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By W. Rostoker

A STUDY of the titanium-oxygen system' involved an associated series of measurements of the lattice parameters of the a and TiO phases. The results permit some interesting deductions which are herein reported. A comprehensive survey of the physical PI-operties of the phases in this alloy system has been made by Ehrlich.2 However, only impure titanium was available at that time, so that some revision of his measurements is to be expected. The lattice parameters were calculated from the high angle lines of Debye-Scherrer patterns taken in a 14 cm camera and using filtered CuKa radiation. The specimens were prepared largely by crushing and screening of lump samples which had been quenched from elevated temperatures. Only in the case of low oxygen contents was it necessary to resort to filing and annealing. The results of the lattice parameter studies are graphically presented in Figs. 1 and 2. It will be seen that oxygen produces a pronounced distortion of the c parameter of the a phase (hexagonal close-packed). The trend is in general agreement with Ehrlich's work, although the divergence of actual parameter values strongly suggests that his titanium was very impure. It will be noted that the a phase of titanium can tolerate the unusually high saturation solubility of about 34 atomic pct 0. By virtue of this unique effect, it is possible to make a calculation of the effective atomic diameter of oxygen when dissolved in a lattice with metallic bonding. This has not been possible before. Ehrlich's2 density measurements demonstrated that oxygen occupies interstitial positions in the a lattice and the trend of the lattice parameters would certainly support this. In a hexagonal close-packed unit cell the largest interstitial positions lie at (2/3, 1/3, 1/4) and (2/3, 1/3, 3/4). Accordingly, if both of these positions were occupied, the ratio of titanium to oxygen would be 1:1. The extrapolated c parameter may be taken as between 4.93 and 4.99?. The a parameter appears to reach a constant value of 2.955? at low oxygen contents. The distance of the center of a titanium atom site from the [vc2/16+a2/3-1.448] Then the atomic diameter of the oxygen atom is represented by the function: where the radius of the titanium atom is 1.448A,

Jan 1, 1953

By W. J. Babyak, J. M. Sheehan, H. W. Paxton

THE- solubility of hydrogen and deuterium in solid niobium up to I-atm pressure has been established bv a number of workers.1-5 X-ray examination at room temperature of specimens reacted in hydrogen at high temperatures from 300° to 1000°C shows the presence of two phases—a bcc phase (a) based on the niobium lattice and with an u0, increasing from 3.30A for Nb to 3.32Afor NbHo.L, and an orthorhombic phase6n = 4.84A, h=4.90A, c =

Jan 1, 1960

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 H. Hu

Observations were made on the recrystallization of a 70 pct cdd-rolled silicon-iron crystal with an initial orientation of (113) [332]. Its polygonization and recrystallization characteristics were studied. Results indicated that re crystallization tendency of the deformed crystal is much weakened by the polygonization of the matrix. Complete recrystallization in such specimens is achieved by the growth of recrystallized grains of sufficient size and of the right orientations in relation to the matrix. Evidence was also furnished which suggests that the difference in the re-crystallization tendency is a result of the difference in the severity of lattice bending rather than the difference in orientation of the deformation texture. DUNN and Koh1,2 have made an extensive study on the rolling and annealing textures in silicon-iron crystals. Their results indicated that the recrystallization tendency can be widely different in crystals with different orientations. A particularly interesting example of their results was a crystal with an initial orientation of (113) [332], which developed a deformation texture of (001) [110] after 70 pct cold-rolling. Recrystallization in this crystal took long time anneals at high temperatures. Other crystals having different orientations recrystallized very rapidly. Wiener and corcoran3 have observed the retention of the (100) [011] deformation texture in a low-temperature annealed specimen of a commercial silicon-iron alloy, corresponding to areas of light-etching low-angle boundaries in the annealed struc-

Jan 1, 1960

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'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,'-' 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

By C. G. Dunn

According to a recently suggested effect of silicon on the re recrystallization textures of high-purity Fe-Si alloys with (111)[112] type rolling textures, the recrystallization texture for a rolled (110)[001] oriented iron crystal probably should be entirely different from that of a (110)[001] oriented 3 pct Si-Fe crystal. Comparative studies of iron and 3 pct Si-Fe crystals, however, show that both have (110)[Ool] recrystallization textures when the rolling textures are the (111)[112] type after reductions in thickness of about 70 pct. Qualitatively the results from the iron crystal are like those of polycrystalline high-purity 3 pct Si-Fe and not like polycrys-talline high-purity iron. The large effect previously noted probably involves unknown impurities or processing variables rather than silicon itself. Some problems on experimental and analytical procedure for a spherical X-ray specimen, which was machined from a laminated composite of sheet specimens, are treated in the Appendix. A possible strong effect of silicon on the textures produced in cold-rolled high-purity Fe-Si (HPFe-Si) alloys during primary recrystallization and normal grain growth was suggested in a recent paper.&apos; All the textures were far from the random-orientation type, but that of iron, or of Fe-Si alloys of low silicon composition, was entirely different from the texture of 3 pct Si-Fe. The same effect was noted for the textures obtained prior to normal grain growth, i.e., for primary recrystallization.2 It is the main purpose of the present paper to provide some clarification of this silicon effect. All the HPFe-Si alloys from zero to 3 pct Si, which were rolled by two or more stages separated by anneals, developed (111)[112] type rolling textures.2 Thus, there was no effect of silicon on the rolling textures. Earlier, Gensamer and Mehl3 also found no effect of silicon on the rolling textures of Fe-Si alloys; they obtained the Kurdjum.ow and Sachs (K-S) rolling texture for iron,4 which is characterized as the three ideal components: (100)[011], (112)[li0], and (111)[112]. There is a difference between the HPFe-Si multiple-stage rolling texture and the K-S single-stage rolling texture, but this is a variable processing effect. Of interest here is the fact that the recrystallization textures from (111) [llZ] type rolling textures were different depending on the amount of silicon in the alloy. There was a relatively strong (110) [001] component in the recrystallization texture of HP 3 pct Si-Fe5,8,2 but no such component in HP 0.6 pct Si-Fe, for example; the recrystallization texture for the latter was two (111) [110] type components and a (111) fiber component 1,2 Several publications have shown that a strong (110) [001] recrystallization texture is derivable from a (111) [112] type rolling texture for 3 pct Si-Fe crystals reduced in thickness by about 70 pct.7-10 Furthermore it appears that the strongest of these (110) [001] recrystallization textures occurred when the orientation of the crystal prior to rolling was (110) [001].7 Barrett and evensoon11 found that the rolling texture of a (110)[001] oriented iron crystal was (111) [llj]. Accordingly, it seemed desirable to determine whether a (110) [001] oriented iron crystal, upon rolling and annealing, would behave like the 3 pct Si-Fe crystal (or the polycrystalline HP 3 pct Si-Fe) and thus produce a (110) [001] recrystallization texture contrary to the suggested silicon effect, or would behave like the polycry stalline HP iron or HP 0.6 pct Si-Fe and thus produce (lll) [110] type components in agreement with a silicon effect. Briefly, the idea here involves the use of more precisely defined textures to obtain if possible better control of important variables that affect the recrystallization process. PROCEDURE A (110) oriented crystal of Ferrovac "E" iron (99.9 pct pure) was prepared in sheet form 0.080 in. thick with the [001] direction parallel to the long dimension of the specimen.&apos;&apos; This crystal was etched to 0.073 in. thickness (to remove some small included grains) and then was cold rolled in a 6-in.-diam mill to a final thickness of 0.022 in. The rolling was unidirectional except for an inadvertent reversal at 0.061 in. thickness. At this thickness, and also at 0.040 in., the rolling was interrupted for transmission Laue photographs. Molybdenum Ka-radiation filtered with zirconium was used in a transmission method1&apos; to obtain the cold-rolled (110) pole figure. The sample was a 0.002-in.-thick section taken from the central region of the 0.022-in.-thick cold-rolled crystal. For the primary recrystallization study, cold-rolled samples were etched from 0.022 to 0.021 in. thick and annealed in hydrogen at 850°C. Primary recrystallization to a fine-grained structure, Fig. 1, was obtained in a 5-min anneal. Eleven sheets after

Jan 1, 1963

By H. P. Stüwe

HE recent papers of Aust and Rutter112 have again brought to mind the importance of certain "special" orientation relationships between the lattices of two fcc crystals on the mobility of the grain boundary separating them. No theoretical treatment of this problem has been offered till now. The only principle published so far that has given an indication why certain orientation relationships should be "special" is the counting of "coincidence sites" according to the suggestions by Kronberg and Wilson.3 The "coincidence plots" published by these authors show, for instance, that two fcc lattices rotated by 38 deg around a common (111)-axis have 1/7 of their lattice sites in common. Such an orientation relationship is also characteristic for high boundary mobility. The accuracy of the orientation relationship needed for high mobility is not too rigid. Deviations up to 10 deg from the ideal orientation seem to be tolerable as can be gathered from the experimental data.&apos;j4 The auestion arises, then. how the density of coincidence sites will be affected by a deviatioi from mathematical accuracy. This can be checked by a simple model. Two sieves are prepared, the arrangement of the holes corresponding to lattice sites on a (111)-plane in a fcc crystal. They are placed upon each other, Fig. 1. One is kept fixed, the other is rotated around an axis pushed through one hole in common to both. The light falling through holes of both sieves is then a measure for the density of coincidence sites. If the diameter of the holes is very small, light intensity is contributed only by holes the centers of which coincide "exactly." If the diameter of the holes is rather large, some intensity will be contributed by

Jan 1, 1962

By D. Weinstein, F. C. Holtz

AS a possible method of improving the elevated temperature strength properties of zirconium, an investigation was initiated on the feasibility of producing a dispersion-strengthened material. Because of the high reactivity of zirconium, its high solubility for oxygen, and the stability of the Zr-0 solid solution, the major problem in such a development is choice of a suitable dispersant. Thus, in the present investigation we were concerned primarily with the stability of various dispersants in the zirconium matrix. The experimental procedure consisted of blending powders of zirconium and a dispersant, followed by cold compaction and extrusion. The best available source of -325 mesh zirconium powder contained between 1500 and 3500 ppm Oz; to this material, powders of zirconium carbide (5 p max), vanadium carbide (5 p max), alumina (0.03 p average), lan-thana (0.8 to 2 p), ceria (0.8 to 2 p), yttria (0.8 to 2 p), calcia (44 p rnax), or thoria (0.6 to 0.8 p) were added in amounts of 7 vol pct and compacted at 65 tsi. A cylindrical compact having a density between 70 and 80 pct of theoretical and dimensions of 1 in. diam by 1-114 in. high was thus produced. After canning in copper, these billets could be extruded (5: 1) on a 54-ton capacity, slow-traverse hydraulic press with the billet temperature at 1550°F and the extrusion die at 900°F. However, lack of densifica-tion of some of the extruded billets necessitated ratios of at least 23 :1. Ultimately, all billets were successfully extruded at 1500°F to 0.190 in. diam (32 :I), fully dense rods using a 200-ton capacity press and a ram speed of 90 ipm. The microstructures of as-extruded Zr-7 vol pct LazOS and Zr-7 vol pct Y2Os are shown in Fig. l(a) and (c), respectively. These structures are similar to all the as-extruded materials and consist of an elongated, single-phase zirconium matrix dispersed with oxide or carbide particles. Very little porosity is observed, and the interface between matrix and particles appears satisfactory. The size and distribution of particles, however, are not ideally of the type desired for dispersion strengthening. Since the primary study was of particle stability with respect to zirconium, no attempt was made to overcome agglomeration during powder blending and fabrication. Some areas exhibit fine, well-distributed particles; undoubtedly, a small proportion is submicroscopic and has the

Jan 1, 1963

By Hsun Hu

Based on Kurdjumoiv-Sachs orientation relationship for the fee bee transformation in metals, the jirzal crystal orientation resulting from successive transformations of bee-fee-bee has been analyzed mathematically. There are 528 different variants; many of ther are crystallograpyically equirvalent. Specific examples show that, for equal probability of all the variants, the principal crystallographic axes [100 ], [110], and [111] of the initial bcc crystal can be transformed into vairous axes in the fina1 crystal However, fur each of these principal crystallographic axes, a continuous range of orientation within certain regions of the unit triangle is completely avoided by the finctl Crystals. For uses of higher indices, the final orientations are more uniformly distributed throughout the unit triangle. Results from the PI-esent analysis are in good agreement with preferred Oientations Observed in a zone-meltecl iron bar. THE allotropic forms of iron are characterized by the unusual fact that at both high and low temperatures a bcc structure is stable, whereas at intermediate temperatures (1400" to 910°C) the metal is fcc. Hence, during cooling from its melting temperature, iron undergoes successive phase transformations ofd—? —a with corresponding changes in the crystal structure of bcc — fcc -bcc. while numerous studies have been made in the past of the 1 — a transformation in iron and in various iron-base alloys, no information is available in the literature as to the mechanism of 6 — l transformation and the lattice orientation relationship between these two phases. Experimental difficulties have apparently prevented researchers from undertaking these studies. The laltice orientation relationship between the parent and the new phases of iron resulting from

Jan 1, 1965

By C. G. Dunn, J. L. Walter

COULOMB&apos; and Coulomb and Lacombe2,3 have recently discussed secondary recrystallization in soft iron (99.5 pct Fe). They found that the appearance of this phenomenon was dependent on both the presence of impurities and the thickness of sheet specimens. They concluded that impurities such as carbon, sulfur, and oxygen in the soft iron stabilized the matrix structure and allowed growth of a few grains of specific orientations. They also found that secondary recrystallization ceased when the final thickness was small and attributed this complete inhibition of growth in thin sheet to the restraining action of thermal grooves. When purer iron (99.99 pct Fe) was used, normal grain growth but not secondary recrystallization was obtained. On the other hand it is known that the necessary stabilization of the matrix structure for secondary recrystallization in high-purity silicon iron probably does not depend on impurities but more likely results from the specimen thickness effect of Beck et al.,4 according to evidence and ideas advanced by Walter and Dunn,5,6 and Detert.7 Furthermore, Mullins8 has indicated that if a gas-metal surface energy difference exists across a grain boundary equal to or greater than about 3 pct of the grain boundary energy, then such a grain boundary should not become stuck. Similarly, Walter and Dunn have estimated that any increase in restraining force due to increased thermal grooving with decrease in

Jan 1, 1962

By Nicholas J. Grant, Robert H. Kane, Bill C. Geissen

The platinum-rich section of the Ta-Pt Phase diagram was worked out by metallographic and X-ray techniques, using twenty alloys; solidus temperatures and solid solubilities were determined. Besides s phase, four intermediate stoi-chiometric phases were found: TaPt (high-temperatzrre phase, structure unknown); TaPt2 (ortho-rhomhic, new type); a TaPt3 (orthorhombic, TiCu3 type); ß TaPf3 (monoclinic, new type). TaPt2 and TaPt3 melt congmentlv; two eutectic, two beritec-tic, and one eutectoid reactions occur in the inuestigated range. THE Ta-Pt system was examined as part of a study of the phase diagrams and the intermediate phases of niobium and tantalum with Group VIII transition metals. Since the main scope of this work was the relation among the ordered close-packed phases occurring in the concentration range from AB to AB3 (A = Nb, Ta; B = Pd, Pt, and so forth), only the platinum-rich side of the diagram was worked out thoroughly, while spot checks were made to determine the approximate outline of the tantalum-rich portion. The system has not been thoroughly treated in the literature; Greenfield and Beck1 in their survey of refractory metal intermediate phases found a o phase between -18 and 37 at. pct Pt which coexists at higher platinum concentrations with an unidentified intermediate phase. Browning2 worked on the range between 55 and 100 at. pct Pt; however, this preliminary study did not cover temperatures >1500°C, and included no conclusive crystallo-graphic data. More recently, a study of the platinum-rich section of the Ta-Pt system has been carried out by Ray,3 while Hartley, Parsons, and steedly4 have studied the tantalum-rich section. The crystal structures of TaPt2, a TaPt3, ß TaPt3, and others have been reported in abstracted form by Giessen and Grant.5 EXPERIMENTAL METHODS The methods of alloy preparation and processing and of the metallographic and X-ray procedures follow very closely those described by Ritter, Giessen, and rant&apos; for other refractory metal-noble metal systems, and will not be repeated except where significant differences exist. Starting materials were: tantalum rod of 99.95 pct purity, supplied by National Research Corp., and platinum sponge 99.9 pct, supplied by The International Nickel Co. An oxygen analysis of the tantalum rod showed 30 ppm O; other impurities were C, N, Si, Nb, Mo, none of these exceeding 50 ppm, and 100 ppm W. Homogeneous buttons were readily prepared as follows: ingots of 5 g were weighed and arc-melted under welding grade argon, followed by two remelts after inverting the button. Between 40 and 100 at. pct Pt, weight losses during the first melt rarely exceeded 0.1 pct, in which case the alloy was rejected, and were nil on subsequent remelts. Since the vapor pressure of platinum far exceeds that of tantalum, the small evaporation loss could be assumed to consist of platinum; therefore, a corresponding amount of platinum was added on the second melt. Since it was confirmed on pure tantalum samples that no weight gain through oxygen or impurity pickup occurs (see Ref. 71, it could be assumed that the uncertainty in the composition did not exceed ±0.1 at. pct for the range 40 to 100 at. pct Pt. For the four control melts from 0 to 40 at. pct Pt, an error of ±0.5 at. pct was calculated. Microscopic examination of the whole buttons after melting showed no inhomogeneity other than local coring. This was eliminated by a homogenization heat treatment. A total of twenty-three alloys were prepared. Heat treatments were carried out in a tantalum

Jan 1, 1965

By W. R. Hibbard Jr., R. W. Guard, N. G. Ainslie

Evidence is presented that copper-base solid solutions of different solutes having equal grain sizes, no preferred crystal-lographic orientation, equal electron-atom ratios, and, within experimental scatter, identical initial yield strengths, need not have identical stress-strain curves at strains larger than about 0.04. The stress-strain behavior is rationalized in terms of the proposed Suzuki chemical interaction between solute atoms and extended dislocations using what is thought to be a somewhat different means of representing stress-strain data. ALTHOUGH the effect: of alloying element upon the strength characteristics of sold solutions is a subject which has received considerable attention in the past, the exact relationships between the common deformation parameters and certain common variables are not really known in some cases. As a result some of the experiments reported in the literature in which these variables are inadequately controlled lose some of their persuasion regarding underlying principles. Nonetheless, facts are known which bear pointing up: When the true stress, a, and true plastic strain, E, of tensile deformatic~n are plotted on a double logarithmic coordinate system, one may observe a straight-line relationship at strains greater than 0.02. The form of the curve in the linear region is given by a = Ken! where a represents true stress, E, true strain, and K and tn, constants. If the relationship holds, K and m define the flow characteristics of the material being tested. m and K, however, may vary with other parameters. Hollomon found that in a-brass, m is influenced by grain size. French and HibbardZ found in alloys of copper that inverse relationships existed between m and 1) the solute concentration for a given solute, 2) the 0.01 yield strength, and 3) the constantK. Lacy and Gensamer3 observed (du/d~) (= U/Em) to increase with increasing values of K in systems of alloyed ferrites (although with considerable scatter of data which may be attributed to uncontrolled grain size). Brick, Martin, and Angier* deduced in copper-base alloys a straight-line relationship (with some scatter) between the change in the Dph number due to solid-solution strengthening and the change in the Dph number due to work hardening which suggested that copper-base alloys having equal yield strengths might have identical stress-strain curves in the plastic flow regions. French and HibbardZ concluded that the yield strength of copper-base solid solutions is the proper basis for comparing the effects of solute elements. Also, Allen, Schofield, and ate&apos; showed that, within their experimental variation, copper-base alloys of zinc, gallium, germanium, and arsenic having the same electron-atom ratios have the same true-stress true-plastic strain curves. Dorn, Pietrokowsky, and ~ietz&apos; also found that with aluminum-base alloys the stress-strain curves in the flow regions are approximately the same if "equivalent" concentrations of alloying elements are used. Solute valence and lattice parameter distortion were the parameters used to determine equivalency. The present report describes an investigation in which an attempt was made to obtain copper-base solid-solution alloys of four solute elements having within close tolerances equal grain sizes and yield strengths, and to see if the level of yield strength does indeed define the flow curve regardless of solute type. During analysis of the data certain unexpected features of the stress-strain curves became apparent which gave rise to some speculation and are discussed at length in the paragraphs that follow. EXPERIMENTAL PROCEDURES Alloy Preparation—Using the data of French and HibbardZ as a first approximation, four different binary copper-base alioys were designed so as to have the same yield strength. In addition, other alloys were prepared in which the solute aoncentrations varied slightly from those calculated above so as to span a range of yield strengths, see Table L The yield strengths of all alloys prepared except the copper-tin alloys were subsequently found to Lie fairly close to one another. The copper used in the alloys was produced by the American Smelting and Refining Co. and was of very high purity (99.999 pct). The alloy additions and their initial purities are as follows:

Jan 1, 1960

By J. P. Neumann, L. Raymond

At temperatures near 1000°C, only the (112) (111) slip systems are operatire in tungsten. Therefore, the substructure introduced into the billet upon rleforming a single crystal by rolling at 1000 "C can be controlled by proper selection 01. processing ral&apos;iubles. Using a reduction of 10 pct pel- pass, the (001)[110] and the (110)[001] crystals will deform by duplex slip rip to a 50 pet reduction in thickuess. These rolled single-crystal sheels are characlerized by anisotropic hardening, retention of ductility with warm working, lattice bending which is related to the conlacl (angle, and macroscopic dimensional changecs in the length bid not the width of the billet. When several slip systems become operative, a greater degree of work hardening is itztvoducetl into the crystal. This rolling- condition is characlerized by isotropic hardening, loss of ductilily with warm working, complex lattice distortions, and macro-scopic dimensional changes in both the length rind Width of the billel. IN tungsten, the {1 10}(111) slip systems are operative below room temperature,&apos; while above 700°C only the {112{ (111) slip systems are observed.2,3 In the transition region, i.e., room temperature. both systems appear. It is the purpose of this investigation to show that tungsten single crystals deformed by rolling at a temperature where only one slip system is operative generate dislocation substructure which depends on the crystal orientation. For a specific crystal orientation. the resulting dislocation substructure can be further influenced by modifying the rolling procedure. Crystals oriented for multiple slip display less substructural sensi- tivity to modifications in processing techniques than do single crystals oriented for duplex slip. Under simple slip modes of deformation, very little work hardening is introduced into a rolled single-crystal sheet. Mechanical properties such as room-temperature strength. ductility, and hardness are used to confirm the existence of the different work-hardened conditions generated within the crystal by modified warm-rolling techniques. EXPERIMENTAL PROCEDURE Material. Single-crystal billets of four different crystal orientations. grown by the Arc-Verneuil technique. were ground to a size of 0.25 by 0.375 by 3 in. In terms of their rolling plane and rolling direction, the billets had the following orientations: (1101 [001 ] (110) [110] (001) [110] (001) [100] The actual orientation of all crystals was within 5 deg of the ideal orientations. The typical impurity content of the crystals is given in Table I. Polishing and Etching. Polishing was done elec-trolytically in a 20 g per liter aqueous solution of NaOH at approximately 10 v. It was established by the Laue back-reflection X-ray technique that the surface damage due to grinding and cutting operations with a diamond wheel did not exceed 0.001 in. Therefore after each cutting or grinding operation at least 0.002 in. was removed electrolytically from the surface in order to eliminate surface effects. By lowering the voltage to 3 v, subgrain boundaries and individual dislocations are identified in agreement with Berlec 4 where the etch-pit traces on a cubic plane form a square. The etching time was about 5 sec at room temperature. Rolling. Rolling was carried out on a Loma 2-high mill (Model 600). The peripheral velocity of the 6-in.-diameter rolls was 500 in. per min, with the surface temperature of the rolls about 400° to 450° C The billets were heated before each pass for 30 min in argon to 1000 C. Oxidation of the crystals during rolling in air resulted in a thin layer of greenish-yellow WO 3 This oxide was removed after each pass by immersing the crystals for a few minutes in a boiling NaOH solution. Prior to the initial rolling pass, a surface layer of 0.001 in. was removed by polishing. The crystals were then annealed in vacuum (10-4 torr) at 2400 C for 30 min. All crystals were rolled in the same direction; i.e., the same end was always introduced into the rolls. The rolling program was conducted in

Jan 1, 1965