence interparticle bonding, such as surface cleanliness, relative movement, and deformation of the mating surfaces. Kuzmic and seelig4 found that contamination of powder particle surfaces with lubricants reduced the strength of unsintered iron and copper compacts. Interparticle shear has been shown to promote bonding by Train and Hersey7 while Gregory has shown that die rotation is beneficial. Eilender and schwalbe6 concluded that most bonding occurred during the early stages of pressing iron powder compacts when interparticle shear is one of the principal processes occurring. mile there can be little doubt that these and other factors, such as particle size and shape, affect the extent of interparticle bonding produced by compaction, evaluation of the influence of individual factors is not easy. Particle deformation and relative movement, for example, occur simultaneously during compaction, making any precise measurement of their relative influences difficult. Because of these and other difficulties encountered in studying interparticle bonding in actual powder compacts, the approach adopted in this study was to

Jan 1, 1963

By C. H. Li, R. J. Stokes, T. S. Liu

Poly crystalline silver chloride specimens having different micro structures were prepared by extruding monocrystals or precompressed powder at varying temperatures. Extrusion at high temperature (370°C) produced a Fully recrystallized equi-axed material which was brittle and fractured by simple cleavage below its transition temperature (60°C for notched specimens). Extrusion at low temperatures (down to -196°C) produced an extremely tough cold-worked material with grains elongated in the extrusion direction. This material fractured below its transition temperature (which varied from —20" to —200°C) by an intergranular mode. It is concluded that cold work increases the resistance to transgranular cleavage. Fracture is then de-flected to propagate intergranularly ouer surfaces making an angle with the tensile axis with a corresponding improvement in notch toughness. This deflection is greater for extruded powder than for extruded monocrystals because of the extremely elongated grain shape. PREVIOUS work1,&apos; on the fracture properties of fully recrystallized silver chloride under notch impact conditions has indicated that the fracture behavior is rather invariant. Thus polycrystalline materials originating from a number of sources ranging from relatively pure Harshaw single crystals to commercial-purity powder and prepared by hot extrusion at 370°C all fracture by simple cleavage with a ductile-brittle transition at 60°C, see Fig. 1. This behavior is also typical for fully annealed single crystals and appears to be fundamental to silver chloride for the particular loading conditions and notch configuration adopted. One way in which this characteristic fracture behavior can be modified is by the dispersion of alumina particles in the silver chloride matrix.&apos; Then, particularly when the alumina particles are in the shape of spheres, the duc tile-brittle transition is much less sharply defined and occurs over a range of temperature, the transition temperature is lowered considerably and the fracture mode changes from simple cleavage to a fibrous or shear mode. The reason for this change is believed to be partly due to the nucleation of cavities in the region of the dispersed alumina particles which influences the state of stress locally and the distribution of plastic constraint at the root of the notch. It is emphasized however that this is not the sole factor responsible for the increase in toughness. In extruded materials it is reasonable to expect that the resultant grain size, texture, and the residual cold work will be influenced by the presence of a dispersed phase. The present experiments were initially designed to determine the extent to which cold work influenced the fundamental ductile-brittle transition temperature and fracture mode of silver chloride. They were stimulated by the discovery that silver chloride could be extruded at temperatures as low as -25°C when commercial-purity powder was used and as low as -196°C when single crystals were used. This working temperature was far below that previously used (370°C) and it was found that such extruded material was exceedingly tough. The reasons for the enhanced toughness and its relation to the previous work on silver chloride-alumina compacts will be discussed. EXPERIMENTAL PROCEDURE Materials Used. Two forms of silver chloride were used in this study: i) silver chloride powder

Jan 1, 1964

By P. K. Koh, G. C. Dunn

Si-Fe single crystals in a number of selected orientations were cold rolled 70 pct and analyzed to obtain quantitative (110) pole figures. Stable end orientations were ddetermined, and the effect of orientation on deformation behavior was investigated. WHEN single crystals are cold rolled sufficiently, they rotate into end orientations that are stable or unchanged in position with additional deformation. The end orientations of heavily cold-rolled iron crystals, positioned in holes in copper to limit lateral flow and to simulate polycrystalline conditions during deformation, were determined by Barrett and Levenson.&apos; They found that the sum of the end orientations, a pole figure for all the crystals studied, reproduced the essential features of the cold-rolled texture of polycrystalline iron. In. an investigation of Fe-Si alloys, Barrett, Ansel, and Mehl&apos; observed little effect of silicon content on the textures of heavily cold-rolled samples. Since alloys with less than 4 pct Si are known to have the same slip systems as iron," it seems logical to expect that they would also have the same end orientations as those for iron. Whereas Barrett and Levenson in their study of single crystals were interested in the problem of the origin of the cold-rolled texture of polycrystalline iron, the present authors are more interested in the final cold-rolled textures of single crystals of Si-Fe from the point of view of their relationship to subsequent recrystallization phenomena which will be reported in another paper. Nevertheless, such points as the tendency of an end orientation not to rotate (stability), the tendency of a pole concentration to spread out, and the tendency of the crystal to widen during cold rolling become interesting separately when the initial orientations are selected already in end orientations. Also the initial orientations having a [I101 axis parallel with the transverse direction, which include the two end orientations (111) [Ti21 and (001) [110], comprise a series that needs further clarification regarding the way such crystals rotate during deformation. Finally the present use of quantitative pole figure methods* represents an advance over the X-ray photographic method employed by Barrett and Levenson in their work on end orientations. The present investigation provides information on the cold-rolling behavior of two groups of Si-Fe crystals: 1-—crystals initially oriented in recognized end orientations for iron crystals with a [I101 direction parallel with the rolling direction, and 2— crystals initially oriented with a [I101 direction 90" to the rolling direction and in the rolling plane. For the second group, there is a 90" range between the (001) [110] orientation and the (110) [001] orientation. Since the 35" portion of this range from (110) [OOl] to (111) Di2] was included in a previous investigation," only the remaining 55" portion from (111) fii2] to (001) [I101 needs further consideration. Also, since both (111) [xi21 and (001) [I101 are end orientations for iron crystals,&apos; there might be a critical orientation* or orientation range be- • W. W. Martin and C. G. Dunno noted that (112) [Till was such a critical orientation. tween them such that early in the deformation an orientation within this critical range splits into two orientations. Upon further deformation, these two orientations rotate to produce a final texture consisting of (001) [1101 and (111) [?i2] components. The end orientations obtained are discussed in connection with the work of Barrett and Levenson, while the observed tendency for lateral flow of crystals in these orientations is treated in terms of the theory of Hibbard and Yen.&apos; Lateral flow according to the theory increases with deviation of the plane containing the rolling direction and the slip direction from a position perpendicular to the plane of rolling. Experimental Procedure Single crystals in sheet form with preselected orientations were prepared by methods that have been described elsewhere." Three lots designated A, B,

Jan 1, 1956

By Y. C. Liu, R. H. Richman

From rolling textures of polycrystalline AgCl determined as a function of temperature, changes in the amounts of the individual textural components are correlated with temperature-dependent changes in glide geometry. The preferred orientations are influenced by the slip behavior as follows: 1) pencil glide, characterized by (110) slip directions and a greater participation in the deformation the higher the temperature, leads to a(012) fiber texture; 2) low-temperature deformation, primarily on (110) (110) systems, generates the {237}-(11, 9, 7) component; and 3) slip on {111}(110), comprising a significant portion of the room-temperature deformation, generates the {135}(211) and {110}(112) components. Typical re crystallization textures are also presented and briefly discussed. SPECIFIC relations between flow mechanisms in crystals and the individual orientations or components in deformation textures are necessary for a thorough understanding of the origin of such textures. Within each ordinary class of crystal struc- tures there is insufficient variety in the observed preferred orientations to permit direct and unambiguous correlation between flow mechanism and texture. A second approach to this problem is the correlation of textural changes with some known variation in glide geometry within one substance,1 In this paper, the latter approach is applied directly to a material in which there are distinct changes in the character of glide with changes in temperature. Silver chloride, although a nonmetal, is reported to exhibit slip,2,3 fiber textures,4 and rolling textures5,6 crystallographically similar to those of the well-studied fcc metals;7,8 in addition, there is a marked temperature sensitivity of the glide planes upon which flow occurs.3 Previous investigations of textures in AgCl unfortunately did not employ methods sufficiently sensitive to define possibly important minor components in the texture, nor did they utilize the temperature dependence of the glide systems. Thus, in order to clarify the effects of changes in slip mechanism, this paper reports a survey, using semiquantitative methods, of preferred orientations in rolled AgC1. Inasmuch as the influence of prior deformation texture upon preferred orientations after annealing is also of interest, some representative annealing textures are presented.

Jan 1, 1965

By N. K. Chen, R. Maddin

THE textures of straight-rolled and of cross-rolled molybdenum were first determined with the aid of pole figures by Custers and Riemersma.&apos; These authors have shown that for straight-rolling, the main texture was (100) [0111 with a considerable spread about the rolling direction. After cross-rolling a second texture was obtained in which there was a [111] axis perpendicular to the rolling plane, possessing a rotary symmetry. Recently Semchy-shen and Timmons2 in their study of preferred orientation of arc-cast molybdenum sheet obtained similar pole figures. In these two investigations, polycrystalline materials were used. In the main, the textures of molybdenum in these cases are qualitatively consistent with rolling textures of other body-centered cubic metals, such as iron and Fe-Si alloys." In the present investigation, single crystals of molybdenum were deformed by rolling with respect to specific crystallographic planes and directions. Since the deformation textures of polycrystalline aggregates have been related intimately to the behavior of individual grains,4 a study of possible correlations of final textures with respect to the initial orientations of the single crystals might conceivably lead to a better understanding of the textures. Annealing treatments were carried out after deformation in order to study the recrystallization characteristics as well as the recrystallization texture. Rolling of Single Crystals Single crystals of molybdenum (about 1/8 in. in diarn x 1-in. long), grown by the method previously described,5 were cold-rolled without intermediate anneals. Except for specimens MR-1 and MR-2, which were rolled at random in the preliminary test in order to find a proper rate of reduction, all other specimens were carefully documented as to their respective orientation before deformation by means of X-ray Laue back-reflection methods. A stereo-graphic projection was constructed from which it was possible to determine a particular plane and direction to be considered for rolling. Parallel flat surfaces were then polished metallographically with respect to a reference scratch on the specimen which was mounted in sealing wax. These flat surfaces contained the plane chosen for rolling. After etching, a Laue back-reflection photogram was again made of one of the flat surfaces to determine the exact plane of rolling. The initial orientations of all the specimens (specified by two elements for each crystal, direction of rolling and the pole of the rolling plane) are summarized in Fig. 1. The specimens were mounted in plasticene between two hardened Si-Fe plates. The sandwich was then rolled down, keeping the direction constant in the case of straight-rolling. In cross-rolling (MR-10, MR-11, and MR-12) the sandwich was rotated 90" after each pass so that every first and third pass contained the same rolling direction. Specimens MR-14, MR-15, and MR-16 were compression-rolled following the manner of Barrett." In these cases the direction of the sandwich through the rolls was changed by 3" to 5" for each pass until the specimens were rolled to the desired reduction in thickness. It was found that if extreme care was exercised in rolling, i. e., the amount of deformation per pass was extremely small, the specimens could be rolled to a large reduction in thickness. The rate of reduction used, with a single exception of MR-1. was generally 0.001 in. per 10 passes. Thus, it took about 800 passes to reduce a specimen to a final reduction in thickness of 87 to 98 pct. The results of rolling are shown in Table I. Cold-Rolling Textures The final orientations were determined by the conventional Laue transmission method," using molybdenum radiation, with or without a zirconium filter. Pole figures were plotted from (1101 and (200) reflections in which three degrees of intensity— heavy, medium, and light—were determined visually. Three main types of textures have been observed from the deformed single crystals. These are: 1—a

Jan 1, 1954

By J. A. Berge, R. S. Mateer, R. G. Aspden

IN a study of the cold-rolling characteristics of iron-base alloys with 3 to 12 pct Al, the influence of aluminum content on the cold-rolling textures was evaluated. This work was undertaken to determine if binary iron-aluminum alloys possessed cold-rolling textures similar to other body-centered-cubic alloys and to contribute additional information on the effect of solute concentration on the cold- rolling textures. Gradual changes in cold-rolling textures with an increase in solute content have been observed in copper1 and in titanium.2 Iron-base alloys containing 3.0, &apos;6.0, and 12.0 pct aluminum were vacuum-induction-melted in a magnesia crucible and permanent-mold cast. The materials used were high-purity electrolytic iron and 99.99 pct grade aluminum. Each ingot was 1 in. square in cross section by 12 in. in height. The bottom half of each ingot was soaked for 1 hr at 1000°C and rolled at 1000°C to a thickness of 0.055 in. with the long axis of the ingot parallel to the rolling direction. The strip was reheated between passes to maintain a rolling temperature of 1000°C.

Jan 1, 1960

By O. N. Carlson, H. A. Wilhelm, J. M. Dickinson

On the basis of microscopic studies, melting-point observations, and X-ray analyses, a phase diagram is proposed for the Cb-V system. A complete series of solid solutions is formed with a minimum in the solidus at 1810°C near 35 wt pct Cb. No compounds or intermediate phases were found in the system above 650°C. THERE is an ever increasing need for better structural metals and alloys for use in nuclear reactors. In addition to the normal properties of engineering structural materials, such as high temperature strength, resistance to corrosion, and fabric-abil~ty, the nuclear properties of the material must be considered. In a nuclear reactor it is important to conserve neutrons, so a material which removes these neutrons from the reaction excessively is considered to have unfavorable nuclear properties. In nuclear-reactor design the engineer must have nuclear as well as other data available on alloys in order to make a wise selection of materials. Due to the fact that many of the common structural materials have undesirable nuclear properties, it is vital that new alloys of metals having more favorable nuclear properties be investigated. Columbium and vanadium are both high melting metals, both exhibit resistance to chemical attack, and no great difficulty is encountered in fabricating them into desired shapes. With proper treatment both metals can be cold rolled extensively without failure. In addition they have desirable nuclear properties for certain types of reactors. Therefore, the alloys of columbium and vanadium should be of interest in the atomic energy program. Since an alloy-development program is enhanced by a knowledge of the phase equilibria of the components, this investigation was undertaken to establish the phase diagram for the Cb-V system. According to the Hume-Rothery rules for alloying,&apos; the chemical similarity, crystal structure, and atomic-size factor are favorable for a complete series of solid solutions for this system. Both elements are in the same family of group V of the periodic table and thus are quite similar chemically. The crystal structures of columbium and vanadium are compatible for extensive solid solubility, since both have body-centered-cubic structures. The atomic diameters of columbium and vanadium are 2.85 and 2.62Å, respectively. This difference of slightly more than 8 pct is well within the 15 pct maximum difference allowed for extensive solid solubility. Experimental Procedures Source of Materials: Columbium powder and sheet trimmings were obtained from the Fansteel Metallurgical Corp. According to the manufacturer the metal contains less than 1 pct impurity. An analysis of the metal showed approximately 1800 ppm C in the powder while the sheet trimmings contained less than 500 ppm C. Spectrographic analysis showed minor amounts of Ca, Cr, Fe, Mn, Si, Ti, V, and Zr in both forms of the columbium. No commercial source of vanadium having the ductility and purity desired was available to the authors at the beginning of this investigation. As a result, all of the vanadium used in this study was prepared by the bomb reduction of vanadium pen-toxide with calcium employing the method reported by Long.&apos; Yields of massive vanadium normally were about 80 pct. Chemical analysis of the vanadium prepared in this manner showed the presence of 200 to 500 ppm N and 800 to 1000 ppm C. Minor amounts of Ca, Fe, Mn, Si, Zr, Cr, and Cb were detected by spectrographic analysis. This vanadium metal was ductile and was cold rolled into 5 mil sheet. Annealing was not necessary during this rolling and the metal retained its cold-rolling characteristic after are-melting. Preparation of Alloys: The Cb-V alloys were prepared by melting pieces of vanadium sheet togethel-with columbium in the form of sheet or pellets of powder. The melting was carried out under argon in conventional arc-melting equipment employing a tungsten electrode and a water-cooled copper crucible. Each alloy was remelted three or four times, inverting the alloy after each melting in order to assure complete mixing. Alloys normally were obtained as round flat disks, weighed approximately 70 grams, and had roughly the shape of a disk 1 1/2 in. in diameter and 1/4 in. thick. Half of each alloy

Jan 1, 1955