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By A. D. Schwope, L. R. Jackson, K. F. Smith

Burghoff and Blank1 have pointed out that the creep properties of hard-drawn coppers are closely associated with their individual softening characteristics and have further shown that the creep resistance of various types of copper is improved, under certain circumstances, by cold stretching. In the design of certain types of electrical machinery, it is important to have the creep resistance as high as possible; furthermore, short-time creep strength is important since in many cases stresses are large only during warming-up and cooling-down periods. In this paper, data are presented showing the effect of cold work on the short time creep strengths of various types of commercial copper under several conditions. It is shown that trends from short-time creep tests are evident at longer times. Materials Used in the Investigation The coppers used in this investigation were commercial grade and of two basic types, oxygen free high conductivity (OFHC) and tough pitch. Additions of silver in amounts of 15 and 25 oz per ton were added to each of the two coppers. The analyses of these six coppers are given in Table 1. Originally, they started as wire bars 4 X 4 X 54 in. A. square rod was made by hot rolling the wire bars to 9/16-in. rod in 8 passes. This rod was then cold drawn to 0.445-in.-diam rod and annealed for 3 1/2 hr at 1000°F. It was then cold drawn to 0.325-in. rod and again annealed at 1000°F for 3 1/2 hr. Hard square rods were then made by cold rolling to 0.257 X 0.257-in. rod. Soft wire was made from the hard- drawn material by annealing at 650°F for 3 hr. The final rolling was performed using a set of 9-in. grooved rolls revolving at 30 rpm, which produced square wires. Reductions of approximately 5, 20, 30, and 40 pct were obtained using several passes in the same direction for the large reductions. The 5 pct reduction by drawing was accomplished using a steel die having 2 parallel bearing surfaces. The die angle was 7 1/2 degrees and the wires were lubricated with a paste of ceresin wax dissolved in carbon tetrachloride. The speed of drawing was 13 fpm. Since work was done on only two sides of the wire simultaneously, it was necessary to rotate it 90 degrees each pass to insure uniform deformation. The room-temperature tensile properties of the various tempers are given in Table 2. The grain size of the an- nealed 0.257-in. wires was uniform and averaged about 0.035-0.045 mm. Experimental Procedures for Short-time Creep Tests Standard creep-test frames (Fig 1) were used for the testing. Special fixtures were designed to apply axial compressive and tensile loads to the copper wires. The compression specimens were 1 in. long and the ends were ground flat and parallel. The creep in compression was indicated by the movement of reference marks s-ratched on intersliding platinum strips attached to the moving heads of the fixture. The movement was measured with an optical micrometer fitted with a filar eyepiece on which the smallest division was 0.00005 in. The tensile creep specirriens were 4 in. long which provided ample gripping surface for the jaw-type grips. The platinum strips were attached to a one-inch gauge length of the wire and the creep measured as previously described. The single-specimen furnaces were connected to individual power and control sources. The controlling equipment consisted of Foxboro controllers

Jan 1, 1950

By G. R. Purdy, J. G. Parr

The intermetallic compound Ti2Co was studied by X-ray diffraction and metallographic techniques. The phase occurs off stoickzometric composition, with its greatest variance at high temperature. The solubility limits of the phase have been cletermined, and an amendment to the titanium-cobalt phase diagram is suggested. THE first intermetnllic compound to appear at the titanium-rich side of the titanium-cobalt system was found by Laves and wallbauml to be Ti2Co. They described this compound as isomorphous with Ti2Ni and Ti2Fe, and demonstrated that it had a face-centered-cubic structure with 96 atoms per unit cell. This contention is supported by the work of Duwez and Taylor2 and Orrell and Fontana3 who also determined the lattice parameter to be about 11.30A. Rostoker4 believed that Ti2Co did not exist, and that the phase considered by the other workers to be Ti2Co was Ti,Co20. However, Orrell and Fontana determined oxygen and nitrogen contents and found that their alloys did not contain sufficient of these elements to produce significant quantities of a stoichiometric oxygen compound. The present investigation was initiated to determine the composition limits of the phase Ti,Co.

Jan 1, 1961

By Nicholas J. Grant, Rolf Nordheim, Bill C. Gissen

The system Cb-Re was examined in detail utilizing pure metals, careful melting techniques, and heat treatments. Metallographic and X-my methods were utilized for phase identification. In addition to soli-dus determinations, the composition limits and mode of formation of the intermetallic compounds 0 and X were determined. The binary constitution diagram Cb-Re has been the subject of a number of investigations.'-7 Two intermetallic phases have been described and tentative diagrams have been proposed. It was the aim of this investigation to obtain a complete and more accurate diagram through the use of purer alloys and improved techniques. The diagram worked out by Knapton7 was published after our experiments were concluded. EXPERIMENTAL METHODS The starting materials were Re powder of 99.95 pct purity, supplied by the Chase Brass and Copper Co., and Cb rondelles of 99.6 pct purity, supplied by the Electro Metallurgical Co. Typical analyses are given in Table I. The alloys were prepared from compacted Re powder and Cb rondelles; for critical compositions master alloys were used. The melts varied from 5 to 50 g and were melted nonconsumably in an Heraeus arc furnace, under ti-tanium-gettered laboratory grade argon. It was necessary to invert the buttons and remelt, followed by crushing and further remeltings, the number of which depended on the nature of the fracture of the alloy. The weight of each alloy was carefully checked after each melting operation. It was found that significant weight losses occurred only when loose Re powder was used. These losses amounted to a maximum of 3 wt pct in such instances, but did not occur after the charge was once molten, regardless of the composition. Typical loss of weight after 4 remelts, including crushing, amounted to 0.2 wt pct. Oxygen pickup during successive melting cycles did not appear to be significant, since the weight gain values never exceeded 0.01 wt pct. Control of the composition of the alloys was not too difficult; however, the problem of homogenization was a far greater one. Optimum alloying conditions were finally achieved by a combination of master alloy production and repeated crushing and remelting cycles. The compositions of the alloys utilized to determine the constitution diagram are listed in Table 11. The weight balance method was used ultimately as the sole analytical method, since repeated checks indicated that it was accurate to 0.2 pct, if the weight losses were small. The results were double-checked by a metallographic study of the homogeneity of the samples, since this was presumed to be the more serious factor. Heat treatments at 1200°C or lower were accomplished by sealing the specimens in Vycor tubes, heating in a Globar furnace, followed by air cooling. This was considered to be an adequate quench because of the very low temperatures involved. For temperatures of 1200" to 1900°, alloys were homogenized and heat treated in a tungsten-filament resistance vacuum furnace. From 1900" to 2750" a tantalum-tube resistance furnace was utilized, operating under a vacuum of 105 mm Hg. The temperature measurements up to 1200" were made by means of platinum-platinum 10 pct Rh thermocouples, with an accuracy of 5°C. For temperature measurements greater than 1200°C, optical pyrometers were used. They were calibrated against a standardized instru-

Jan 1, 1962

By Nicholas J. Grant, William H. Ferguson, Bill C. Giessen

Ta-lr alloys have been examined over the complete range of compositions using metallographic and X-ray techniques. The terminal solid-solubility limits, solidus temperatures, and intermediate phases were determined. There are four inter-mediate phases: o, tetragonal, analogous to a (Fe-Cr); 0,. orthorhombic; az, tetragonal; and a TaZr,, cubic, AuCu, structure. Of these, o and a, melt peritecticaLly, a, decomposes peritectoidally, and a TaIrs has a congruent melting point. Three peri-tectic and one eutectic reactions occur. 1 HE Ta-Ir phase diagram has not been treated in the literature. Intermetallic phases and terminal solid solubilities have been described and estimated.'-4 The previous findings have been confirmed in this work. A complete diagram with additional phases and solidus curves is presented. EXPERIMENTAL METHODS Starting materials were tantalum powder of 99.8 pct purity, supplied by the National Research Corp., Cambridge, Mass., and iridium powder of 99.9 pct purity, supplied by the Bishop Co., Malvern, Pa. Both powders were -200 mesh. Table I lists the analyses as given by the suppliers. A standard procedure was employed in making the alloy buttons, which was described in detail in Refs. 5 and 6, and which included repeated arc-melting of powder compacts and determination of the composition by the weight-balance method. This is especially justifiable due to the similar vapor pressures of tantalum and iridium. In the critical parts of the diagram, a spacing of 1/2 at. pct was used, based on premelted master alloy material. The observed structures and X-ray spectra were consistent with the composition sequence of the alloys. Table II lists the final alloy atomic percentages with the calculated percent error of composition. Cross sections representative in grain size and composition were selected for the study, as described in Ref. 5. Based on prior experience, no contamination from the tungsten electrode was considered. Temperature measurements were obtained using a Leeds and Northrup optical pyrometer and have been described extensively in Refs. 5 and 6. All heat treatments were made in the high-vacuum tantalum tube furnace mentioned in Ref. 5. Samples annealed in tantalum containers cooled from 1800" to 1000"~ in 5 sec; those annealed in ceramic crucibles cooled over the same range in 15 to 30 sec. The thermal treatments are listed in Table 111. All specimens were homogenized at 1735°C for 24 hr. Tantalum-rich compositions were treated in tantalum buckets. Iridium-rich compositions were annealed in tantalum buckets below the eutectic temperature of 1950°C; up to 2200°C, tungsten-lined tantalum baskets were used; and above 2200°C thoria crucibles were used. It was found that refractory oxides (in early stages of the investigation alumina crucibles were used up to 1800°C and thoria crucibles were used to 2400"~) give off minute amounts of oxygen and thereby influence the microstructure considerably, or react directly with the alloys.

Jan 1, 1963

By Nicholas J. Grant, Hanna Ibach, Bill C. Giessen

The system Ta-Rh was investigated over the entire comnposition range using metallogvaphic and X-ray techniques as well as thermal analysis. Terminal solubility limits, solidus temperatures, and the crystal structures of two new intermediate phases were determined. There are five intermediate phases: o, tetragonal, isostructural with o(Fe-Cr); a1, orthorhomnbic : a2, orthorhombic, isostructural with CozSi; 0 3, a high -temperature phase of unknozun structure; and a TaRh3, cubic, AuCu3 structure. a, aL, a,, and a melt peritectically; and a TaRh, has a maximum melting point. Five peritectic and one eutectic reactions occur. THE Ta-Rh phase diagram has not been fully treated in the literature; however, two inter metallic phases have been described.&apos;-&apos; This study attempts to work out the diagram covering the details of phase boundaries as well as the crystallography of the intermediate phases. EXPERIMENTAL METHODS Starting materials were tantalum powder of 99.8 pct purity, supplied by National Research Corp., Cambridge, Mass., and rhodium powder of 99.9 pct purity, supplied by Bishop Co., Malvern, Pa. Analyses as given by the manufacturers are presented in Table I. In addition to the spectroscopic analysis, an oxygen analysis has been made of the tantalum powder. After preliminary trials, the standard procedure employed in making the alloys was as follows (see Ref. 4 for further details). The powders were weighed, mixed manually, compacted under 16,000 psi, and arc-melted at not more than 500 amp under thoroughly titanium gettered welding-grade argon of 400 mm Hg pressure. The gettering process was repeated after each melt. It had been shown previously5 that under these conditions no oxygen pick-up exceeding 0.001 pct in a hafnium button could be detected. The buttons, ranging from 5 to 10 g in weight, were inverted or, if possible, crushed and remelted three times. Melting presented no difficulty, except for tantalum-rich al- loys, which showed considerable spashing during melting. The average weight loss of 1 wt pct rose to 2.5 wt pct in these cases. Subsequent melting, however, resulted in losses of less than 0.1 wt pct. The melts obtained frequently showed small in-homogeneities, mostly in the tantalum-rich part of the system below 25 at. pct Rh. This was not due to insufficient blending of the elements, but to crystallization taking place from the cooled bottom. This condition was not improved by further re-melting; therefore the following precautions were taken. Cross sections of as-cast buttons were made. For the investigation only buttons were used where these inhomogeneities did not exceed 1 at. pct (estimated from the amounts of haSeS resent). In addition, only the center portions of such buttdns were utilized to minimize errors. Smaller buttons showed smaller concentration gradients and were used as a check. Finally, all alloys were homogenized to eliminate coring (see below). After this, the error in alloy composition due to inhomogeneity was cl at. pct. In order to confirm the concentrations of the alloys and to provide an impurity check, wet-chemical analyses and oxygen-fusion analyses of four key alloys were carried out. The results, together with the concentrations as calculated with the weight balance method, are presented in Table 11. It was found that for three alloys the agreement is very good (< 0.2

Jan 1, 1964

By Nicholas J. Grant, Irmgard Rump, Bill C. Giessen

The system W-Hf was determined by use of metal -lographic and X-ray methods. The only interrnetal-lie phase W2Hf melts peritectically at 2650° ± 50°C. A eutectic between W2Hf and ß-Hf solid solution exists at 78 at. pct Hf arul 1930º ± 10°C. The addition of tungsten loulers the hafnium transfornzation; there is a eutectoid at 93 at. pct Hf and 1560°C. The solubility limits of the terminal solid solutions were determined. At the beginning of this investigation, the system had not been elaborated; only crystallographic work had been done to determine the structure of the occurring intermetallic compound W2Hf, and a certain analogy to the system W-Zr was to be expected. Special emphasis was placed in this program on the Hf-rich part of the diagram. Following the completion of our experiments, a phase diagram was suggested by Braun and RUdY.1 EXPERIMENTAL METHODS The investigation utilized tungsten powder supplied by the General Electric Co. with a purity of about 99.9 pct and hafnium crystal bar of about 97.7 pct purity, 2.3 pct Zr, supplied by Foote Mineral Co. Typical analyses are given in Table I. The procedures followed were identical with the ones described for the Re-Nb diagram.&apos; Tungsten powder was compacted at 16,000 psi and the necessary amount of hafnium was added in the form of small pieces cut from the crystal bar, with a reasonable excess of tungsten powder to make up for powder losses on melting. High hafnium or tungsten melts were prepared from premelted tungsten and hafnium or by employing master alloys. The melting was done in a Heraeus arc-furnace under argon. Melting and remelting up to 8 times resulted in fairly homogeneous alloys. No weight

Jan 1, 1962

By E. J. Rapperport, M. F. Smith

A presentation of the W-Ru constitution diagram is given. Techniques utilized in the determination of phase boundary values include electron micro-probe analysis of two-phased alloys and diffusion couples, as well as normal metallographic and X-ray methods. The primary features of the diagram are: 1) a terminal solid solution of ruthenium in tungsten with a maximum solubility of 23 at. pct Ru at 2300°C; 2) a terminal solid solution of tungsten in ruthenium with a maximum solubility of 48 at. pct W at 2205°C; 3) a o phase of maximum breadth about 6 at. pct based on the composition W3Ru2 which forms peritectically from the melt at 2300°C, and which decomposes eutectoidally at 1667 °C to form a twigs ten and 0 ruthenium; 4) a eutectic at 45 at. pct Ru and 2205°C with the products being o plus ß ruthenium. THE W-Ru diagram has previously been studied only in a cursory fashion. Raub and alter&apos; obtained a 1400°C isotherm in which they observed no intermediate phases, and on which they established the limits of solubility as 36.5 at. pct W in ruthenium and about 1.5 at. pct Ru in tungsten. In addition, Obrowski2 found a o phase forming peritectically from the melt and existing only above 1650°C. Below this temperature the phase was presumed to decompose eutectoidally. The present work finds the diagram as given in Fig. 1. I) EXPERIMENTAL PROCEDURE The materials used for alloy preparation in determining the W-Ru constitution diagram were 99.9 pct pure ruthenium powder supplied by Baker Chemical Co., and 99.9 pct pure tungsten powder from General Electric Co. Typical analyses of these elements are given in Table I. Initial alloys at 10 at. pct intervals were prepared from the metal powders by the following method. Powders sufficient for 25 g of the alloys were weighed out with an accuracy of 0.1 mg and blended mechanically. After blending, the powders were compacted, in a steel die, at approximately 30,000 psi. The compacts were sintered in an electric vacuum furnace in order to remove adsorbed gases and to achieve partial densification prior to arc-melting. Vacua of 10-4 mm Hg or less were maintained in sintering as the furnace temperature was raised to approximately 2000°C. Sintering times ranged from 10 to 20 hr. The sintered compacts were arc-melted under a protective atmosphere of purified helium. Melting was conducted on a water-cooled copper hearth, utilizing a nonconsumable tungsten electrode. In the melting process, each alloy was turned over and re-melted on opposite sides from four to six times to ensure complete melting and to eliminate gross in-homogeneities. The arc-melter used had a vacuum capability of 5 X 10-6 mm Hg, and a leak rate of about 20 -liters per hr. Chemical analysis techniques for refractory metal-platinum group metal combinations are not well-established; therefore, composition control and determination depended principally upon weight-loss observations and calculations. This consisted in weighing each alloy after sintering and after arc-melting, and calculating the maximum and minimum composition values, assuming the total weight losses to be first all tungsten, and then all ruthenium. Since composition uncertainty was directly related to weight loss, care was taken to minimize losses in handling, compacting, and melting. Prior to homogenization and equilibration the as-arc-melted alloys were analyzed in several

Jan 1, 1964

By J. W. H. Clare

An equilibrium isotherm at 550°C is given for ternary alloys rich in aluminum containing 0 to 15 wt pct Cr and 0 to 20 wt pct Mn. Phases encountered are: aluminum solid solution; stable temary compound G; and MnAl8,. In addition, a limited number of alloys were annealed at 450°C to check for differences from the 550°C isotherm. These experiments limited the composition of the G phase at 550°C and further experiments established that the G Dhase is not stable above 590 ± 1 °C. RAYNOR and Little1 established several equilibrium isotherms using aluminum-rich alloys containing up to 5 pct of the elements chromium and manganese. These isotherms showed that, in addition to an a solid solution and the two binary intermediate compounds 8 and MnAl6, a stable ternary compound ex-isted in the system. This phase was called the G phase because of its ghostly appearance in micro-sections. Little, Raynor, and Hume-Rothery2 found a similar phase in binary aluminum-manganese alloys and, as a result of their experiments, concluded that the G phase was a metastable phase existing in the aluminum-manganese system. This phase was stabilized by the addition of chromium. The constitutional work of Raynor and Little,&apos; although showing the existence of the G phase in the aluminum-chromium-manganese system, did not establish precisely the composition limits of the phase or the temperature above which the phase became unstable and disappeared from the system. The work described in this paper was undertaken to provide this information. An examination of the previous work&apos; showed that an isotherm at 550°C would provide the required data regarding composition in the shortest possible time, as the (a + G) phase field narrows considerably at higher temperatures. The same work showed that the G phase ceased to exist between 580° and 595°C. A more precise estimate of the transformation temperature would therefore be obtained by annealing selected alloys at successively higher temperatures beginning at 580°C. EXPERIMENTAL PROCEDURE 1) Materials Used—The experimental alloys were prepared from four master alloys containing 15.00 w pct Cr, 15.28 wt pct Cr, 19.80 wt pct Mn, and 19.38 wt pct Mn which were made from super-purity aluminum, electrolytic chromium, and electrolytic manganese. The aluminum was of 99.996 pct purity, the principal impurities being copper, iron, and silicon. The chromium and manganese were 99.9 pct pure, the principal impurities being antimony, calcium, and magnesium. 2) Preparation of the Experimental Alloys—The alloys were prepared in 20-g quantities by melting together the requisite amounts of master alloy and aluminum in an alumina-lined crucible and, after thorough stirring with an alumina rod, cast into a cold copper mold to give ingots 1/4 in. in diam and 3 in. in length.

Jan 1, 1960

By Horace Pops

Isothermal sections in the copper -rich region of the Cu-Si-Zn a1by system have been determined at 8473 760; 6003 and 482°C by means of microscopic examination with confirmatory X-ray diffraction work. The stability of the bee 0 phase decreases both with decreasing temperature and with increasing copper content. The silicon-n&apos;ch 0 phase decomposes upon quenching from high temperatures either by a martensitic or by a "massive" transformation, depending upon the solute content. A two-phase equilibrium is found to exist in the Cu-Si-Zn system between the hep < phase of the Cu-Si system and the bee ß phase of the Cu-Zn system. It is shown that the isothermal limits of the primary solid solution at 760; 6003 and 482°C are in part affected by the intermediate phases which follow them in the ternary system Possible electron-concentration and size effects upon phase boundaries are discussed. ALTHOUGH the mechanical and physical properties of silicon brasses have been measured in great detail, the factors which influence these properties are not well-understood, partly because the knowledge of the phase relationships in the Cu-Si-Zn system is limited. Gould and Ray1 studied the effects of silicon upon the hardness and structure of Cu-15 pet Zn and Cu-40 pet Zn alloys. They proposed an isothermal section at 800°C which was not based upon experimental data, since the binary phase diagrams had not been completely determined. Using Cu-Si-Zn alloys containing approximately 5 wt pet Si, vaders2 determined the boundary, at 750°C, between the copper-rich solid solution and an unidentified second phase. Masing and wallbaum3 examined a vertical section through the ternary diagram in the region between Cu-20 pet Zn and Cu-10 pet Si alloys, but they emphasized uncertainty about their data. Mima and Hasegawa4 studied the liquidus surface of Cu-Si-Zn alloys, phase transformations in high silicon-bearing (20 to 25 at. pet) alloys,5 and the phase relations in low silicon-bearing Cu-Si-Zn alloys.6 Their experiments were based upon thermal analyses and metallographic observations. The compositions of the phase boundaries were not determined with high precision, and the crystal structures of the phases were not reported. Because of uncertainties in the existing literature, it became of interest to determine more accurately the phase relations in copper-rich Cu-Si-Zn alloys. The crystal structures, stability, and phase boundaries of the primary solid solutions and several intermediate phases were determined, and the data are reported as partial isothermal sections.

Jan 1, 1964

By A. A. Bauer, M. S. Farkas, F. A. Rough

An investigation of the d-phase relationships between the uranium-zirconium and uranium-molybdenum systems was conducted. A ternary cut joining U-31.5 at. pct Mo to U-74 at. pct Zr is presented on the basis of differential thermal analysis, metallographic and X-ray diffraction data. HyDothetical isothermal ternary sections, inferred from the determined d-phase relationships, are presented for the uraniztm-zirconium-molybdenum system. A ternary eutectoid, at 454ºC, was found in zirconium-rich alloys. Its composition, based on metallography and electron-beam micro-analysis, is estimated as U-61.7 at. pct Zr-7.1 at. pct Mo. URANIUM binary systems have been studied extensively in the past to supply basic information needed in reactor-fuel development. Alloys of uranium with zirconium, molybdenum, and titanium are of particular interest because, in these binaries, extensive or complete solid solubility between the body-centered-cubic forms of these elements and y uranium exists. In addition, an intermediate phase of limited solid solubility forms in each of these systems by transformation of the high-temperature ?-uranium phase. Previous investigation of the phase relationships existing between the intermediate 6 phases in the uranium-zirconium-titanium and the uranium-molyb- denum-titanium ternaries have already been reported.1,2 The results of an investigation of the phase relationships existing between the 6 phases in the uranium-zirconium-molybdenum system is reported here. The phase equilibria that occur in the solid-state portions of the pertinent binary systems are shown in Fig. 1. Phase nomenclature appearing throughout the report is as shown in these diagrams. The crystal structure of the phases in this system are given in Table I. EXPERIMENTAL PROCEDURES Alloys were cast and fabricated to 1/4-in.-diam rod. Specimens were heat treated and examined by metallographic and X-ray techniques. Thermal-analysis data were obtained.

Jan 1, 1960

By W. C. Leslie

The textures of cold-rolled and of annealed iron are compared with those of an iron-0.8 pct copper alloy in which the amount of precipitation after cold rolling was controlled. Previously published pole figures -for cold-rolled and for annealed iron are confirmed. The effects of precipztatiotz after cold rolling are to retain the cold-rolled texture after annealing, to inhibit the formation of the usual allnealing texture, and to produce elongated recrys-tallized ferrite grains. It is suggested that the inhibition of new textures by precipitation after cold rolling is a general phenomenon. A great deal of attention has been paid to the development of texture during the secondary or tertiary recrystallization of ferritic alloys, but very little work seems to have been done on the control of texture during primary recrystallization. If such control were attained, it might be possible to simplify the processing of oriented materials or to change the characteristics of current cold-rolled and an-nealed products. From previous experience, it seemed likely that texture could be controlled by recrystallizing a supersaturated solid solution. Green, Liebmann, and Yoshidal found that the formation of preferred orientation in aluminum (40 deg rotation about <111> relative to the deformed matrix) was inhibited when iron was retained in supersaturated solid solution in the strained aluminum. The authors attributed this inhibition to iron atoms in solid solution. There is, however, an alternative explanation. Green et al, took a highly supersaturated solution of iron in strained aluminum and heated it to an unspecified temperature for recrystallization. It is probable that precipitation occurred prior to and during recrystallization, and it is proposed that the inhibiting agent is this precipitate, rather than the iron atoms in solid solution. It is important to note that precipitation before cold work is ineffective; the effective precipitate is that formed after cold working and either before or during recrystallization. The location and distribution of the precipitate are critical. Precipitation in such a manner has been found to have profound effects upon kinetics of recrystallization and the microstruc-ture of the recrystallized alloys.2-4 It would be surprising, indeed, if this were accomplished with no change in texture. Because of the relative simplicity of the system, and because of previous experience,4-7 it was decided to determine the effect of precipitation on texture in an alloy of iron and copper. Bush and Lindsay5 found an unspecified change in texture in cold-rolled and annealed low-carbon rimmed steel sheets when the copper content exceeded 0.1 pct. MATERIALS In earlier work, the rate of recrystallization of a low-carbon steel was greatly decreased by 0.80 pct copper, and, after the proper treatment, the recrystallized ferrite grains were greatly elongated.4 Accordingly, it was decided to investigate the effect of precipitation on texture at this level of copper content. The iron and the iron-copper alloy were made from high-quality electrolytic iron and OFHC copper, vacuum-melted in MgO crucibles, cast, hot-rolled to 0.2 in., then machined to 0.150 in. The compositions are given in Table I. The plates were heated to 925°C and brine quenched, twice. This produced a ferrite grain size of ASTM 0 in the iron and ASTM 1 in the Fe-Cu alloy. Disk specimens were cut from the heat-treated plates, repeatedly polished and etched, then used to determine (110) and (200) pole figures by reflection. Despite the complication of large grain size, these pole figures strongly indicated a random texture. PROCEDURES The copper content in solid solution in ferrite before cold rolling and recrystallization, and hence, the amount that could precipitate during the recrys-tallization anneal, was controlled at three levels by heat treatment. The specimens as quenched from 925° C were presumed to have all the copper, 0.80 pct, in solid solution. Other samples of the quenched alloy were aged 5 hr at 700°C to retain about 0.5 pct Cu in solid solution.6 A third set of quenched specimens was reheated to 700°C, then slowly cooled in steps, to reduce the amount of copper in solid solution to a very low level. All specimens were cold-rolled 90 pct, from 0.150 to 0.015 in. thick. The rolling was done in one direction only, i.e., the strip was not reversed between passes, with a jig on the table of the mill to keep the short specimens at 90 deg to the rolls. The rolls were 5 in. in diameter and speed was 35 ft. per min. Machine oil was used as a lubricant. In a supersaturated alloy, the maximum effect of the copper precipitate on microstructure and on recrystallization can be developed by a treatment at 500°C, after cold rolling and before recrystallization.&apos;

Jan 1, 1962

By E. P. Klier, Jane Jellison

The course of the transformations on cooling in a series of Cu-A1 alloys has been followed by means of thermal analysis, X-ray diffraction, and optical metallogrAphy. Specimen size was found to have a pronounced effect on the time of completion of the pearlite transformation due to modification in the unmber of nuclei. The ordeving transformation zvas observed for all cooling rates for all alloys studied, and is considered insuppvessible. At intermediate cooling&apos; rates, a transitional struchire for 011 alloy compositions and based ox the bainite reaction was observed. The alloys of aluminum and copper possess a eu-tectoidal region at from about 9.4 to 16 pct Al. Above the critical temperature, the disordered bcc phase, 0, is stable. At subcritical temperatures, the 0 phase decomposes under equilibrium conditions into the stable phases, a and y,. At the eutectoid composition, these phases develop a lamellar pearlite structure, in appearance much like that found in steels. During rapid quenching from supercritical temperatures, the diffusion processes required for the formation of the equilibrium phases are suppressed, and the 0 transforms to an acicular martensitic phase, designated B or y&apos; depending on the aluminum content, or to a mixture of the two. Early investigators of this system concentrated on determining the equilibrium phase diagram, &apos;&apos;&apos; the structure of the equilibrium phases,3 and later the isothermal decomposition of the 0 phase at subcritical temperatures, or the decomposition of the martensite on tempering. Other work which treated the nonequilibrium transformations concentrated largely on the martensite transformations and the structure of the b and y&apos; phases.15"17 Since the pearlite and martensite transformations in this system resemble those in steels, the one being formed by nucleation and growth of adjacent lamellae of the equilibrium phases, and the other by a diffusionless, shear-type transformation, the present study has been undertaken to investigate the structures formed on continuous cooling, with the objective of constructing cooling transformation diagrams analogous to those derived for alloy steel systems. In particular it was desired to determine whether parallels between the A1-Cu and iron-iron carbide systems on continuous cooling extended to encompass the intermediate phase, namely the bainite structures, which form by a combined martensitic-diffusion mechanism,&apos;&apos; but which are supersaturated with respect to the equilibrium phase upon which their crystal structure is based. To this end the transformations in representative alloys of the Cu-A1 B eutectoid system have been followed, using the methods of thermal analysis, X-ray diffraction, and optical microscopy. EXPERIMENTAL PROCEDURE Materials. The materials tested were those used by Klier and Grmko 5 in their study of the isothermal decomposition of these alloys. The alloys were melted in graphite crucibles and chill-cast into 5 by 2 by 1/4 in. ingots. The ingots were then hot-rolled to sheets 1/8, 1/16, and 1/32 in. thick. The compositions are given in Table I. Specimen Preparation. Specimens for thermal analysis were in the form of small squares approximately 1/4 in. on a side. For the 11.9 and 13.5 Al-Cu alloys, the sheet thickness was 1/16 in. and for the 10.5 A1-Cu alloy the 1/32-in. sheet was used. One lead of a chromel-alumel thermocouple was spot-welded to either face of the square with the specimen itself thus forming the hot junction of the thermocouple. Specimens for X-ray analysis were prepared as filings from martensitic sheet stock and were sealed in glass ampoules under 1/2 atm of argon. Metallographic examination of the powder specimens was carried out on a portion of the heat-treated filings mounted in lucite. All specimens were examined metallographic ally after etching

Jan 1, 1965

By R. M. Goldhoff, H. J. Beattie

The high-temperature properties of a 1 Cr-Mo-V forging steel are described. A series of controlled heat treatments was designed to delineate the effects of austenitizing and tempering treatments, temile strength, and grain size on such properties. Studies indicate that the mechanical properties and their varlations under creep can be described by the initial metallurgical structures and their changes droPirzg exposure, particulavly the carbide reactions. Such structures are described and correlated with the mechanical properties. FOR many years the large steam turbine industry has relied on the 1 Cr-Mo-V type forging steel for critical applications. Because of its adequate heat resistance and relative economy, it is currently in use in the temperature range up to about 1050" to 1075°F. Attempts to understand the large property variations attainable in this steel involve the structural modifications due to the wide latitude in its heat treatment. The heat treatment essentially involves a two-step process which includes solution-ing of carbides in the austenite range followed by a suitable tempering treatment below the critical to adjust the level of properties. The latter step is referred to as "secondary hardening" and is basically an ordinary aging reaction involving carbides. In the commercial heat treatment of large components of such steel, homogenizing and stress-relief anneals may be included and have some importance in determining subsequent properties. Several studies of the engineering properties of this steel as a function of transformation micro-structure have been reported.1 3 However, in this steel the carbide reactions, which are a function of composition and heat treatment, appear to be the property-controlling factor rather than the micro-structure defined as a transformation product. Thus, the tempering resistance of this type of alloy steel is mainly a function of the size and distribution of alloy carbides.4 However, it is also necessary to consider the stability of the microstructure and the effect of dynamic carbide reactions on subsequent properties. It is the purpose of this paper to show the interdependence of properties and corresponding structures, particularly carbide reactions, developed for a limited set of controlled heat-treatment conditions applied to 1 Cr-Mo-V steel. MATERIALS AND PROCEDURE The material for this work came from a large production forging whose chemical composition is shown in Table I. The property data accumulated on this steel as a function of heat treatment were room-temperature tensile and smooth- and notch-bar creep rupture at 1050°F (notch geometry: shank diameter = 0.357 in., depth = 50 pct, radius = 0.005 in.). To achieve controlled structural variations the temperature and time of both austenitizing and tempering were varied in a manner to produce a series of eight steels each at one of two grain sizes and one of two hardness levels in proper combination for valid comparisons. This will be clear upon examination of Table I. Structural studies involved the use of optical and electron microscopy as well as X-ray and selected-area electron diffraction. To reveal the nature of carbide precipitations, electrolytic extraction techniques were used with subsequent analysis of the residue by X-ray diffraction. Weight losses of the steel specimens during electrolysis were measured and successive chemical fractionations of the residues were applied and checked by X-ray examination. The details of fine structural distributions, morphologies, and crystallography of the precipitates as well as dislocation distributions were investigated by examining in the electron microscope three common types of preparation. a) Relief Replicas. Mechanically polished sections were etched in 2 pct nital, replicated with a nitrocellulose film, which was shadowed by chromium vapor deposited at a glancing angle of 20 deg. b) Extraction Replicas. A thin film of carbon was vapor-deposited on the polished and etched surface. The carbon films were then etched off and gathered on electron-microscope supporting grids. The carbides left imbedded in the carbon replica in their original distribution were then examined crystallo-graphically by selected-area electron diffraction. c) Thin Films. Specimens were mechanically ground and polished down to a thickness of 0.001 to 0.003 in. Final thinning was done electrolytically in a "chrome-acetic" electrolyte. When holes began to appear in the foil, the voltage was interrupted and applied in several 1-sec bursts. Sections of the foil between holes were thin enough to pass a 100-kv electron beam that carries an image.

Jan 1, 1965

By J. E. Hilliard

Various methods are given for estimating the number per unit volume and average size of convex particles from measurements on a projection through a slice of the structure. The determination of the size distribution is considered specifically for spherical particles. The results are applicable to any type of transmission microscopy and also to the correction of measurements made by reflected light on semitransparent materials. WITH the advent of electron transmission microscopy, the metallurgist is confronted with the problem of relating a projected image to the three-dimensional properties of the structure. This paper deals with the estimation of the number per unit volume and size of particles dispersed in a matrix. The case of convex particles will first be treated (the results will be applicable as approximations to particles of more general shape) and then spherical particles will be considered specifically. The latter represent a special case frequently encountered in practice and one which is also amenable to a calculation of the effect of overlap on the observed particle-size distribution. Although the present treatment was prompted by the needs of the electron microscopist, the results are applicable to transmission studies with any type of radiation. In addition, they can be used in the analysis of semitransparent materials by reflected light, the depth of light penetration corresponding to the thickness of the slice or section used in the transmission studies. 1) CONVEX PARTICLES 1.1) General Expression for N,. We will suppose that a "center" (such as the center of mass) is assigned to each particle. The convention used for defining the center is immaterial providing it does not depend on the orientation or location of the particle. Consider a slice through the structure having a pair of parallel faces a distance t apart. It will be assumed that the slice is randomly located with respect to its perpendicular distance from some fixed point, but it is not necessary to assume that its orientation is random. Our problem is to deduce the relationship between the number of par- ticle images seen on an orthogonal projection through the slice with the number, Nv, of particles per unit volume in the original structure.* *Symbols are listed in the Table. The expected number of particles with centers lying within the slice is Nvt per unit area. In addition, there will be elements in the slice contributed by particles whose centers lie without. The number of such elements will be the same as the number of intersections occurring on a two-dimensional plane through the structure; namely N~K, where K is the mean distance, Fig. 1, between tangent planes to a particle averaged over all particles, i.e., Where Ni is the number of particles of class i having the same shape and size, and pi (4, 8) is the probability that an i particle will have a given orientation with respect to the slice. If the particles are randomly oriented, then K is independent of the orientation of the slice and equal to the mean cali-per diameter. The total number of particle elements in the slice is therefore Nv(t + K) per unit area, but fewer will be seen as separate images on the projection plane because of overlap. If MA is the number of elements "lost" by overlap, the number of images per unit area will be NA = Nv(t + K) -MA 121 MA is a function of the slice thickness and must vanish at t = 0. As t increases, NA at first increases, reaches a maximum, and thereafter decreases as the overlap term MA becomes predomi-

Jan 1, 1962

By P. Greenfield, C. C. Smith, A. M. Taylor

The Mg-Zr alloy ZA and Mg-Mn alloy AM503(S) are shown to have a markedly improved resistance to creep deformation after suitable heat treatments. This improvement makes them suitable for certain stress-bearing fuel element components in nuclear reactors. The extent of strengthening is described and an explanation of the behavior of both materials is given, based on a combination of strain-aging and grain growth. The increase in operating temperatures of fuel element components in Calder Hall type nuclear reactors has necessitated the development of magnesium base alloys with a very high resistance to creep at temperatures up to 500°C. Such alloys are not required for fuel element cans, which require high-creep ductility rather than strength, but for can supporting and stabilizing components, which are needed to support the imposed loads without deforming more than about 1 pct in times of up to 40,000 hr. The amount and type of alloying addition made to magnesium for these parts is limited by the necessity of keeping the cross-section to thermal neutrons as low as possible. The alloys must also possess a high resistance to oxidation in CO2. Alloys which have been developed for this application include ZA, an alloy of magnesium with 0.5 to 0.7 pct Zr and AM503(S), an alloy of magnesium with 0.5 to 0.75 pct Mn. In the as-extruded condition these alloys are very weak and ductile in creep but it has been found that they can be strengthened to a significant extent by heat treatment. This paper describes the method of developing a high-creep resistance in ZA and AM503(S), the extent of the strengthening produced and discusses the probable mechanisms of strengthening. TEST MATERIALS Specimens were taken from typical casts of ZA and AM503(S) alloys extruded into 2 1/4-in.-diam bars, supplied by Magnesium Elektron Ltd. Typical analyses of the bars were as follows: The as-extruded mean grain diameter was 0.001 to 0.002 in. for the ZA alloy and 0.003 in. for the AM503(S) alloy. EXPERIMENTAL METHODS Extruded bars of ZA alloy, 2 1/4 in. in diameter and 9 in. long, were heat treated in electrical resistance furnaces in an atmosphere of flowing CO2 containing 50 to 300 ppm water, thereby reducing the extent of oxidation compared with that which would have occurred in air. Heat treatments were carried out at 600oc for times of 8, 24, 48, 72, and 96 hr and material was subsequently both furnace cooled and water quenched. In order to measure the effect of time of heat treatment, specimens were creep tested at 400°C and 336 psi for about 1000 hr. Subsequently, the behavior of material heat treated for 96 hr at 600°C and furnace cooled was tested at a variety of stresses from 200° to 500°C. Tests were also conducted at 200o and 400°C on material in the as-extruded condition for comparative purposes. With the AM503(S) alloy, only the effect of heat treatment at 565°C for 4 hr was examined. It has been shown1 that such a heat treatment produces marked strengthening in this alloy. Tests on this material were conducted at a variety of stresses at 200°, 300°, and 400oc with comparative tests on as-extruded material at 200o and 400°C. The creep tests were carried out on machines using dead-weight loading and direct micrometer strain measurements on specimens 5 in. long and 0.357 in. diameter. At temperatures of 400° C and below, the creep tests were conducted in air, but at higher temperatures an atmosphere of CO2 was used. Grain size measurements were made on ZA in the extruded and heat treated states and on each specimen after creep testing. This was done by a line count of a minimum of 20 grains in two or three random fields in the longitudinal and transverse directions. The same method was used for measuring the grain size of as-extruded AM503(S), but the grain size of the heat treated material was so large that this method could not be employed. For heat-treated AM503(S) the large grained characteristics (between 0.1 and 1 in.) were confirmed by the measurement of individual grains. In the case of the ZA alloy, specimens taken from various stages in the program were analysed for hydrogen by a combustion method. Material in various states was also analysed for the soluble and insoluble zirconium content by dissolving in dilute hydrochloric acid. This technique has been useda for the determination of amounts of zirconium present

Jan 1, 1962

By P. Greenfield, C. C. Smith, A. M. Taylor

J. E. Harris (Berkeley Nucclear Laboratories, England)—Greenfield et al.11 attribute abrupt changes in slope of their log o/log i curves for heat-treated Mg/0.5 pet Zr alloy (zA) to &apos;atmosphere&apos; locking. It is proposed here that a more reasonable explanation of the apparent strengthening at low rates of strain can be based on precipitation either during the preanneal or during the creep tests. All the tests were carried out above 0.5 Tm where solute atmospheres are likely to be largely evaporated2 and can migrate sufficiently rapidly so as not to impose any &apos;drag&apos; on the moving dislocations. McLean3 has derived an expression for determining the temperature Tc above which, due to the high-migration rate of the atmospheres, Cottrell or Suzuki locking can play no part in determining creep strength. This expression, which holds for an applied shear stress of not greater than 5 X 107 dynes per sq cm is: Tc/Tm= 7/6.8 - log10? where i = secondary creep rate The values for T, corresponding to the maximum and minimum reported creep rates at each temperature have been calculated from the data of Greenfield et al. These are given in Table VII. All the test temperatures were above T,, the margin being greater for the higher temperatures and for the lower strain rates where the breaks in the log s/log ? curves occurred. Dorn and his collaborators14, 17 have studied systematically the effect of solute hardening on the creep properties of an A1/3.2 at. pet Mg alloy. In the temperature range where strain aging occurred in tensile tests, abnormally high-activation energies for secondary creep were obtained but at temperatures above 0.43 Tm, solute alloying did not have any effect on the creep parameters. Moreover, there have been no reports of any strain aging phenomenon during elevated temperature tensile tests with ZA material.18 Instead of the observed strengthening being due to atmosphere locking, it is now proposed that precipitates play an important role in enhancing the creep strength of the material. There are two possibilities—precipitation of zirconium hydride during the high-temperature preanneal and/or precipitation of the hydride or a-zirconium during creep. On the basis of the former the results can be interpreted in terms of a critical stress being necessary to force the dislocations through or over preexisting precipitates. From the latter, if the strengthening is due to pre- cipitation during the test then hardening should be associated with a critical strain rate. At low rates of strain, time is available during the tests for precipitation to occur either directly onto dislocations (thus pinning them) or generally throughout the matrix (which would impede dislocation movements). Examination of the data of Greenfield et al. suggests that both mechanisms may be operative since they observed precipitation during creep and also found that their alloys exhibited high-creep strength in the early stages of the low-stress tests, i.e., before creep-induced precipitation had time to occur. It is not easy to understand why they considered that precipitation of zirconium hydride is unlikely to occur at 600°C while it can take place in tests in air at as low a temperature as 200°C. Precipitation of the hydride during the preanneal cannot be ruled out merely on the basis of metallographic examination. Hydride precipitates in ZA type alloys are very small and can only be accurately resolved in the electron microscope.9 For example, in this laboratory20 hydride platelets with major dimensions <(1/10) µ have been observed by electron transmission through thin film specimens of hy-drogenated ZA material. Complex interactions between dislocations and such particles are illustrated in Fig. 12. Additional evidence for precipitation during pre-annealing is provided by the data presented in Greenfield&apos;s Fig. 1 and Table IT. These show that the creep strength at 200o and 400°C increases with the time of preanneal at 600°C. Such increases cannot be explained on the basis of increases in grain size alone for further improvements in strength were observed when the material was annealed for longer times than that required to stabilize the grains. Although the main discussion is confined to ZA material, similar arguments can be used against the strain aging hypothesis proposed to explain the binary Mg/Mn alloy data. In this case no precipitation is possible during the preanneal, but precipitation-hardening during creep can occur.

Jan 1, 1962

By S. Saito, P. A. Beck

The crystal structure of MoNi3 was determined by means of X-ray diffraction. This structure is isotype with that of ovgered TiCu3. The lattice parameters are: a. = 5.064A, bo = 4.224A, co = 4.448A, and zf 0.157. If the orthorhombic distortion (slight relative to the corresponding orthohexagonal unit cell) is disregarded, the structure may be described in terms of a close-packed ordered atomic layer, stacked in the sequence: abab. The structztres of ordered TiCu3 and TiAl3 are homotectic. The three types of ordered hexagonal phases, iso-structural with TiNi3, MgCd3, and VCo3, are known to occur in AB3 alloys of transition elements of the first, second, ad third long periods. It was noted1 that phases with the TiNi3 structure occur selectively in alloys of Ti-group elements with Ni-group elements. In AB3 alloys of Ti-group and V-group elements with Co-group elements the AuCu3-type structure predominates.&apos; The vCO3 structure, which was determined very recently,&apos; has hexagonal symmetry, but the actual atomic arrangement here, too, is rather closely related to the ordered cubic structure of AuCu3-type. However, an ordered hexagonal close-packed structure of the MgCd3-type occurs in MOCO33 and WCO3.4 Consequently, the question arises as to whether or not the crystal structure of MoNi3 is also of the MgCd3-type. Grube and winkler5 found that MoNi3 has a hexagonal close-packed structure with a = 2.54A and c/a = 1.65. They pointed out that some additional weak diffraction lines could be observed in the powder pattern, which may have been due to an ordered atomic arrangement in this phase. However, no detailed information was obtained by them and the structure was apparently not further investigated by others. The present work was, therefore, undertaken in an attempt to determine in detail the structure of MoNi3, and to investigate the possibility of ordering. EXPERIMENTAL METHODS Alloys used in the present work were arc-melted in a water-cooled copper crucible under helium atmosphere. Electrolytic nickel and molybdenum, both 99.9 pct pure, were used. Chemical analyses were not made, but the melting loss was not higher than 2 pct for any alloy. Ingots were first homogenized at 1200°C for 48hr, quenched, heavily cold worked, and then annealed at 820" or 860°C for 1 week, followed by quenching in cold water. Powder specimens for X-ray work were prepared by crushing the heat-treated solid specimens. In order to remove strains, the powders were reannealed in evacuated scaled fused silica capsules for 6 hr at the same temperature at which the corresponding solid specimens were annealed. X-ray photographs were taken with an asymmetric focussing camera, using unfiltered CrK or CuK radiation. EXPERIMENTAL RESULTS The X-ray diffraction patterns of alloys containing 20.8, 25, and 26.4 at. pct Mo, homogenized at 1200°C, showed the face-centered-cubic structure of the Ni-base a-solid solution. It was revealed, however, by micrographic examination that the 26.4 at. pct Mo alloy contained in addition very small amounts of a second phase, in accordance with the phase diagram.6 On the other hand, the 20.8 at. pct Mo alloy after annealing at 820°C gave the X-ray diffraction pattern of the ordered face-centered-tetragonal MONi4.7 In this pattern several additional weak diffraction lines were also observed, corresponding to the strongest diffraction lines of MoNi3. The alloys containing 25 and 26.4 at. pct Mo after annealing at 820" or 860°C gave X-ray diffraction patterns, as shown in Tables I and 11, corresponding to MoNi3. Each one of the reflections which could be tentatively indexed on the hexagonal close-packed cell of Grube and Winkler,5 with the exception of the basal plane reflections, was split into a doublet, as seen in Table I. Since microscopically the alloy consisted of a single phase, it seemed probable that the lattice of MoNi3 is actually slightly deformed, as compared with the tentative hexagonal unit cell. In addition to these diffraction lines, several weak lines were also present, as shown in Table 11, which could not be indexed at all on the hexagonal close-packed cell considered. Satisfactory indexing of all diffraction lines observed was found to be possible by using an orthorhombic unit cell with ao = 5.064A, ft = 4.224A, and c = 4.448A. These values, whose accuracy is estimated to approximately ± 0.008A, correspond to 95.14A3 for the volume of the unit cell, and to an X-ray density of 9.50 g per cm3. If no attention were paid to the weak reflections listed in Table II, a reduced -unit cell of half the volume (a = 2.532A, b = 4.448A, and c = 4.224A), closely related to the orthohexagonal cell, might be used. The dimensions of the orthohexagonal cell of the same volume as the reduced cell are: a = 2.562A, b = 4.437 A, and c = 4.183A. It may be seen that in the reduced cell the a axis is slightly shorter, while the b and c axes are slightly longer than those corresponding to the orthohexagonal cell of the same volume. This slight orthorhombic distortion is re-

Jan 1, 1960

By D. Harker, E. Epremian

The constitution of the nickel-tungsten system has been studied by a number of investigators, the most recent of which are Ellinger and Sykes.1 On the basis of metallography, electrical resistivity and hardness measurements and some X ray diffraction work, they constructed a consitution diagram (Fig 1). Ellinger and Sykes report a0 for the alpha face-centered cubic phase (nickel saturated with tungsten) as 3.66?.‡ The gamma phase (tungsten saturated with nickel) is given as body-centered cubic, but no value of a. is recorded. At 43 pct tungsten by weight (approximately 20 at. pct) a beta phase is reported, but structure and lattice parameter are not known. Primarily on the basis of metallographic evidence, they conclude that beta is a new phase and rule out the possibility of formation of a superlattice since they- observe a new phase in the microstructure. Grube and Schlecht2 report an ordering reaction in a system similar to the Ni-W (Ni-Mo) and Harker3 has shown that NirMo forms a superlattice upon the pre-existing face-centered cubic lattice of the alpha phase. Elliniger arid Sykes observed a change in the diffraction pattern of a 4.3 pct W alloy upon aging and attributed it to the formation of a new phase. Thus, there appears to be some question as to the character of the beta phase reported by Ellinger and Sykes. The purpose of the present work is to determine precisely the structure and nature of the beta phase in the Ni-w system of X ray diffraction methods. Experimental Procedure One inch diameter ingots of 43.66 pct, 40.15 pct and 34.06 pct .tungsten by weight (19.8, 17.6 and 14.1 at. pct respectively) were melted and cast under vacuum from electrolytic nickel and pure wire filament grade tungsten. The ingots were soaked for 16 hr at 1300°C in a hydrogen atmosphere furnace, then swaged at this temperature and finally drawn to 0.020 in. diam wire. Some of the bar stock was retained in 1/2 in. diam rod for hardness and metallographic studies. Wire samples for diffraction work were sealed in evacuated quartz tubes and subjected to the various solution and aging heat treatments in a hydrogen furnace. X ray photograms were taken in a Debeye-Slierrer camera using copper K radiation filtered by nickel foil. Results X RAY DIFFRACTION The lattice parameters of the alpha and gamma phases at saturation were determined by an X ray photogram of the 19.8 at. pct W alloy after solution heat treatment at a temperature well within the alpha-gamma range above the peritectoid temperature (17 hr at 1150°C—oil quenched). The alpha phase was found to be face-centeted cubic with a. of 3.594 ± 0.001?, while the gamma phase was determined as body-centered cubic with a. of 3.158 ± 0.001?. Exactly the same phases and parameters were ohtained with the 17.6 at. pct W alloy for the same solution heat treatment. Thorough analysis was made of an X ray photogram of a 19.8 at. pct alloy sample in the quenched and aged condition (solution treated 1T hr at

Jan 1, 1950

By B. S. Tani, R. V. Schablaske, M. G. Chasanov

MEASUREMENTS of the solubility of scandium in liquid cadmium from 349" to 606°C by Chasanov, Hunt, Johnson, and eder&apos; led to the isolation and characterization of the intermetallic compound ScCQ. The solid phase found in equilibrium with a saturated solution of scandium in liquid cadmium above 422°C is ScCQ. The equilibrium solid phase below this temperature has not as yet been characterized. Hexagonal needles of ScCG were isolated from a 5 wt pct Sc alloy which had been ice-quenched from 500°C. Free cadmium was leached away from the intermetallic with saturated ammonium nitrate solution. The concentration of cadmium in successive leaches was followed polarographically and the leaching process was terminated when the rate of cadmium dissolution decreased markedly. Chemical analysis of the intermetallic thus isolated is as follows: 11.5 wt pct Sc and 88.3 wt pct Cd. The composition of ScCQ is 11.8 wt pct Sc and 88.2 wt pct Cd. X-ray diffraction powder photographs of ScCds taken in a 114.6-mm Debye-Scherrer camera with CuKa, radiation can be indexed on the basis of a hexagonal nit cell. Lattice coonstants are a. = 6.330 ± 0.001A to 6.324 i 0.001A and co = 4.853 i 0.001A. The a0 has a slight range with the lower value seemingly associated with the cadmium-rich terminus of the phase. With eight atoms in the unit cell the calculated intermetallic density is 7.54 g per cu cm; the density as determined by a liquid-displacement method is 7.7 g per cu cm. Powder-diffraction data for ScCQ are recorded in Table I. Stoichiometry, symmetry, unit-cell dimensions, and the number of atoms per unit cell indicate the MgsCd (D019) type structure for ScCQ; space group is D,&-P6,/mmc. Atomic coordinates are:

Jan 1, 1964

By Nicholas J. Grant, Bill C. Giessen

The phase diagram Ta-Ni has been treated repeatedly; investigations up to 1958 are summed up in Ref. 1. Since then, an equilibrium diagram has been presented by Kornilov and Pylaeva.2 They found the following intermediate phases: Ta2N; (CuA12 type),3 "TaNi" (p phase, Mo8Co7 type), TaNiz, and TaNi3 (Ticus type).5 Of these, the crystal structure of TaNin remained unknown, and no further literature reference was found. According to Kornilov and pylaeva,&apos; TaNil melts peri-tectically at 1420°C. A 5-g alloy of Ta + 66.7 at. pct Ni was prepared by inert-gas arc melting using 99.95 pct Ta rod (NRC-MG) and 99.9 pct Ni shot (Fisher). The weight loss after three melts was <2 mg; a microscopically homogeneous ingot resulted. As shown in Ref. 6, no oxygen or impurity pickup needed to be considered under these conditions. Specimens were annealed for 15 hr at 1350°C, 15 hr at 1205oC, and 15 hr at 875°C with subsequent powdering and stress relief for 10 min at 1350°C, 15 min at 1205oC, and 1 hr at 875oC, respectively. Micrographs and X-ray analysis (114.6 mm Norelco camera, filtered CuK, radiation) showed homogeneous one-phase alloys in the as-cast state and at all three temperatures, all having the same powder pattern except for broad lines in the as-cast state. From this it is concluded that either TaNi, melts congruently or its melting behavior is a transition between the eutectic and peritectic cases. Since it was found that very slight surface contamination on stress relieving can considerably alter the structure of similar phases (e.g.,TaPt3),7 patterns before and after stress relief were also compared; they were identical except for line broadening in the non-stressrelieved condition, and two faint impurity lines in the stress-relieved samples. The powder pattern is presented in Table I. All lines were accounted for by indexing with a tetragonal lattice, 0Yh- I4/mmm , with a, = 3.154 ± 0.001A, co = 7.905 * 0.002i and c/a = 2.506. The atomic positions are: 1000; 1/2, 1/2, 1/2] + 2Ta(a): 000; + 4Ni(e): *(002); z = 0.333 * 0.002 This proves TaNi2 to be a representative of the MoSiz (Cllb) type. The variable parameter was determined by grouping the visually estimated intensi- ties according to their 2 indices, plotting their F values, and varying z for best fit, which was obtained at z = 0.333= 1/3. Since absorption was not considered, only the relative intensities with similar 28 can be expected to agree. The interatomic distances are presented in Table 11; the standard error is *o.o2A, resulting chiefly from the uncertainty in z. These distances indicate a coordination number 10 for both kinds of atoms and show that the pseudohexagonal layers along (110) are rather un-distorted. The mean atomic volume of 13.1A3 is close to the Vegard&apos;s law value of 13.3A3, showing

Jan 1, 1964