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By E. J. Dulis, A. Kasak, R. C. Westgren

The potential of uirought tungsten- and tantaluw-rich alloys of the W-Ta-Mo-Cb system was investigated for high-strength structural applications above 2500° F. Appreciable strengthening of tung-sten and tantalum—essentially attributable to solid-solzction effects—was obtained with binary, ternary, and quaternary alloys. Tensile strengths as high as 67,000 psi were achieved at 3000 OF. ThE quest for wrought structural materials which possess good strength properties at temperatures above 2000°F has led to a considerable research effort during the past decade. In addition to exploring the potential of various high-melting-point refractory metals (such as molybdenum, columbium, tantalum, and tungsten) for very high-temperature structural applications, alloy-development programs have been undertaken to achieve greater strengths than could be achieved with unalloyed refractory metals. The methods of strengthening refractory metal alloys have included both solid-solution and dispersion strengthening. General relationships among the relevant properties (melting point, recrystallization temperature, and high-temperature strength) of refractory metals indicate that the highest strengths at temperatures of 2500°F or higher would be obtained with tungsten-or tantalum-base alloys. Therefore, the present investigation was undertaken to determine the high-temperature strength potential of solid-solution strengthened alloys based on the binary system W-Ta; to effect further strengthening, minor additions of molybdenum and columbium (at the 6 and 12 pct levels) were made. The portion of the W-Ta-Mo-Cb quaternary alloy system of interest is shown schematically in Fig. 1. The component metals—W, Ta, Mo, and Cb—have a bcc structure at all temperatures, and their binary systems are mutually completely soluble.' Complete solid solubility in the W-Ta-Mo and W-Ta-Cb alloy systems has been demonstrated,' and, therefore, it was expected that the quarternary alloys of the system would also exhibit complete solid solubility at all temperatures. In the virtual absence of contamination by interstitial elements, all the alloys would be truly solid-solution strengthened. Twenty specific compositions of this investigation included binary, ternary, and quaternary alloys of the W-Ta-Mo-Cb system as well as unalloyed tungsten and tantalum. The compositions are shown in Table I. EXPERIMENTAL PROCEDURE Consumable-electrode vacuum-arc melting with ac power was used to produce small laboratory-sized, cylindrically shaped ingots (1-1/4 in. in diameter and 2 to 3-1/2 in. long) of the twenty compositions. A furnace was specially constructed to melt as many as four electrode rods simultaneously into molds lined with tungsten or tantalum sheet. High-purity rods of tungsten, tantalum, molybdenum, and columbium were used for consumable electrodes; the diameter of each rod was determined by the desired weight percentage of the component metal in a given alloy. The details of the construction and operation of the melting furnace will be discussed in another p~blication.

Jan 1, 1964

By S. Andrew Kulin, L. Kaufman

A general treatment of the broadening of X-ray double-crystal spectrometer rocking curves due to distributions of tilts and strains has been carried out. The results of this treatment have been applied to the case where dislocations in a crystal give rise to both tilts and strains. On this basis it is found that the rocking-curve halfwidth due to imperfections in the crystal, ßC , increases with increasing Bragg angle, 8. These considerations predict linear relationships between & and tan2 , and ßCand tan 8, for Gaussian and Cauchy distributions of dislocations, respectively. The zero intercept of the ßC us 8 curve, which is a measure of the degree of imperfection of the crystal, is found to depend directly on the distribution rather than the number of dislocations. In addition, the slope-intercept ratio for the ßc - ? curve has been calculated for both the Gaussian and Cauchy distributions. Experimental determination of the - 8 curves for a series of copper single crystals prepared by the Bridgeman and Czochralski methods yields results in agreement with the calculated slope-intercept ratio for a Cauchy distribution of dislocations. CERTAIN X-ray techniques have been used to study the perfection of single crystals. Gay, Hirsch, and Kelly have considered the spreading of spots into arcs on Debye-Sherrer rings due to imperfections. The Double-Crystal Spectrometer has also been applied to this problem.2 The characteristics of Double-Crystal Spectrometer Rocking Curves have been described in the literature by various workers.2-4 By assuming a random spacing of dislocations which give rise to a Gaussian distribution of misorientations relative to some mean orientation in a crystal Gay, et al.,1 arrive at the conclu- sion that the most probable misorientation is given by where h is the spacing between dislocations, and 8 and are the relative misorientations of neighboring regions. If ßC is the halfwidth of the rocking curve (the width at one-half the peak intensity) due to dislocations in the crystal then5

Jan 1, 1960

By C. M. Schwartz, J. R. Bridge, D. A. Vaughan

THERMAL expansion coefficients of a uranium were originally reported' on the basis of X-ray diffraction measurement of lattice constants at 25°, 300°, and 650°C. These data have been reproduced by Katz and Rabinowitch.' CuK radiation had been used in this work, with consequent crowding of the patterns. Considerable overlap of the back-reflection lines was observed as the temperature was raised. Subsequent reexamination of the data led to the conclusion that errors had resulted from failure to obtain unequivocal indexing of the high angle reflections at elevated temperatures. The measurements have been repeated, using FeK radiation, which provided sufficient dispersion to assure proper indexing of the reflections, at each temperature level. The unit cell dimensions were re-determined at ten temperatures, from 25" to 650°C. Schuch and Laquer easured the macroscopic contraction from room temperature down to —253°C, and reported a negative value from —210" to —253°C; they suggested the possibility of the occurrence of a phase change. In the present work, the lattice constants of uranium have been measured down to —253°C, to test this hypothesis. Filings were prepared from a single piece of pure uranium bar stock. They were carefully cleaned with a magnet and pickled in nitric acid to remove traces of iron from the file. They were then annealed at 600°C in a sealed evacuated silica tube. The annealed filings were pickled in strong nitric acid to remove any oxide layer, washed in water and alcohol, quickly dried, and sealed in evacuated thin-walled silica capillary tubes. If properly sealed, the sample could be heated to the a-ß transforination temperature without significant buildup of the diffraction pattern of oxide. The high temperature X-ray diffraction camera was modified from the design of Hume-Rothery and Reynolds.' The thermocouple used to record the specimen temperature was calibrated from lattice-constant measurements of a standard silver specimen, using the Hume-Rothery and Reynolds values for silver over the temperature range from 25" to 700°C. Temperatures were reproducible to 210°C. Temperatures to —210°C were attained by passing precooled gas over the sample. The gas from the cooling train was directed over the sample capillary tube and thermocouple by means of a chimney of 1-mil polystyrene. The 36-gage Cu-constantan thermocouple had been calibrated by

Jan 1, 1957

By A. J. Jacobs, G. Katz

MANY of the studies of intermetallic compounds containing uranium were performed during the early 1940's under the aegis of the Manhattan Project. Subsequently, much of this work was declassified and published after 1949. In some instances this early work, completed with relatively impure materials, represents the only source of X-ray diffraction powder data available in the literature. In the case of the intermetallic compound U,Fe some discrepancies in the powder pattern exist in the literature. Since this compound has been prepared in this laboratory, it is believed that the publication of the indexed powder pattern would help clarify the conflict in the literature. In studies of the U-Fe system, Gordon and Kauf-mannl and Grogan and Clews2 independently reported the intermetallic compound U,Fe in 1950. The crystal structure was described by Baenziger, Rundle, Snow, and Wilson3 in 1950. It is isostructural with U,Mn, U,Ni, and U,Co and crystallizes in a body-centered tetragonal lattice. The lattice constants determined by Baenziger et al. are: giving an X-ray density = 17.7 g cm-3 for 4 mol per unit cell. The compound used in this study was prepared by melting a stoichiometric mixture of the constituent metals in an argon-arc furnace using a nonconsum-mable tungsten electrode. Before the argon of 99.98 pct purity was introduced into the furnace, it was passed through CaC1, to remove water vapor and afterwards through a stainless steel tube containing calcium turnings heated at 600°C for the removal of nitrogen and oxygen. The purity of the uranium used was better than 99.9 pct and that of the iron was 99.97 pct. Before and during melting a zirconium getter was used to further purify the argon atmos-

Jan 1, 1962

By C. Altstetter

THE work herein reported is restricted to the carbides which occur in quenched and tempered AISI 43XX steels with carbon contents up to 0.40 pct and silicon additions of up to 3 pct. In view of the instability and extremely small size of the carbides formed at low tempering temperatures, the technique for successfully preparing specimens for X-ray diffraction will be outlined. The alloys listed in Table I were obtained through the courtesy of the United States Steel Corp. in the form of 1/2-in. rounds forged from 100 lb. induction furnace heats (except for 4337 which was a commercial heat). The stock was normalized and then swaged and drawn to 15 mil wire with anneals at 1200F between passes. The wire was austenitized for 45 min in evacuated vycor capsules and quenched into iced brine with simultaneous smashing of the capsule. Tempering was done in air with a water quench after tempering. The carbides were extracted in a simple cell using a solution of 1M KC1 and 0.5 pct citric acid with an initial current density of 0.1 amp per sq cm. One end of a short length of wire was immersed in the solution, and the current at constant voltage was noted as a function of time. After about an hour the current dropped sharply because of the decrease in specimen cross-section. At this point it was found that the dissolution could be stopped and that the very fine wire which then resulted was just large enough to permit handling of the extracted precipitate still clinging to it, yet so small that it diffracted and absorbed only a negligible amount of the X-radiation. This rod of residue with a convenient handle of undissolved wire was rinsed in distilled water. alcohol, and acetone. Then it was dipped in a thin solution of cellulose-acetate cement and dried in vacuum. The resulting specimen was straight, uniform in density, easily handled, but most important, was completely sealed and never exposed to air. Furthermore, the residue had never been subjected to strong acids or rough handling such as in the extraction-replica technique or in the complete extraction to a powdered residue. It was found that improperly coated specimens were pyrophoric, turning to oxide with a dull red glow as they were exposed to air and yielding patterns of Fe2O3 and Fe3O4. The steels containing 3 pct Si were especially difficult to prepare for this reason. The specimens were put in a 57 mm Straumanis camera with double pinholes or slits and irradiated with filtered-chromium radiation. Readable patterns were obtained in less than an hour. A preliminary finding of some note was that for both tempered and as-quenched specimens of steels 4337 and 4337 (1.5 Si). M23C6 patterns were found along with the patterns of other constituents of the residues. This result was somewhat surprising in that previous investigators had reported that this carbide did not appear in a 0.38 pct C, 0.48 pct Mo steel1 or in chromium steels of less than about 10 pct Cr.2 Although the total amount of carbide-forming alloying elements is less than 2 pct, due to their mutual interaction and the action of the plastic deformation in promoting equilibrium, this carbide was able to form even in the steel containing 1.5 pct Si. M23C6 was not detected in the 4337 (3.0 Si) steel and the lower-carbon steels were not investigated in this condition. It is very likely then that the steels studied herein underwent a fourth stage of tempering during the anneals at 1200°F. This result has significance in that even a small amount of undissolved M23C6 in a low-carbon, low-alloy steel would exert a large effect on its hardenability. Its presence would also influence the mechanical properties by decreasing the carbon content of the matrix. Annealing in vacuum for 1 to 4 hr in the austenite field removed all traces of MZ3C+ The results on carbide precipitation during tempering, summarized in Table I, are in agreement with those of Klingler et al.3 for the higher carbon steels. For the AISI 4337 steels it is noteworthy that in the steels with added silicon the E carbide persists to longer times and higher temperatures and that silicon delays the formation of cementite. The results for the lowzr-carbon steels parallel those of the higher-carbon grade. The appearance of E carbide in the AISI 4315 is significant. There is considerable disagreem-nt in the literature as to whether this carbide forms in the tempering of steels containing less than about 0.2 pct C. Following the detection of E carbide in a 0.18 pct C plain-carbon steel,4 its occurrence in a steel containing chromium and molybdenum should be expected. The fact that the low-carbon steels have the same carbide-precipitation sequence as the high-carbon steels has bearing on the larger problem of the exact tempering reactions in all steels. Following the suggestion of Roberts et al.,' the first stage has been generally assumed to result in a metastable equilibrium of c carbide and martensite of about 0.25 pct C. From this it was concluded that a steel having less than 0.25 pct C should then be under-saturated with respect to c carbide and should not precipitate this carbide upon tempering. In view of the experimental findings of c carbide in steels hav-

Jan 1, 1962

By F. von Gemmingen, E. J. Fasiska, L. Zwell

EARLIER studies of the dependence of creep on structure1 and of the dependence of creep rupture on creep behavior2 did not include detailed discussion of the phases present in the specimens under examination. It is of interest to determine the nature and amounts of such phases present since it is well known that these are dependent on composition, heat treatment and creep conditions.3 This investigation has therefore been undertaken to identify these constituents and to determine their relative amounts. This report presents the results of this investigation and describes an improved "extraction replica" technique developed in the course of the work. The composition of the Type 316 austenitic stainless steels studied in this investigation is given in Table I. The specimens were solution treated at 2000°F for 1/2 hr and water quenched. Those specimens subjected to prestrain at room temperature Methods for extracting precipitate particles from materials for electron and X-ray diffraction analysis have been described by Fisher,4 Smith and Nutting: and Booker and coworkers.6'7 Electrolytic extraction methods have been described by Andrews and Hughes.8 The first two methods have been used at this Laboratory, but have not proved satisfactory for many problems requiring X-ray diffraction analysis. It has been difficult to remove the replicas or to avoid tearing them during removal. These difficulties are overcome by backing the replica with a water-soluble plastic such as Dupont 51-05 Elvanol (polyvinyl alcohol). The backing increases the thickness of the replica so that it can be mechanically stripped from unloosened particles without folding or tearing. This procedure eliminates the stripping of wet replicas, which usually have a low tear strength. By stripping replicas after drying, it is possible to extract partially loosened particles which otherwise would remain imbedded in the metal. The modified method is as follows: after the specimen is polished, it is etched for 60 min in modified glyceregia consisting of 30 ml glycerol, 7 ml nitric acid, and 4 ml of hydrochloric acid. The sample is then washed, air dried, and coated with a 20 pct Baker and Adamson 1611 collodion (85 pct amyl acetate by volume) film. After the collodion film is dry (about 15 min), the sample is again etched in the modified glyceregia for 50 min, washed with isopropyl alcohol (to prevent dissolving the collodion) and air dried. A very thick coat of polyvinyl alcohol (about 50 pct solution "Elvanol Dupont 51-05" in water) is poured over the sample and is permitted to dry for about 24 hr. The composite film containing the precipitates is then stripped from the specimen and floated, polyvinyl alcohol side down, in water (at about 50°C) until the polyvinyl alcohol dissolves. This usually takes about 15 min. Should any of the polyvinyl alcohol remain on the replica, it does not give a crystalline diffraction pattern and therefore does not hinder identification of the precipitates. The extraction replica, floating in water, is picked up on a glass fiber and mounted in the Debye-Scherrer camera for X-ray diffraction analysis. Concentration of the etchant, and also etching time, had to be increased for several of the samples. Fig. 1 shows two extraction replicas taken from different areas of spec. M74-37; X-ray analysis showed a strong diffraction pattern of M23C6 and a medium one of u phase. A

Jan 1, 1962

By J. A. Berger, R. J. Towner

The pjPocesses of polygonization and subgrain growth were followed in slightly stretched 99.99 pct A1 single crystals heated for cumulative times at 400°, 500°, and 600°C. Changes in sub-grain size and boundary angle were determined from measurements on X-ray micrographs. CAHN1, 2 studied polygonization in stretched and heated aluminum single crystals of 99.99 pct A1 using various techniques, including etch pits, Laue patterns, and a slight restretching of heated specimens to reveal small changes in lattice orientation by the direction of new slip lines. He found that kink bands, which had well-defined boundaries lying in a plane perpendicular to the slip direction (at least in the early stages of deformation), formed during stretching. Also, he noted that bending occurred about the <211> axis lying in the (111) slip plane perpendicular to the <110> slip direction. His studies of polygonization were largely confined to the kink bands rather than to the weakly bent matrix regions between bands. The minimum temperature required to bring about polygonization was established at about 450 "C. Guinier and Tenevin used a focusing Laue X-ray diffraction technique to study polygonization in aluminum single-crystal specimens of 99.99 pct purity. Stretching the crystals 5 pct in tension caused a widening of the focused Laue spots. After heating for 4 hr at 450°C, their method revealed no change in the specimen. Above 450°C polygonization was detected and further annealing near 600°C led to subgrain growth. They concluded that the orientation of the crystal relative to the axis of deformation had no marked effect on polygonization. Gay and Honey-combe4 using an X-ray microbeam technique found that polygonization did not occur in a stretched aluminum crystal heated at 250oC, although some decrease in the yield strength occurred. When the temperature was raised to 475oC, the asterism became broken up as a result of polygonization. Honeycombe5 noted that reflections on X-ray mi-

Jan 1, 1961

By Ganesh P. Mohanty, James J. Wert

THE brittleness of the intermetallics usually render their deformation studies at ordinary temperatures using conventional techniques inadequate. On the other hand, although X-ray line broadening measurements is not a complementary technique, it provides a means for gaining limited but useful information on the cold worked state of these materials. In the present instance, a study of the effects of cold work in the lead telluride intermetallic compound was carried out by analyzing the diffraction profiles of the deformed and the corresponding annealed samples. An ingot of PbTe was prepared by induction melting high-purity lead and tellurium in a quartz crucible under an atmosphere of argon. After homo-genization, the ingot was ground to -325 mesh at room temperature, and using a polished die the cold- worked powder was pressed into the form of flat faced briquets for diffraction measurements. A spectrometer with 0.125 deg per min scanning velocity, CuKa radiation, pulse height analyzer, and a proportional counter were employed in the X-ray measurements, and the powder peaks were collected from the sample in fully cold-worked state and after it had been annealed to relieve the effects of cold work completely. For reliable estimates of the peak extremities, small angular ranges where the tails merged into the background were point counted. Fourier inversions of the experimental peaks were carried out in an IBM 705 computer using the procedures introduced by stokes.&apos; Both the cosine and sine components of the Fourier series were used to take into account any peak assymetry arising

Jan 1, 1963

By D. Geiselman, A. G. Guy

Single cvystals were grown from high-purity magnesium containing known amounts of nitvogen in the range 0.0008 to 0.0048 wt pet. Crystals of known ovientation were tested in tension in an Instron ma chine to determine the yield strength and to obsevue wheather a yield point occurred. Slowly cooled crystals or those given a solution heat treatment did not show a yield point. However, crystals that were aged following a solution treatment showed a yield point for all of the nitrogen contents studied. It was concluded that nitrogen caused the yield point by the Cottrell mechanism. NITROGEN has been shown to produce sharp yield points in single crystals of cadmium, zinc,2&apos;3 ß-brass,4 and iron,5,6 as well as in polycrystalline iron7 and molybdenum.8,9 Since magnesium has a structure similar to zinc and cadmium, it seemed reasonable that magnesium should also exhibit a sharp yield point provided it contained sufficient nitrogen. Bobalek and Shrader10 reported a total nitrogen content of 0.002 to 0.0065 wt pct in com- mercial magnesium alloys, an amount well in excess of that required by theory. However. magnesium differs from cadmium and zinc in that it forms a stable nitride, Mg3N2, which has a standard free energy of formation of -95,480 cal per mole at 25" c." If rather than being in solid solution, the nitrogen were predominantly combined as the nitride, it could not act to produce a yield point. This type of behavior is the basis for the elimination of strain aging and a yield point in steel by the addition of strong nitride formers such as titanium,12 columbium,13 aluminum,14 vanadium,15 and boron.16,17 Thus, there appeared to be factors both favorable and unfavorable to the production by nitrogen of a sharp yield point in magnesium, and the purpose of this investigation was to determine the actual behavior of magnesium crystals containing known amounts of nitrogen.

Jan 1, 1960

By Joachim J. Hauser

Experiments on latent hardening were peyformed by compressing single crystals along a direction perpendicular to the tension axis. The slope and length of easy glide in the tension test were found to depend only on prior deformation in the same slip plane. Prior deformation on a different slip plane changes the stress level of the resulting stress-strain curve. The yield points appearing upon reloading after prior extension and unloading were related to the end of easy glide. SEVERAL researchers have studied the latent hardening due to deformation of a crystal by slip on a slip System after prior deformation. These experiments can be divided into those in which the prior deformation was on the same plane as the subsequent and those in which the two deformation processes were in different planes. In the former category are the experiments of Buckley and Entwistle,1 Parker and washburn,2 and Haasen and Kelly.3 The latter case has not been studied systematically; it was the main purpose of this investigation to produce this type of latent hardening and explain the results in terms of the existing theories of work hardening. In general, tension producing slip on a certain slip system can be preceded by tension, transverse compression or longitudinal compression, each with predictable dislocation movement and intersection. The intersection of dislocations can lead to glissile or sessile jogs, Cottrell-Lomer locks and other sessile dislocations. The effect on the stress-strain curve could depend on which combination of the former mechanisms is operating. Haasen and Kelly3 have studied the yield points which occur in aluminum and nickel single crystals upon reloading after prior unloading in a tension experiment. They attributed this effect to the anchoring of dislocations occurring during unloading. As Cottrell and stokes4 have shown that dislocations cutting through the "forest" could only lead to reversible changes, they attributed the anchoring to the formation of sessile dislocations during unloading. However, different kinds of sessile dislocations could be formed during unloading, and it was the purpose of this experiment to determine whether Cottrell-Lomer locks are responsible for the yield effect and for the end of easy glide. The case where a longitudinal compression is followed by tension along the same axis is commonly referred to as a Bauschinger test. This type of effect was studied by Buckley and Entwistle1 on aluminum single crystals and by Parker and washburn2 on zinc single crystals. In such a test, the tension and the compression activate the same slip plane with opposite slip directions. The use of sideways compression in the present experiments permits the activation of different types of slip systems and the study of their effect on the easy glide region and on the transition between the elastic and easy glide region. The theory of seeger5 for the flow stress in fee materials is applied to explain the latent hardening. EXPERTMENTAL PROCEDURE All the single crystals used in this investigation had an axial orientation close to <210>, called the "0.5" orientation. This is the orientation for which the tensile axis is 45 deg from both the slip plane and the slip direction. The single crystals were grown from the melt under a helium atmosphere using milled graphite boats,=at a rate of 8.6 mm per min. The silver used in the experiment was 99.98 pct pure. The single crystals had a square cross section about 0.9 by 0.9 cm and a length of 14 cm. The orientation of the specimen was determined within ±2 deg by the Laue back-reflection method. The specimens were annealed at 940&apos; ± 2°C in a helium atmosphere for 24 hr and then furnace cooled over a period of 7 hr. The specimens were electropolished in a solution of 9 pct KCN in water. The specimens were tested in a soft-type tensile machine (the load is prescribed) up to 3 pct strain. The stress was increased continuously at approximately 30 g per mm2 per min. The strain was measured over a 5 cm gage length with a mechanical extensometer employing an optical lever. The strain and stress were measured with accuracies of i 2 X 10-5 and ± 2 g per mm2, respectively. The remainder of the stress-strain curve up to 20 pct strain was obtained in a hard-type tensile machine (the strain rate is prescribed). The strain and the stress were measured in that machine with an accuracy of ±2 pct. The compression tests were performed in the hard-type machine using accurately machined steel blocks without lubrication. The blocks were used so as to apply a uniform compression over a length of 13 cm. The strains were measured on the hard-type machine and with a micrometer.

Jan 1, 1962

By T. J. Koppenaal, M. E. Fine

A yield point effect attributed to short-range ordevi?g (SRO) occurs in Cu base Al. At at 296°K varies with heat treatment, decreasing as the annealing ternperature is raised .from 433Oto 598°K. Davies aid Cahn&apos; observed a corresponding decrease in SRO. (523 °K anneal, measured at 77°K) is approximateZy proportional to the variations of A7 with strain rate and testing temperature are also Consistent with the idea that is associated with SRO. A preliminary investigation of the tensile properties of a Cu-Al single crystals showed the presence of a rather strong yield-point effect (drop in flow stress after initial yielding). The object of this research was to investigate its origin and behavior. a Cu-Al alloys are particularly interesting because diffuse X-ray scattering measurements by Davies and Cahn,&apos; Houska and Averbach,&apos; and Borie established the presence of short-range order. The degree of local order may be changed with heat treatment.&apos; cottrel14 suggested that the presence of local order might result in a yield-point effect, and thus the possibility exists here for experimentally ascertaining the importance of short-range order with respect to yield points in these alloys. Since a 12 pct difference exists between the atomic sizes, elastic or Cottrell locking5 must also be considered. Further, Howie and swanne have shown that the stacking fault energy of copper is reduced by aluminum additions. The width of extended dislocations should thereby increase. hus the conditions appear attractive for Suzuki locking.&apos; Finally, the possibility of stress-induced order at dislocations, schoeck locking,&apos; must also be examined, EXPERIMENTAL PROCEDURE Alloys up to 14 at. pct Al were prepared by induction melting high-purity (99.999 pct) Cu and (99.996 pct) Al in a graphite boat under a dynamic vacuum of 5 X 10o mm of Hg. After homogenizing the ingots at 900°C for at least 24 hr under vacuum, they were rolled with intermediate anneals to strips 1.55 mm thick. Single crystals 10 in. long were grown by lowering strips, contained in a split graphite mold sealed in fused quartz at 5 X lo-&apos; mm of Hg, through a single coil induction heater at a constant rate of 1/2 in. per hr. Tensile specimens 1.25 in. long were cut from the single crystal strips and reduced cross sections about 0.7 in. long and 3.0 to 3.5 mm2 in area were introduced by filing and abrading.8 To remove the worked portion about 10 pct of the cross-sectional area was removed by etching. Back-reflection Laue photographs of a filed and etched specimen were taken before and after annealing at 900°c for 24 hr. Small, well defined Laue spots were obtained with no visual difference in the two photographs. Further, specimens with and without the reduced sections began yielding at about the same stress. Hence, for our purposes, filing and abrading did not affect the structure of the specimens. Each single crystal specimen was annealed at 900° c in vacuum for at least 24 hr and furnace cooled; while cooling through the range of 250o to 200°c, the rate was about 55°C per hr. Orientations were determined by the usual back-reflection Laue

Jan 1, 1962

By W. C. Elli, M. E. Fine

YOUNG&apos;S modulus of elasticity in metals ordinarily decreases with rising temperature. The range of the thermoelastic coefficient at room tem- 1/E dE/dT perature (temperature coefficient of modulus, is illustrated1 by the values for tungsten and hard-drawn aluminum, —95 and —1220x10-6 eg C-1. However, a nearly zero thermoelastic coefficient is observed in some ferromagnetic alloys over a limited temperature range. In these alloys, as the temperature is raised, an increase in modulus arising from loss of ferromagnetism compensates the normal decrease. Iron-nickel alloys containing 36 to 52 pct Ni behave in this manner. In the present investiga- tion, the dependence of the modulus and thermo-elastic coefficient on cold working and annealing were studied in iron-nickel alloys in this range of nickel. Although these alloys, when fully annealed, have a coefficient near zero over a very small temperature interval, the temperature range of low coefficient can be extended greatly by straining and then stress-relief annealing. The modulus of face-centered cubic iron-nickel alloys annealed at 1000°C does not vary linearly with composition at room temperature but, as shown by the solid line of fig. 1, from Koster,&apos; is minimum at 40 pct Ni and maximum at 87 pct Ni. The modulus increases with applied magnetic field but retains the minimum near 40 pct Ni. Schematic change of modulus with temperature for three compositions is shown in fig. 2.&apos;. &apos; With increasing temperature, the slope becomes less negative, goes through zero (temperature of minimum modulus for the alloy), becomes positive, and resumes its normal negative value above the Curie

Jan 1, 1951

By P. Chiotti, G. R. Kilp

Thermal, metallographic, vapor pressure, and X-ray data were obtained to establish the phase diagram for the zinc-zzrconiz~m system. Five compounds corresponding to the stoi-chiometric formulas ZrZn, ZrZn,, ZrZn,, ZrZn,, and ZrZn14 were observed. All these compounds, with the exception of ZrZn2, which melts congruently at 1180°C under constrained zinc-vapor conditions, undergo pexitectic reactians. The temperature at which the zinc vapor pressure is I atm for a series of alloys was determined from vapor-pressure measurements. The data obtained are summarized in the construction of a I-atm-pressure phase diagram and a phase diagram corresponding to a pressure of less than 10 atm. THE purpose of this investigation was to establish the phase diagram for the zinc-zirconium system. Thermal, metallographic, vapor pressure, and X-ray data were employed in determining the phase regions. Partial investigations of this system have been conducted by Gebhardt1 and Carlson and Borders.&apos; Carlson and Borders studied the high-zirconium region and established the existence of a eutectic at 69 wt pct Zr with a melting point of 1015°C. The terminal phases of the eutectic horizontal were shown to be an intermetallic compound ZrZn and a solid solution of ß zirconium containing 21 wt pct Zn. The ß solid solution decomposes into ZrZn and a zirconium at 750°C. The eutectoid composition is given as 15 wt pct Zn, and the solubility of zinc in a zirconium at temperatures below 750°C is indicated to be negligible. Gebhardt studied the zinc-rich region and observed a lowering of the melting point of zinc from 419.5" to 416°C and temperature horizontals at 545" and970°C. Some preliminary observations by Chiotti, Ratliff, and Kilp were reported by Hayes.2 pietrokowsky3 has reported the compound ZrZn2 to have a cubic MgCu2 structure with ao = 7.396A. MATERIALS AND EXPERIMENTAL PROCEDURES The metals employed in the preparation of alloys were Bunker Hill slab zinc or Baker analyzed reagent granulated zinc, both 99.99 pct pure and hafnium-free iodide-process crystal bar zirconium obtained from the Westinghouse Electric Corp. The zirconium contained 200 ppm Fe, 200 ppm Si, 100 ppm C, and minor amounts of other impurities. The zirconium was milled or machined into thin chips or shavings. These were cleaned with a nitric-hydrofluoric acid solution, rinsed with water, and acetone, and dried just prior to their use in alloy preparation. The granulated zinc was similarly cleaned using dilute nitric or hydrochloric acid. Weighed quantities of these materials, 20 to 30 g total, were mixed and pressed at 20,000 to 70,000 psi to give relatively dense compacts. During the early part of this investigation the pressed compacts were placed in MgO-15 wt pct MgF, crucibles which were then sealed inside of quartz ampules. The compacts were given various prolonged heat treatments prior to their use for thermal analyses, or vapor-pressure measurements. Because of expansion of the compacts and the relatively high zinc vapor pressure it was difficult to heat to the melting temperatures of the alloys without failure of the quartz ampules. Homogenization at temperatures below the melting temperature gave brittle, porous alloys unsuitable for metallographic examination. It was also difficult to prevent condensation and segregation of zinc on the colder parts of the quartz ampules during heating and cooling operations. These problems were eliminated to a great extent by the use of tantalum crucibles. Tantalum proved to be a satisfactory container with little or no reaction between the alloys and the tantalum. Small tantalum thermocouple wells were successfully welded in the bottom of these crucibles. Pressed compacts were sealed inside the tantalum crucibles by welding on preformed caps under an argon atmosphere. Heat treating and differential thermal analysis were combined into a single operation. The experimental sample assembly is shown in Fig. 1. This assembly was enclosed inside a stainless-steel tube heating chamber which could be evacuated and filled with an inert gas. The thermocouple leads were brought out of the heating chamber between two rubber gaskets used to provide a vacuum seal for the water-cooled head. Most of the compounds in this system undergo peritectic decomposition. After heating above the temperature of a particular peritectic horizontal the sample was cooled to just below the peritectic temperature and held at temperature for several hours. The sample was then reheated through the peritectic temperature and the size of the thermal arrest, if still present, compared with the one previously obtained. If the thermal arrest was not characteristic for the alloy composition being investigated its magnitude diminished and repeated cycling and annealing eventually eliminated it. The peritectic thermal arrests characteristic of a particular composition were established in this manner.

Jan 1, 1960

By E. T. Hayes, A. H. Roberson, M. H. Davies

ZIRCONIUM has been produced on a pilot-plant scale for only a few years, but the potential uses have led a large number of research establishments to engage in a thorough study of the metal and its alloys. The work described in this paper is part of a cooperative project between the Bureau of Mines and the Air Materiel Command. The Zr-Cr system was one of the first investigated because of the possibilities of improving the properties at elevated temperatures, the chemical corrosion resistance, and the mechanical properties of zirconium in a manner similar to the enhancement of the properties of titanium by additions of chromium. There is no published work on the Zr-Cr system but from the similarity of the metals involved it was expected that it would be similar to the Zr-Fe&apos; and Ti-Cr&apos; systems. The materials used in this investigation were prepared in the Bureau of Mines laboratory at Albany, Ore. Zirconium was produced by magnesium reduction of zirconium tetrachloride, and a typical analysis is as follows: Fe, 0.06 pct; Ox, 0.08; N?, 0.01; C, 0.02; and other impurities such as Al, Pb, Ni, Ti, and Si less than 0.01 pct each. High purity chromium was prepared by treating crushed electrolytic chromium in a stream of dried and purified hydrogen." The resulting powder contained about 0.01 pct 0 and about 0.1 pct total metallic impurities. All alloys were prepared by arc-melting 50 g briquetted compacts of the desired composition in a Kroll-type" arc furnace using an inert atmosphere. The furnace was evacuated twice and backfilled with helium, which was gettered by melting a center zirconium button immediately before the alloys were melted. Alloys were remelted at least once to insure greater uniformity of composition and subsequently were annealed in vacuum at 1250°C for 48 hr. Fairly homogeneous alloys were obtained by this means; a slight loss of chromium from the surface by evaporation during the high temperature homogenization was noted. All alloys were analyzed for chromium and gave results in good agreement with the nominal composition. Spot checks on tungsten and nitrogen showed pick-up of these elements to be negligible. Over 70 alloys were prepared for use in this investigation; only the critical ones are shown in Table I. Alloys containing up to 10 pct Cr were amenable to hot working at 850°C and a number of these were sheath rolled to 1/16 in. thickness. Specimens were cut from the sheet for use as metallographic samples. For the thermal analysis a differential couple was used in conjunction with an X-Y recorder, the temperature of the specimen and the difference in ternperature between it and the standard nickel body were recorded simultaneously. Heating and cooling rates of 5°C per min were used. The sensitivity of the instrument was such that a difference in temperature between the specimen and standard equivalent to 0.1 mv produced a deflection of 1 in. on the recording chart. The chromel-alumel thermocouples were checked against a Bureau of Standards calibrated thermocouple. Melting-point determinations were made in a high vacuum induction furnace using an optical pyrometer. The pyrometer, calibrated against nickel, copper, and zirconium (iodide process) under near black body conditions, was focused on the base of a hole drilled in cylindrical samples. A North American Philips Geiger counter X-ray spectrometer was used for all diffraction studies. This instrument, in addition to supplying precise intensity measurements of planar reflections, has an added advantage in that metallographic specimens mounted in bakelite can be used directly, and this

Jan 1, 1953

By R. L. Smith, J. L. Rutherford

ZONE refining, as developed by W. G. Pfann,1 has been used extensively for the purification of semiconductors. This method has made it possible to obtain the extremely high purity material necessary for the transistor industry. It has also been utilized to some extent for the purification of relatively low-melting-point metals. However, very little attention has been given to reactive, high-melting-point materials, with the exception of silicon. For this element, it has been necessary to use the floating zone technique in order to avoid contamination from the crucible containing the melt. The method is one in which a narrow molten zone is formed in a vertical rod by induction heating. The molten zone is supported between the two solid sections of the rod by surface tension. It is then moved longitudinally along the rod in order to effect a redistribution of solute. This technique has an advantage over the horizontal boat method, since crucible contamination is avoided. It has the disadvantage of being a much more difficult technique than zone refining in a crucible. Furthermore, it is necessarily a slow process, since only one zone at a time can be formed. However, the floating zone process offers a means of obtaining high-purity metals that are either not available, or can only be obtained in powder or pellet form as the result of complex chemical or electrochemical methods. It should be emphasized that the process is not effective in removing all impurity elements. Those that cannot be redistributed in an ingot during zone melting must be removed by some other means. Very little is known of the prope~ties of very high purity reactive metals such as iron, titanium, zirconium, beryllium, etc. It is quite likely that trace elements in such metals can affect their properties drastically. Therefore, one of the primary objectives of this work is to study the properties of metals which have been obtained in the purest form available and then zone refined. Trace elements can be introduced in a variety of ways, such as by inserting wafers between solid portions of the ingot to be melted, by placing the

Jan 1, 1958

By C. H. Mathewson

EXCEPTING the joint sessions on gases in metals held during the day on Tuesday, the Institute of .Metals opened its activities with a division dinner at the Commodore on Tuesday evening, with Sam Tour, retiring chairman, presiding. W. M. Corse, secretary-treasurer, outlined the financial status of the division and stated the investment fund is becoming large enough so that in the near future it will be possible to pay all expenses of a foreign lecturer once in two years and not rely on an extended speaking tour to cover expenses. W. B. Price reported on his attendance at the Zurich, Switzerland, meeting of the International Society of Testing Materials and gave a graphic account of his visit to the Grand Salon, his meeting with Mussolini, and his audience with the Pope. Buffalo was announced as the place of the fall meeting, to be held during the week of Oct. 3.

Jan 1, 1932

Jan 1, 1946

Jan 1, 1943

By E. A. Anderson

THIS seems to be the year for superlatives in A.I.M.E. meetings. The programs of the various Divisions and Institute committees offered an abundance of interesting and valuable information in the form of technical papers, symposia. and lectures to large and interested audiences. The Institute of Metals Division may hold up its head with pride for its own program. With six technical sessions, three full-day symposia, and the annual I.M.D. dinner, four meeting days were not enough and many simultaneous sessions were required. The quantity and quality of the paper were equaled by the numbers and interest of those attending.

Jan 1, 1944

By F. H. Spedding

From thermal, metallographic, X-ray, dilatometric, and electrical resistance data a Phase diagram is proposed for the La-C system. TWO compounds are formed, body-centered-cubic Laz C, having a large range of solid solubility, and body -centered-tetrago-nal Lac2 . The former melts incongruently at 1415°C, and at 25OC it has an electrical resistivity about two and one-half times that of bure lanthanum. The latter melts congruently at 2356°C and at room temperature has an electrical resistivity about equal to that of bure lanthanum. The addition of carbon to La lowers the melting Point of La about 115&apos; C, raises the higher (B-Y) transfomzation about 10" C and appears to have no effect on the lower ( a-0) transformation. The addition of carbon appears to lower the oxygen content in the metal and improve the machinability; however, the tendency to oxidize is increased. Two eutectics are formed in the system. The first occurs at 2.2 pct C and melts at 806" C, while the second occurs between Lac2 and C with a melting point of2271"C. PETTERSSON,~ in 1895, was the first to prepare lanthanum dicarbide by heating the oxide with carbon in an electric furnace. He showed that this yellow, crystalline but brittle carbide had a formula corresponding to LaCz and that it reacted with water with the evolution of hydrogen and hydrocarbons and the formation of the hydrated oxide. Von Stackelberg&apos;s investigation of the crystal structure of the MCz carbides showed that the lanthanum dicarbide is of the tetragonal calcium dicarbide-type structure. He found the lattice parameters were a = 3.92 and c = 6.56.* Bredig,&apos; using X-ray methods, showed that the room-temperature form of lanthanum dicarbide is stable up to 1750 °C and that above this temperature it transformsoto a face-centered-cubic structure, a = 6.0 ± O.lA, probably of the pyrite, FeSzstruc- typ? The reported discovery of two new cerium carbides, suggested that a corresponding face-centered-cubic lanthanum monocarbide and a body-centered-cubic lanthanum sesquicarbide might exist. This paper describes work on the lanthanum-carbon system which is part of a study of the rare earth metals and their alloys now in progress in this laboratory. EXPERIMENTAL PROCEDURE Source of Materials—The lanthanum metal was prepared at the Ames Laboratory by metal1o;hermic reduction of the fluoride with calcium metal. The results of spectrographic and chemical analysis indicated the presence of 0.01 pct Y, Al, Cu, Fe, and Si; 0.02 pct Ca and Mg; 230 ppm C; and 115 ppm N. The carbon used was of two types: 1) "National Special Graphite Spectroscopic Electrodes," and

Jan 1, 1960